Upload
others
View
22
Download
0
Embed Size (px)
Citation preview
International Conference
(Bio)Degradable Polymersfrom Renewable Resources
Vienna, November 18 – 21, 2007
ABSTRACTS
Polish Academy of SciencesScientific Centre in Vienna
The Conference is held under auspices of the
European Polymer Federation
Sponsors
Polish Academy of SciencesPolska Akademia Nauk
Ministry of Science and Higher Education, PolandMinisterstwo Nauki i Szkolnictwa Wyzszego
Federal Ministry of Transport, Innovation and Technology, AustriaBundesministerium für Verkehr, Innovation und Technologie
ACS PUBLICATIONSHIGH QUALITY. HIGH IMPACT.
CONTENTS
Conference Committees and Organizers . . . . . . . . . . . . . . . . . . . . . . . . . 5
Conference Programme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Conference Venues. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
Overview of Abstracts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Abstracts of Invited Lectures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
Abstracts of Poster Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
List of Participants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
SCIENTIFIC COMMITTEE
Ann-Christine Albertsson (Sweden) – co-ChairGerhart Braunegg (Austria) – co-Chair
Francesco Ciardelli (Italy)Danuta Ciechanska (Poland)
Andrzej Dworak (Poland)Zbigniew Florjanczyk (Poland)
Shiro Kobayashi (Japan)Izabella Krucinska (Poland)
Andrej Krzan (Slovenia)Christopher K. Ober (USA)Gabriel Rokicki (Poland)
Tadeusz Spychaj (Poland)Robert F. Stepto (UK)Piotr Tomasik (Poland)
Jean-Pierre Vairon (France)Danuta Zuchowska (Poland)
Chairman of the Conference
Stanislaw Penczek
Chairman of the Organizing Committee
Stanislaw Slomkowski
Conference Secretary
Andrzej Nadolny
CO-ORGANIZERS OF THE CONFERENCE
Polish Academy of Sciences, Scientific Centre in Vienna, Austria
International Network (Bio)degradable Polymers from Renewable Resources
Centre of Molecular and Macromolecular Studies,Polish Academy of Sciences, Lodz, Poland
Institute of Biotechnology and Biochemical Engineering,Graz University of Technology, Graz, Austria
5
CONFERENCE PROGRAMME
TIME VENUE
Sunday, November 18 Scientific Centre
17:00 – 21:00 Registration and Welcome Party
Monday, November 19 Studio 44
8:00 – 9:15 Registration
9:15 – 9:25 Opening: Stanislaw Penczek and Stanislaw Slomkowski
Chair: Maria Nowakowska9:25 – 10:00 I-01 Ramani Narayan: BioPlastics and Biodegradable Plastics – Role
in sustainability, Reducing Carbon Footprint and EnvironmentalResponsibility
10:00 – 10:20 Coffee break
Chair: Zbigniew Florjanczyk10:20 – 10:55 I-02 Ann-Christine Albertsson: (Bio)Degradable Polymers from
Renewable Resources
10:55 – 11:30 I-03 Andrzej Duda: Controlled Polymerization of Cyclic Esters
11:30 – 11:50 Coffee break
Chair: Mariastella Scandola11:50 – 12:25 I-04 Philippe Dubois: Polylactide-based Materials: from Micro- to
Nanocompositions
12:25 – 13:00 I-05 Andrzej Galeski: Physical Modification of Polylactide
13:00 – 14:30 Buffet lunch
Chair: Andrzej Dworak14:30 – 15:05 I-06 Richard A. Gross: New Biocatalytic Routes to Monomers,
Macromers and Polymers
15:05 – 15:40 I-07 Francesco Ciardelli: Modification of Biorelated Macromoleculesthrough Grafting of Short and Long Side Chains
15:40 – 16:15 I-08 Yves Gnanou: Dextran Based Block Copolymers: Synthesis andSelf Assembly in Solution
16:30 – 18:30 Poster session, Wine and cheeseAuthors-in-attendance time:16:30 – 17:30 odd numbers, 17:30 – 18:30 even numbers
6
TIME VENUE
Tuesday, November 20 Studio 44
Chair: Danuta Ciechanska9:00 – 9:35 I-09 Piet J. Lemstra: Petro vs. Bio-based Plastics
9:35 – 10:10 I-10 Jan Feijen: Injectable Biodegradable Hydrogels for ProteinDelivery
10:10 – 10:40 Coffee break
Chair: Izabella Krucinska10:40 – 11:15 I-11 Martin Moeller: Polyether - Polyester Conjugates for
Biodegradable Hydrophilic Microgels and Hyperbranched Polymers
11:15 – 11:50 I-12 Emo Chiellini: Hydro- and Oxo-Biodegradable Polymers fromFossil Feedstock vs. Their Counterparts from Renewable Resources
11:50 – 12:25 I-13 Gerhart Braunegg: Polyhydroxyalkanoates (PHAs):Biodegradable Polyesters from Agricultural Waste and SurplusMaterials
Renaissance Penta Vienna Hotel
19:00 – 23:00 Conference Dinner
Wednesday, November 21 Scientific Centre
Chair: Andrej Krzan9:00 – 9:35 I-14 Marek M. Kowalczuk: (Bio)degradation of Polymeric Materials
Containing PHA and their Synthetic Analogues
9:35 – 10:10 I-15 Andreas Greiner: Novel Biodegradable Polymers and Scaffoldsfor Tissue Engineering
10:10 – 10:40 Coffee break
Chair: Gerhart Braunegg10:40 – 11:15 I-16 Maria Nowakowska: Novel Photosensitizers Based on
Polysaccharides
11:15 – 11:50 I-17 Piotr Tomasik: The Polarized Light-Induced EnzymaticFormation and Degradation of Biopolymers
11:50 – 12:00 Closing remarks
7
CONFERENCE VENUES
Scientific Centre of the Polish Academy of Sciences in ViennaBoerhaavegasse 25, A-1030 Wien
and
Studio 44, Austrian LotteriesRennweg 44, A-1038 Wien
1
2
50m
ARTIS Hotel
71
Aspangstr.
Schützeng.
S7
Rennweg
Bo
erh
aave
g.
Kle
istg
.
Sta
nis
lau
sg.
Esla
rng.
Aspangstr.
Kleistgasse
1 – Scientific Centre 2 – Studio 44entrance: Kleistgasse
8
OVERVIEW OF ABSTRACTS
Invited LecturesI-01 R. Narayan: BioPlastics and Biodegradable Plastics – Role in sustainability, Reducing Carbon
Footprint and Environmental Responsibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
I-02 A.-C. Albertsson: (Bio)Degradable Polymers from Renewable Resources . . . . . . . . . . . . . . . . . . . . . . 15
I-03 A. Duda: Controlled Polymerization of Cyclic Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
I-04 M. Murariu, A. Da Silva Ferreira, M. Pluta, M. Alexandre, L. Bonnaud, and P. Dubois:Polylactide-based Materials: from Macro- to Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
I-05 A. Galeski, E. Piorkowska, and M. Pluta: Physical Modification of Polylactide . . . . . . . . . . . . . . . . . . . 18
I-06 R. A. Gross: New Biocatalytic Routes to Monomers, Macromers and Polymers . . . . . . . . . . . . . . . . . . 20
I-07 F. Ciardelli, S. Bronco, M. Bertoldo, F. Signori, M. B. Coltelli, and G. Zampano: Modification ofBiorelated Macromolecules through Grafting of Short and Long Side Chains . . . . . . . . . . . . . . . . . . . . 21
I-08 C. Houga, J.-F. Lemeins, R. Borsali, D. Taton, and Y. Gnanou: Dextran-Based BlockCopolymers: Synthesis and Self-Assembly in Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
I-09 P. J. Lemstra: Petro vs. Bio-based Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24I-10 C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen: Injectable
Biodegradable Hydrogels for Protein Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
I-11 H. Keul, M. Hans, M. Erberich, J. Meyer, and M. Moeller: Polyether- Polyester Conjugates forBiodegradable Hydrophilic Microgels and Hyperbranched Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
I-12 E. Chiellini: Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock vs their Counterpartsfrom Renewable Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
I-13 G. Braunegg, A. Atlic, M. Koller, and C. Kutschera: Polyhydroxyalkanoates (PHAs):Biodegradable Polyesters from Agricultural Waste and Surplus Material . . . . . . . . . . . . . . . . . . . . . . . . 28
I-14 M. M. Kowalczuk: (Bio)degradation of Polymeric Materials Containing PHA and their SyntheticAnalogues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
I-15 Y. Chen, R. Dersch, M. Gensheimer, U. Bourdiot, S. Agarwal, J. H. Wendorff, and A. Greiner:Novel Biodegradable Polymers and Scaffolds for Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 30
I-16 M. Nowakowska, K. Szczubiałka, S. Zapotoczny, and Ł. Moczek: Novel Photosensitizers Basedon Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
I-17 A. Molenda-Konieczny, M. Fiedorowicz, and P. Tomasik: The Polarized Light-induced EnzymaticFormation and Degradation of Biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Poster Contributions
P-01 A. Piegat and M. El Fray: Biodegradation of Polyester Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . 34
P-02 P. Rychter, G. Adamus, and M. M. Kowalczuk: ESI-MS Studies of Slow-release Conjugate of2,4-D with a-PHB for Agricultural Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
P-03 P. Wozniak, S. Sosnowski, and S. Slomkowski: Polymer-inorganic Hybrid Materials for TissueEngineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
P-04 E. Vidovic, D. Klee, and H. Höcker: Biodegradable Hydrogels Based on Poly(vinyl alcohol)-graft-[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
P-05 J. B. Chardhuri, M. G. Davidson, M. J. Ellis, M. D. Jones, and X. Wu: Fabrication ofHoneycomb-Structured Polylactide and Poly(lactide-co-glycolide) Films and their Use forOsteoblast-Like Cell Culture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
P-06 H. Nilsson, A. Olsson, M. Lindström, and T. Iversen: Bark Suberin as a Renewable Source ofLong-chain ω-Hydroxyalkanoic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
9
P-07 A. Tiwari and A. P. Mishra: Studied on Electrical Conducting Biopolymer-poly(thiazole)Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
P-08 A. Zemaitatitis, R. Klimaviciute, and R. Kavaliauskaite: Antibacterial Activity of CationicStarch-iodine Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
P-09 A. Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra: Chitosan-co-polyaniline/WO3.nH2ONanocomposites: Green Polymer Composite for Sensor Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 42
P-10 K. Wilpiszewska, S. Spychaj, and T. Spychaj: Chemical Modification of Starch withHexamethylene Diisocyanate Amide Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
P-11 K. Wilpiszewska and T. Spychaj: Starch Plasticisation via Twin-screw Extrusion . . . . . . . . . . . . . . . . . 44
P-12 C. Duncianu and C. Vasile: Study of Interpolymeric Complexes Based on Polymers fromRenewable Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
P-13 A. Pandey and B. Garnaik: Homopolymerization and Copolymerization of L, L-Lactide inPresence of Novel Zinc Proline Organocmetallic Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
P-14 F. Faÿ, I. Linossier, and K. Vallée-Réhel: Poly(lactic acid) Microcapsules Containing BioactiveMolecules: Study of Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
P-15 W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk: Degradation Studyof Polymers from Renewable Resources and their Blends in Industrial Composting Pile . . . . . . . . . . . 48
P-16 D. Macocinschi, D. Filip, and S. Vlad: Polyurethanes from Renewable Resources as Candidatesfor Friendly Environment New Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
P-17 P. Dacko, M. Sobota, H. Janeczek, J. Dzwonkowski, J. Gołebiewski, and M. M. Kowalczuk:Viscoelastic and Thermal Proprieties of the Biodegradable Polymer Materials ContainingPolylactide, Aliphatic-Aromatic Polyester and Synthetic Poly[(R,S)-3-hydroxybutyrate] Receivedvia Injection Moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
P-18 V. Sedlarik, N. Saha, J. Bobalova, and P. Saha: Biodegradation of Blown Films Based onPolylactide Acid in Natural Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
P-19 M. Bertoldo, F. Cognigni, F. Signori, S. Bronco, and F. Ciardelli: Molecular Modification ofGelatine by Reaction with Isocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
P-20 M.-B. Coltelli, F. Signori, C. Toncelli, C. E. Rondán, S. Bronco, and F. Ciardelli: Biodegradableand Compostable PLA-based Formulations to Replace Plastic Disposable Commodities . . . . . . . . . . 53
P-21 C. Peptu, V. Harabagiu, B. C. Simionescu, G. Adamus, and M. M. Kowalczuk: MassSpectrometry Studies of Cyclic Esters Ring Opening Oligomerization in the Presence ofDisperse Red 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
P-22 D. Ciolacu and F. Ciolacu: Supramolecular Structure – a Key Parameter for CelluloseBiodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
P-23 M. Kawalec, G. Adamus, H. Janeczek, P. Kurcok, M. M. Kowalczuk, and M. Scandola: Kineticsof Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
P-24 R. P. Dumitriu and C. Vasile: Novel Biodegradable Matrices for Drug Delivery . . . . . . . . . . . . . . . . . . . 57
P-25 M. Michalak, M. Kawalec, C. Peptu, P. Kurcok, and M. M. Kowalczuk: Divergent Synthesis ofβ-Cyclodextrin-Cored Star -Poly([R,S]-3-hydroxybutyrate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
P-26 J.-R. Sarasua, E. Zuza, A. López-Arraiza, N. Imaz, and E. Meaurio: Crystallinity and CrystallineConfinement of the Amorphous Phase in Polylactides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
P-27 D. Filip, A. I. Cosutchi, C. Hulubei, and S. Ioan: Liquid Crystal Template Applied forPolyimide-Cellulose Derivative Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
P-28 I. Spiridon, M. Ichim, and N. Anghel: Biomass Compounds with Pharmacological Applications . . . . . 61
P-29 M. Socka, M. Florczak, and A. Duda: Homo- and Copolymerization of Cyclic Aliphatic Esterswith Suppression of Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
P-30 C.-I. Liu and C.-Y. Huang: Acid Modification and Application of Biodegradable Polymer-Starch . . . . . 63
10
P-31 H.-K. Lao, E. Renard, V. Langlois, X. Pennanec, M. Cuart, K. Vallee-Rehel, and I. Linossier:Characterization of the Radical Polymeric Grafting of Hydroxylethyl Methacrylate ontoPoly(3-hydroxybutyrate-co-3-hydroxyvalerate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
P-32 J. Jaworska, Y. Hu, J. Wei, J. Kasperczyk, P. Dobrzynski, and S. Li: Degradation Process ofBioresorbable PGLC Terpolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
P-33 G. Bogoeva-Gaceva, M. Avella, V. Srebrenkoska, A. Grozdanov, A. Buzarovska, M. E. Errico,and G. Gentile: Sustainable Green Polymer Composites Based on PLA . . . . . . . . . . . . . . . . . . . . . . . . 66
P-34 A. Błasinska and J. Drobnik: Accelerated Wound Repair by Di-O-butyrylchitin, the Polymer forNew Non-Woven Dressing Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
P-35 A. Šišková, W. Sikorska, M. Musioł, M. M. Kowalczuk, and W. J. Kowalski: Characterization ofBiodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means ofElectrospray Ionization-mass Spectrometry after a Partial Depolymerization . . . . . . . . . . . . . . . . . . . . 68
P-36 M. Scandola, E. Zini, and M. L. Focarete: Commercial Biodegradable Polymers Reinforced withFlax Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
P-37 K. Gebarowska, J. Kasperczyk, P. Dobrzynski, M. Scandola, and E. Zini: Investigation of NovelShape-Memory Polymers’ Chain Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
P-38 M. Scandola, C. Gualandi, M. L. Focarete, P. Dobrzynski, M. Kawalec, and P. Wilczek:Bioresorbable Electrospun Non-woven Scaffolds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
P-39 J. M. Cardamone: Keratin Coating for Wool Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
P-40 K. S. Mikkonen, M. P. Yadav, S. Willför, K. B. Hicks, and M. Tenkanen: Films from SpruceGalactoglucomannan Blended with Poly (Vinyl Alcohol), Corn Arabinoxylan and KonjacGlucomannan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
P-41 B. Zywicka, E. Zaczynska, A. Czarny, S. Pielka, J. Karas, and M. Szymonowicz: Activation ofTranscription Nuclear Factor NF-κB and Induction of Inflammatory Cytokines in ImmuneResponse on Resorbable Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
P-42 M. Szymonowicz, B. Zywicka, S. Pielka, L. Solski, D. Haznar, and J. Pluta: Influence of theGelatin-Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and TissueReaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
P-43 M. Szymonowicz, A. Marcinkowska, B. Zywicka, S. Pielka, A. Gamian, D. Haznar, and J. Pluta:Cellular Response after Stimulation of the Gelatin-Alginate Matrixes . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
P-44 R. Makuška and R. Kulbokaitë: Synthesis and Properties of Chitosan – Poly(ethylene glycol)Comb Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
P-45 M. Koller, P. Hesse, A. Atlic, C. Hermann-Krauss, C. Kutschera, and G. Braunegg:Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
P-46 U. Janèiauskaite and R. Makuška: Synthesis and Study of Chitosan – Oligosaccharide GraftCopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
P-47 M. Koller, P. Hesse, A. Atlic, C. Hermann-Krauss, C. Kutschera, and G. Braunegg: Selection ofCarbon Feed Stocks for Cost-Efficient Polyhydroxyalkanoate (PHA) Production . . . . . . . . . . . . . . . . . . 80
P-48 W.-L. Lu, C.-I. Liu, and C.-Y. Huang: Properties and Degradation of PVA/Starch Blends with aPVA-g-MA Compatibilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
P-49 L. Santonja-Blasco, J. D. Badia, R. Moriana, and A. Ribes-Greus: Thermal and MechanicalBehaviour of a Commercial Poly(lactid acid) Submitted to Soil Burial Test . . . . . . . . . . . . . . . . . . . . . . 82
P-50 J. D. Badia, R. Moriana, L. Santonja-Blasco, and A. Ribes-Greus: A ThermogravimetricApproach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid) . . . . . . . . . . . . . 83
P-51 R. Moriana, L. Santonja-Blasco, J. D. Badia, and A. Ribes-Greus: Comparative Study about theBiodegradability and the Mechanical Performance of Different Biocomposites Based onThermoplastic Starch Reinforced with Cotton Fibre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
11
P-52 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Improving the Processing Ability and MechanicalStrength of Starch/PVA Blends through Plasma and Acid Modification . . . . . . . . . . . . . . . . . . . . . . . . . 85
P-53 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Biodegradation of Starch and PVA/Starch BlendEnhanced by Rhizopus Arrhizus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
P-54 M. Kowalczyk and E. Piorkowska: Biodegradable Blends of Polylactide and Natural Rubber . . . . . . . 87P-55 G. Adamus and M. M. Kowalczuk: Synthetic Analogues of PHA Anionic Ring-opening
Polymerization of β-alkoxy Substituted β-lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88P-56 D. Ciechanska, J. Wietecha, J. Kazimierczak, D. Wawro, and E. Grzesiak: Biopolymer-based
Fluorescent Sensors for Quality Control of Food Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89P-57 S. Povolo and S. Casella: Polyhydroxyalkanoates Production by Isolates from a Polluted
Salt-lagoon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90P-58 M. Sobota, H. Janeczek, P. Dacko, and M. M. Kowalczuk: Thermal Properties for Blend of
Poly[(L)-lactide] and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate] . . . . . . . . . . . . . . . . 91
P-59 I. Poljanšek, B. Brulc, M. Gricar, E. Žagar, A. Kržan, and M. Žigon: Synthesis of Poly(asparticacid)-b-Polylactide Block Copolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
P-60 K. Krasowska, M. Rutkowska, and M. M. Kowalczuk: Compostability of Aliphatic-aromaticCopolyester and their Blends under Natural Weather Depending Conditions . . . . . . . . . . . . . . . . . . . . 93
P-61 A. Konieczna-Molenda, M. Molenda, M. Fiedorowicz, and P. Tomasik: Illumination of Cellulosewith Linearly Polarized Visible Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
P-62 W. Tomaszewski, A. Duda, M. Szadkowski, J. Libiszowski, and D. Ciechanska: Poly(l-lactide)Nano- and Micro-fibers by Electrospinning: Influence of Poly(l-lactide) Molecular Weight . . . . . . . . . . 95
P-63 G. C. Chitanu, I. Popescu, A. G. Anghelescu-Dogaru, and I. Dumistracel: BiomedicalApplications of Maleic Anhydride Copolymers and Their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
P-64 D. M. Suflet, G. C. Chitanu, and V. Trandafir: Complexation of Phosphorylated Cellulose withCollagen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
P-65 I. M. Pelin, G. C. Chitanu, V. Trandafir, and Z. Vuluga: Effect of Collagen on Sparingly SolubleInorganic Salts Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
P-66 I. Popescu, M. I. Popa, and G. C. Chitanu: Supramolecular Systems from Natural Polymers andMaleic Polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
P-67 M. Gadzinowski, B. Miksa, and S. Slomkowski: Polylactide-polyglycidol Block Copolymer as aNew Nanoparticles Forming Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .100
P-68 M. Pluta and A. Galeski: Structure Evolution in Amorphous Poly(L/DL-lactide) upon Plain StrainCompression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .101
P-69 M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, and P. Dubois: Structureand Physical Properties of PLA/Calcium Sulfate Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .102
P-70 M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak: Materials of Functional PropertiesBased on Biodegradable Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103
P-71 D. Babic, Z. Kacarevic-Popovic, G. Mikova, and I. Chodak: Influence of Gamma-radiation onPCL/PHB Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104
P-72 S. Agarwal and L. Ren: Synthesis and Properties Evaluation of a New Class of DegradablePolymers: Poly(vinyl-co-ester)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105
P-73 A. Gregorova and R. Wimmer: Dynamic-Mechanical and Thermal Properties of BiodegradableComposites from Polylactic Acid (PLA) Reinforced with Wood Fibres . . . . . . . . . . . . . . . . . . . . . . . . .106
P-74 T. Eren and B. Taslica: New Derivatives of Methyl Oleate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .107
12
ABSTRACTSOF INVITEDLECTURES
13
I-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
BioPlastics and Biodegradable Plastics -- Role in sustainability,
Reducing Carbon Footprint and Environmental Responsibility
Ramani Narayan
Department of Chemical Engineering & Materials Science,
Michigan State University, East Lansing MI 48824
BioPlastics offers the intrinsic value proposition for managing our carbon in a sustainable
manner and provide a carbon neutral footprint in complete harmony with the natural
biological carbon cycle. Biodegradable plastics offers the potential to manage single use,
short-life, disposable packaging and consumer goods in a environmentally responsible
manner. Plastics recycling and waste to energy operations also offer environmentally
responsible approaches to managing plastic waste.
Many questions arise:
What is a biobased plastic? Why and how are they sustainable and environmentally
responsible? How does one identify and measure biobased content? How does one document
and quantify the positive environmental attributes of biobased plastics?
What about biodegradable plastics? Is degrading the plastic the goal? Or is it more important
to ensure that these degraded fragments are completely consumed/assimilated by the
microorganisms within a reasonable and short time in the specified disposal environment?
Composting is one such environment under which biodegradability occurs. In the composting
environment, the nature of the environment, the degree of microbial utilization
(biodegradation), and the time frame within which it occurs are specified in an ASTM
standard. What are the environmental consequences and risks associated with degradable or
partially biodegradable plastics without ensuing complete biodegradability? What is the
relationship between biobased and biodegradable, biobased but not biodegradable? How does
one document the reduced carbon footprint (LCA) and obtain carbon credits.
The answers to these fundamental questions provide the basis and scientific rationale for
designing and engineering biobased, and biodegradable plastics, and lay the foundation for
standards and regulations world-wide. Life Cycle Assessment (LCAs) of these
renewable/biobased materials often show reduced environmental impact and energy use when
compared to petroleum-based materials, which we will review, and learn. We will look at
successful technology exemplars that showcase the above “bio” model.
Keywords: bioplastics; biodegradable plastics; carbon footprint
____________________________________
[1] Narayan, Ramani, Biobased and Biodegradable Materials, Rationale, Drivers, & Technology Exemplars,
ACS (An American Chemical Society Publication) Symposium Ser 939, Ch 18, pg 282, 2006
14
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-02
(Bio)Degradable Polymers from Renewable Resources
Ann-Christine Albertsson
Fibre and Polymer Technology, School of Chemical Science and Engineering,
Royal Institute of Technology, SE-100 44 Stockholm, Sweden
During the last years, the interest in renewable and biodegradable materials has
increased tremendously in the global community. The global market for renewable and
biodegradable materials is anticipated to increase immensely in the near future following the
raising societal awareness of the climate situation and the expected results of a continued
consumer mentality. Still, the use of renewable and biodegradable materials has not been
realized to any significant extent and few really renewable materials are available on the
market.
Increasing the fundamental knowledge of the degradation and environmental
interactions of materials based on renewable and biodegradable polymers are the keys to
fulfilling the increasing demand of new materials. There is also a need for new materials and
more discriminating tools to predict the safety and degradation performance of the new
materials throughout the life cycle of the material and products. Indicator products and
chromatographic fingerprinting are thus powerful tools for the degradation state prediction [1-
3]. The material should have right mechanical properties and, if degradable, a suitable
degradation time for the given application and it should totally degrade to non-toxic water
soluble degradation products. The environment where the material is going to be used has a
large influence on the degradation and release rate. Materials of the future need to be
developed and made to function in all aspects of its existence, including production, use and
waste management.
Forestry and agricultural biomass holds huge potential as a renewable source of
reactants and materials, being cheap and abundant. Hemicelluloses present such a material
group, available for the production of functional materials, mainly hydrogels [4] and barrier
films [5-6]. PLA is another interesting candidate and one of the very few polymeric materials
today that are available from renewable resources, e.g. by fermentation of agricultural waste.
Keywords: degradable; bioresorbable polymers; renewable, green materials
____________________________________
[1] M. Hakkarainen; A.-C. Albertsson Adv. Polym. Sci., 169, 177 (2004).
[2] M. Hakkarainen; A. Höglund; K. Odelius; A.-C. Albertsson J. Am. Chem. Soc., 129, 6308 (2007).
[3] L. Burman; A.-C . Albertsson; M. Hakkarainen Adv. Polym. Sci.(2007)
http://dx.doi.org/10.1007/12_2007_114.
[4] M.S. Lindblad; E. Ranucci; A.-C. Albertsson Macromol. Rapid Comm., 22 (12), 962 (2001).
[5] J. Hartman, A.-C. Albertsson, J. Sjoberg Biomacromolecules, 7(6), 1983 (2006).
[6] J. Hartman, A.-C. Albertsson, M.S. Lindblad, J. Sjöberg, J.Appl. Polym. Sci., 100(4), 2985-2991 (2006).
15
I-03 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Controlled Polymerization of Cyclic Esters
Andrzej Duda
Centre of Molecular and Macromolecular Studies Polish Academy of Sciences,
Sienkiewicza 112, Lodz, Poland
Ring-Opening Polymerization (ROP) of cyclic esters will be discussed, stressing that
independently on the initiator/catalyst used, i.e.: covalent metal alkoxide [1], carboxylate [2,
3], or acetyloacetonate [3], polymerization proceeds on the alkoxide species. Preparative
applications of the most often used catalysts: aluminum tris-isopropoxide and tin(II) bis-
octoate will be presented in more detail, on the example of synthesis of linear and star-like
poly(ε-caprolactone)s and polylactides [1-5] as well as poly[(R)-lactide]/poly[(S)-lactide]
stereocomplexes [6, 7].
It will be also shown that initiation with aluminum alkoxides that bear bulky, bidendate
phenolate-type ligands at the metal atom, results in an efficient suppression of both intra- and
intermolecular transesterification [6, 8, 9]. The latter finding enabled preparation of the (S,S)-
LA and ε-caprolactone (CL) di- and triblock copolymers via the poly(CL) (PCL) block
growth initiation with the living poly[(S,S)-LA] (PLA*) [9]. In the previous attempts to
prepare block copolymers this way only random copolyesters were obtained because the
PLA* + CL cross-propagation rate was lower than that of the PLA-CL* + PLA
transesterification.
Finally, it will be revealed that inversion of the initiator configuration may lead to a
substantial change of the reactivity ratios [10]. It is a well-known fact that CL
homopolymerization rate constant (kCC) exceeds considerably that of (S,S)-LA
homopolymerization (kLL). For example, in polymerizations initiated with (S)-(+)-2,2’-[1,1’-
binaphtyl-2,2’-diylbis-(nitrylomethylidyno)]-diphenolate aluminum isopropoxide (SBO2Al-
OiPr): kCC/kLL ≈ 60 (THF, 80 °C). However, the LA comonomer is consumed first from the
CL/(S,S)-LA mixture. The corresponding reactivity ratios are equal to: rL = 322 and rC = 19.
The observed phenomena can be explained assuming that the cross-propagation rate constant
kLC is relatively low. Change of the initiator configuration, from S to R, results in consumption
of both comonomers with a comparable rate (rL = 1.5 i rC = 1.9).
Keywords: aliphatic polyesters; lactide; ε-caprolactone; living polymerization; star-shaped polymers;
stereocomplexes; block copolymers; reactivity ratios; transesterification
____________________________________
[1] A. Kowalski, J. Libiszowski, A. Duda, S. Penczek, Macromolecules 33, 1964 (2000).
[2] A. Kowalski, J. Libiszowski, T. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38, 8170 (2005).
[3] A. Kowalski, J. Libiszowski, K. Majerska, A. Duda, S. Penczek, Polymer 48, 3952 (2007).
[4] T. Biela, A. Duda, H. Pasch, K. Rode, J. Polym. Sci., Part A: Polym. Chem., 43, 6116 (2005).
[5] T. Biela, I. Polanczyk, J. Polym. Sci., Part A: Polym. Chem., 44, 4214 (2006).
[6] A. Duda, K. Majerska, J. Am. Chem. Soc. 126, 1026 (2004).
[7] T. Biela, A. Duda, S. Penczek, Macromolecules 39, 3710 (2006).
[8] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38, 2027 (2005).
[9] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28, 1385,
(2007).
[10] M. Florczak, A. Duda, in preparation.
16
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-04
Polylactide-based Materials: from Macro- to Nanocomposites
M. Murariu1, A. Da Silva Ferreira
1, M. Pluta², M. Alexandre
1,
L. Bonnaud1, and Ph. Dubois
1
1Laboratory of Polymeric and Composite Materials, Materia Nova Research Center &
University of Mons-Hainaut, Place du Parc 20, 7000- Mons, Belgium 2Department of Polymer Physics, Centre of Molecular and Macromolecular Studies, Polish
Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
The market for biodegradable polymers is growing every year and important demands can be expected for those applications where biodegradability offers clear advantage for customers and environment. In this context, polylactide (PLA) is undoubtedly one of the most promising candidates; it is not only biodegradable but also produced from renewable resources (sugar beets, corn starch, etc.). Because PLA has been recently considered as alternative in replacing petrochemical polymers, there is a strong demand to enlarge the range of PLA properties.
For further applications, the profile of PLA properties and its price can be changed by combining this matrix with different dispersed phases: fillers or reinforcements, (nano)additives, other polymers. Therefore, several types of mineral (nano)fillers (e.g., clays, calcium phosphate, hydroxyapatite, etc.) can be incorporated into PLA in order to obtain (nano)composite materials. For some applications where the property of transparency is not strictly needed, the use of PLA with mineral (micro)fillers can be an interesting solution to reduce the global cost and to improve some specific properties such as rigidity, heat deflection temperature, processability, isotropic shrinkage, etc.
In this objective, two products with the same source as origin, i.e., issued from the production and use of lactic acid, PLA and one main byproduct - calcium sulphate, have been first mixed by melt-compounding to prepare new polymer composites. The calcium sulphate microfiller was previously dried during one hour at 500 °C, to isolate the anhydrite II form (AII), which was specifically used for any further melt-compounding processes. Various
amounts of AII (10 to 50 wt%) were mixed together with PLA pellets at 190 °C. Interestingly, remarkable AII filler dispersion could be achieved even at high filler loadings resulting in a very good stiffness vs. toughness compromise. Other properties like durability, thermal stability and gas barrier properties have been evaluated as well and proved efficient with respect to the starting unfilled PLA.
The thermo-mechanical performances of these novel PLA/gypsum compositions have been further tuned up via the addition of plasticizers, toughening polymeric agents and nanofillers like organo-clays. Indeed, the field of polymer nanocomposites based on clays, such as montmorillonite, has given rise to a steadily increasing interest from scientists and industrials, as the nanoscale distribution of such high aspect ratio fillers brings up some large improvements to the polymer matrix in terms of mechanical, fire retardant, rheological, gas barrier and optical properties, especially at low clay content (as tiny as 1 wt%). As a result, novel ternary formulation, i.e, PLA filled with both AII and selected organo-clays, have been produced by melt blending yielding unequal thermo-mechanical properties, e.g., significantly improved flame retardancy behavior.
Keywords: biodegradable; polyesters; nanocomposites; organoclays; blends.
____________________________________
M. Murariu, A. Da Silva Ferreira, Ph. Degée, M. Alexandre, Ph. Dubois, Polymer, 48, 2613 (2007)
M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, Ph. Dubois, J. Polym. Sci. B: Polym.
Phys., 45, 2770-2780 (2007)
G. Gorrasi, V. Vittoria, M. Murariu, A. Da Silva Ferreira, M. Alexandre, Ph. Dubois, Biomacromolecules, in
press (2007)
17
I-05 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Physical Modification of Polylactide
A.Galeski, E.Piorkowska, and M.Pluta
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
90-363 Lodz, Poland
Light weight and durability, valuable feature of plastics, become serious flaws when they turn
to waste: post-consumer polymer packaging degrade slowly and they occupy large space in
plastics waste disposal. One of the solutions are biodegradable polymers that are transformed
quickly by enzymes into water and carbon dioxide. Most interesting is polylactide (PLA) that
can be produced from renewable resources: agricultural products and side products of food
production. Potential applications of PLA are: foil packaging, foil fibers, injection
mouldings and extruded profiles.
Due to a broad range of applications PLA must be subjected to serious modifications in order
to accomplish the best performance. Chemical modification is achieved by introducing a
fraction of lactide of opposite chirality or by copolymerization with selected biodegradable
co-monomers. Simpler and easier way is by physical modification. In our research we
explored various means of physical modifications: by thermal treatment, plastification, filling
with natural fibrous fillers and particulate mineral fillers, compounding with various organo-
modified nanoclays and by molecular orientation resulting from cavity-free plastic
deformation [1-10]. The driving force of the investigation was an expected improvement of
mechanical and physical properties of PLA and PLA based systems.
Plastic deformation in cavity-free manner (channel die) of amorphous copolymer P(L/DL)LA,
70/30 (i.e. unable to crystallize thermally), was studied at the temperature from 60 to 90 oC.
Evolution of structure and modification of mechanical properties were investigated as a
function of compression ratio. Transformation of amorphous P(L/DL)LA to crystalline texture
oriented in the direction of plastic flow without a trace of lamellar structure was clearly
detected. Formed crystalites (α crystallographic form) were small up to 9 nm in the transverse
direction to the flow, while the crystallinity was not exceeding 9% at highest compression
ratios. Significant increase of Tg and few fold increase of tensile strength of 120 MPa as
compared to 33 MPa for unoriented PLA.
Improvement of deformability of PLA both amorphous and crystalline was achieved by
elaborating of a new plasticizer – poly(propylene glycol) (PPG). PPG is soluble in PLA and is
not exuded by a crystallizing front of spherulites and remains dissolved in the amorphous
phase of PLA. Improvement of deformability depends on the amount of plasticizer and is very
effective for amorphous PLA. However, in the case of crystalline PLA PPG is concentrated in
the amorphous phase between crystalline lamellae and plasticizes PLA very efficiently: by a
decrease of yield stress, an increase of strain at fracture up to 100%, and an increase of tensile
impact strength from 36 to 60 kJ/m2 for 10wt.% of plasticizer. Improvement of mechanical
properties of crystalline PLA by plastification demonstrated the use of crystalline PLA at
temperature higher than its Tg, up to the melting point of crystals (+160-170oC), i.e. cups for
hot drinks, plates for hot food, micro-oven heating etc.
Filling PLA with natural fibrous fillers such as hemp fibers, grinded cacao shells, grinded
apple pomace, oat chaff and other leads to the increase of tensile modulus. Plasticizing such
systems with PPG or poly(ethylene glycol) allows the recovery of drawability.
Studies of nanocomposites of PLA with organo-modified nanoclay showed that the dispersion
of nanoclay depends on the nature of organo-modification and it is best with Cloisite 30B.
Exfoliation of nanoclay can be increased by increasing the mixing time with fixed other
compounding parameters. It indicates that the main mechanism of exfoliation is stripping clay
18
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-05
platelets one by one. Nanocomposites were characterized by thermal, rheological, structural
and mechanical studies. It was found that the molar mass of PLA decreases during mixing,
nevertheless the main parameter influencing the performance of PLA nanocomposites is their
phase structure. The best exfoliated PLA nanocomposite showed the best barrier properties
for gas diffusion. The barrier properties of PLA nanocomposites are especially important
because of possible application of PLA for food and drink packaging. The presented results
illustrate a broad range of physical modifications including plastification, molecular
orientation, filling with fibrous and particulate natural fillers as well as nanofillers. The role of
those factors is extending beyond to interaction during mechanical loading to modification of
supermolecular structure and all physical properties of PLA based systems.
____________________________________
[1] Z.Kulinski, E.Piorkowska, Polymer, 46, 10290- 10300 (2005).
[2] A.Gałęski, E.Piórkowska, M.Pluta, Z.Kuliński, R.Masirek, Polimery, 50, 562-569
(2005).
[3] Z.Kulinski, E.Piorkowska, K.Gadzinowska, M.Stasiak, Biomacromolecules, 7, 2128-
2135 (2006).
[4] E.Piorkowska, Z.Kulinski, A.Galeski, R.Masirek, Polymer, 47, 7178-7188 (2006).
[5] R.Masirek, E.Piorkowska, A.Galeski, M.Mucha, J.Appl.Polym.Sci. 105, 282–290
(2007).
[6] R.Masirek, Z.Kulinski, D.Chionna, E.Piorkowska, M.Pracella, J.Appl.Polym.Sci. 105,
255–268 (2007).
[7] M.Kozlowski, R.Masirek, E.Piorkowska and M.Gazicki-Lipman, Appl.Polym.Sci. 105,
269–277 (2007).
[8] E.Lezak, Z.Kulinski, R.Masirek, E.Piorkowska, M.Pracella, K.Gadzinowska,
Composites Polym.Sci,. in print.
[9] E.Piórkowska, A.Gałęski, Z.Kuliński, Polish patent application URP, 2006, Nr.
P376080, Worls patent application.
[10] M.Pluta, A.Galeski, Biomacromolecules, 8, 9-16 (2007).
[11] M.Pluta, J Polym Sci Part B:Polym Phys, 44, 392 (2006).
[12] M. Pluta, M. Murariu, A. S. Ferreira, M. Alexandre, A.Galeski and Ph. Dubois,
J.Polym.Sci. Phys Ed. in print (2007).
[13] M. Pluta, J.K. Jeszka, G. Boiteux, Europ.Polym.J. 43, 2819-2835 (2007).
[14] Pluta M, Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B-Polym.Phys., 44 (2):
299-311, (2006).
[15] Pluta M, Polymer , 45 (24): 8239-8251, (2004).
[16] Pluta M., Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B-Polym.Phys., 44 (2):
312-325, (2006).
[17] Galeski A, Piorkowska E, Pluta M, Kulinski Z, Masirek R, Polimery, 50 (7-8): 562-569
(2005).
[18] Pluta M, Galeski A, J.Appl.Polym.Sci., 86 (6): 1386-1395, (2002).
[19] Pluta M, Galeski A, Alexandre M, Paul MA, Dubois P, J.Appl.Polym.Sci., 86 (6): 1497-
1506, (2002).
19
I-06 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
New Biocatalytic Routes to Monomers, Macromers and Polymers
Richard A. Gross
NSF I/UCRC for Biocatalysis and Bioprocessing of Macromolecules, Department of
Chemical and Biological Sciences; Polytechnic University, Six Metrotech Center,
Brooklyn, NY 11201
New and versatile biocatalytic methods were developed that offer mild and efficient options
for macromer and polymer synthesis. Lipase B from Candida antartica (CALB), physically
immobilized on hydrophobic macroporous resins, is a remarkable catalyst for both ring-
opening and step-condensation reactions. CALB catalysis enabled the synthesis of aliphatic
polyolpolyesters and polycarbonates by using a wide range of building blocks including sugar
alcohols such as glycerol and sorbitol. Lipase regioselectivity enables direct
copolymerizations of polyols with diols and diacids to give non-crosslinked high molecular
weight materials with controlled branching. The mild reaction conditions (50 to 90 oC)
allowed incorporation of chemically and/or thermally sensitive co-monomers such as
silicones. For example, poly(ester-amides) were prepared containing silicone chain segments
and carbohydrates were directly linked to silicones (“sweet silicones”), the latter giving
materials with interesting surfactant properties.
Enzymatic routes to new monomers and their polymerization will also be discussed. For
example, fatty acids were transformed by an engineered Candida tropicalis strain to their
corresponding α,ω-dicarboxylic acids, α-carboxyl-ω-hydroxyl fatty acids, or a mixture of
these products. Enzyme-catalyzed copolymerizations of these fatty acid derived monomers
resulted in new functional copolyesters. Also, sophorolipids were prepared by microbial
fermentation of Candida bombicola were converted by metathesis polymerization to
functional biomaterials.
Cutinases from different micro-organisms have been evaluated for polymer synthesis and
modification reactions. It was discovered that cutinases also possess impressive catalytic
activity for lactone ring-opening and diacid/diol polycondensation reactions. In addition to
polymer synthesis, cutinases have been revealed that have interesting activities for polymer
modification and hydrolysis. As examples, the results of cutinase-catalyzed hydrolysis of PET
and de-acetylation of poly(vinyl acetate) will be presented.
Keywords: Enzyme-catalysis, lipase, cutinase, polyesters, polycarbonates, immobilization
____________________________________
Hunsen, M.; Azim, A.; Mang, H.; Wallner, S. R.; Ronkvist, A.; Xie, W.; Gross, R. A.
A Cutinase with Polyester Synthesis Activity. Macromolecules; 2007; 40(2); 148-150 (2007).
Gao, W.; Hagver, R.; Shah, V.; Xie, W.; Gross, R. A.; Ilker, M. F.; Bell, C.; Burke, K. A.; Coughlin,
E. B. Glycolipid Polymer Synthesized from Natural Lactonic Sophorolipids by Ring-Opening
Metathesis Polymerization. Macromolecules;40(2); 145-147 (2007).
Hu, J; Gao, W.; Kulshrestha, A.; Gross, R.A. "Sweet polyesters": Lipase-catalyzed condensation -
Polymerizations of alditols, Macromolecules 39 (20): 6789-6792 (2006).
Kulshrestha, A. S.; Gao, W.; Gross, R.A. “Glycerol Copolyesters: Control of Branching and
Molecular Weight Using a Lipase Catalyst”, Macromolecules, (2005); 38(8); 3193-3204.
Sahoo, B.; Brandstadt, K. F.; Lane, T. H.; Gross, R. A. “Sweet Silicones": Biocatalytic Reactions to
Form Organosilicon Carbohydrate Macromers Org. Lett.; 7(18); 3857-3860 (2005).
Mei, Y.; Miller, L.; Gao, W.; Gross, R. A.; Imaging the Distribution and Secondary Structure of
Immobilized Enzymes Using Infrared Microspectroscopy Biomacromolecules; 4(1); 70-74 (2003).
20
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-07
Modification of Biorelated Macromolecules through
Grafting of Short and Long Side Chains
Francesco Ciardelli1,2, Simona Bronco
1, Monica Bertoldo
1, Francesca Signori
2,
Maria Beatrice Coltelli3 , and Giovanni Zampano
2
1PolyLab-CNR, Pisa, Italy
2Dipartimento di Chimica e Chimica Industriale, Università di Pisa,
via Risorgimento 35, 56126, Pisa
3C.I.P.,Mestre,Venezia Italy
Macromolecules of natural origin are either characterized by a hyprophobicity and low
content of polar reactive groups ( as polyesters ) or by a high number of functional hydrogen
bonding side chains . In order to improve the possible use of this materials as bioplastics , the
chemical modification of the side chains and/or the combination with other macromolecules
are highly necessary. Following our previous and current work in the functionalization [1] and
blending [2] of polyolefins we are now attempting similar routes for proteins, polysaccharides
and polylactic acid to improve their suitability in the development of innovative multiphase
materials combining renewability and biodegradability with advanced thermomechanical and
functional properties.
As far a proteins are concerned we combined an experimental approach [3] with a molecular
dynamic modelling [4] to study the modification of molecular and supramolecular structure of
Collagen and Gelatine. In the experimental approach gelatine was successfully modified
according to different routes namely crosslinking with 1,6-diisocyanatohexane (HDI) [5], side
chain binding of hydrophobic florescent groups with 1-naphtylisocyanate (NpI) and grafting
of isocyanate terminated polypropylenglycole monobutyl ether chains (PPG). The modified
gelatine derivatives showed that the modification procedures all based on the reaction of
isocyanate with reactive side chains provides materials with a large variety of water swelling
and solubility properties.
The controlled modification of cellulose fibres by grafting with a synthetic polymer was also
investigated. The first step was the controlled esterification of cellulose fibre surface with α-
bromoisobutyrylbromide (BIBB), an ATRP initiator. Ethyl acrylate (EA) was grafted-
polymerised from functionalised cellulose under ATRP conditions with or without the
presence of a sacrifical free radical initiator (ethyl α-bromoisobutyrate). The adopted
polymerisation methods allowed to control grafting degree, grafted polymer chain length and,
in perspective, grafted polymer structure, namely random and block copolymers.
Finally in case of polylactic acid the number of reactive groups in the original homopolymer
was increased by transesterification with citric acid.
____________________________________
[1] S. Coiai, E. Passaglia, M. Aglietto, F. Ciardelli, Macromolecules, 37, 8414 (2004).
[2] M.-B. Coltelli, M. Angiuli, E. Passaglia, V. Castelvetro, F. Ciardelli, Macromolecules,
39, 2153 (2006).
[3] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules, 38, 1385
(2005).
[4] (a). Bronco, S.; Cappelli, C ,Monti, S. J. Phys. Chem. B , 108, 10101(2004).;
(b) Monti,S., Bronco, S.; Cappelli, C J. Phys. Chem. B ,109,11389(2005).
[5] M. Bertoldo, S.Bronco, T. Gragnoli, F. Ciardelli, Macromolecular Bioscience, 7, 328-338
(2007).
21
I-08 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Dextran-Based Block Copolymers: Synthesis and Self-Assembly in Solution
Clément Houga, Jean-François Lemeins, Redouane Borsali,
Daniel Taton, and Yves Gnanou
Université BORDEAUX I-ENSCPB-CNRS, Laboratoire de Chimie des Polymères
Organiques, 16 Avenue Pey Berland, 33607 PESSAC cedex, France
Naturally occurring polysaccharides such as cellulose, dextran, etc… are an abundant source of
raw materials that attract an increasing interest due to their biodegradability and renewable
character. A convenient and classical means to tailor the physicochemical properties of these
natural macromolecules is to modify their backbone by graft copolymerisation. A number of
applications have thus been developed from such graft copolymers but seldom as nanodevices
or nanosystems.
An attractive route to obtain nanostructures with well-defined morphologies is to let block
copolymers to self-assemble in a selective solvent, but the synthesis of polysaccharide-based
block copolymers has so far presented challenging difficulties. In this work, we describe the
first synthesis of dextran-b-polystyrene diblock copolymers from a dextran-based ATRP
macroinitiator and the preliminary results of the self-assembly of such diblocks in water.
Dextran is a highly water-soluble polysaccharide composed of α-D-glucopyranosyl units
mainly linked by (1→6) bonds and exhibiting a low degree of branching. The first step in our
synthetic endeavor was to introduce an appropriate ATRP site at the anomeric extremity of a
commercial dextran of Mn= 6600 g.mol-1. This terminal anomeric aldehyde was subjected to
reductive amination, using a specifically designed coupling agent fitted with ω-amino and α-
tertiary bromide groups. Before growing the polystyrene (PS) block by ATRP from the tertiary
bromide-ended dextran, the OH groups of the latter were silylated to make it soluble in regular
organic solvents.
Next, styrene was polymerized from the corresponding silylated dextran-based ATRP
macroinitiator. ATRP experiments were carried out in toluene using CuBr/PMDETA as
catalyst. Five diblock copolymers whose DPn of the PS block ranged from 5 to 775 were
synthesized from the same dextran-based precursor and characterized by SEC using THF as
eluent. Finally, these (silylated dextran)-b-PS block copolymers were readily desilylated under
acidic conditions (Scheme 1), affording the targeted amphiphilic dextran-b-PS block
copolymers.
OMe3SiO
Me3SiO
Me3SiO
Me3SiO O
OMe3SiO
Me3SiO
Me3SiOO
OHO
HO
HO
HOO
OHO
HO
HO O
OHHO
HO
HONH
HN
O
Br
OSiMe3Me3SiO
Me3SiO
Me3SiONH
HN
Br
O
n
i) Toluene PMDETA CuBr Styrene
ii) HCl
n
Next, the self-assembling properties in water of these diblock copolymers were investigated.
Block copolymers with the smallest content in PS could be directly dissolved in water at ~90°C.
The nanoparticules thus formed adopted a micelle-like spherical shape with a diameter of 56
22
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-08
nm, as determined by dynamic light scattering (DLS) and 50 nm from atomic force microscopy
(AFM). Samples with larger contents in PS could not be directly transferred in water; they were
first dissolved in a DMSO/THF mixture before slowly substituting water for the organic phase,
the latter being totally removed by dialysis. For instance, a sample with a 87% content in PS
exhibited a vesicular morphology as seen by Transmission Electron Microscopy (TEM). DLS
and static light scattering measurements on the same sample afforded a ratio of 1 for Rg/RH,
thus confirming the formation of a vesicle.
The self-assembly in water of other diblock copolymers led to a variety of stable morphologies
(vesicles ovoides, etc.) whose size strongly depended on the overall composition.
23
I-09 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Petro vs. Bio-based Plastics
P. J. Lemstra
Eindhoven University of Technology/Dept SKT,
Eindhoven, The Netherlands
Currently, approximately 200 million tonnes of plastics are produced annually, viz. 30
kg/capita in the world. In view of the unbalanced distribution regarding the consumption of
plastics, appr. 150 kg/capita in the Western world and Japan, and less than an average of 10
kg/capita in Asia, expectations are running high regarding the future growth of plastics. Some
EU studies predict the plastic consumption to grow even by a factor of 10 in the year 2100,
viz. 2000 million tonnes/annum!
Plastics are based on oil and currently appr. 5% of the world oil production is used to make
plastics. If the consumption of plastics increases in this Century as forecasted by several
studies then we might need up to 50% of the current oil production to produce plastics. In
view of oil depletion towards the end of this Century, this growth can not be realized based on
oil.
Bio-based plastics are promoted as an alternative to replace petro-based plastics and many
marketing studies predict that bioplastics will grow with at least 20% per annum. The
European Bioplastics society (www.european-bioplastics.org), however, predict a much faster
growth, close to 900.000 tonnes/annum by 2010, of which 800.000 tonnes based on
bioplastics based on renewable sources (Thermoplastic Starch/TPS, PLA and PHB).
At this point in time, however, one has to conclude that the expectations regarding the growth
of bio-based plastics as alternatives for petro-based plastics is below any forecast. The main
problem with bio-based polymers is their poor processability, notably of biopolymers which
have grown intra-cellular and possess a very high molar mass (to reduce the osmotic pressure)
such as PHB and starch, and/or they lack the physical/mechanical properties of synthetic
counterparts, viz. PLA vs. PET.
Bio-based plastics might have a growth potential if proper legislation is implemented and but
alternative sources to make plastics are also coming up soon, e.g. ethylene derived from bio-
ethanol (Braskem) and feedstock (monomers) from gas (Sasol, BP, Shell).
In this lecture, some fact and figures will be presented aiming to forecast the (near) future.
Keywords: petro-based plastics; bio-based polymers; forecast
24
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-10
Injectable Biodegradable Hydrogels for Protein Delivery
C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen
University of Twente, Faculty of Science and Technology, Institute for BioMedical
Technology (BMTi), Department of Polymer Chemistry and Biomaterials (PBM), P.O.Box 217, 7500 AE Enschede, The Netherlands
Injectable biodegradable hydrogels that are formed in situ from aqueous polymer solutions
under physiological conditions are of particular interest for tissue engineering and protein
delivery applications. In situ formed hydrogels provide many advantages. For instance, they
allow easy homogenous encapsulation of cells and/or proteins, preparation of complex
shapes, as well as minimally invasive implantation. However, current injectable hydrogels
often require photo-irradiation, auxiliary crosslinking agents, and/or organic solvents, which
may damage the cells or proteins of interest. In the past few years, we have developed several
novel types of rapidly in situ forming biodegradable hydrogels.
Stereocomplexed hydrogels. Based on stereocomplex formation between enantiomeric PLLA
and PDLA blocks, in situ forming hydrogels have been prepared from eight-arm
poly(ethylene glycol)-poly(L-lactide) (PEG-PLLA) and poly(ethylene glycol)-poly(D-lactide)
(PEG-PDLA) star block copolymers, wherein the gelation time (from instantaneous to 1 h)
and storage modulus (up to 14 kPa in PBS at 37 °C) were shown to depend on PLA block
length and polymer concentration [1, 2]. These stereocomplexed hydrogels have been used for
in vitro and in vivo protein release [3, 4].
Michael addition hydrogels. Highly elastic hydrogels were rapidly formed in situ under
physiological conditions by Michael type addition upon mixing aqueous solutions of dextran-
vinyl sulfone (dex-VS) and multi-functional PEG-SH at a concentration of 10 to 20 w/v% [5].
These dextran hydrogels have a low initial swelling and are degradable under physiological
conditions with degradation time varying from 3 to 21 days depending on the DS,
concentration, dextran molecular weight and PEG-SH functionality. Dextran hydrogels with
slower degradation (degradation time ranging from 3 to over 21 weeks) could be obtained
from thiol functionalized dextran (dex-SH) and PEG tetra-acrylate [6].
Enzymatic hydrogels. Dextran-tyramine (Dex-TA) conjugates have been designed to prepare
hydrogels via enzymatic oxidative crosslinking [7]. Interestingly, hydrogels were rapidly
formed under physiological conditions from Dex-TA at or above a concentration of 2.5 wt%
in the presence of H2O2 and horseradish peroxidase (HRP). The swelling/degradation studies
showed that under physiological conditions, Dex-TA hydrogels are rather stable with less
than 25% loss of gel weight in 5 months. Hydrogels with faster degradation could be achieved
by linking tyramine to dextran via an ester group.
Keywords: hydrogels, biodegradable, drug delivery systems
____________________________________
[1] C. Hiemstra et al., Macromol. Symp., 224, 119 (2005).
[2] C. Hiemstra et al., J. Biomacromolecules 7, 2790 (2006).
[3] C. Hiemstra et al., J. Control. Release, 116, e19 (2006).
[4] C. Hiemstra et al., J. Control. Release, 119, 320 (2007).
[5] C. Hiemstra et al., Macromolecules, 40, 1165 (2007).
[6] C. Hiemstra et al., J. Biomacromolecules, 8, 1548 (2007).
[7] R. Jin et al., J. Biomaterials, 28, 2791 (2007).
25
I-11 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polyether- Polyester Conjugates for Biodegradable Hydrophilic Microgels
and Hyperbranched Polymers
Helmut Keul, Marc Hans, Michael Erberich, Jörg Meyer, and Martin Moeller
Institute of Technical and Macromolecular Chemistry, RWTH Aachen, and DWI an der
RWTH Aachen e.V., Pauwelsstr. 8, D-52056 Aachen, Germany
Anionic polymerization of protected glycidols with mono- and multifunctional initiators
results in polymers with linear, graft, or star-shaped architectures. Removal of the protection
groups leads to polyglycidols which are used as multifunctional macroinitiators for the ring
opening polymerization of ε-caprolactone. Core-shell polymers with a hydrophilic polyether
core and a hydrophobic polyester shell are obtained. These amphiphilic core shell polymers
are able to encapsulate guest molecules or catalytically active hydrophilic species. In this
respect, polyether-polyester conjugates are attractive materials for drug delivery systems,
because of the biodegradability of the polyester arm building blocks and the biocompatibility
of the polyether core. Regarding biomedical applications increasing interest has been devoted
to enzyme catalyzed polymerization of lactones. In this respect, a comparison between
chemical and enzymatic catalysis using multifunctional macroinitiators for the ring opening
polymerization of ε-caprolactone was performed.[1]
Polyglycidols with two orthogonal protective groups were obtained via anionic ring-
opening copolymerization of allyl glycidyl ether (AGE), tert.butyl glycidyl ether (tBuGE),
and ethoxyethyl glycidyl ether (EEGE). Poly(AGE-co-tBuGE), poly(AGE-co-EEGE), and
poly(EEGE-co-tBuGE) were obtained with controlled degree of polymerization, narrow
molecular weight distribution and a predetermined ratio of repeating units. The following
conversions were achieved by selective removal of only one protection group: using aqueous
hydrochloric acid, poly(AGE-co-EEGE) was converted to poly(AGE-co-GE); using
trifluoroacetic acid, poly(AGE-co-tBuGE) was converted to poly(AGE-co-glycidyl
trifluoroacetate); and by using Pd/C and p-toluene sulfonic acid poly(AGE-co-tBuGE) was
converted to poly(GE-co-tBuGE). A selective removal of only one protection group from
poly(EEGE-co-tBuGE) was not possible.[2]
Free hydroxymethyl groups of the polymers were partially converted in a polymer
analogous reaction to give multifunctional polyglycidols or by using bifunctional reagents to
result in amphiphilic microgels.
P(tBuGE)-co-P(AGE): R1 = -C(CH3)3; R2 = -CH2-CH=CH2
P(tBuGE)-co-P(EEGE): R1 = -C(CH3)3; R2 = -CH(CH3)-O-CH2CH3
P(AGE)-co-P(EEGE): R1 = -CH2-CH=CH2; R2 = -CH(CH3)-O-CH2CH3
OO
R2O
OR1
m+n
OO
HO
OR1
m+n
selective deprotection
Keywords: biodegradable polymers; chemical and enzymatic ring-opening polymerization, grafting from
____________________________________
[1] M. Hans, P. Gasteier, H. Keul, M. Moeller, Macromolecules 39, 3184 (2006).
[2] M. Erberich, H. Keul, M. Moeller, Macromolecules 40, 3070 (2007).
26
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-12
Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock
vs their Counterparts from Renewable Resources
Emo Chiellini
INSTM Unit - Department of Chemistry and Industrial Chemistry,
University of Pisa, via Risorgimento 35, 56126 Pisa, Italy
BIOlab, via Vecchia Livornese 1291, 56122 Loc. S. Piero a Grado (Pi)
Synthetic and semisynthetic polymeric materials were originally developed for their durability
and resistance to all forms of degradation as promoted by physical, chemical and biological
means or combinations therefrom. Special performances are achieved in relevant items
produced under conditions guaranteeing for the maintenance of molecular weight and
functionality of the raw polymeric materials both during processing and under service
conditions. The polymeric materials had been and are currently widely accepted because of their
ease of processability and amenability to provide a large variety of cost effective items that
helped enhance the comfort and quality of life both in modern industrial society and in
developing countries. However all those good features, that make the polymeric materials so
convenient and useful to the human life and societal needs, have contributed to create a serious
plastic waste burden sometime exageratedly amplified by mass media and public opinionists.
On the other hand future expectations for polymeric materials demand in the next two decades
are in favour of two to three fold increase in production as a consequence of the increase of the
plastic consumption in developing countries and countries in transition.
The design, production and consumption of polymeric materials for commodity and specialty
plastic items have certainly to face all the constraints and regulations already in place or to be
issued in the near future, dealing with the management of primary and post-consume plastic
waste. In this respect the formulation of environmentally sound degradable polymeric materials
and relevant plastic items will constitute a key option among those available for the
management of primary and post-consume plastic waste. The technologies based on the
recovery of free energy content through recycling, including also the energy recovery by
incineration will be flanked by the increasing option of environmentally degradable polymeric
materials and plastics. These should be entitled to replace the conventional commodity plastics
in those segments in which recycling is difficult and labour-intensive with hence an heavy
penalisation on the cost-performance of the “recycled’ items. Moreover one has to take into
account the downgrading of the original material properties occurring both during the service
life of the items as well as during their reprocessing stages once they enter the post-consume
rank.
The strategies that are nowadays receiving a considerable deal of attention both at fundamental
and applied level imply design of new biobased polymeric materials, introduction of hybrid
polymeric formulations and revisiting and reengineering well-consolidated polymeric materials
of synthetic and natural origin.
In this connection the present contribution is aimed at providing an outline of the polymeric
materials consisting of macromolecules characterized by a full carbon as well as an
heteronuclear backbone. Whilst the latter are included into the class of hydro-biodegradable
systems, the former in order to be converted to oxo-biodegradable systems need to be eventually
reengineered to polymer grades susceptible to controlled and modulated environmental
oxidation followed by fragmentation and then ultimately by biodegradation to carbon dioxide,
water and cell biomass under aerobic conditions.
Case studies specifically focused on polyvinyl alcohol (as a water soluble thermoplastic) and
oxo-biodegradable polyethylene (as a water-insoluble thermoplastic) will be presented in
comparison to hydro-biodegradable counterparts.
27
I-13 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polyhydroxyalkanoates (PHAs): Biodegradable Polyesters
from Agricultural Waste and Surplus Material
G. Braunegg, A. Atlic, M. Koller, and C. Kutschera
Graz University of Technology, Institute of Biotechnology and Biochemical Engineering,
8010Graz, Petersgasse 12, Austria
Polyhydroxyalkanoates (PHAs) are biodegradable polyesters that are stored intracellular in
granules when growth of the producing bacteria is limited by essential nutritional compounds
like the nitrogen or phosphate source of the growth and production medium [1]. Under such
conditions the PHA content in the cells can increase to more than 80% of the cell dry weight
formed, and the quality of the polyesters stored can be influenced by feeding precursors for
synthesis of copolyesters or terpolyesters. A drawback for this development is the fact that in
most cases production costs for PHAs are still higher than costs for conventional resins.
Biotechnological polymer production occurs in aerobic processes, therefore only about 50%
of the main carbon sources, and even a lower percentage of the precursors used for production
of co-polyesters end up in the products wanted. To overcome this problem, cheap carbon and
nitrogen sources for microbial growth and PHA synthesis are needed to lower the production
costs. Such sources are available as agricultural waste and surplus materials, for example
lactose in cheese-whey or glycerol liquid phase (GLP) from the biodiesel production process
to be used as a cheap carbon source (Fig. 1), or meat and bone meal (MBM) to be used as
nitrogen source after hydrolysis [2]. Based on these renewable resources new technologies for
polymer production can be developed, integrating the principles of “Cleaner Production” and
“Life Cycle Analysis” into the strategies for process design [3].
a
0
5
10
15
20
25
0 24 48 72 96 120 144 168
Time [h]
Glycerol [g/L]
0
5
10
15
20
25
Protein, PHA [g/L]
b
0
2
4
6
8
10
12
14
16
0 24 48 72 96 120 144 168
Time [h]
PHA, 3-PHB [g/L]
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
2
3-PHV [g/L]
Figure 1: Production of poly-(3HB-co-3HV) from glycerol liquid phase (GLP) with
Haloferax mediterranei. (a) Patterns of glycerol, protein and PHA; (b) polyester formation
during the process
Keywords: polyhydroxyalkanoates; sustainable production; waste materials
____________________________________
[1] G. Braunegg, G. Lefebvre, K.F. Genser, J. Biotechnol. 65, 127 (1998).
[2] M. Koller, G. Braunegg, R. Bona, C. Herrmann, P. Horvat, J. Martinz, J. Neto, L. Pereira, M. Kroutil, P.
Varila, Biomacromolecules 6, 561 (2005).
[3] G. Braunegg, R. Bona, M. Koller, Polymer-Plastics Technology and Engineering 43, 1779 (2004).
28
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-14
(Bio)degradation of Polymeric Materials Containing PHA
and their Synthetic Analogues
Marek M. Kowalczuk
Polish Academy of Sciences, Centre of Polymer and Carbon Materials,
34 M. Curie-Skłodowska St, 41-800 Zabrze, Poland
Anionic ring opening polymerization (ROP) of β-butyrolactone (the monomer which
could be obtained using synthetic gas derived from coal or waste biomass gasification) has
been reported over twenty years ago.[1] The polymer chain growth proceeds regio-selectively
and stereo-selectively entirely via carboxylate anions. Propagation on carboxylate active
centers (much less sensitive to impurities than any other anionic species) enables scaling up
the anionic ROP process of β-butyrolactone to atactic poly[(R,S)-3-hydroxybutyrate]
(a-PHB), a synthetic amorphous analog of n-PHB.
Synthetic a-PHB undergoes heterogeneous enzymatic attack (by PHB depolymerse) in
the presence of second crystalline polymer which can be in form of component of binary
blend or block in a-PHB containing block copolymer. Moreover, the heterogeneous enzymatic
hydrolysis of a-PHB occurred both when the crystalline component was itself susceptible to
enzymatic attack as well as when it was non-biodegradable by the PHB depolymerase
employed. The enzymatic degradation of a-PHB can be induced also by its blending with
amorphous polymers with high glass transition temperature, e.g. atactic poly(L,D-lactic acid).
The plain a-PHB could be degraded to the mixture of monomer, dimer and trimer in the
presence of PHA depolymerases purified from Paucimonas lemoignei (PhaZ7) as well as
Acidovorax Sp. TP4 (PhaZaci).[2, 3]
Review of innovative results concerned with (bio)degradation of atactic PHB will be
presented. Novel results concerned with evaluation of the environmental degradation of
polyester blends containing a-PHB will be discussed.[4] Moreover, the ability to control
thermal degradation and stability of a-PHB as well as of its blends via concentration of the
carboxylate polymer end groups will be demonstrated.[5]
Acknowledgement. This research was supported by Eureka E! 3420 project and by Marie Curie Transfer of
Knowledge Fellowships of the European Community’s Sixth Framework Programme under the contract number
MTKD-CT-2004-509232.
Keywords: biodegradable polymers; atactic poly(3-hydroxybutyrate)
____________________________________
[1] Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651-1656;
[2] Handrick, R.; Reinhardt, S.; Focarete, M.L.; Scandola, M.; Adamus, G.; Kowalczuk, M.; Jendrossek, D.
J. Biol. Chem. 2001, 276, 36215-36224.
[3] Wang, Y.; Inagawa, Y.; Osanai, Y.; Kasuya, K.; Saito, T.; Matsumura, S.; Doi, Y.; Inoue, Y.
Biomacromolecules 2002, 3, 894-898.
[4] Rychter, P.; Biczak, R.; Herman, B.; Smylla, A.; Kurcok, P.; Adamus, G.; Kowalczuk, M.
Biomacromolecules 2006, 7, 3125-3131.
[5] Kawalec, M.; Adamus, G.; Kurcok, P.; Kowalczuk, M.; Foltran, I.; Focarete, M. L.; Scandola, M.
Biomacromolecules 2007, 8, 1053-1058.
29
I-15 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Novel Biodegradable Polymers and Scaffolds for Tissue Engineering
Y. Chen, R. Dersch, M. Gensheimer,
U. Bourdiot, S. Agarwal, J.H.Wendorff, and A. Greiner
Philipps-University Marburg, Department of Chemistry and Scientific Center
for Materials Science, Hans-Meerwein-Str., D-35032 Marburg, Germany
Biodegradable polymers are important for subcutane medical applications such as drug
delivery, implants, suture materials, and tissue engineering. For bone tissue engineering new
biodegradable polymers with excellent mechanical properties may be required as well as
special scaffold design.
Here we will present new synthetic routes to new biodegradable polyesters and their
invitro degradation behaviour [1-7]. Speciality scaffold design based on electrospun
polylactide nanofibers [8] will be reported as well as their compatibility to mesenchym stem
cells for applications in tissue engineering [9]. Bacteria containing electrospun nanofibers will
be reported as a potentially new biohybrid material for applications in tissue engineering [10].
Acknowledgements
The authors are indebted to Deutsche Forschungsgemeinschaft for financial support.
Keywords: tissue engineering; bioresorbable polymers; biocompatibility, nanofibers, electrospinning
____________________________________
[1] G. Haderlein, H. Petersen, C. Schmidt, J. H. Wendorff, A. Schaper, D. B. Jones, J. Visjager, P. Smith, A.
Greiner; Macromol. Chem. Phys. 200, 2080 (1999)
[2] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Chem. Mater. 15, 694 (2003)
[3] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Biomacromolecules 4, 974
(2003)
[4] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Polymer 44, 5513-5520 (2003)
[5] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Chem Mater. 15, 694(2003).
[6] L. Ren, S. Agarwal, Macromol. Chem. Phys., 2007, 208, 245.
[7] S. Agarwal, Polymer J., 2006, 39, 163.
[8] Greiner, J. H. Wendorff, Angew. Chem., Int. Ed. 46, 5670 (2007).
[9] U. Boudriot, R. Dersch, A. Greiner, J. H. Wendorff, Artificial Organs 30, 785 (2006).
[10] M. Gensheimer, M. Becker, Astrid Brandis-Heep, J. H. Wendorff, R. K. Thauer, A. Greiner, Adv. Mat.19,
2480 (2007).
30
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-16
Novel Photosensitizers Based on Polysaccharides
Maria Nowakowska, Krzysztof Szczubiałka,
Szczepan Zapotoczny, and Łukasz Moczek
Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Ingardena 3, Poland
There is a growing interest in the development of novel polymeric photosensitizers.
Because of the environmental concerns the possibility of using the systems based on natural
polymers is considered. We have chosen polysaccharides as the most abundant natural
polymers in biosphere. They have a lot of advantages; they are cheap, can be easily modified
and are biodegradable. Polysaccharides such as cellulose, dextran, starch and chitosan were
modified by covalent attachment of required chromophores: naphthalene, anthracene, Rose
Bengal, porphyrin and chlorophyll [1-7] The lecture describes the synthesis, characterization,
photophysical/photochemical properties of these photosensitizers as well as their potential
applications. All the photosensitizers are soluble in water. Due to the presence of
hydrophobic substituents, the modified polysaccharide chains adopted a pseudomicellar
conformation in the aqueous solutions allowing an efficient solubilization of hydrophobic
compounds sparingly soluble in water. The obtained photosensitizers absorb light from the
near UV-visible spectral region, including solar light. Photophysical studies demonstrated
that the attachment of the chromophores to the polymeric chain does not influence
considerably their properties. The aggregation of chromophores is limited while the
efficiency of the energy migration is high and the energy transfer to the suitable acceptors is
efficient. It was found that these photosensitizers can induce various photochemical
reactions. The mechanisms of these processes are dependent on the type of chromophore
present in the system and the type of reactant. Two main mechanisms of the primary
photochemical process were identified and utilized in our studies: the photoinduced electron
transfer from the electronically excited chromophores of the photosensitizer to the reactant
(molecule of organic compound and/or oxygen) and energy transfer to the molecule of
reactant (molecule of organic compound and/or oxygen). These processes result in the
formation of very reactive species such as radical-ions, hydroxyl radicals or singlet oxygen
which induce secondary photochemical reactions. It was demonstrated that the
photosensitizers based on polysaccharides can induce the oxidation of pollutants and toxins
present in water such as polynuclear aromatics, chlorinated organic compounds, cyanides, or
pesticides. Finally, the fate of the photosensitizers after their prolonged irradiation in aqueous
solution was studied. It was found that they undergo slow photo-assisted degradation.
Keywords: photosensitizers, polysaccharides, pollutants
____________________________________
[1] M. Nowakowska, M. Sterzel, K. Szczubiałka, J. E. Guillet, Macromol.Rapid Commun., 23, 972 (2002).
[2] M. Nowakowska, S. Zapotoczny, M. Sterzel, E. Kot, Biomacromolecules 5, 1009 (2004).
[3] M. Nowakowska, M. Sterzel, S. Zapotoczny, Photochem.Photobiol. 81, 1227 (2005).
[4] M. Nowakowska, M. Sterzel, S. Zapotoczny, E. Kot, Appl.Catal. B: Environ. 57, 1 (2005).
[5] M. Nowakowska, M. Sterzel, K. Szczubiałka, J.Polym.Environ. 14, 59 (2006).
[6] Ł. Moczek, M. Nowakowska, Biomacromolecules 8, 433 (2007).
[7] M. Nowakowska, Ł. Moczek, unpublished results.
31
I-17 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
The Polarized Light-induced Enzymatic Formation
and Degradation of Biopolymers
Anna Molenda-Konieczny, Maciej Fiedorowicz, and Piotr Tomasik
Departament of Chemistry, Agricultural University,
Balicka Street, 122, 30-149 Cracow, Poland
It has been reported [1] that moonlight stimulated decomposition of polysaccharides in
plants. That phenomenon was interpreted [2] in terms of the activation of hydrolases with
polarized light of the moon. Subsequent studies [3-7] showed that white, linearly polarized
light decomposes starch, provided starch is crystalline. Definitely, no enzymes were involved
in that process. Initially, side branches of amylopectin undergo scission followed by
repolymerization of resulting short chains into linear amylose-like polysaccharide. Studies
with polarized color light [8] showed that red light stimulated depolymerization whereas
green light stimulated repolymerization.
Independently, focus on effect of the polarized light upon enzymatic reactions of
polysaccharides resulted in interesting discoveries. Thus, white, linearly polarized light
activated α-amylolysis of starch [9], hydrolysis of xylane with xylanase [10], hydrolysis of
chitin with chitinase and chitosan with chitosanase [11], hydrolysis of cellulose with cellulase
[12], and interestingly influenced production of cyclodextrins with cyclodextrin
glycosyltransferase [13]. Effect of duration of illumination of cyclodextrin glucosyltransferase
with polarized light had certain effect upon the yield and isomer ration of three isomeric
cyclodextrins.
Application of the polarized light required 1-2 hour illumination of the enzymes in a
small reaction vessel followed by admixture of so activated enzymes to a bioreactor. Further
reaction did not require any illumination. These studies are under development.
Keywords: chitin; chitosan; cyclodextrins, starch;
____________________________________
[1] E.S. Semmens, Nature 159, 613 (1947).
[2] A.E. Navez, B.B. Rubenstein, J. Biol. Chem. 80, 503 (1928).
[3] M. Fiedorowicz, P. Tomasik, C.Y. Lii, Carbohydr. Polym. 45, 75 (2001).
[4] M. Fiedorowicz, C.Y. Lii, P. Tomasik, Carbohydr Polym. 50, 57 (2002).
[5] M. Fiedorowicz, K. Rębilas, Carbohydr. Polym. 50, 315 (2002).
[6] M. Fiedorowicz, G. Khachatryan, J. Sci. Food Agric. 84, 36 (2004).
[7] M. Fiedorowicz, G. Khachatryan, V.P. Yuryev, L.A. Wasserman, From starch containing sources to
isolation of starches and their applications, Eds: V.P. Yurev, H. Ruck, P. Tomasik, Nova Science
Publishers, New York, 2004, ISBN:1-59454-014-4.
[8] H. Staroszczyk, M. Fiedorowicz, P. Janas, P. Tomasik, Polimery 52 (11-12), 63 (2007).
[9] M. Fiedorowicz, G. Khachatryan, J. Agric. Food. Chem. 51, 7815 (2003).
[10] [M. Fiedorowicz, A. Konieczna-Molenda, V.M.F. Lai, P. Tomasik, in preparation.
[11] [M. Fiedorowicz, A. Konieczna-Molenda, W. Zhong, P. Tomasik, Carbohydr. Res. submitted.
[12] [A. Konieczna-Molenda, Macromol. Symp..accepted.
[13] [M. Fiedorowicz, A.Konieczna-Molenda, G. Khachatryan, P. Tomasik Polish Patent, Appl. P-379950
(2006).
32
ABSTRACTSOF POSTER
CONTRIBUTIONS
33
P-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Biodegradation of Polyester Nanocomposites
Agnieszka Piegat and Miroslawa El Fray
Szczecin University of Technology, Polymer Institute, Division of Biomaterials and
Microbiological Technologies, ul. Pulaskiego 10, 70-322 Szczecin
Poly(ethylene terephthalate) (PET) is a thermoplastic polyester widely used in fibres and
packing industry. PET is known as a material resistant to hydrolysis, therefore several
modifications have been made with the aim to render PET biodegradation. One of
commercially produced aliphatic-aromatic copolyester of PET is Biomax® [1]. This material
is fully biodegradable under composting conditions, because of the copolymerization of PET
with poly(lactic acid) (PLA), a common polymer from renewable resources. Other modifiers
of such origin are poly(glycolic acid) (PGA), poly(3-hydroxybutyrate) (PHB) [2],
polysaccharides like starch or cellulose [3]. Another group of biodegradable monomers from
renewable resources are dimer fatty acids, e.g. dilinoleic acid (DLA), obtained by
dimerization of unsaturated fatty acids derived from vegetable oils. This group of monomers
is widely used as modifier for polyurethanes, adhesives but also for thermoplastic elastomers
(TPE), where they form the soft phase. Their chemical and physical properties can be tuned
by the soft/hard segments ratio. For PET/DLA copolymers, higher susceptibility to
degradation was observed for copolymers with higher amount of DLA soft segments [5].
In this work, we report on PET modification with DLA and TiO2 nanoparticles. Such
physical modification with nanoparticles enhances not only mechanical properties, but also
controls the degradation profile [6]. The addition of ceramic components is already know as
an effective modification with the aim to obtain more controlled degradation conditions of
polymer/ceramic composites. Such solution was already applied for biodegradable poly(L,L-
lactide-co-glycolide) (PLGA), where addition of tricalcium phosphate reduced acidity of
degradation products and changed hydrophilicity of the material, what had strong influence
on the porosity of obtained scaffolds [7]. PET/DLA copolymers containing TiO2
nanoparticles (0.2 and 0.4 wt%) were degraded in PBS for 6 months. TiO2 nanoparticles
incorporated into copolymer matrix demonstrated a strong influence on such properties as:
absorption, crystallinity and molecular weight of composites. The decrease in Mn after 6
months was 68.8% for the neat PET/DLA copolymer, whereas only 41% for the same
copolymer containing 0.2 wt% TiO2 and 55% for this one containing 0.4 wt% TiO2. Changes
of thermal properties for PET/DLA were mainly observed in the hard segments region,
showing decrease of melting temperature from 130.6 to 102.4˚C. The melting temperature of
nanocomposites decreased by 6˚C and 18.4˚C for 0.2 and 0.4 wt% TiO2 nanoparicles,
respectively. Also the absorption level was highest for copolymer without TiO2 nanoparticles.
These results confirm that both DLA and TiO2 nanoparticles are effective modifiers of PET
enabling preparation of materials with controlled mechanical properties and degradation time.
Acknowledgements: This work was partially financed from research project 3T08E03628.
Keywords: biodegradation, polymer/ceramic nanocomposites, PET modification
____________________________________
[1] V. Nagarajan, M. Singh, H. Kane, M. Khalili, M. Bramucci, J Polym Environ 281, 14 (2007)
[2] D. Kint, S. Munoz-Guerra, Polym Int, 1999, 48, 346
[3] B.G. Girija, R.R.N. Sailaja, Giridhar Madras, Polym Degr Stability 147, 90 (2005)
[4] M. El Fray, Nanostructured Elastomeric Biomaterials for Soft Tissue Reconstruction, Publishing House of
the Warsaw University of Technology, Warszawa 2003, 1-144
[5] A. Piegat, M. El Fray, Polimery, in press
[6] M. El Fray, A.R. Boccaccini. Materials Letters, 2300, 59 (2005)
[7] F. Yang, W. Cui, Z. Xiong, L. Liu, J. Bei, S. Wang, Polym Degr Stability 3065, 91 (2006)
34
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-02
ESI-MS Studies of Slow-release Conjugate of 2,4-D with a-PHB
for Agricultural Applications
P. Rychter1, G. Adamus
2, and M. M. Kowalczuk
1,2
1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University of
Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 Polish Academy of Sciences, Centre of Polymer and Carbon Materials
34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland
Depending on the natural conditions, only about 10% of the applied agrochemicals
reach their objectives. This process leads to undesirable side-effects causing increase of the
active agent concentration levels in surrounding environment. From the point of view of
public health, application of hazardous pesticides in agriculture should be limited.
Biodegradable polymers to be used as a matrix for agrochemicals may constitute one of the
possible way to solve this problem. The advantages of control release of agricultural chemical
systems are prolongation of action of such agrochemicals (by providing continuous, low
amounts of biocides maintaining appropriate dosage for the desired period of time), decrease
of cost and pollution [1,2].
In this communication the results concerned with synthesis of conjugate of selected
herbicide i.e. 2,4-dichlorophenoxyacetic acid (2,4-D) covalently bounded with atactic
oligo[(R,S)-3-hydroxybutyrate] will be demonstrated. Herbicide 2,4-D belongs to the
phenoxyacetic acids group of pesticides and is one of the most common and widely used for
control of broad leafed weeds and grasses in plantation crops such as sugar cane, oil palm
and weeds along highways. As previously reported, poly([R,S]-3-hydroxybutyrate) as well as
its degradation products are non-toxic for natural environment [3]. Moreover, [R,S]-3-
hydroxybutyric acid oligomers are biocompatible and can be potentially applied to
formulation of chemical conjugates for delivery of active agent, improving its taken up by
cells in vitro [4]. The ring opening anionic polymerization of [R,S]-β-butyrolactone initiated
with activated 2,4-dichlorophenoxyacetic acid salts as well as [R,S]-β-butyrolactone
oligomerization induced by 2,4-D have been selected as methods of synthesis of 2,4-D oligo-
3-hydroksybutyrate conjugates. Evaluation of the subtle structure of the conjugates obtained,
based on sequencing of individual macromolecular ions with the aid of ion-trap multistage
mass spectrometry (ESI-MSn), will be presented.
Keywords: slow-release formulations; biodegradable polymers; biocides
____________________________________
[1] J. Zhao, R.M. Wilkins, J. Agric. Food Chem. 53, 4076 (2005)
[2] M.G. Mogul, H. Akin, N. Hasirci, D.J. Trantolo, J.D. Gresser, D.L. Wise, Resources, Conservation and
Recycling 16, 289 (1996)
[3] P. Rychter, R. Biczak, B. Herman, A. Smylla, P. Kurcok, G. Adamus, M. Kowalczuk, Biomacromolecules 7,
3125 (2006)
[4] V. Piddubnyak, P. Kurcok, A. Matuszowicz, M. Glowala M., A. Fiszer-Kieszkowska, Z. Jedliński, M. Juzwa,
Z. Krawczyk, Biomaterials 25, 5271 (2004)
35
P-03 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polymer-inorganic Hybrid Materials for Tissue Engineering
Pawel Wozniak, Stanislaw Sosnowski, and Stanislaw Slomkowski
Centre of Molecular and Macromolecular Studies, Polish Academy of Science,
Sienkiewicza 112, 90-363 Lodz, Poland
There is a great interest in manufacturing objects with surface properties adaptable to
environment (e.g. exposing hydrophilic or hydrophobic surface elements to hydrophilic or
hydrophobic exterior). Such properties are very desirable in fabrication of scaffolds for tissue
engineering. Since we are interested in scaffolds for hard tissue building cells our efforts were
concentrated on modification of silica and glass (nanosilica and model glass plates) in a way
allowing changes of their interfacial hydrophilic/hydrophobic properties in contact with
hydrophilic or hydrophobic liquids. The mentioned above nanosilica has been used as a filler
increasing mechanical strength of polymer scaffolds made from polylactide and poly(lactide-
co-glycolide).
Modification of silica and of glass plates was did consist of grafting 3-glycidoxypropyl
trimethoxysilane (GPS) onto silica (reaction with hydroxyl groups on silica surface). In this
way epoxide groups were introduced. The next step included grafting of biocompatibile
polymers. Living poly(ethylene oxide) was grafted onto silica in reaction with epoxide
groups. Active centers created in this way initiated polymerization of lactide. In result
hydrophilic poly(ethylene oxide) and hydrophobic poly(L-cactide) chains were tethered to the
surface. Depending on hydrophilicity of the liquid being in contact with modified silica the
hydrophilic or hydrophobic chains were in expanded conformation. The resulting materials
were characterized by photoelectron spectroscopy, wetting angle measurements and (in case
of nanosilica) by 13
C CP MAS NMR. Mechanical properties of poly(L-lactide) and
poly(lactide-co-glycolide) with modified silica fillers were investigated.
Schematic illustration of modification of silica surface.
Keywords: silica; (3-glycidoxypropyl)trimethoxysilane; surface modification; poly(ethylene oxide); poly(L-
lactide)
Financial support of BIOMAT project and Ministry of Science and Higher Education is acknowledged.
36
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-04
Biodegradable Hydrogels Based on Poly(vinyl alcohol)-graft-
[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)]
Elvira Vidović1, Doris Klee
2, and Hartwig Höcker
2
1Faculty of Chemical Engineering and Technology, University of Zagreb,
10000 Zagreb, Croatia 2Department of Textile and Macromolecular Chemistry, RWTH Aachen,
52056 Aachen, Germany
In this work a synthetic procedure is described towards a class of poly(vinyl alcohol)-graft-
[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)] copolymers which are sensitive to hydro-
lysis and therefore can be used for the development of controllably biodegradable hydrogels.
Poly(D,L-lactide) and poly(D,L-lactide-co-glycolide) with various composition were obtained
by reacting 2-hydroxyethyl methacrylate with D,L-lactide or glycolide dimers, followed by
the transformation of the terminal hydroxyl group into carboxylate with the assistance of
succinic anhydride. Coupling of those polyesters (PES) onto poly(vinyl alcohol) (PVA) was
performed via the carboxylate group in dimethyl sulfoxide using N,N-carbonyldiimidazole.
The graft copolymers were crosslinked via the methacrylate groups using a free radical
initiator [1,2].
crosslinking site
PVA backbone
R = H or CH3
PES graft chain
AIBN
50oC
n
O O
O O
R
R
O
O O
O
O
OH
O
p
z
q-z
O
CCH3
O
The resulting copolymers, in the course
of synthesis, were characterized with
respect to their molar composition by
means of 1H NMR spectra. Furthermore,
polymer networks were detected and
studied qualitatively by means of IR
spectroscopy. The influence of the glyco-
lide content in the polyester grafts and of
the number of ester units in the grafts on
thermal behavior and swellability were
studied, as well as surface properties of
hydrogels. Differential scanning calori-
metry showed a single glass transition
temperature that occurs in the range
between 51 °C and 69 °C indicating the
absence of phase separation.
Thermogravimetry analysis of the networks showed the main loss in weight in the
temperature range between 290 °C and 370 °C. The high swellability in water is characteristic
of all hydrogels. Hydrophilicity, an important property of hydrogels relevant to their
biomedical applications, was identified by the captive-bubble contact angle method.
Hydrogels display the values of contact angle between 37 and 45 ° which are significantly
higher in comparison with the polylactide sample (57°).
Keywords: biodegradable hydrogels; poly(vinyl alcohol); poly(D,L-lactide); poly(D,L-lactide-co-glycolide);
swellability; thermal properties; contact angle
____________________________________
[1] C.R. Nuttelman, S.M. Henry, K.S. Anseth, Biomaterials 23, 3617 (2002).
[2] E. Vidovic, Dissertation, RWTH-Aachen, Germany (2006).
37
P-05 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Fabrication of Honeycomb-Structured Polylactide and Poly(lactide-co-
glycolide) Films and their Use for Osteoblast-Like Cell Culture
Julian B. Chardhuri1, Matthew G. Davidson
2, Marianne J. Ellis
1,
Matthew D. Jones2, and Xujun Wu
1, 2
1Centre for Regenerative Medicine, Department of Chemical Engineering,
University of Bath, Claverton Down, Bath, UK, BA2 7AY 2Department of Chemistry, University of Bath, Claverton Down, Bath, UK, BA2 7AY
Biodegradable polymers have been widely applied in tissue engineering and drug delivery
systems [1,2]. Recently, honeycomb-structured thin films have been reported to be good
candicates as scaffolds for cell culture [3]. In the present study, polylactide (PLA) and
poly(lactide-co-glycolide) [PLGA] were used to prepare honeycomb-structured thin films by
using a water droplet templating method. The influence factors on pattern formation, such as
solvents, humidity and ethanol sterilization were investigated. To study cell attachment and
proliferation on honeycomb-structured films, MG63 osteoblastic-like cell lines were cultured.
Cellular responses on PLA and PLGA with various compositions are discussed.
Keywords: honeycomb-structured film; Water droplet template; Polylactide; Poly(lactide-co-glycolide); Tissue
engineering
____________________________________
[1] Langer, R. and Vacanti, J. P. Science, 1993. 260 (5110): p. 920-926.
[2] Srivastava, R. K., Albertsson, A.-C. Biomacromolecules, 2006, 7, p. 2531-2538.
[3] Fukuhira, Y., Kitazon, E., Hayashi, T., Kaneko, H., Tanaka, M., Shimomura, M., Sumi, Y., Biomaterials,
2006. 27 (9): p. 1797-1802.
38
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-06
Bark Suberin as a Renewable Source of Long-chain
ω-Hydroxyalkanoic Acids
Helena Nilsson, Ann Olsson, Mikael Lindström, and Tommy Iversen
STFI-Packforsk AB, Box 5604, SE-114 86 Stockholm, Sweden
Production of paper pulp and timber results in by-product streams of which some have
potential commodity values. One example is bark, a low value by-product today mainly used
for energy production. The outer bark of birch species in northern Europe contain about 30%
of the natural aliphatic polyester suberin [1]. cis-9,10-Epoxy-18-hydroxyoctadecanoic acid
(1) is the principal monomer comprising about 100 g/kg dry outer bark in Betula verrucosa.
This epoxy acid, together with straight-chain even numbered C16 – C24 ω-hydroxy fatty acids,
can be isolated in high yield from alkali hydrolyzed birch outer bark, by extraction followed
by selective precipitation by acidification.
Lipase catalyzed polymerizations may sometimes allow straightforward synthesis strategies
for polyesters from sensitive monomers that do not survive more conventional polymerization
catalysts and this has, for example, been used for the preparation of polyesters from epoxy
containing monomers.
In this study we report polycondensations of cis-9,10-epoxy-18-hydroxyoctadecanoic (1)
acid isolated from birch outer bark using immobilized Candida antarctica lipase B
(Novozyme 435) as catalyst. The polycondensation performed in both toluene and bulk gave
the polyester (2) with fairly high molecular weights. For example, a Mw of 15 000 was
obtained after 3 hours reaction time (Mw/Mn 2.2) by bulk polymerization in an open vial
without any drying agent present.
O
(CH2)8 (CH2)7HO CO
O
(CH2)8 (CH2)7(O CO)n
O
(CH2)8 (CH2)7O COOH
O
(CH2)8 (CH2)7HO COOH 1
2
39
P-07 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Studied on Electrical Conducting Biopolymer-poly(thiazole) Copolymers
Ashutosh Tiwari1 and A. P. Mishra
2
1National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India
2Department of Science and Technology, Technology Bhawan,
New Maharauli Road, New Delhi –110 016, India
Water-soluble, biodegradable and electrical conducting copolymer of arabinogalactan-
poly(thiazole) was synthesized by adopting oxidative-radical polymerization method. UV-vis
and FTIR spectra were used to characterize the resulting copolymer. Electrical conductivity
and biodegradable behavior of copolymer was studied and optimized the composition to get
appropriate material for technological applications as varying concentration of thiazole
(THA), pH of the material and temperature. The electrical conductivity of the copolymer was
physically regulated via varying pH and temperature and could have interesting features on
these effects, as are semiconductors. Therefore materials have potential application for the
biosensor especially for the specific detection of microorganisms and hazardous gases.
Moreover, conducting biopolymer-based materials could be usefully exploited as
multifunctional electronic materials for technological applications. The materials might be of
great importance in the fabricating various sensor devices for in vivo and in vitro applications.
Keywords: arabinogalactan-polythiazole copolymer; electrical conductivity; biodegradability
Fig. Co-polymerization of biopolymers with synthetic polymer
40
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-08
Antibacterial Activity of Cationic Starch-iodine Derivatives
Algirdas Zemaitatitis, Rima Klimaviciute, and Rasa Kavaliauskaite
Kaunas University of Technology, Radvilenu 19, Kaunas LT-50524, Lithuania
Different compounds, such as phenol, halogen or derivatives of aldehydes, as well as
quaternary ammonium salts exhibit bactericidal properties and are used as disinfectants. It is
known, that cationic polymers with quaternary ammonium groups have higher antimicrobial
activity than corresponding low molecular weight compounds. Starch is a valuable material
for the production of cationic polysaccharides because of its high chemical activity and
peculiarities of structure. For this reason considerable efforts are now being made in the
research and development of modified polysaccharides as the basic material for new
applications.
The aim of this study was to synthesize cationic (CS) or cross-linked cationic (CCS) starch
chlorides and their iodine derivatives and to examine their antimicrobial activity.
CS or CCS with preserved micro granules, the degree of substitution from 0.2 to 0.6 and the
reaction efficiency from 82% to 93% might be obtained during catalytically etherification of
starch or cross-linked starch with a 2,3-epoxypropyltrimethylammonium chloride. In the ion
exchange reaction with inorganic iodide in water, CS or CCS chloride (CSCl or CCSCl) was
converted to CS or CCS iodide (CSI or CCSI). The chemical analysis confirmed that iodide
substituted for at least 95% of chloride counter ions.
In aqueous solutions having KI, cationic starches rapidly bind iodine and form polymer–
iodine complexes. Investigations of iodine binding by different cationic starches at
equilibrium showed that starches with quaternary ammonium groups were able to bind about
300 wt % of iodine from I2-KI solution and form complexes CSI·Im or CCSI·Im, where m ≤ 4.
Maximum two molecules of iodine could be incorporated, i.e., polymeric complexes of
pentaiodide could be formed. The stability of cationic starch–iodine complexes depended on
the quantity of involved iodine. Cationic starch triiodides (CSI·I2 or CCSI·I2) were the most
stable complexes.
The antibacterial activity of different starch derivatives against Enterococcus faecalis,
Bacillus subtilis, Pseudomonas aeruginosa, Salmonella typhimurium, Staphylococcus aureus,
Escherichia coli, Lysteria monocytogenes was studied by measuring the inhibition zone
diameter (agar diffusion plate test). It was found, that the diameter of inhibition zone
depended on both the counter ion of CS or CCS and examined microorganisms. In general,
cationic starches were bacteriostatic rather than bactericidal. The studied cationic starches can
be arranged in the following order according to their increasing antibacterial activity: CCSI <
CCSCl ≤ CSCl. However, cationic starch–iodine complexes were the most effective and
showed an excellent prolonged antibacterial activity. CCSI·I2 obtained from CCS with DS>0.2
were bactericides and 0,1 mg/mL of them killed 100% of E. Coli. The higher activity of
cationic starch–iodine complexes has been interpreted in terms of their stability in water at the
presence of iodine acceptors.
Keywords: highly cationic starch; cationic starch-iodine complexes; antibacterial activity
41
P-09 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Chitosan-co-polyaniline/WO3.nH2O Nanocomposites:
Green Polymer Composite for Sensor Applications
Ashutosh Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra
National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India
A monodispersed WO3.nH2O nanoparticles embedded chitosan-co-polyaniline have been prepared by one pot chemical precursor method. UV-visible, FTIR XRD and SEM analytical
tools were used to confirm the formation of nanocomposite. The composition of
WO3.nH2O precursor to chitosan-co-polyaniline was tailored in order to develop materials of controlled electrical conductivity. The electrical conductivity of the chitosan-co-
polyaniline/WO3.nH2O was stimulated with the exposure of HCl and NH3. Under
controlled conditions, hybrid material showed electrical conductivity in the range of 6.82
X 10-4 Scm
-1 at room temperature. The intercalations of cationic biopolymer based
electrically conducting copolymer apart with layered nanostructured inorganic solids
provide multifunctional nature, which have combined significant special features towards thermal-mechanical stability, biocompatibility, solubility, porosity and redox surface property.
Layered conducting biopolymer based host could be interesting regarded as an alternative
to obtain eco-friendly interlayer transition metal oxide bio-nanocomposites for
technological applications.
Figure: Layered structure of Chitosan-co-polyaniline/WO3.nH2O nanocomposite
Keywords: chitosan-co-polyaniline, WO3.nH2O nanocomposites, electrical conductivity, green
polymer composite, sensor applications
Chitosan-co-polyaniline WO3.nH2O Chitosan-co-polyaniline/WO3.nH2OChitosan-co-polyaniline WO3.nH2O Chitosan-co-polyaniline/WO3.nH2O
42
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-10
Chemical Modification of Starch with Hexamethylene
Diisocyanate Amide Derivatives
Katarzyna Wilpiszewska, Stanislawa Spychaj, and Tadeusz Spychaj
Polymer Institute, Szczecin University of Technology,
ul. Pulaskiego 10, 70-322 Szczecin, Poland
The growing interest in materials from renewable resources is observed [1]. Starch is a
biodegradable and easily available biopolymer. In Europe 45% of its total production is used
for nonfood applications (mostly paper industry) [2]. However, starch plastics are not widely
used because of some drawbacks, like: brittleness or sensitivity to water [3]. Chemical
modification of starch could, at least partially, prevent mentioned problems. Recently paper
describing synthesis of urethane and urea derivatives of hexamethylene diisocyanate (HMDI)
and their usage for starch chemical modification has been published [4].
Preparing starch plastics is in fact achieving a compromise between a few contradictory
features, such as: degree of substitution, level of hydrophobisation, susceptibility to
biodegradation, and melt flow features.
In this contribution chemical modification of potato starch with amide derivatives of
HMDI in a two-step process has been presented. At the first stage starch modifiers, i.e.
isocyanate amide derivatives were synthesised in the equimolar reaction between HMDI and
monocarboxylic acids, containing 2 to 18 carbon atoms in alkyl chain. HMDI was used as it is
relatively environmentally friendly [5]. FTIR spectra of the obtained HMDI derivatives
revealed the presence of bands for NCO, in the range of ~2300 cm-1 and amide groups at ca.
1700 cm-1.
At the second step the starch was modified with the synthesised HMDI derivatives, in
N-methylpyrrolidone (NMP) slurry. Some properties of the obtained starch polymers were
investigated and compared, i.e. efficiency of substitution, IR spectra, hydrophobic/hydrophilic
features, rheometric characteristics in temperature range up to 200°C, as well as moldability
(hot press melt flow).
Physicochemical properties of starch products depend greatly on degree of substitution
and alkyl chain length attached. The influence of the alkyl chain length attached to
polysaccharide as well as degree of substitution on some physicochemical and thermal
properties were evaluated. The hydrophilic/hydrophobic properties of the modified starches
evaluated by the measurement of their swelling indices in water were compared.
Keywords: thermoplastic starch; chemical modification of starch; urethane-amide starch derivatives
____________________________________
[1] Fakirov, S. & Bhattachatyya, S., Ed. Handbook of engineering biopolymers: homopolymers, blends, and
composites. Munich, Hanser Verlag (2007).
[2] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27, 67 (2004).
[3] G. Engelmann, E. Bonatz, I. Bechthold, G. Rafler. Starch, 53, 560 (2001).
[4] K. Wilpiszewska, T. Spychaj. Carboh. Polym. doi:10.1016/j.carbopol.2007.04.023 (2007).
[5] T. Ohkita, S. Lee. J. Adh. Sci. Technol. 18, 905 (2004).
43
P-11 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Starch Plasticisation via Twin-screw Extrusion
Katarzyna Wilpiszewska and Tadeusz Spychaj
Polymer Institute, Szczecin University of Technology,
ul. Pulaskiego 10, 70-322 Szczecin, Poland
The growing interest in materials from renewable resources is observed. Starch is
potentially useful material for technical uses because of its biodegradability, availability and
relatively low cost. In Europe 45% of total starch production is used for nonfood applications
(mostly for paper industry) [1]. Granular starch cannot be processed with conventional
technologies because its melting point (Tm = 220-240°C) and Tg are higher than its
degradation temperature (ca. 220°C) – it degrades before melting [2]. The addition of
plasticiser (commonly used glycerol) decreases Tg of starch, preventing its decomposition [3].
Moreover, the kind of plasticiser influences the mechanical and thermal properties of starch
material [4]. Extrusion is the most widespread method for producing thermoplastic starch.
In this contribution the preliminary results of starch twin-screw extrusion with
ε-caprolactam in the presence of glycerol with water admixture has been presented. Some
microorganisms could utilise ε-caprolactam as the sole source of carbon, nitrogen and energy
[5]. The extruded mixture contained: 9 – 17 wt. % ε-caprolactam, 11- 47 wt. % glycerol (with
water admixture) and 40-70 wt. % starch. The main processing parameters, i.e. temperature
regime, rotational speed as well as die pressure were changed. Their effect on extrusion
operating as well as extruded product is discussed.
Some properties of obtained starch products were investigated and compared, i.e.
hydrophobic/hydrophilic features and elongation at break. Water uptake of extruded starch
materials depends greatly on polysaccharide content and rises with its increase.
For comparison starch extruding with glycerol itself has been also performed. The
influence of starch/plasticizers content in the system on the water uptake and mechanical
properties was evaluated. Comparison of plasticised starch extrudates containing 70 wt. % of
starch and 30 wt. % of plasticiser(s) shows that material with ca. 18 wt. % ε-caprolactam and
11 wt. % glycerol + 1 wt. % water swells in water up to 270 % whereas starch plasticised with
30 wt. % glycerol (no water addition) up to 140 %. The probable reason for this finding is
both the presence of additional water as well as amide bond in the lactam ring.
Keywords: thermoplastic starch; starch extrusion; starch plasticisation
____________________________________
[1] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27, 67 (2004).
[2] T. Czigany, G. Romhany, J.G. Kovacs. Chapter 3 in: Fakirov, S. & Bhattachatyya, S., Ed. Handbook of
engineering biopolymers: homopolymers, blends, and composites. Munich, Hanser Verlag, pp. 81-108 (2007).
[3] S.H.D. Hulleman, F.H.P. Janssen, H.Feil. Polymer, 39, 2043 (1998).
[4] K. Wilpiszewska, T. Spychaj. Polimery, 51, 325 (2006).
[5] C.C. Wang, C.M. Lee. J. Hazard. Mat. 145, 136 (2007).
44
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-12
Study of Interpolymeric Complexes Based on Polymers
from Renewable Sources
Catalina Duncianu and Cornelia Vasile
„Petru Poni” Institute of Macromolecular Chemistry,
41 A, Gr.Ghica Voda Alley, 700487, Iasi, Romania
The hydrogen-bonded interpolymeric complexes (IPC) have attracted great interest
due to their unique physical and chemical properties in comparison with pure components and
their wide applications in pharmaceutics as drug delivery carriers.
Intermacromolecular interactions via hydrogen bonds between a natural, renewable,
non-toxic polymer e.g. alginic acid (AgA) and syntethic polymers e.g. polyethyleneglycol
(PEG), poly (N-isopropyl acrylamide) (PNIPAM), polyacrylamide (PAM) in diluted and
semi-diluted solutions were investigated by means of viscometry, potentiometry and
conductometry. Thermodynamic functions have been evaluated. It has been established that
the alginic acid at a pH = 4 forms interpolymeric complexes with all three synthetic polymers
but their strengths vary with chemical structure and temperature.
Keywords: interpolymeric complexes, alginic acid, polyethyleneglycol, poly (N-isopropyl acrylamide),
polyacrylamide,
45
P-13 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Homopolymerization and Copolymerization of L, L-Lactide
in Presence of Novel Zinc Proline Organocmetallic Catalyst
A. Pandey and B. Garnaik
Polymer Science and Engineering Division, National Chemical Laboratory,
Pune 411008, India
Poly (L, L-lactide) (PLA) and its copolymers from renewable resources have been studied
extensively because of their vast potential applications in many fields. Ring-opening
polymerization (ROP) of L, L-lactide to form poly (L, L-lactide) s by single-site metal
alkoxide precursors has attracted considerable recent attention since the properties of PLA are
determined by molecular weight, molecular weight distribution, and most importantly by its
microstructure analysis. Many metal complexes such as Al, Li, Mg, Fe, Sn, and Zn etc. have
been used as initiators/catalysts for ring opening polymerization (ROP) of cyclic esters [1-2].
However, in many cases, backbiting reaction/transesterification take place as side reactions,
resulting in the formation of macrocycles with a wide range of molecular weight distribution.
Using a bulky legands (both isomers of L- and D-proline ) coordinatively attached with
active metal center (zinc) and provided an asteric barrier for prevention of undesired side
reactions and minimized the undesired backbiting/transesterification reactions. The
homopolymerization of (L, L-lactide) and copolymerization by using PEG as macroinitiator
were conducted in presence of zinc proline catalyst. The kinetic and thermodynamic
parameters of ROP of L, L-lactide using zinc proline were studied. Polylactides were
characterized by various techniques such as GPC, DSC, FT IR, NMR, XRD and MALDI ToF
etc. The configurational sequence determination of PLA polymers were carried out by 13C
NMR quantitative analysis and compared by 13 CP/MAS NMR. The results of ROP of L, L-
lactide using zinc proline ( L- and D-proline) will be highlighted .
Figure 1. 13C NMR (500 MHz) of polylactide(CDCl3)
Keywords : renewable resources; zinc proline; polylactide; configurational sequence
____________________________________
[1] K. S. Fun, B. Teo, S.G. Teoh, K. Chinnakali, Acta Crystallog. C51, 244 (1995).
[2] Bradley M. Chamberlain, Ming. Cheng, David. R. Moore, Tina. M. Ovitt, B. Emil Lobkovsky, Geoffrey
W. Coate, J.C.A.S. 123, 3229 (2001).
46
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-14
Poly(lactic acid) Microcapsules Containing Bioactive Molecules:
Study of Activity
F. Faÿ, I. Linossier, and K. Vallée-Réhel
Laboratoire de Biotechnologie et Chimie Marines EA 3884, Université de Bretagne-Sud,
BP92116, 56321 Lorient cedex, France
In order to prevent the development of marine biofilm on immersed surfaces, it is required to
conceive preventing systems. Actually, this is realized by the blending of
poly(methylmethacrylate-co-butylmethacrylate) resins (PMMA-PBMA) with two types of
biocides : an organic biocide used in agriculture (herbicides, pesticides) and a mineral biocide
such as cuprous oxide. However, due to severe environmental degradations, the use of toxic
molecules and non degradable polymers is questioned. These concerns have created a
considerable interest to produce a new generation of protective systems based on
biodegradable polymers [1,2] and non toxics molecules. Two essential properties have been
clearly identified as discriminating factors of antifouling efficiency: erosion which is
controlled by biodegradable polymer such as polyester or poly(ester-anhydride) and presence
of biocides at the coating surface during immersion [3].
In this work, two active molecules were studied. The first is a bactericide molecule, called
chlorhexidine. Chlorhexidine is a bisdiguanide antiseptic widely used in dentistry as an anti-
plaque agent and has demonstrated good antibacterial activity against a wide range of
bacteria. The second is a quorum sensing autoinducer for the bacterial cell-to-cell
communication (furanone). However, previous works are shown that hydrosoluble molecules
were too rapidly released. These characteristics implicate their microencapsulation.
In a first part, this study presents i) the encapsulation of a commercial furanone (tetronic acid)
and chlorhexidine by using biodegradable polymer (PLA), prepared by the water-in-oil-in-
water solvent evaporation method ; ii) their characterization for their size, morphology and
encapsulation efficiency : imaging of the particles was performed by scanning electron (SEM)
and confocal laser microscopies (CLSM) ; iii) their incorporation in paint formulation.
The second part reports the influence of encapsulation : i) on biocide release determined by
EDX analysis and UV-spectrometry ; ii) on the growth, adhesion and viability of several
marine bacteria.
Keywords : PLA, encapsulation, antifouling
____________________________________
[1] F.Faÿ, I. Linossier, V. Langlois, E. Renard, K. Vallée-Réhel, Biomacromolecules. 7, 857 (2006).
[2] F. Faÿ, I. Linossier, V. Langlois, K. Vallée-Rehel, Biomacromolecules. 8, 1751 (2007).
[3] M. Thouvenin, J.J. Peron, C. Charreteur, Ph. Guerin, J.Y. Langlois, K. Vallee-Rehel, Prog. Org. Coat., 44, 75 (2002).
47
P-15 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Degradation Study of Polymers from Renewable
Resources and their Blends in Industrial Composting Pile
W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk
Centre of Polymer and Carbon Materials,
M.C.-Skłodowskiej 34, 41-819 Zabrze, Poland
New trends in solid waste management and rapid changes in public legislation made scientist
in increase activities on the design of new generation of biodegradable polymers as important
biomaterials for environmental, biomedical and pharmaceutical applications [1, 2]. For the
last few years, intensive research and development of new materials for packaging has been
also observed [3]. The most commercially available plastics are non-degradable and their
recycling is not feasible economically in many cases due to the deterioration of mechanical
properties and excessive cost. Selective use of biodegradable packaging materials in certain
applications may provide a solution to the above-mentioned environmental problems.
Polyesters, produced from renewable resources and susceptible to hydrolysis under the
industrial composting conditions offer ecological advantages as compared to thermoplastics
polymers and elastomers produced from fossil carbon sources [4]. Additionally, traditional
packing waste needs to have the PE it is coated with removed in the repulping process during
the recycling in paper-mill.
In the paper the results of degradation behavior of polymer blends of a-PHB,
poly[(D,L)-lactide] and additionally BTA in natural environment such as industrial
composting pile, consisting of leaves - 40%, branches - 30% and grass - 30%, have been
presented. The macroscopic observations of surface changes, the weight loss, changes of
molecular weight, polydispersity and composition of the tested materials were monitored
during experiments performed. The obtained results revealed that the investigated blends was
degradable in the industrial compost pile and in this environment the hydrolytic degradation
was occurred. Moreover the biodegradable polyesters systems are promised materials, which
can be use as paper coatings for multilayer packaging materials.
This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the
European Community’s Sixth Framework Programme under the contract number
MTKD-CT-2004-509232. The financial support of Polish Ministry of Science and Higher
Education: R&D project no. R05 055 02 is also acknowledged.
Keywords: renewable resources; biodegradable polymers; industrial composting pile
____________________________________
[1] Biodegradable Plastics: North America, Europe, Asia, Market-Technology Report PO119, New York, 2001.
[2] B. Kessler and B. Witholt, Macromol. Symp. 130, 245 (1998).
[3] M. Kowalczuk, Plastic Review, 4(26), 48 (2003).
[4] G. Adamus, P. Dacko, M. Musioł, W. Sikorska, M. Sobota, R. Biczak, B. Herman,
P. Rychter, K. Krasowska, M. Rutkowska, M. Kowalczuk, Polimery, 51, 539 (2006).
48
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-16
Polyurethanes from Renewable Resources as Candidates
for Friendly Environment New Materials
D. Macocinschi, D. Filip, and S. Vlad
“Petru Poni” Institute of Macromolecular Chemistry,
Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania
Because of the importance of biomaterials in medical applications, their development
has been a long-term area of research and has become one of the principal challenges to
polymer scientists. In the present study new types of polyurethane-cellulose derivative
biomaterials based on urethane prepolymers functionalized with hydroxypropylcellulose are
presented. In the literature are reported studies on materials with better haemocompatibility,
biocompatibility and amphiphilic microphase-separated domain structures [1-4]. Few
biodegradable elastomers have been synthesized, and new materials are required to meet the
need for an increasingly diverse range of physical properties. It is worthy of note that block-
polyurethanes based on cellulose derivatives were found to be biodegradable and
haemocompatibles. Biodegradable elastomers are expected to be suitable for any application
requiring the use of a flexible, elastic material, such as soft tissue engineering.
The remarkable chemical versatility characteristic to polyurethane materials combined
with polymers derived from nature like cellulose derivatives resulting in bulk and surface
properties is evidenced by means of different techniques like DSC, TGA, FT-IR, AFM,
mechanical tensile tests. The influence of various factors on the developed morphologies and
the microstructural changes is investigated. Both polyester and polyether macrodiols have
been used to prepare these polyurethanes. The aim of this study is to find also alternative
methods for improving biostability while maintaining the excellent biocompatibility and other
properties. In these applications a balance between the surface hydrophilic and hydrophobic
qualities is essential for achieving enhanced bioproperties.
Keywords : renewable resources; biodegradable polyurethanes; morphology.
____________________________________
[1]. T. Hanada, Yu-J. Li, T. Nakaya, Macromol. Chem. Phys. , 202, 97 (2001).
[2] A. Vaidya, M. K. Chaudhury, J.Colloid Interf. Sci., 249, 235 (2002)
[3] R. W. Thring, M.N. Vanderlaan, S. L. Griffin, Biomass Bioenerg, 13, 125 (1997).
[4] You-X. Wang, J. L. Robertson, W. B. Spillman Jr., R. O. Claus, Pharm Res 21, 1362 (2004).
49
P-17 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Viscoelastic and Thermal Proprieties of the Biodegradable Polymer
Materials Containing Polylactide, Aliphatic-Aromatic Polyester and
Synthetic Poly[(R,S)-3-hydroxybutyrate] Received via Injection Moulding
P. Dacko1, M. Sobota
1, H. Janeczek
1, J. Dzwonkowski
2,
J. Gołębiewski2, and M. M. Kowalczuk
1
1Centre of Polymer and Carbon Materials, 41-819 Zabrze, Poland
2Institute for Plastics Processing METALCHEM, PL-87-100 Toruń, Poland
The injection moulding is one of most important technologies in the processing of plastics and of biodegradable polymer materials. In this method the material is plastified to the viscous-flow state in the plastifying system and then introduced under pressure to the form, where it solidifies or hardens at the change of the temperature. The influence of temperature and pressure during the process on plastics, especially on polymer compositions, can make essential structural changes of initial components and consequently seriously influence on proprieties of final materials.
The main goal this work was to examine the viscoelastic and thermal proprieties of biodegradable polymer materials containing the amorphous poly-lactide (PLA-b), aliphatic-aromatic copolyester of terephthalic and adipic acids and butanediol (BTA), and synthetic poly[(R,S)-3-hydroxybutyrate] (a-PHB), received via injection moulding The a-PHB (Mn = 6000, IP = 1,3) was synthesized by bulk polymerization of (R,S) – β-butyrolactone at room temperature, using tetrabutylammonium acetate as the initiator [1]. The BTA ( Mn =34000, Mw/Mn = 2,1) was obtained from BASF, and the PLA-b (GALASTIC, PABR-L-68, 12 % D(-) content units, Mn = 53000, Mw/Mn = 2,7) obtained from Galactic S.A. Both polymers were used as received.
Results, obtained by means of DMTA and DSC showed that polymer compositions received from PLA-b and BTA mixtures via injection moulding are two-phase systems. This suggestion is confirmed by presence of two maxima on the temperature dependence of the mechanical loss coefficient - tg δ (DMTA) and two glass transition temperatures Tg1 - in the negative area of temperatures and Tg2 – in the positive area of temperatures (DSC). It is characteristic that BTA and PLA-b mixtures show values of Tg1 lower than for pure BTA (Tg = -25,6 °C) in spite that Tg of PLA-b amounts 52,9 °C. Values of Tg2 practically do not change with the PLA-b content change in the composition. DSC data show that maximum degree of compatibility becomes visible at the weight ratio BTA/PLA-b equal 50/50. PLA-b mixtures with containing a small amount of a-PHB (5% and 10%) create compositions that show one glass transition temperature, and this is confirmed by presence of single peaks on the temperature dependence of tg δ.
The introduction of a-PHB to BTA/PLA-b mixtures leads to enlarged compatibility of components and to improving of their mechanical proprieties.
This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD-CT-2004-509232. The financial support of Polish Ministry of Science and Higher Education: R&D project no. R05 055 02 is also acknowledged.
Keywords: biodegradable polymer materials, compatibility, mechanical properties
____________________________________
[1] Kurcok P., Śmiga M., Jedliński Z. J. Polym. Sci. Polym. Chem. 40, 2184 (2002).
50
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-18
Biodegradation of Blown Films Based on Polylactide Acid
in Natural Conditions
Vladimir Sedlarik1, Nabanita Saha
1, Jana Bobalova
2, and Petr Saha
1
1 Polymer Centre, Faculty of Technology, Tomas Bata University in Zlin,
Nam. T. G. Masaryka 275, 76272 Zlin, Czech Republic 2 Innovation Centre, University Institute, Tomas Bata University in Zlin,
Mostni 5139, 76001 Zlin, Czech Republic
The environmental pollution by non-degradable plastic waste attracts attention to the development of biodegradable polymers made from renewable resources [1]. Polylactic acid (PLA) is polymer which fulfills these conditions. [1]. In the environment it can be degraded within less than two years in contrast to conventional plastics such as PE or PS [2]. Nowadays, the development of PLA based materials is commercially available in applications including medical items production or compostable packaging. In this work, we deal with the assessment of biodegradation course of blown film base of PLA in composting environment. The main attention is paid to mechanical properties of investigated samples and their changes during the time of biodegradation. Beside that, mass loss, and observation of structural changes of PLA films are the subsequent aims of this paper. The material investigated in this work is commercially available polymeric blend of PLA and biodegradable co-polyester Bioflex® 219F, density 1380 kg.m-3, melting point 155°C, softening temperature Vicat A 72°C. The film preparation was performed on mono-extrusion blown moulding machine at the temperature range of 170-175°C. The L/D ration was 26. The thickness of resulting film was about 45 µm. The rectangular shape specimens were cut off the film and introduced into the composting environment. The composting conditions were kept in accordance to the standard ČSN EN ISO 14855. The total time of biodegradation assessment was 6 weeks. The influence of microbial attack on mechanical properties, physico-chemical structure, mass loss and surface morphology was studied weekly. The results obtained during 6 weeks of composting indicate relatively good accessibility to biological degradation. Figure 1 shows the macroscopic surface changes of the blown films after 6 weeks of the testing. The interesting results were also found in the course of mechanical, thermal and physico-chemical properties and mass loss, which will be presented at the conference in detail.
(a) (b)
Figure 1: Optical micrographs of PLA based blown film before (a) and after 6 weeks (b) of composting
Keywords: biodegradable polyester; composting; mechanical properties; blown films Authors are grateful to the Ministry of Education, Youth and Sports of the Czech Republic for financial support (Grant No. MSM7088352101 and 1PO5ME736). ____________________________________
[1] L. Chen, X. Qui, M. Deng, Z. Hong, R. Luo, X. Chen, X. Jing, Polymer 46, 5723 (2005). [2] M. Pluta, Polymer 45, 8239 (2004).
51
P-19 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Molecular Modification of Gelatine by Reaction with Isocyanates
Monica Bertoldo1, Federica Cognigni
2, Francesca Signori
2,
Simona Bronco1, and Francesco Ciardelli
1,2
1PolyLab-CNR, via Risorgimento 35, 56126 Pisa, Italy
2Dipartimento di Chimica e Chimica Industriale, Università di Pisa,
via Risorgimento 35, 56126, Pisa, Italy
Gelatine is a very common denaturated protein of collagen widely available at low cost [1].
Its chain is formed by various aminoacid residues, some of which bearing nucleophyl groups,
which can react with isocyanates. In addition, the amide groups of the protein main chain are
polarizable groups and are expected to catalyze urethane and urea group formation[2]. Several
mono- and di- isocyanate derivatives were used to study the reaction of modification of
gelatine to obtain structurally modified derivatives for biomedical, adhesive, paint,
photographic and films.
In this work gelatine was successfully modified according to different routes namely
crosslinking with 1,6-diisocyanatohexane (HDI), side chain binding of hydrophobic florescent
groups with 1-naphtylisocyanate (NpI) and grafting of isocyanate terminated
polypropylenglycole monobutyl ether chains (PPG). Dimethylsulfoxide was used as reaction
solvent as, to our knowledge, is the only solvent that dissolves gelatine but does not react with
isocyanates under mild conditions.
HDI and NpI were commercial products, whereas the terminal isocyanate derivative of PPG
(PPG-NCO) was synthesized in this project. The preparative reaction was carried out with an
excess of PPG in order to minimize the amount of unreacted HDI which was then removed by
evaporation under reduced pressure at 70°C.
Gelatine was then reacted with different amount of HDI, NpI or PPG-NCO in DMSO at 40°C.
Isocyanate species went to a non detectable concentration after raction times of the order of
minutes as evidenced by FT-IR analysis of the reaction mixtures. Therefore, the presence of
somewhat autocatalytic effect on the reaction environment seemed to be confirmed.
In the case of NpI, the occurring of a quantitative bonding of naphtyl groups to gelatine was
assessed by UV-Vis spectroscopy analysis through the well detectable adsorption band of the
naphtyl group. A calibration performed with propyl 1-naphthylcarbamate allowed to quantify
the bonding yields, which could be modulated to a considerable extent on the bassi of the
reactive components molar ratios .
Modified gelatine showed a reduced hydrophilic character with respect to the pristine
proteineven if modulable solubility: in particular NpI modified gelatine is swallable but not
soluble, whereas gelatin-g-PPG is more soluble then the the pristine protein..
The three modification procedures all based on the reaction of isocyanate functionality with
recative side chains of gelatine provide useful route to biopolymer based materials with a
large variety of water swelling and solubility properties. ____________________________________
[1] B. Brodsky, J. A. Werkmeister, J. A. M. Ramshaw, in Biopolymers, (Polyamides and Complex
Proteinaceous Materials II), A. Steinbuchel, Ed. Wiley-VCH Verlag GmbH, Weinheim, Germany, 2003,
Vol. 8, 119-147.
[2] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules 2005, 38(4), 1385-1394
[3] M. Bertoldo, S. Bronco, T. Gragnoli, F. Ciardelli, Macromol. Biosci. in press.2007
52
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-20
Biodegradable and Compostable PLA-based Formulations
to Replace Plastic Disposable Commodities
M.-B. Coltelli1, F. Signori
2, C. Toncelli
3, C. Escrig Rondán
4,
S. Bronco3, and F. Ciardelli
2,3
1Centro Italiano Packaging and DCCI;
2DCCI-Dipartimento di Chimica e Chimica
Industriale, Università di Pisa, via Risorgimento 35-I-56126 Pisa, Italy; 3CNR-INFM-
PolyLAB Pisa and DCCI; 4AIMPLAS, C/ Gustave Eiffel, 4 València Parc Tecnològic,
46980 Paterna-Valencia, Spain
For several traditional applications, in particular those related to agriculture and fresh
food packing, the use of a 100 % biodegradable plastics could represent a convenient
alternative to polyolefin based materials. In this perspective, poly(lactic acid) (PLA), (a
biodegradable linear aliphatic polyester), is receiving much attention thanks to its peculiar
thermomechanical behavior, which makes it a possible polypropylene substitute, and its
availability from renewable resources. However, standard grade PLA presents high E-
modulus (E-Mod: 2.5-3.0 GPa) and high brittleness (elongation at break < 5%). Although the
copolymerization of lactides with various cyclic monomers resulted highly effective in the
reduction of PLA brittleness, blending of PLA (hard component) with low molecular weight
additives [1] or elastomeric-like polymers [2] (soft component) appears a more sustainable
approach to tailor the properties of the final material. In this framework, our work has been
focusing on the preparation and the characterization of binary PLA-based blends, where
poly(butylene adipate-co-terephtalate) (PBAT), a commercially available biodegradable
polyester, was selected as the soft component. Process conditions were firstly assessed, and
then thermal, rheological and mechanical behavior of the prepared blends in all the
composition range were investigated, in search of a composition with properties similar to
those of standard poly(propylene) (PP). Among the prepared blends, those richer in PLA
showed more suitable properties, mainly in terms of E-Mod and elongation at break (EaB).
Remarkably, we identified a promising PLA-based formulation to obtain a 100 %
biodegradable PP-like material. The fine tailoring of the mechanical parameters, especially in
terms of E-Mod and EaB, required to better mimic target PP behavior, was carried out by
means of different reactive blending approaches, in order to improve PLA/PBAT phase
compatibility by the promotion of PLA-PBAT block or graft copolymer synthesis during the
blending process. The PLA-PBAT block or graft copolymers are meant to dislocate at the
PLA/PBAT interfaces, thanks to their structure which combine features of the two
homopolymers, thus lowering the interfacial tension. Two approaches were investigated, e.g.
the use of a transesterification catalyst and the radical promoted grafting reaction. Indeed, the
transesterification catalyst was expected to produce macromolecules containing random
distributed short and long segments from PLA and PBAT, while the use of a peroxide initiator
was expected to provide some inter-chains grafting extension to a branched macromolecular
structure containing very long PLA and PBAT segments. Note that the addition of increasing
amount of a non toxic, biodegradable low molecular weight plasticizer as third component to
the selected blend was investigated, to further tailor mechanical performances. The obtained
results indicate that the followed approaches were successful to generate PLA-based
biodegradable polymeric blends fitting a wide spectrum of thermomechanical characteristics.
Keywords: PLA; biodegradable polymer blends; reactive blending
____________________________________
[1] I. Pillin, N. Montrelay, Y. Grohens Polymer 47, 4676 (2006).
[2] L. Jiang, M. P. Wolcott, J. Zhang, Biomacromolecules 7, 199 (2006).
53
P-21 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Mass Spectrometry Studies of Cyclic Esters Ring Opening Oligomerization
in the Presence of Disperse Red 1
C. Peptu
1, V. Harabagiu
2, B.C. Simionescu
2, G. Adamus
3, and M. M. Kowalczuk
1,3
1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University
of Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 "Petru Poni" Institute of Macromolecular Chemistry,
Aleea Grigore Ghica Voda 41A, 700487 Iasi, Romania 3 Polish Academy of Sciences, Centre of Polymer and Carbon Materials,
34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland
Azobenzene containing polymers are used as polymeric dyes, molecular probes, electrooptic
liquid crystals, and materials for nonlinear optics and optical storage [1]. One of their major
commercial applications is the preparation of ophthalmic lenses [2].
Poly(ε-caprolactone) (PCL) and polylactides (PLA) crystalline polymers are well known as
hydrophobic, biocompatible and biodegradable materials [3]. They are prepared mainly by
ring opening polymerization (ROP) of cyclic esters. The catalysts used in ROP are generally
derivatives of metals, such as Al, Sb, Sn, Ge, and might leave impurities. The bulk
polymerization without using catalysts avoids the contamination of the products, being
preferred in application where high purity is required. The polymerization in absence of metal
catalysts can be initiated by various active hydrogen containing compounds, such as amines
[4], alcohols [5], amino acids [6] or cyclodextrins [7].
The presentation deals with the synthesis and characterization of low molecular weight
poly(ε-caprolactone) and poly(D,L-lactide) end functionalized with Disperse Red 1,
considering that they could prove interesting optical applications. Well defined oligomers
were obtained by bulk polymerization initiated only by the means of hydroxyl groups.
Structural details were provided by classical characterization techniques like NMR, GPC, and
mass spectrometry - MALDI and ESI techniques. Characterization by tandem mass
spectrometry of the resulting polymer products, with respect to their structure, end-groups
content and composition, showed that these are best described as endcapped azobenzene
oligomers with linear structure.
Acknowledgment. This research project has been supported by a Marie Curie Early Stage
Training Fellowship of the European Community’s Sixth Framework Program under the
contract number MEST-CT-2005-021029.
Keywords: poly(ε-caprolactone), poly(D,L-lactide), azobenzene olygomers
____________________________________
[1] S. K. Yesodha et al.; Prog. Polym. Sci. 29, 45 (2004).
[2] R. A. Evans et al.; Nature Materials, 4, 249 (2005).
[3] A. Albertsson and I. K. Varma; Biomacromolecules, 4, 1466 (2003).
[4] W. Tian; European Polymer Journal, 39, 1935 (2003).
[5] P.Cerrai, M.Tricoli, F. Andruzzi, M. Paci; Polymer, 30, 338 (1989).
[6] J. Liu and L. Liu; Macromolecules, 37, 2674 (2004).
[7] Y. Takashima, M. Osaki, A. Harada; J. Am. Chem. Soc., 126, 13588 (2004).
54
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-22
Supramolecular Structure – a Key Parameter for Cellulose Biodegradation
Diana Ciolacu1 and Florin Ciolacu
2
1 “Petru Poni” Institute of Macromolecular Chemistry, Dept. of Chemistry-Physics of Polymers,
41A, Gr. Ghica-Voda Alley, 700487, Iasi, Romania 2 “Gh. Asachi” Technical University of Iasi, Dept. of Natural and Synthetic Polymers,
Blvd. Mangeron, 700050, Iasi, Romania
One of the major obstacles that have to be cleared for the full understanding of the
enzymatic degradation of cellulose is the influence of parameters such as accessibility,
crystallinity and supramolecular structure of the substrata.
For a better understanding of the cellulose biodegradation it was chosen three different
cellulosic substrata, like microcrystalline cellulose, cotton cellulose and spruce dissolving pulp in
order to be biodegraded. The kinetics of the enzymatic hydrolysis of these celluloses by
Trichoderma reesei has been investigated. The experiments proved the fact that both the
morphological structure and the crystalline one are crucial to the process and the ratio of the
reactions.
In this paper the effect of cellulose polymorphism on its biodegradability, was also
evaluated. It was studied the celluloses with different crystalline forms and a variety of structural
features, like cellulose I, II and III, obtained from cotton cellulose, in order to obtain the most
accessible cellulose substratum. The insoluble cellulose fraction remaining after enzymatic
hydrolysis was examined by X-ray diffraction method and it was established the degree of
crystallinity and the average crystallite size. The roentgenograms of the residues resulted after
different times of hydrolysis shown a slight increase in the crystallinity index, during the process.
This fact can be attributed both to a preference in the attack over the domains poorly organized
and also to their higher speed of hydrolysis. The enzymatic degradation is also proved by the
decrease in the degree of polymerization of hydrolyzed samples.
Keywords: enzymatic degradation, Trichoderma reesei, cellulose allomorphs, kinetic
55
P-23 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Kinetics of Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates
M. Kawalec1, G. Adamus
1, H. Janeczek
1, P. Kurcok
1,
M. M. Kowalczuk1, and M. Scandola
2
1 Centre of Polymer and Carbon Materials, Polish Academy of Sciences ,
34 M. Curie-Skłodowskiej St., 41-819 Zabrze, Poland 2 Department of Chemistry “G. Ciamician”, University of Bologna,
via Selmi 2, 40126 Bologna, Italy
Controlling of thermal properties of thermoplastics is of great importance from
technological point of view since thermoplastics are processed mainly in melt. Knowledge of
degradation mechanism allows one to predict and control thermal resistance of the plastic.
The control of thermal properties means also decrease of thermal stability in order to obtain
valuable short-chain products even in mild conditions.
Considering poly([R]-3-hydroxybutyrate) (PHB), which is a very well known
thermoplastic bioresorbable material, there were many papers published on its thermal
degradation mechanism [1,2] and the problem seemed to be examined thoroughly. It was
reported that the PHB thermal degradation mechanism pathway led via intramolecular cis-
elimination were trans-crotonate-terminated polymer chains and trans-crotonic acid were
generated as the main degradation products. Moreover, it was also reported that the same
degradation products were found when synthetic analogues of PHB have been degraded [3].
However, our recent studies of PHB degradation mechanism [4,5] revealed competitive
degradation reaction proceeding even at moderate temperatures which is induced by basic
agents.
In this work kinetics of degradation of poly([R,S]-3-hydroxybutyrate)/acetate, as well as
poly([R]-3-hydroxybutyrate)/acetate systems has been investigated by DSC and TG
techniques. The results have enabled the determination of the activation energy of these
processes. Moreover, the obtained results have allowed for explanation of the influence of
carboxylate groups concentration as well as the counterion size on the kinetics of poly-3-
hydroxybutyrate degradation.
The authors would like to acknowledge financial support of projects: Eureka E! 3420,
MTKD-CT-2004-509232 and Regional Stipend Fund for PhD Students under the European
Social Fund (EFS-2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD).
Keywords: degradation, kinetics of degradation, energy of activation, E1cB, thermal analysis, PHB; poly(3-
hydroksybutyrate); poly(3-hydroxyalkanoates),
____________________________________
[1] A.C. Bertoli, M.D. Schmidt, Macromol. Symp. 252, 197 (2005).
[1] N. Grassie, E.J. Murray, P.A. Holmes, Polym. Degrad. Stab. 6, 47 (1984).
[2] F.D. Kopinke, M. Remmler, K. Mackenzie, Polym. Degrad. Stab. 52, 25 (1996).
[3] P. Kurcok, M. Kowalczuk, G. Adamus, Z. Jedliński, R.W. Lenz, J. M. S.-Pure Appl. Chem. A32, 875
(1995).
[4] M. Kawalec, G. Adamus, P. Kurcok, M. Kowalczuk, , I. Foltran, L. Focarete, M. Scandola,
Biomacromolecules 8, 1053 (2007).
[5] M. Scandola, M.L. Focarete, I. Foltran, M. Kowalczuk, P. Kurcok, M. Kawalec, G. Adamus, PCT Patent
application (filed on March 20, 2006) at No. PCT/IB2006/000898.
56
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-24
Novel Biodegradable Matrices for Drug Delivery
Raluca P. Dumitriu and Cornelia Vasile
“Petru Poni” Institute of Macromolecular Chemistry, Department of Physical Chemistry,
41A Gr. Ghica Voda Alley, 700487, Iasi, Romania
Nowadays the development of biodegradable polymeric hydrogels is gaining growing
attention. Synthesis of hydrogels based on polysaccharides has attracted biomedical
researchers due to their excellent biocompatibility and biodegradability. [1] In an attempt to
obtain biodegradable materials with sensitivity to external stimuli, like pH and/or temperature,
biopolymers from renewably resources were associated with thermo-sensitive
macromolecules. [2,3,4] Such “smart” hydrogels can regulate drug release through responding
to environmental stimuli by swelling and deswelling.
New biodegradable hydrogels containing a natural polysaccharide, alginic acid and a
synthetic thermo-responsive polymer, N-isopropylacryl amide (NIPAM) were obtained and
characterized by swelling kinetic studies in different media and scanning electron microscopy
(SEM). The studies performed allowed us to ascertain that the semi-interpenetrating networks
obtained possess thermo- and pH-responsive properties dependent on composition and
crosslinking degree. SEM micrographs showed a porous structure with pores dimensions
dependent on the composition of the hydrogels.
Fig.1. SEM micrograph of 75/25 NIPAM/ALG Fig. 2. Swelling kinetic study in various media
hydrogel . at 250C: a) twice distilled water; b) ethanol.
Keywords: biodegradable polymers; hydrogels; drug delivery
____________________________________
[1] C. Xiao, G. Zhou, Polym. Degr. Stab. 81, 297 (2003).
[2] S.Y. Kim, S.M. Cho, Y.M. Lee, S.J. Kim, J. Appl. Polym. Sci. 78, 1381 (2000).
[3] E. Marsano, E. Bianchi, A. Viscardi, Polymer 45, 157 (2004).
[4] J. Shi, N.M. Alves, J.F. Mano, Macromol. Biosci. 6, 358 (2006).
0 50 100 150 200 250
0
500
1000
1500
2000
2500
3000
3500
4000
Swelling ratio (%)
Time (min)
T = 250C
NIPAM/ALG 75/25 (a)
NIPAM/ALG 75/25 (b)
57
P-25 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Divergent Synthesis of β-Cyclodextrin-Cored
Star -Poly([R,S]-3-hydroxybutyrate)
M. Michalak1, M. Kawalec
2, C. Peptu
1, P. Kurcok
1,2, and M. M. Kowalczuk
1
1 Institute of Chemistry and Environment Protection, Jan Dlugosz University,
13/15 Armii Krajowej Ave., 42-200 Częstochowa, Poland 2 Centre of Polymer and Carbon Materials , Polish Academy of Sciences,
34 M. Curie-Skłodowskiej St., 41-819 Zabrze, Poland
Poly([R,S]-3-hydroxybutyrate) is a synthetic analogue of natural polyester poly([R]-3-
hydroxybutyrate) which is produced and stored by many prokaryotic organisms as carbon and energy source [1]. The synthetic analogue can be obtained, among other ways, via ring-opening polymerization (ROP) of β-butyrolactone [2-5].
Recent work of preparation of star-poly([R,S]-3-hydroxybutyrate) have arose from a task of increasing the content of carboxylic groups of atactic poly([R,S]-3-hydroxybutyrate) while keeping polymer’s high molecular weight. Obtaining of a biodegradable, non-toxic polymer has been the second requirement for the material.
Cyclodextrins [6] are cyclic oligosaccharides which have the characteristic size of a truncated cone. Commonly, they are constituted by 6, 7 or 8 glucose rings linked to each other by a 1-4-α-glucosidic bond and they are named α-, β- and γ-cyclodextrins, respectively. Nowadays β-cyclclodextrin is produced in larger quantities and it is the cheapest available. Moreover, 7 anhydro glucose units offer total number of 21 hydroxy groups, which can be modified, per single cyclodextrin molecule. Furthermore, this hydroxycarbon is biodegradable, non-toxic and it is from renewable sources.
Thus, bearing in mind general purposes it has been contrived to prepare a star-shaped polymer by applying polycarboxylate molecules for initiation of anionic polymerization of β-butyrolactone. As the core, β-cyclodextrin polycarboxylate derivative has been chosen.
The method describes synthesis of poly(carboxysuccinate) β-cyclodextrin in similar manner as it was reported previously [7]. The degree of esterification of the derivative has been determined by potentiometric and NMR analyses (spectra prove substitution of C2-OH as well as C3-OH mainly and hardly C6-OH). After it was titrated, the final polycarboxylate derivative has been used for initiation of β-butyrolactone polymerization in DMF solution. The resulting star-poly(3-hydroxybutyrate)s have been analysed with 1H, 13C NMR, MALDI-TOF and SEC techniques after they were isolated from reaction mixtures.
The detailed data on synthesis and properties of star-poly([R,S]-3-hydroxybutyrate will be presented in this communication.
The authors would like to acknowledge financial support of project Regional Stipend Fund for PhD
Students under the European Social Fund (EFS-2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD).
Keywords: biodegradable polymers; PHB, poly(3-hydroxybutyrate), star polymers, anionic polymerization, β-cyclodextrin
____________________________________
[1] Y. Doi, Microbial Polyesters; VCH Publishers: Weinheim, 1990. [2] L. R. Rieth, D. R. Moore, E. B. Lobkovsky, G. W. Coates, J.Am.Chem.Soc. 124, 15239(2002). [3] Z. Jedliński, P. Kurcok, M. Kowalczuk, J. Kasperczyk, Makromol. Chem. 187, 1651 (1986). [4] H. Abe, I. Matsubara, Y. Doi, Y. Hori, A. Yamaguchi Macromolecules 27, 6018 (1994). [5] P. Kurcok, M. Śmiga, Z. Jedliński, J.Polym. Sci. Polym. Chem. 40, 2184 (2002). [6] J. Szejtli, Cyclodextrin Technology; Kluwer Academic Publishers, 1988. [7] R. Dicke, Cellulose 11, 255 (2004).
58
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-26
Crystallinity and Crystalline Confinement
of the Amorphous Phase in Polylactides
Jose-Ramon Sarasua, E. Zuza, A. López-Arraiza*, N. Imaz, and E. Meaurio
University of the Basque Country (EHU-UPV), School of Engineering, Bilbao 48013, Sp. *present address: Mondragon University, MGEP, 20500 Mondragón, Sp.
In many aspects there is still a lack of understanding of the fundamentals of physical
chemistry that govern the segmental relaxation of polymer chains in both non-confined and
confined environments. Nonetheless, it is well established that constraints of polymer chains
caused by crystallinity lead to an increase in the temperature of the glass transition, for chains
find a growing hindrance to relax. Since macromolecules are longer than the crystal lamellae
are thick, they can cross the phase boundaries and cause various degrees of coupling; on weak
coupling, the dynamics of the non-crystalline segments shows usually a broadening of the
glass transition range, yet on stronger coupling the non-crystalline material may also show a
distinct glass transition, at higher temperature of the bulk amorphous phase due to a rigid
amorphous phase. [1]
Stereo-regular polylactides such as poly (L-lactide) (PLLA) or poly (D-lactide) result from
polymerization of optically pure lactides and are semicrystalline. Optically non-active
polylactides (PDLLA) can be regarded as random or atactic copolymers, show a random
moiety distribution, and are completely amorphous [2]. In this work three phases, comprising
mobile amorphous fraction (MAF, χMA), rigid amorphous fraction (RAF,χRA) and crystalline
fraction (χc) were determined in PLLA. It will be shown that RAP fraction not only elevates
Tg but also increases the dynamic fragility (m) of polylactide chains around the Tg [3]. These
results agree with reported cases in which topologycal constraints inhibit longer range
dynamics and suggest a smaller length scale of cooperativity in confined environments [4].
Figure 1
Angell’s plot of fully amorphous polylactide
(▲PDLLA) and semicrystalline polylactides
crystallized by annealing after water
quenching (● PLLA-WQA) and by slow
cooling from the melt (■ PLLA-SC).
0.90 0.92 0.94 0.96 0.98 1.00
-5
-4
-3
-2
-1
0
fragile
strong
log a
Tg/T
Keywords: polylactide, crystalline confinement; dynamic fragility.
____________________________________
[1] Wunderlich, B. Prog. Polym. Sci. 28, 383-450 (2003).
[2] Sarasua, J. R.; Prud'homme R. E.; Wisniewski, M.; Le Borgne A.; Spassky, N. Macromolecules 31, 3895
(1998); Meaurio, E.; Zuza, E.; Sarasua, J. R. Macromolecules 38, 9221 (2005).
[3] Angell, C. A. Journal of Non-Crystalline Solids 131, 13-31 (1991); Science 67, 1924 (1995).
[4] Qin, Q.; McKenna, B. Journal of Non Crystalline Solids 352, 2977-2985 (2006).
59
P-27 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Liquid Crystal Template Applied for Polyimide-Cellulose
Derivative Thin Films
D. Filip, A.I. Cosutchi, C. Hulubei, and S. Ioan
“Petru Poni” Institute of Macromolecular Chemistry
Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania
Thin polyimide films are the most commonly employed liquid crystal alignment
layers. Two techniques [1] are used to produce LC alignment on polyimide films : standard
method of rubbing and polarized UV irradiation of polyimides which result in anisotropy of
the surface. Thin solid films prepared from lyotropic solutions of cellulose derivatives can be
used also as alignment layers for liquid crystals [2]. For hydroxypropylcellulose solid thin
films prepared from lyotropic solutions it was found that the band size constitutes a
controlling factor in the anisotropy of the material properties. Tailoring the surface
topography and altering the structure of polyimide enable to control orientation at the surface
which is important in adhesion properties. Spatially ordered polymer microstructures from LC
templates in a pattern-forming state is obtained. A new approach of polymerization and
patterning of thin films based on partially aliphatic polyimides is achieved. The synthesis of
the polyimides was reported previously [3]. The precursor lyotropic solution of
hydroxypropylcellulose was used as liquid crystal template. The films were exposed to UV
irradiation and the photosensitive properties have been investigated. The detailed structures
of the resulting films were studied by polarized optical microscopy, atomic force microscopy
and scanning electron microscopy.
Keywords: polyimide; liquid crystalline cellulose derivative. ____________________________________
[1] D. Andrienko, Y. Kurioz, M. Nishikawa, Y. Reznikov, J.L. West, Jpn. Appl. Phys. 39, 1217 (2000).
[2] M. H. Godinho, J. G. Fonseca, A. C. Ribeiro, L. V. Melo, P. Brogueira, Macromolecules 35, 5932 (2002).
[3] E. Hamciuc, R. Lungu, C. Hulubei, M. Bruma, J. Macromol. Sci. Part A: Pure and Appl. Chem., 43, 247
(2006).
60
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-28
Biomass Compounds with Pharmacological Applications
Iuliana Spiridon1, Maria Ichim
2 and Narcis Anghel
1
1“Petru Poni” Institute of Macromolecular Chemistry,
Grigore Ghica-Voda no. 41, Iasi, Romania 2S. C. “Bioing“ S. A.,Calea 13 Septembrie no. 105, Bucuresti, Romania
Plants vary within and among species in the types and concentrations of phytochemicals due
to variables in plant growth, soil, weather conditions and the age of the plant. Phenolic
phytochemicals are the largest category of phytochemicals and the most widely distributed in
the plant kingdom. Polyphenolic compounds, one of the most numerous and best studied
groups of plant biomass, are well known to exhibit various biological and pharmacological
effects.
It is quite possible that several of these components could contribute to the
antidepressant activity, either directly, or indirectly by making other compounds in the extract
more active or more bioavailable (this latter possibility reflects the concept known as
synergy).
In our paper, the results obtained using the polymeric compounds separated from
some biomass species to prepare a formula with therapeutic effect on nervous central system
are presented.
Keywords: polymers; polyphenols; antidepressant
61
P-29 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Homo- and Copolymerization of Cyclic Aliphatic Esters
with Suppression of Transesterification
Marta Socka, Marcin Florczak, and Andrzej Duda
Centre of Molecular and Macromolecular Studies Polish Academy of Sciences,
Sienkiewicza 112, Lodz, Poland
Aliphatic polyesters [...−(CnH2nC(=O)O)m−...] become a new, emerging class of polymers
that reveal interesting properties, like biocompability, ability to hydrolytical and biological
degradation accompanied with useful mechanical and thermal parameters. Moreover, some of
those monomers and/or polymers can be obtained from the renewable resources. The most
convenient method for aliphatic polyesters synthesis is the ring-opening polymerization
(ROP) of the corresponding cyclic esters. This method provides sufficient control of
polymerization of lactones, lactides, and cyclic carbonates, giving polymers of the required
molecular weights and fitted with the desired end-groups. In the appropriately chosen
polymerization conditions the side reactions, like termination and transfer to the monomer
could be eliminated [1].
Moreover, application of initiators that bear bulky, sterically demanding ligands, such as
aromatic Schiff’s base (SB) derivatives (e.g. (R)-(−)- or (S)-(+)-2,2’-[1,1’-binaphtyl-2,2’-
diylbis-(nitrylomethylidyne)]-diphenolate aluminium isopropoxide (SBO2Al-OiPr)), leads to a
considerable suppression of the inter- and intramolecular transestrification (see e.g. papers
[2] - [4] and references cited therein) as well as disproportionation of the end-groups.
The present contribution reports on application of SBO2Al-OiPr in the controlled ROP of
ε-caprolactone (CL), L,L-lactide (LA), and cyclic carbonates (2.2-dimethyltrimethylene
carbonate (DTC) and trimethylene carbonate (TMC)).
It will be shown that SBO2Al-OiPr initiation of LA copolymerization with CL or cyclic
carbonates leads to a particularly interesting results. Namely, the corresponding diblock and
multiblock copolymers could be prepared for the first time employing the ‘living poly(LA)
block first’ synthetic route [3,4].
Keywords: aliphatic polyesters; L,L-lactide; ε-caprolactone; 2.2-dimethyltrimethylene carbonate; trimethylene
carbonate; living polymerization; block copolymers; transesterification
____________________________________
[1] A. Duda, S. Penczek, “Mechanisms of Aliphatic Polyester Formation”, in Biopolymers, Vol. 3b: Polyesters
II – Properties and Chemical Synthesis, ed. by A. Steinbüchel, Y. Doi, Wiley-VCH, Weinheim, 371 (2002).
[2] A. Duda, K. Majerska, J. Am. Chem. Soc. 126, 1026 (2004).
[3] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38, 2027 (2005).
[4] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28, 1385,
(2007).
O
O
O
H3C
H3CO
O
O
O
O
OO
H3C
CH3
O
O
( CL ) ( LA ) ( TMC ) ( DTC )
62
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-30
Acid Modification and Application of Biodegradable Polymer-Starch
Chia-I Liu and Chi-Yuan Huang
Dep.of Materials Engineering, Tatung University, No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan
The blends with acid hydrolysis starch present a smooth face, because acid would break the molecular chains of starch. XRD and DSC analysis also confirmed crystallinity decrease and then increase as concentration of acid increased. MFI of blends could reach to 300g/10min as additive of 0.3M CA-starch was 70wt%.
1. Experimental
1.1 Acid hydrolysis of starch with ultrasonic treatment
A different concentration of Citric acid (reagent grade)(0.1M, 0.3M, 0.5M) water were ap-plied to hydrolysis tapioca starch (food grade). The modified starch were added into tapioca starch/ glycerol the blends, and the additive was 30wt%, 50wt%, 70wt% ,separately. A sin-gle-screw extruder was employed to compound the blends at four step temperatures of 90, 100, 70, 40°C and the rotating speed was 20rpm.
2. Results and discussions
2.1. SEM observation of blends with acid hydrolysis starch: the cryo-fractured surfaces of blends presents a smooth face as the content of acid hydrolysis starch increased (Fig.1). It indicated that acid would break the molecular chains of starch and the granule of starch was easy to melt in the process [1].
2.2. DSC analysis of acid hydrolysis starch: The melting peak of 0.1M CA-starch shift to a low temperature, but the melting peak of 0.3M and 0.5M CA-starch shift to high temperature (Fig.2). It indicated that higher concentration acid would process a higher relative crystallinity. 2.3. XRD analysis of acid hydrolysis starch: The XRD pattern of 0.1M CA-starch present weak peaks but the patterns in 0.3M and 0.5M CA-starch appeared strong peaks at 2θ about 15°, 17°, 18° and 23°(Fig.3). 2.4. MFI analysis of blends with acid hydrolysis starch: the MFI of blends appear an increase as additive of acid hydrolysis starch increase. Especially, the blend with 70wt% 0.3M CA-starch, the MFI of blend could reach to 300g/10min (Fig.4).
Figure 1. SEM morphology of blends with different content of acid hydrolysis starch: 0.1M CA-starch(a)30wt% (b) 50wt% (c) 70wt%; 0.3M CA-starch (d)30wt% (e) 50wt% (f) 70wt%; 0.5M CA-starch (g)30wt% (h) 50wt%.
50 100 150 200 250
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
Tapioca starch
0.1M CA-starch
0.3M CA-starch
0.5M CA-starch
Heat Flow ( w/g)
Temperature (OC)
10 20 30 40 50 60 70 80 90
0
50
100
150
200
250
300
350
Tapioca starch
0.1M CA-starch
0.3M CA-starch
0.5M CA-starch
Intensity
2 theta
Fig. 2. DSC curves in different con-centration of acid hydrolysis starch.
Fig. 3. XRD curves in different con-centration of acid hydrolysis starch.
Fig. 4 .MFI curves in different con-centration of acid hydrolysis starch.
Keywords: biodegradation, acid hydrolysis, recrystallinity
____________________________________
[1] N. Atichokudomchai, S. Shobangob, S. Varavinit, Starch, 52, 283(2000).
(a) (d) (b) (c) (f) (e)
(h)
30 40 50 60 70
0
50
100
150
200
250
300
350
Hydrolysis starch
0.1M CA-starch
0.3M CA-starch
0.5M CA-starch
Melt Flow Index (g/10min)
Content (wt%)
(g) (h)
(a) (b) (c) (d) (e) (f) (g) (h)
63
P-31 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Characterization of the Radical Polymeric Grafting of Hydroxylethyl
Methacrylate onto Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
Hoi-Kuan Lao
1,2, Estelle Renard
2, Valérie Langlois
2, Xaviera Pennanec
1,
Mylène Cuart1, Karine Vallee-Rehel
1, and Isabelle Linossier
1
1LBCM, EA 3884, Université de Bretagne-Sud, BP92116, 56321 Lorient Cedex, France
2SPC, ICMPE, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais, France
Polyhydroxyalkanoates (PHAs) are biosynthesized by a wide range of microorganisms
as intracellular energy and carbon storage materials. These materials have been evaluated for
a variety of medical applications, which include controlled release, surgical sutures, wound
dressings, lubricating powders, orthopaedic uses and as a pericardial substitute. However, the
surfaces of PHB and PHBHV are quite inert and hydrophobic. They have no physiological
activity which is unfavourable for adhered cell growth in tissue engineering. Therefore, as for
many polymer surfaces, the cytocompatibility should be improved by either chemical
modification with functional groups or modification of the surface topography.
Graft polymerization is a well-known method for the modification of chemical
structure to obtain properties for specific applications such as bone scaffolds [1]. Many
methods are used such as plasma, ozone treatment and gamma radiation [1-3]. In order to
improve the general wettability of the PHBHV, graft copolymerization of 2-
hydroxyethylmethacrylate (HEMA) was achieved. We have previously proposed a simple
way of grafting HEMA onto PHBHV, this synthesis was carried out in aqueous solution with
the benzoyl peroxide as chemical initiator [4].
In the framework of free radical grafting of vinylic monomer, it is generally speculate
that the graft polymerization on PHBHV is conducted by formation of primary radicals from
hydrogen abstraction of the methine protons on the PHBHV backbone, which can react with
HEMA [5]. No literature data ascertain this hypothesis. In order to determine the localization
of the grafted chains 2D 1H-NMR was carried out to elucidate the mechanism pathway.
The free radical polymerization is known to lead to broad molecular weight: the
determination of the molecular weight of the grafted chains by free radical grafting (UV,
ozone, or chemical initiation …) was not explored yet. Indeed, it is difficult to access to these
data and it is supposed to be the same order of magnitude of the homopolymer formed during
the grafting procedure. Molecular weight of the grafted chain from the degradation of the
PHBHV was characterized to ascertain the real size of the grafted PHEMA.
Enzymatic biodegradability was investigated in order to know if the grafted polymer is
still degradable.
____________________________________
[1] Grondahl, L., Chandler-Temple, A.,Trau, M., Biomacromolecules 6, 2197 (2005).
[2] Kang, I. K.,Choi, S. H.,Shin, D. S.,Yoon, S. C., Int. J. Biol Macromol. 28, 205 (2001).
[3] Ke, Y.,Wang, Y.,Ren, L.,Lu, L.,Wu, G.,Xiaofeng,Chen, C. J., J. Appl. Polym. Sci. 104, 4088 (2007).
[4] Lao, H. K.,Renard, E.,Linossier, I.,Langlois, V.,Vallee-Rehel, K., Biomacromolecules 8, 416 (2007).
[5] Chen, C.,Peng, S.,Fei, B.,Zhuang, Y.,Dong, L.,Feng, Z.,Chen, S.,Xia, H., J. Appl. Polym. Sci. 88, 659
(2003).
64
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-32
Degradation Process of Bioresorbable PGLC Terpolymers
J. Jaworska1, Y. Hu
2, J. Wei
2, J. Kasperczyk
1, P. Dobrzyński
1, and S. Li
2,3
1Centre of Polymer and Carbon Materials, Polish Academy of Sciences,
34 Str.Curie-Sklodowska, 41-808 Zabrze, Poland 2Department of Materials Science, Fudan University, Shanghai 200433, China
3Research Center on Artificial Biopolymers, Max Mousseron Institute on Biomolecules, UMR
CNRS 5247, Faculty of Pharmacy, University Montpellier I, 34093 Montpellier, France
Introduction
Bioresorbable and compatible with human tissues aliphatic polyesters undergo hydrolytic and
enzymatic degradation in biological environment to nontoxic components eliminated via the
Krebs cycle. They are considered in a variety of medical and pharmaceutical applications in
controlled drug delivery systems and in tissue engineering. In this work, we report a study on
the hydrolytic degradation of PGLC terpolymers in order to elucidate the effect of the chain
microstructure. On the basis of changes in chain microstructure the choice of appriopriate
terpolymer to desired medical application is possible.
Experimental methods
Terpolymers of glycolide, lactide, and ε-caprolactone have been prepared by the ring opening
polymerization held in a bulk using zirconium and tin initiators. Obtained terpolymers were
pressed and allowed to degrade in a phosphate buffer solution pH=7,4 in 37°C for a different
period of time. The composition and chain microstructure of obtained terpolymers and
degradation products have been determined by 1H and
13C NMR.
Results and discussion
A series of glycolide, lactide and caprolactone terpolymers, were synthesized using Zr(acac)4
or Sn(oct)2 as initiators in order to obtain various chain microstructure. The results revealed
that the degradation rate depends not only on the terpolymer composition but also on its chain
microstructure. For example in the case of high concentration of lactide units in terpolymer
chains at the beginning of degradation, longer L sequences and alternating CGC and CLC
segments in ordered domains are resistant for degradation but degradation of G-L, G-C and L-
C ‘mixed’ segments occurs faster. In consequence stable level of all monomeric units during
degradation is observed. Such stable level is noticed also in the case of high amount of
caproyl units in terpolymer chains. Alternating CGC and CLC sequences, which are resistant
for degradation, influence on the content of G and L units in polymer chain and prevent
decrease of glycolide and lactide units concentration in terpolymer chain during degradation
process.
Conclusions
Chain microstructure of terpolymer influence its degradation and can be investigated by NMR
method. According to various microstructures of the chain (random and block terpolymers)
clear differences in degradation mechanism have been observed. On the basis of changes in
chain microstructure it is possible to chose appriopriate terpolymer to desired application.
Acknowledgements Joint French-Polish CNRS-PASc. Grant No. 18256 and Regional Scholarship EFS-2.6 ZPORR No.
Z/2.24/II/2.6/17/04 RFSD
Keywords: hydrolytic degradation; bioresorbable polymers, NMR, microstructure
65
P-33 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Sustainable Green Polymer Composites Based on PLA
G. Bogoeva-Gaceva1, M. Avella
2, V. Srebrenkoska
3, A. Grozdanov
1,
A. Buzarovska1, M. E. Errico
2, and G. Gentile
2
1Faculty of technology and Metallurgy, Rugjer Boskovic 16, 1000 Skopje,R.Macedonia
2Institute for Chemistry and Technologyof Polymers-ICTP,
Via Campi Flegrei 34, 80078 Pozzuoli,Napoli, Italy 3Kompozitna Oprema, Industriska bb, Prilep, R.Macedonia
In the framework of the ECO-PCCM project [http://elchem.ihtm.bg.ac.yu/ECO-PCCM/],
sustainable green polymer composites based on thermoplastic biodegradable polymer matrix
(Polylactide acid – PLA) reinforced with natural fibers (kenaf) and agricultural fillers (rice
straw) have been analyzed [1,2]. Production of green-composites has been performed by
conventional techniques, such as melt mixing (T=170 oC t=10min) and compression molding
(T=185oC t= 10min). Characterization includes analysis of mechanical behavior (tensile test,
flexural test, impact resistance), thermal stability (by TGA) and morphological analysis (by
SEM).
The obtained results for the studied composites with both reinforcements, have shown
increased modulus, both tensile and flexural (EPLA/kenaf d=60mm ρ=40kg/m3 = 1,1 GPa, EPLA/kenaf
d=50mm ρ=40kg/m3 = 0,08 GPa). Tensile and flexural strength were slightly decreased. SEM
analysis indicated on the satisfied durability of the PLA polymer based composites.
Fig. 1 SEM of PLA/RS/CA “neat”
composites (75/20/5 wt%, x150).
Fig. 2 SEM of PLAx1/RS/CA composite
obtained with recycled PLA (75/20/5
wt%, x200).
Keywords: green composites; recycling; mechanical properties
____________________________________
[1] G.Bogoeva-Gaceva, D.Dimeski, Z.Manov, V.Srebrenkoska, A.Grozdanov, A.Buzarovska, M.Avella,
IUMACRO’07, IUPAC and ACS Conference on Macromolecules for a Safe, Sustainable and Healthy World 2nd
Strategic Polymer Symposium, NewYork USA , June 10-13 (2007).
[2] M.Avella, G.Bogoeva-Gaceva, A.Buzarovska, M.E.Errico, G.Gentile, A.Grozdanov, J.Appl.Polym.Sci., 104,
3192 (2007)
66
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-34
Accelerated Wound Repair by Di-O-butyrylchitin,
the Polymer for New Non-Woven Dressing Material
A. Błasińska1 and J. Drobnik
2
1Department of Fiber Physics and Textile Metrology, Technical University of Lodz,
Zeromskiego 116, 90-924 Lodz, Poland 2Department of Connective Tissue Metabolism, Medical University of Lodz,
Narutowicza 60, 90-136 Lodz, Poland.
Di-O-butyrylchitin (DBC) is the technologically friendly chitin derivative, obtained
after introduction of the two butyryl groups to chitin at position C-3 and C-6 [1,2]. Well
solubility of DBC in common solvents and high biocompatiblity makes this polymer the
good candidate for application in biological subjects [3,4]. The present study is aimed at
testing DBC action on a healing process, as well as, explaining the mechanisms of its’ effect.
Moreover, the comparison of DBC action with other dressing materials effects (butyrylchitin,
regenerated chitin and chitosan) is planned.
Experiments were made on male Wistar rats. Polypropylene nets (2cmX3cm) were
implanted subcutaneously to the rats. The implants alone served as control but in other
groups the nets were covered with the dressing material made of investigated polymers:
DBC-1 and DBC-2 with intrinsic viscosity [η]DMAc/25deg.C equal 1.75dl/g and 2.08dl/g
respectively, butyrylchitin, regenerated chitin and chitosan. Four weeks after implantation
samples were taken for biochemical analysis. DBC-dressings were showed to increase
granulation tissue weight and glicosaminoglycans content in the scar. Total collagen content
was not changed but the soluble fraction of the protein (not polymerized collagen) was
reduced. One can state the improvement of collagen polymerization by DBC. Number of
fibroblasts isolated from the wounds and cultured on DBC films was elevated but reduction
of died cells was seen. Contrary to DBC, chitosan reduced glicosaminoglycans level in the
wound and increased water content in the granulation tissue. Some general effects of DBC
were observed. Thus the polymer decreased body weight of rats and reduced body
temperature.
Beneficial effects of DBC dressings on wound repair have been documented. The most
promisable effects were obtained after application of DBC-1 with intrinsic viscosity [η]
DMAc/25deg.C=1.75 dl/g. Thus the DBC elevated the granulation tissue mass in the wound and
increased glycosaminoglycans content and polymerization of collagen level. One can explain
the observed phenomenon by direct influence of DBC on the cells in the wound (increased
cells number and weight of granulation tissue). The effects of the butyrylchitin and
regenerated chitin on repair were not better as compared to DBC (di-O-butyrylchitin).
Keywords: dibutyrylchitin; non-wovens; wound healing
____________________________________
[1] L. Szosland, G. Janowska, Method for preparation of dibutyrylchitin, Patent PL169077B1 (1996).
[2] L. Szosland, Di-O-butyrylchitin, in Chitin Handbook; Muzzarelli, R.A.A., Peter, M.G., Eds. 53-60, (1997).
[3] L. Szosland, I. Krucińska, R. Cisło, D. Paluch, J. Staniszewska-Kuś, L. Solski, M. Synthesis of
dibutyrylchitin and preparation of new textiles made from dibutyrylchitin and chitin for medical applications,
Fibres & Textiles in Eastern Europe, 9(34), 54-57 (2001).
[4] A. Chilarski, L. Szosland, I. Krucińska, A. Błasińska, R. Cisło, Non-wovens made from dibutyrylchitin as
novel dressing materials accelerating wound healing, Proceedings of 6 th International Conference of the
European Chitin Society, EUCHIS’04, Poznań, Poland (2004).
67
P-35 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Characterization of Biodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means of Electrospray Ionization-mass Spectrometry
after a Partial Depolymerization
Alena Šišková1, Wanda Sikorska2, Marta Musioł2 , Marek M. Kowalczuk2, and Witold J. Kowalski1
1Institute of Chemistry and Environmental Protection, Faculty
of Mathematics and Natural Sciences, Jan Dlugosz University,
13/15 Armi Krajowej, 42–200 Czestochowa, Poland 2Polish Academy of Sciences, Centre of Polymer and Carbon Materials,
34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland
Synthetic polymers are highly complex multicomponent materials. Their different
heterogeneities can be summarized in a term “molecular heterogeneity“, meaning different
aspects of molar mass, chemical composition, functionality type and molecular architecture
distribution. Among the distributed properties in the case of co- and terpolymers are, e. g.,
sequence and length of incorporation (alternating, random or block) distributions [1].
Copolyesters containing aliphatic and aromatic repeating units formed of terephthalic acid, adipic
acid and 1, 4-butanediol, (e.g., Ecoflex trade-mark series) present different degrees of (bio)-
degradability and are interesting materials for medicinal and environmental applications.
We intended to characterize these materials by means of the electrospray ionization
coupled with mass spectrometry (ESI-MS), and chromatographic methods. The first step
included a reduction of their molecular mass in order to enable the MS analysis by means of the
accessible equipment [2,3]. Depolymerization processes of selected Ecoflex samples were carried
out in selected conditions: in methanolic and aqueous solutions, at ambient and elevated
temperatures, in basic media (tetrabutylammonium hydroxide). The degradation products were
analyzed by means of steric exclusion chromatography (SEC) and the obtained fractions were
submitted to 1H NMR and ESI-MS spectrometry.
The highly reproductible partial depolymerization procedures gave rise to an assumption
that the subsequent application of ESI-MS would significantly contribute to determination of the
molecular architecture of studied polyesters.
Acknowledgement: This work was supported by the European Community, Marie Curie Actions:
MEST-CT-2005- 021029, „POLY-MS”.
Keywords: partial depolymerization; molecular size fractionation; repeating units incorporation sequence
____________________________________
[1] H. Pasch and B. Trathnigg, HPLC of polymers, Sprinter-Verlag, Berlin, Heidelberg, New York, (1999).
[2] U. Witt et.al. Biodegradation of aliphatic-aromatic copolyesters: evaluation of the final biodegradability and
ecotoxicological impact of degradation intermediates, Chemosphere 44,289-299 (2001).
[3] F. Pardal, G. Tersac, Kinetics of poly (ethylene terephthalate) glycolysis by diethylene glycol. I. Evolution
of liquid and solid phases, Polymer Degradation and Stability 91, 2840-2847 (2006).
68
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-36
Commercial Biodegradable Polymers Reinforced with Flax Fibers
Mariastella Scandola, Elisa Zini, and Maria L. Focarete
University of Bologna, “G.Ciamician” Department of Chemistry,
via Selmi 2, 40126 Bologna, Italy
Increasing environmental concern over waste disposal has recently promoted research towards
new biodegradable materials for a wide range of applications. In particular composites made of
natural fibers and biodegradable polymers are presently considered new environmentally
friendly materials suitable for lightweight structural parts [1]. At the end of their service life,
biocomposites can be completely degraded in compositing units (in specific cases also in the
environment) or alternatively they can be incinerated for energy recovery.
Two biodegradable commercial polymers were used as the matrix in biocomposite
manufacturing: a bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), NodaxTM
[average 3-hydroxyhexanoate content: 12 mol %] and cellulose acetate, CA (degree of
substitution 2.5, food-grade plasticizer content: 34 wt%), while the reinforcing fibers were flax
fibers, bleached with hydrogen peroxide in the presence of NaOH and Na2CO3. Two series of composites were prepared: long fiber (LF) and short-fiber (SF) composites. LF
composites were obtained by high temperature compression molding alternated polymer films
and fiber mats (five-layered sandwich), and contained 5mm-long fibers randomly distributed
in the plane of the sheet. Mechanical investigations of LF composites indicated that long flax
fibers are able to reinforce both polymeric matrices.
SF composites were obtained by high temperature mechanical mixing polymer and fibers,
followed by compression molding into sheets. In these composites the fibers were shortened
during processing and their length was in the range 100-220 µm. The tensile modulus of SF
composites increased, as expected, with increasing fiber content in both CA and NodaxTM
composites. The tensile strength of SF composites, instead, only increased in the CA
composites. In order to observe a reinforcing effect of the NodaxTM
copolyester, a chemical
modification (acetylation) had to be applied to the fiber surface to improve fiber-matrix
adhesion, a technique that has been previously adopted [2,3] and does not substantially affect
fiber biodegradability [4].
The NodaxTM biocomposites showed a remarkable increase of crystallization rate from the
melt, attributed to heterogeneous nucleation of the vegetable fibers, that exhibited a
transcrystalline polymer layer at their surface. From a practical standpoint, this results in
faster composite solidification and reduces processing time.
Acknowledgments: we thank Mazzucchelli 1849 s.p.a. (Castiglione Olona, Italy) and Procter and Gamble
Company (West Chester, OH, USA) for the gift of plasticized CA and of NodaxTM respectively and Linificio e
Canapificio Nazionale s.p.a for kindly providing the flax fibers.
Keywords: biocomposites; biodegradable polymers; mechanical properties; natural fibers
____________________________________
[1] A.K. Bledzki, J. Gassan, Prog. Polym. Sci. 24, 221 (1999).
[2] M. Baiardo, E. Zini, M. Scandola, Composites Part A: Appl. Sci. Manu. 35, 703 (2004).
[3] E. Zini, M. Baiardo, M. Scandola, Macromol. Biosci. 4, 286 (2004).
[4] G. Frisoni, M. Baiardo, M. Scandola, D. Lednikà, M.C. Cnockaert, J. Mergaert, J. Swings,
Biomacromolecules 2, 476 (2001).
69
P-37 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Investigation of Novel Shape-Memory Polymers' Chain Microstructure
Katarzyna Gębarowska1, Janusz Kasperczyk
1, Piotr Dobrzyński
1,
Mariastella Scandola2, and Elisa Zini
2
1Centre of Polymer and Carbon Chemistry, Polish Academy of Sciences, Zabrze, Poland
2University of Bologna, Department of Chemistry, Bologna, Italy
Introduction Synthetic biodegradable lactide, glycolide and trimethylene carbonate (TMC) based
materials can possess the ability to recover from intermediate shape to primal when applying
e.g. severe temperature change. Such property is called shape-memory behaviour. [1] Shape-
memory polymers (SMP) find wide application in medical field, for instance in manufacturing
surgical pins, selfexpanding stents, etc. [2,3] The knowledge of microstructure of polymer
chain dependence with shape-memory behaviour may be crucial in elaborating the process of
obtaining material that exhibit appropriate mechanical parameters and temperature (in the
range of body temperature) of transition form intermediate to primal state.
Experimental The investigations of chain microstructure of LL-lactide/glycolide/TMC terpolymers`,
obtained on zirconium initiator (Zr(acac)4), were performed by means of 1H and
13C nuclear
magnetic resonance spectroscopy. All terpolymer`s samples differed in the initial
comonomeric unit contents.
Results Results of
1H NMR spectra enabled to calculate the content of all comonomeric units:
lactidyl LL, glycolidyl GG and carbonyl T. Much more information was obtained from 13C
NMR spectra. The most sensitive spectral region, best for detailed analysis of groups and
sequences appearing in terpolymer`s chain, were methine carbon region from lactide and
methylene carbon regions from glycolide and TMC. Therefore very detailed resonance lines
assignment was performed. Furthermore, the 13C NMR spectra allowed to evaluate percentage
molar content of long polymer blocks and mixed segments. It was found that depending on
the comonomeric unit ratio, different long blocks and mixed segments appear in terpolymer
chain microstructure.
Conclusions NMR spectroscopy is a very useful tool for analysing LL-lactide/glycolide/TMC
terpolymer`s microstructure. According to obtained results it is to state that different
monomeric unit content influences the polymer chain microstructure and, therefore, shape-
memory behaviour of investigated materials.
Acknowledgements Financial support: EU6FP Excellence – BIOMAHE, FP-6-509232
Keywords: shape-memory polymers; biodegradable materials; NMR
____________________________________
[1] Jeonga, B.; Gutowska, A.; Trends in Biotechnology 2002, 20, 305–311.
[2] Wache, H. M.; Tartakowska, D. J.. Heinrich, A. Wagner, M. H.; J. Mat. Sci.: Mat.Med. 2003, 14,109-12.
[3] Kawai, T. I in.; Plastic molded articles with shape memory property, US Patent 4, 950, 258.
70
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-38
Bioresorbable Electrospun Non-woven Scaffolds
Mariastella Scandola1, Chiara Gualandi
1, Maria L. Focarete
1,
Piotr Dobrzynski2, Michal Kawalec
2, and Piotr Wilczek
3
1 University of Bologna, Dept of Chemistry “Ciamician”, via Selmi 2, 40126 Bologna, Italy
2Centre of Polymer and Carbon Materials, M.Curie-Skłodowskiej 34, 41819 Zabrze, Poland 3Foundation for Development of Cardiac Surgery, ul. Wolnosci 345a 41800 Zabrze Poland
Polymeric scaffolds obtained by electrospinning, in the form of non-woven mats, are
promising materials for applications in the tissue engineering field [1], owing to their close
similarity to the extra-cellular matrix, in terms of topology. Electrospun porous scaffolds,
made of hydrolysable polymers, can efficiently support cell growth [1] and their
bioabsorbability in vivo may be properly designed, through an accurate tuning of the rates of
scaffold hydrolysis and tissue regeneration.
In the electrospinning process for scaffold fabrication, a careful tuning of the processing
parameters allows the obtainment of nanofibres with desired diameter and orientation. This
aspect is important because it is well known that the micro/nano-architecture of the scaffold
may affect cell behaviour.
A random copolymer of poly(lactide-co-glycolide) (PLGA, molar ratio: 50:50), synthesized
using a low-toxicity zirconium-based initiator [2], was used. Non-woven mats of PLGA were
fabricated through electrospinning, after optimization of the processing parameters (solution
composition, applied voltage, solution flow rate and needle-to-collector distance) in order to
obtain defectless fibres (average diameter of 800 nm).
Electrospun PLGA mats were subjected to an in vitro degradation study in phosphate buffer
(pH=7.4) at 37°C. The molecular weight of PLGA was found to decrease from the very
beginning of the degradation experiment, whereas the samples showed weight loss only after
20 days of exposure to buffer solution. All collected GPC curves were mono-modal, yielding
no evidence of autocatalytic effect during degradation. After 20 days also fibre morphology,
investigated by SEM analyses, began to change from smooth to porous. After 50 days the
scaffold lost about 50% of its initial weight.
In addition, endothelial cell growth supplement (ECGS) was suspended in the eletrospinning
polymer solution and nanofibrous mats were obtained. A preliminary study on the effect of
ECGS incorporation in the scaffold was conducted using mesenchymal stem cells from bone
marrow.
Keywords: scaffold; tissue engineering; electrospinning; bioabsorbable polymers
____________________________________
[1] A.G. Mikos et al., Tissue engineering, 12, 1197 (2006).
[2] P. Dobrzynski et al., Macromolecules, 34, 5090-5098 (2001).
71
P-39 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Keratin Coating for Wool Fiber
Jeanette M. Cardamone
U.S. Department of Agriculture, Agricultural Research Service,
Eastern Regional Research Center,
600 East Mermaid Lane, Wyndmoor, PA 19038, USA
Keratin as the major structural fibrous protein comprising wool, hair, feathers, and nail is rich
in amino acids and cystine disulfide bonds which provide flexibility and tenacity to hair and
wool. We applied alkali to break peptide and disulfide bonds and obtained keratin protein in
the form of keratin hydrolysate (KH) and powder (KP) with molecular weight of 6 to 30 kDa.
Then we used the unaffected glutamine and lysine amino acids of the protein as sites for
enzyme-mediated crosslinking of wool, of KH and KP. We showed that keratin hydrolysate
imparted shrink-resistant properties to wool textiles; the hydrolysate application is an eco-
friendly alternative to chlorine-Hercosett treatment, which can be a source of AOX
(Adsorbable Organic Halogens). The control of the dimensional stability of wool fabric by
applying KH and KP proceeded through a mechanism involving in-situ crosslinking mediated
by transglutaminase enzyme through the formation of isopeptide linkages between glycine
and lysine residues of keratin peptide. Scanning electron and confocal fluoresence
microscopy showed keratin protein localized on the surface of wool to smooth the fiber
surface, thereby preventing the scales from interlocking. Wool material, including
hydrolysates and powders crosslinked by transglutaminase enzyme-mediation, will provide a
rich resource for the production of modified keratin-based biomaterials.
72
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-40
Films from Spruce Galactoglucomannan Blended with Poly (Vinyl
Alcohol), Corn Arabinoxylan and Konjac Glucomannan
Kirsi S. Mikkonen1,2, Madhav P. Yadav
3, Stefan Willför
4,
Kevin B. Hicks3, and Maija Tenkanen
1
1Department of Applied Chemistry and Microbiology, University of Helsinki,
P.O. Box 27, 00014 Helsinki, Finland 2Department of Food Technology, University of Helsinki,
P.O. Box 66, 00014 Helsinki, Finland 3Eastern Regional Research Center, ARS, United States Department of Agriculture,
600 East Mermaid Lane, Wyndmoor, PA 19038, USA 4Process Chemistry Centre, Åbo Akademi University, Porthansgatan 3, 20500 Åbo, Finland
O-acetyl-galactoglucomannans (GGM) are the main hemicelluloses in softwoods and
can be recovered as by-products from process water of mechanical pulping of spruce wood
[1]. GGM can be used as raw material for biodegradable films, but the tensile strength and
elongation at break of GGM films are rather low [2]. The aim of this study was to improve the
mechanical properties of GGM-based films by blending GGM with poly (vinyl alcohol)
(PVOH), corn arabinoxylan (CAX), and konjac glucomannan (KGM). In addition, thermal
behavior of the blend films was examined using dynamic mechanical analysis (DMA) and the
film structure was studied with scanning electron microscopy (SEM).
GGM was recovered from process water of thermomechanical pulping of spruce [1] and
CAX from fiber fractions from commercial corn wet milling (CFG-1) [3]. PVOH (98-99%
hydrolyzed, Mw 146,000-186,000) was from Sigma and KGM from Baoji, China. Blend
ratios of GGM to PVOH, CAX, and KGM were 1:0, 3:1, 1:1, 1:3, and 0:1. Films were
prepared by casting and drying aqueous solutions of polymer blends (10 g/l) and glycerol
(Sigma) (4 g/l). Tensile strength and elongation at break of films were determined at 21ºC and
65% RH using an updated Instron 1122 mechanical property tester (Instron Corp., Norwood,
MA, USA) with TestWorks 4 data acquisition software (MTS Systems Corp., Minneapolis,
MN, USA). Dynamic mechanical analysis was done on a Rheometrics RSA II solids analyzer
(Piscataway, NJ, USA) for film specimens dried under vacuum for 30 min prior to testing.
Images of cross-sections of freeze-fractured films were collected using a Quanta 200 scanning
electron microscope (FEI Co., Hillsboro, OR, USA).
Adding other polymers increased the elongation at break of GGM blend films. The tensile
strength of films increased with increasing amount of PVOH and KGM, but the effect of
CAX was the opposite. The mechanical properties of GGM:CAX 1:3 and 0:1 films could not
be measured, because CAX was very sensitive to changes in ambient RH and these films were
difficult to handle at 65% RH, which was used for mechanical testing. DMA showed two
separate loss modulus peaks for blends of GGM and PVOH, but a single peak for all other
films. SEM confirmed good miscibility of GGM with CAX and KGM. In contrast, for blend
films from GGM and PVOH, SEM showed phase separation. Blending GGM with KGM was
found to be an applicable way to improve the mechanical properties of GGM-based films.
Keywords: spruce galactoglucomannan; poly (vinyl alcohol); corn arabinoxylan; konjac glucomannan; films;
mechanical properties; dynamic mechanical analysis; scanning electron microscopy
____________________________________
[1] S. Willför, P. Rehn, A. Sundberg, K. Sundberg, B. Holmbom, Tappi J. 2, 27 (2003). [2] K. Mikkonen, H. Helén, R. Talja, S. Willför, B. Holmbom, L. Hyvönen, M. Tenkanen, Proceedings of the 9th European Workshop on Lignocellulosic and Pulp (EWLP), Vienna, Austria, 27-30 August 2006, 130 (2006). [3] M.P. Yadav, D.B. Johnston, A.T. Hotchkiss Jr, K.B. Hicks, Food Hydrocolloids, 21, 1022 (2007).
73
P-41 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Activation of Transcription Nuclear Factor NF-κB and Induction of Inflammatory Cytokines in Immune Response on Resorbable Biomaterials
B. śywicka1, E. Zaczyńska2, A. Czarny2, S. Pielka1, J. Karaś3, and M. Szymonowicz1
1Department of Experimental Surgery and Biomaterials Research,
Wroclaw Medical University; ul. Poniatowskiego 2, 53-326 Wrocław, Poland 2Institute of Immunology and Experimental Therapy,
Polish Academy of Science, ul Weigla, Wrocław, Poland 3Institute of the Glass and Ceramics, ul Postępu 9,Warszawa, Poland
Implantation materials grafted intratissularly overtaking determined functions in the living
organism should not show unfavorable influence on the immunological system and should
disturb its homeostasis in the least possible degree. Growth of the level of inflammatory
cytokines is observed in the tissues surrounding the implant. But in pathophysiology of
implants there are not compatible data whose tissue markers play a key role in the evoked
inflammatory process. Activation of the immune response on an external stimulator requires
coordinated expression of numerous factors. So, a question appears if there are key
modulators of immune and inflammatory reaction, observation of which could be the purpose
of the more efficient estimation of biocompatibility of implantation materials. Transcription
nuclear factor NF kappa B plays the role of one of more important potential
immunoregulators. It regulates the expression of many genes connected mainly with the
course of inflammatory process, proliferation and cells differentiation including inflammatory
cytokines II-1, IL-6, TNF-α, IL-8; it is also connected with appearing of giant cells of the
foreign body type. In our study we evaluated three kinds of resorbable materials prepared on
the basis of calcium phosphate (CaSO4 .1/2H2O with 0.5%mass. KHSO4). One of them was
enhanced by poli(alchol-vinyl), with the aim to increase its mechanical resistance. The second
one was enriched with the growth activator of bone tissue tri-calcium phosphate and the third
calcium phosphate was used as control. These modifications could cause the local activation
of leukocytes to produce the mediators of inflammatory processes, which leads to long term
complications. The present study was designed to determine in vitro whether gypsum
materials treatment of leukocytes from peripheral human blood (PBL) results in changes in
activation of NF-κB and production of cytokines. The immunocytochemical localization and
expression of NF-κB in leukocytes was assessed using anti-c-Rel- antibody. The NF-κB
activation was expressed as the percentage of NF-κB(+)cells after 24 and 72 hour incubation.
The level of cytokines IL-6, IL-8 and TNF-α in the supernatants from leukocytes culture with
tested materials was determined by an immunoabsorbent assay (ELISA) after 24 and 72
hours. On the basis of the performed tests it was observed that calcium sulphate materials
without modifications activated nuclear factor NF-κB after 24-hour incubation (p<0.05) and
not significantly decreased its expression after 72 hours (p>0.05). Calcium sulphate materials
with addition of tri-calcium phosphate did not activate NF-κB, while calcium sulphate with
poli (alchol-vinyl) turned out toxic for leucocytes both after 24 and 72–hour incubation. The
level of IL-6, IL-8, TNF-α after stimulation for 24 and 72 hours with gypsum materials was
compared to untreated leukocytes (p<0.05). The monitoring of the stimulation of NF-κB
mediator could give us the answer about cells reaction for the new biomaterials and it could
prove to be the sensitive test for their selection.
Keywords: NF-κB, TNF-α, IL-6, IL-8, peripheral human leukocytes
74
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-42
Influence of the Gelatin-Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and Tissue Reaction
M. Szymonowicz1, B. śywicka1, S. Pielka1, L. Solski1, D. Haznar2
, and J. Pluta2
1Department of Experimental Surgery and Biomaterials Research, Medical University
Poniatowskiego 2, 50-326 Wroclaw, Poland 2Department of Drug Form Technology, Medical University
Szewska 38, 50-139 Wroclaw, Poland
Porous biodegradable matrixes for implantation are interesting drug forms in
pharmaceutical technology. Owing to their structure, sponges are likely to be used as drug
carriers of modified releasing or used in tissues engineering as a cell carrier. Introduction of
material belonging to a different species into a living organism causes systemic and local
tissue reaction with a different degree of intensity dependent on the time and size of the
contact area.
The aim of the study was to evaluate the influence of gelatin-alginate matrixes with
calcium lactate on blood hematologic parameters and the assessment of the local tissue
reaction, and biodegradation and resorption after implantation into soft tissues. Gelatin-alginate matrices in a form of a sponge were used in the study. Sponge was prepared
of mixture of gelatin and sodium alginate in 20:1 proportion with an addition of 3% of
glycerol as well cross-linking agent calcium lactate. The samples sponge were implanted into
back muscles of the rat for the following periods: 1, 2, 3, 5, 7 and 14 days. After time a blood
for analysis was collected as well as the implanted samples with surrounding tissues. In the
whole blood were designated: the value of hematocrit (Ht), hemoglobin concentration (Hb),
red cells count (RBC) and red cells indexes: mean red cell volume (MCV), mean hemoglobin
mass in red cell (MCH), mean hemoglobin concentration in red cells (MCHC). White cells
count (WBC) was also determined. Results were analyzed by use of Statistica 5.5 software.
Mean values RBC, HCT, Hb (p<0,01, p<0,001), MCV, MCH (p<0,05) and MCHC
(p<0,05, p<0,01) to 3 days reduction to control group were observed. The result values are
not higher then the reference values. The parameter values from 5 days to 14 days was in
relation to the control group values. Values WBC in the blood were close and comparable to
the values in the control group in all the times of the investigation. In the macroscopic
assessment during the post mortem there were no any changes in the implantation sites.
Collected samples were the subject of histological assessment. After 24h the strong
inflammation were observed which lasted also up to 48h after implantation. At the
implantation site the small leftovers of the sponge were noticed and exudation with the
numerous inflammatory cells. In results, after 3 and 5 days the thin layer of the connective
tissue with new, young vascularisation was formed. After 7 and 10 days the small portion of
the implanted samples were observed which were surrounded by connective tissue with
numerous fibroblasts and some lymphocytes, polymorphonuclear and plasma cells. There
were also visible collagen and single muscle fibers. The small leftovers of the sponges
surrounded by the tissue were visible until 14 days after implantation. On the basis of those all results we can stated that the sponge were surrounded and
infiltrated by the tissues and partially undergone resorption. Also we can stat that the tested
sponges did not produce the foreign body reaction.
The study was supported by the project no. 1260 of the Wroclaw Medical University.
Keywords: gelatin-alginate sponge white calcium lactate, blood parameters, implantation, soft tissue reaction,
biodegradation and bioresorbable polymers
75
P-43 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Cellular Response after Stimulation of the Gelatin-Alginate Matrixes
M. Szymonowicz1, A. Marcinkowska2, B. śywicka1, S. Pielka1, A. Gamian2, D. Haznar3, and J. Pluta3
1Department of Expermental Surgery and Biomaterials Research, Medical University,
Poniatowskiego 2, 50-326 Wroclaw, Poland 2Department of Medical Biochemistry, Medical University,
50-368 Wroclaw, Chalubińskiego 10, Poland 3Department of Drug Form Technology, Medical University,
Szewska 38, 50-139 Wroclaw, Poland
Polymeric biomaterials have been used in medicine. Among the biomedical polymers
there is family of resorbable sponges. The used of scaffolds settled as specific carriers for
cells which after implantation into the system makes supporting the tissue and creates good
conditions for the tissue regeneration. The evaluation with use of cells culture are quick
sensitive tests for the assessment of the biological impurities in the tested sample. The aim of
the work was to evaluate the changes in morphology and biological cells viability after
directing its temporary contact with gelatin-alginate matrixes in testing in vitro.
Four kinds of gelatin-alginate matrixes in a form of a sponge were used in the study.
In order to obtain a form of sponge liofilization of foam originated from foaming of mixture
of sterile solution of gelatin (20%), natrium alginate (2% or 4%) and glycerol (3% or 5%)
selected in an appropriate ratio was performed. Biological material consisted of quickly
proliferinghuman carcinoma cells of the lymphoblastic T lymphoma cells Jurkat grow in the
suspension of medium, whereas epithelial lung carcinoma cells- A549 (adhering to the bed in
the culture), show the superficial growth on substrate and slowly prolifering human umbilical
vein endothelial wells – Huvec (adhering to the bed in the culture).
The cells culture were performed In culture bottles at 37 with 5%CO for 24 hours
addend. Next, cells were taken for temporary contact with sponges. The quantitative changes
in selected of cells growth fixation after 24 hours and morphological changes observed after
24, 48 hours. For this purpose the dyed methods with neutral and trypane blue were used.
Shape, adhesion to the bed, agglutination, vacuolization and lysis of the cells were
determined. Division, proliferation, colonization (to build, construct colony) ability to
reproduce and survival rate of cells were observed. Viability measured by means of MTT.
In all cultures, after 18 hours the sponges were completely dissolved, and culture
medium was clear. The cells were evaluated microscopically. No agglutination, vacuolization,
separation from the bed neither lysis of the cell’s walls were observed. Proliferation of the cell
was correct and the cells formed proper colonies. They demonstrated the proper structure,
ability to growth and no significantly different when comparing to control group. No
difference between cells after contact with sponges was observed, as well. Dead cells were
not observed. In case of Jurkat, A549, Huvec cells shoved viability comparable with control
group. Viability of those cells was over 90%. The survival rate of cells after contact with
sponges was comparable. The longest time of viability of cells after contact with sponge and
4% of natrium alginate and 3% glycerol.
On the basis of received results it was gelatin-alginate matrixes did not have anty
cytotoxicy effects.
The study was supported by the project no. 1260 of the Wroclaw Medical University.
Keywords: gelatin-alginate sponge, cells cultured, aglutynation, proliferation, viability cells.
76
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-44
Synthesis and Properties of Chitosan – Poly(ethylene glycol)
Comb Copolymers
Ričardas Makuška and Rūta Kulbokait÷
Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania
Chitosan, a naturally occurring linear cationic polysaccharide, has been widely employed as a
drug delivery system, wound dressing, anticoagulants, and scaffolds for tissue engineering
owing to its biocompatibility, biodegradability, and low toxicity. Recently prepared comb like
chitosan derivatives containing methoxy poly(ethylene glycol) (MPEG) grafts [1, 2] may find
application in household and personal care products maintaining appropriate rheological
properties and conditioning contact surfaces.
Derivatisation of chitosan with a functionalized MPEG-2000 resulted in variety of chitosan-
MPEG comb copolymers differing in graft location, degree of substitution and molecular
weight. Chitosan-2-N-MPEG comb copolymers were synthesized by reductive amination of
chitosan using MPEG aldehyde [1]. Chitosan-O-MPEG copolymers were synthesized using
MPEG iodide or MPEG dichlorotriazine as alkylating agent and silver oxide as a catalyst [2].
Oxidation of N-phthaloyl chitosan by the use of TEMPO radical led to 5-formyl-2-N-
phthaloylchitosan which was proper precursor for preparation of chitosan-6-N-MPEG [3].
A serious problem is purification of chitosan comb copolymers from unreacted MPEG. To
avoid this, the method of “click” chemistry (a copper-catalysed Huisgen reaction) was
employed which usually gives nearly quantitative yields of the main products at mild
conditions generating virtually no by-products. Azidated chitosan was prepared by reacting
azidated epichlorohydrin with chitosan. MPEG azide was made by mesylation of MPEG
followed by nucleophilic substitution using sodium azide. Alkyne containing derivatives were
synthesized by reacting MPEG or N-phthaloyl chitosan with propargyl bromide.
Chitosan-MPEG derivatives with the degree of substitution (DS) of chitosan ca. 20 % were
water soluble in a wide pH range. 2-N-PEGylated chitosans were high-molecular-weight
products (Mw up to 2 million) with the DS of chitosan varying from 23 to 89 %. Solution
viscosity of these chitosan copolymers was moderate and had tendency to decrease for the
derivatives with high DS down to 0.29 dL/g. O-substituted chitosans were the products with
low molecular weight, Mw ranging from several to twenty thousand.
Positively charged chitosan brush polyelectrolytes adsorb readily to negatively charged silica
or mica surfaces. The rate of chitosan adsorption is much higher compared to its derivatives,
though according to adsorbed amount chitosan derivatives are preponderant. The adsorption
of O-PEGylated chitosans is sufficiently large to give rise to a brush structure that generates
strong steric repulsive forces. Thus, chitosan-6-O-MPEG oligomers act as a steric stabilizer
and can be used for modification of surface properties. The adsorption layers of N-PEGylated
chitosans are heavily hydrated and much less compact than the layers of chitosan. Chitosan-2-
N-MPEG graft copolymers could be used as protein-repellent vectors [4]. Keywords: Chitosan derivatives; PEGylation; brush polyelectrolytes; “click” chemistry; chitosan adsorption.
____________________________________
[1] N. Gorochovceva et all., Eur. Polym. J., 41, 2653 (2005).
[2] N. Gorochovceva, R. Makuska, Eur. Polym. J., 40, 685 (2004).
[3] R. Makuska, N. Gorochovceva, Carbohydrate Polymers, 64, 319 (2006).
[4] Y. Zhou et all., J. Colloid Interface Sci., 305, 62 (2007).
77
P-45 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose
M. Koller, P. Hesse, A. Atlić, C. Hermann-Krauss, C. Kutschera, and G. Braunegg
Graz University of Technology; Inst. of Biotechnology & Biochemical Engineering,
Petersgasse 12, A-8010 Graz, Austria
The increasing demand for polymeric compounds acting as packaging materials for
the safe distribution of goods is undisputed. Contemporary strategies for disposing of end-of-pipe plastics cause serious global problems such as increasing piles of waste. Incineration of petrol-based polymers not only generates noxious compounds, but also elevates the atmospheric CO2 concentration. This aggravates frequently discussed problems such as greenhouse effect and global warming. Recycling systems do not function as effectively as required for a real solution of the problem.
Although data for remaining amounts of mineral oil are changing quickly due to advanced methods for tracing and discharging, the reserves of fossil feed stocks are limited. In May 2005, the price per barrel of mineral oil amounted to US-$ 55; recently, this value has rocketed up to US-$ 74 (July 2007).
Utilizing alternative polymeric materials such as polyhydroxyalkanoates (PHAs) unites two major advantages: Firstly, they can be produced from renewable resources such as carbohydrates, making them independent from the availability of fossil feed stocks. Secondly, when being composted, these biopolymers undergo a biodegradation process by the action of various microbes resulting merely in CO2 and H2O, the starting materials for the photosynthetic regeneration of carbohydrates by green plants. Thus, the mass stream for carbon in the biotechnological production lines for PHAs is embedded into a closed circle. This is clearly in contrast to the life cycle of classic polymers, where carbon fixed in the bowels of earth since millions of years is converted to CO2 which is released in the atmosphere.
Because recent studies point out that PHA production from purified sugars has been optimized to a high degree, further improvement of the fermentation technologies by using cheaper carbon sources as basis feed stocks is urgently needed.The work at hand studies the utilization of whey, the major by-product from cheese and casein production, as feed stock for the biotechnological production of PHA. Whey is not only a cheap raw material, but 13500000 tons of whey per year which contain 620000 tons of lactose (D-gluco-pyranose-4-β-D-galactopyranoside) constitutes a surplus product in the EU, causing a huge disposal problem for the dairy industry. Hence, the utilization of whey lactose for PHA production unites the diminishing of a waste problem and the increase of cost-efficiency in the bioinspired production of ecologically benign materials.
The work at hand presents and compares kinetic data and polymer characteristics for three different microbial strains that turned out to be capable of PHA accumulation from whey lactose (the eubacterial species Pseudomonas hydrogenovora and Hydrogenophaga pseudoflava as well as Haloferax mediterranei). Advantages and drawbacks of the organisms as potential PHA producers from whey on industrial scale are compared. The industrial significance of the study is underlined by economic appraisals for the investigated processes. Keywords: Biodegradable polymers; Renewable resources; polyhydroxyalkanoates; whey
____________________________________
[1] G. Braunegg et al., Polym. Plast. Technol.Eng. 43(6), 1779 (2004) [2] M. Koller et al., Biomacromol. 23(5), 561 (2005) [3] M. Koller et al., Bioproc. Biosyst. Eng. 29(5-6), 367 (2006) [4] M. Koller et al., Macromol. Biosci. 15(6), 218 (2007).
78
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-46
Synthesis and Study of Chitosan – Oligosaccharide Graft Copolymers
Ugn÷ Jančiauskaite and Ričardas Makuška
Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania
Grafted brush polyelectrolytes are of immense technological importance, both for
rheology control and for modification of surface properties. The latter application includes
such vastly different areas as control of colloidal stability, non-specific protein adsorption,
cleaning applications and lubrication. Comb polyelectrolytes partially or fully made from
naturally occurring building blocks are of particular interest. The proper representatives of
such polyelectrolytes are chitosan comb copolymers combining charge regulating positively
charged backbone with flexible and affined to polysaccharides grafts of inulin or dextran. The
presence of oligomeric hydrophilic side chains is expected to influence the adsorption of the
polyelectrolytes on negatively charged surfaces, to affect the forces acting between the coated
surfaces and to have impact on the attachment of the macromolecules of proteins or
glycoproteins.
Two types of dextran containing comb polyelectrolytes were synthesized attaching
dextran-1500 (FLUKA, Mr 1500) or dextran-6000 (FLUKA, Mr 6000) to amine or C(6)-OH
groups of chitosan (FLUKA, Mr 400000). The synthesis of chitosan-N-dextran graft
copolymers was done by the method of reductive amination resulting in high-molecular-
weight products. Peculiar property of these polyelectrolytes was necessity to use freeze-
drying process in order to obtain soluble products. Degree of substitution (DS) of chitosan in
the copolymers varied from 16 to 62 %. Chitosan derivatives with higher DS had lower
intrinsic viscosity [µ], moreover, grafting of dextran-6000 resulted in lower viscosity of
aqueous solutions. Chitosan-O-dextran graft copolymers were synthesized by reacting dextran
with tosylated derivatives of N-phthaloyl chitosan. Unfortunately, deprotection of amino
group functionality in these copolymers always resulted in low-molecular-weight products.
Inulin, a known reserve carbohydrate of Cychorium intybus, consists mainly of beta (2-1)
fructosyl fructose units with normally, but not always, a glucopyranose at the reducing end
[1]. Two different methods were chosen to graft inulin oligomer (ORAFTI, Mr up to 2000) to
chitosan. The first one is EDC induced coupling between chitosan and inulin succinate the
latter being prepared by the reaction between inulin and succinic anhydride in dry DMF [2].
The second method is based on the reaction between chitosan and inulin activated with
cyanuric chloride. Graft-copolymers were purified by dialysis against water and precipitated.
Chitosan – inulin derivatives were white powders easily soluble in water possessing low
intrinsic viscosity. FTIR and 1H NMR spectra of the products were consistent with the
presumable structure of chitosan – inulin graft copolymers.
Acknowledgement: Financial support from the Lithuanian State Science and Studies Foundation (project
TECHNOSACHARIDAS, N-04/2007) is gratefully acknowledged. ORAFTI is acknowledged for a kind
donation of inulin.
Keywords: chitosan derivatives; dextran copolymers; inulin derivatives; comb polyelectrolytes.
____________________________________
[1] C.V. Stevens, A. Meriggi, K. Booten, Biomacromolecules, 2, 1 (2001)
[2] X.Y. Wu, P.I. Lee, J. Appl. Polym. Sci. 77, 833 (2000).
79
P-47 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Selection of Carbon Feed Stocks for Cost-Efficient
Polyhydroxyalkanoate (PHA) Production
M. Koller, P. Hesse, A. Atlić, C. Hermann-Krauss, C. Kutschera, and G. Braunegg
Graz University of Technology; Inst. of Biotechnology and Biochemical Engineering,
Petersgasse 12, A-8010 Graz, Austria
Raw materials require the major part of biopolymer production costs; this share contributes with up to 50% to the entire process expenses. Recent studies indicate that PHA production from pure sugars such as glucose or sucrose has already been optimized to a high degree. Therefore it is of importance to enhance cost efficiency of PHA production by substituting pure substrates by cheaper carbon feed stocks or by integrating PHA production into energetically autarkic production lines of the carbon sources. Whey from dairy industry
The utilization of polluting whey combines an economic progress with solving an ecological hazard. Whey was applied as carbon source for three wild type PHA producers: Haloferax mediterranei, Ps. hydrogenovora and Hydrogenophaga pseudoflava. Among these strains, H. mediterranei constitutes an outstanding candidate for PHA production on whey. This is due to its high robustness and stability; the risk of microbial contamination during cultivation is negligible, saving a lot of energy for sterility precautions. The strain grows on whey with a max. specific growth rate µmax. of 0.11 h
-1. PHA was accumulated at a max. specific production rate of 0.08 g/g h. Conversion yield for whey to PHA amounted to 0.3 g/g. The production of PHA copolyesters without co substrates, the excellent polymer characteristics together with a cheap isolation method make the strain of special interest [1,2,3]. Raw glycerol liquid phase from Biodiesel production
H. mediterranei was also used for PHA-production on glycerol liquid phase (GLP), a side stream of the biodiesel production from plant oils and tallow, containing about 70 wt.-% glycerol. In all Europe, the total production of biodiesel is estimated for 2008 with 2,649.000 metric tons. GLP nowadays constitutes a surplus material. Its utilization leads to an enormous cost advantage compared with commercially available pure glycerol, possessing a market value of 900 € per metric ton (year 2002). On bioreactor scale, H. mediterranei was able to grow on GLP at a specific growth rate of 0,06 h-1 and produced PHA (76% of cell mass) at a specific rate of 0,08 g/g·h. The yield for PHA from glycerol was calculated with 0,23 g/g, resulting in a final concentration of 16,2 g/L PHA [1,2,3].
Sugar cane sucrose
A different approach is provided by the utilization of carbon sources that feature a considerable market value and do not constitute waste materials, but are produced within a process integrating the fabrication of the carbon substrate and PHA. This will soon be realized in the south-central region of Brazil: starting from sugar cane, saccharose, ethanol and PHB are produced by Wautersia eutropha. The needed energy for polymer production is directly available from burning bagasse, a major by product of the sugar production. Due to the autarkic energy supply and the at-house availability of the carbon source saccharose, the production costs per kilogram PHB are estimated with less than US$ 3 [3, 4]. Keywords: biodegradable polyesters; polyhydroxyalkanoates; whey; raw glycerol phase; sugar cane sucrose
____________________________________
[1] M. Koller et al., Macromol. Biosci. 15(6), 218 (2007). [2] M. Koller et al., Biomacromol. 23(5), 561 (2005) [3] M. Koller et al.,article in press [4] R. Nonato et al., Appl. Microbiol. Biotechnol.57, 1 (2001)
80
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-48
Properties and Degradation of PVA/Starch Blends
with a PVA-g-MA Compatibilizer
Wan-Ling Lu1, Chia-I Liu
2, and Chi-Yuan Huang
2
1Dep. of Raw Materials and Yarn Formation,Taiwan Textile Research Institute,Taipei,Taiwan
2Dep.of Materials Engineering, Tatung University,
No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan
It can enhance the strain to 100~200 % by dissolving Polyvinyl alcohol (PVA) into one or
two time water in the starch/PVA blend system. Adding a compatibilizer (MA-g-PVA) also
has a well display in the strain at the break.
1. Experimental
1.1 MA grafting polymerization onto PVA: the general experimental procedure and an
example were as follows: PVA 5g and MA 5g were dissolved in 95g DMSO after being
stirred in an atmosphere of nitrogen. The reaction temperature was adjusted as needed (such
as 60°C), then 0.5g of potassium persulfate was added as a initiator. The reaction lasted for
5h. The reaction mixture was concentrated to about 20%, and was then added to chloroform
to precipitate the polymer.
1.2 Blend: in the series A, MA and PVA were dissolved in GA with 120°C for 30min before
compounding. In series B and C, MA and PVA were dissolved individually in 300g or 150g
distilled water with 70°C for 30min before compounding. For D series, MA-g-PVA (MA
Grafting polymerization onto PVA) and PVA were dissolved in 300g distilled water with 70;
for 30min before compounding. Then, the tapioca starch and GA were mixed with above
composition.
2. Results and discussions
2.1 FTIR Spectra: FTIR spectra, Figure 1, were obtained from MA-g-PVA and PVA films by
a JASCO Micro-IR. The IR spectra showed that the characteristic peaks of –COO– at 1720
cm-1
and –C=C– at 1640 cm-1
[1] at Figure .1 could confirm MA graft onto PVA.
2.2 Tensile Strength Measurement:There was a significant distinction of tensile strength for
blends in Figure 2. The starch presented stiffness and brittleness in this blends. It was the
reason that the maximum stress of A series was much higher than those of B, C and D series
blends. Water is a good plasticizer for PVA/starch blends in this work. The strain of B series
by adding 150g water was increased above 20 times (Figure 8). Adding 300g water, the strain
of C5 was up to about 192 %.
Thinking about the graft degree of MA-g-PVA (compatibilizer), the quantity of adding
compatibilizer was converted into the amount of adding MA in the blends. The maximum
stress range between D series blends was about 1.5 MPa and the strange range between D
series blends was about 30 %.
0 2 4 6 8 10 12 14 16 18
2
4
6
8
10
12
14
16
A series
B series
C series
D series
Stress (MPa)
MA (g)
0 2 4 6 8 10 12 14 16 18
0
20
40
60
80
100
120
140
160
180
200
220
A series
B series
C series
D series
Strain (%)
MA (g)
-2 0 2 4 6 8 10 12 14 16 18
50
60
70
80
B series
C series
D series
Weight Loss (wt %)
MA (g)
Keywords: Polyvinyl alcohol (PVA)、maleic anhydride (MA), compatibilizer, MA-g-PVA, SEM micrographs.
____________________________________
[1] W. Y. Chiang, C. M. Hu, J. Appl. Polym. Sci., 30, 3895(1985).
Fig. 1.The IR spectra of (a)pure
PVA and (b)MA-g-PVA.
Fig. 2.The tensile strength
of four series starch /PVA
blends.
Fig. 3.The strain at break of
four series starch /PVA
blends.
Fig. 4.The weight loss
measurement of starch/PVA
blends.
Wavenumber [cm-1]
-C=C- 1640 cm-1
4000 400 1000 2000 3000
%T -COO- 1720 cm-1
(a)
(b)
81
P-49 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Thermal and Mechanical Behaviour of a Commercial
Poly(lactid acid) Submitted to Soil Burial Test
L. Santonja-Blasco, J.D. Badia, Rosana Moriana, and A. Ribes-Greus
Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior
de Ingeniería del Diseño. Universidad Politécnica de Valencia,
Camino de Vera s/n 46022 Valencia
The replacement of petroleum-based polymers, with biodegradable ones is an actual
goal because of the increasingly aware in the environmentally friendly materials [1]. Poly(lactic acid) (PLA) an aliphatic, biodegradable and compostable polyester, can be obtained from renewable resources such as starch to yield articles for being used in industrial packaging or in agriculture field, as mulching films. A commercial PLA, supplied by Natureworks.DDL, Minnetonka, U.S.A, was buried in soil in order to characterize non controlled further disposal when it is used in packaging and its service life when it is used as mulching film. Samples were submitted to accelerated soil burial test in a culture oven at 28 ± 0.5ºC during 690 days according to the DIN 53739 standard [2]. Samples were extracted at 0, 30, 150, 300, 450 and 690 days and thermally characterized by means of Differential Scanning Calorimetry(Mettler Toledo DSC822), HR/CR=10ºC/min from 0-200ºC, under N2 atmosphere and by Dynamic-Mechanical-Thermal Analysis experiments in a Mark IV DMTA (Rheometric Scientifics) using dual cantilever clamping by bending mode. Specimens were heated from 35 to 150ºC in isothermal mode at 2ºC/min in the frequency range:0.1-39 Hz. DSC thermograms show that when degradation time advances two melting peaks are formed at 450 days. The lamellae thickness distribution calculated by means of Thompson equation [3] is in a range from 75 to 115 Ǻ. In the curves of the samples without degradation it is observed a wide shoulder that becomes narrower when degradation time in soil advances. When 450 days are reached, the lamellae distribution is presented by two separated peaks, however at 690 days both peaks are less pronounced and the distribution is wider. DMTA spectra performed at 1 Hz have been compared, in terms of loss tangent (tan δ) and storage modulus (E’). The relaxation temperature related to glass transition has been calculated by means of the temperature at the maximum of the fitting of the experimental loss modulus (E’’) data to Fuoss-Kirkwood [4] model. During degradation in soil: E’ value increases, the temperature related to the glass transition shifts to higher temperatures and the recrystallization occurs at lower temperatures. PLA has increased its crystallinity, due to the linkages weakening in the amorphous phase. Degradation in soil improves a faster linkage of the amorphous phase of the PLA, enhancing segregation of the crystallite size distribution until 690 days when seems to be homogenised. It also provides a higher E’ increased and recrystalization is produced at lower temperatures. Acknowledges: Ministerio de Educación y Ciencia and the European Region Development Fund for the economical support through the Project CTM2004-04977/TECNO and for the concession of pre-doctoral grants FPI and FPU. Keywords: poly (lactid acid); DSC; DMA; degradation in soil ____________________________________ [1] A.-C. Albertsson, S. Karlsson, Acta Polymerica, 1995, 46, 114. [2] DIN 53739 Testing of plastics. 1984.
[3] Hoffman, J. D., Davis, G. T. & Lauritzen, J. I. in Treatise on Solid State Chemistry (ed. Hannay, N. B.) 497−614 (Plenum, 1976). [4] R.M. Fuoss, J.G. Kirkwood, J. Am. Chem. Soc. 1941, 63, 385.
82
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-50
A Thermogravimetric Approach to Study the Influence of a Biodegradation
in Soil Test to a Poly(lactic acid)
J. D. Badia, Rosana Moriana, L. Santonja-Blasco, and A. Ribes-Greus
Instituto de Tecnología de Materiales. Escuela Técnica Superior de Ingeniería del Diseño.
Universidad Politécnica de Valencia. Camino de Vera s/n, 46022, Valencia, Spain
Poly(lactic acid) (PLA) is a green polymer, due to it can be obtained from renewable
resources and can be compostable when its service life has finished. The knowledge of the
degradation mechanisms involving the disposal stage of PLA must be assessed, in order to
assure the complete life cycle of a biodegradable material.
PLA with a 3.8% of meso-lactide content samples (supplied by Natureworks.DDL,
Minnetonka, U.S.A) were submitted to accelerate soil burial test in a culture oven Heraeus 12
at 28 ± 0.5ºC during 450 days following the DIN 53739 standard[1]. Specimens extracted at 0,
30, 150, 300 and 450 were analyzed by thermogravimetry. Measures were carried out in a
Mettler-Toledo TGA/SDTA 851, from 25 to 750ºC at a heating rate of 20ºC/min, under Ar
atmosphere. The DTG temperature peak (Tpeak), the degradation onset (Ton) and endset (Tend),
as well as the activation energy of the degradation process (Ea) were selected as
characterization parameters to analyze the degradation in soil influence on poly(lactic acid).
A f (α) = (1-α) n (with n=1) degradation kinetic model was previously hypothesized to employ
the kinetics models proposed by Broido[2] and Chang[3] for calculating the Ea of the
degradation mechanism. These results were compared to the Ea values obtained by the
method developed by Coats and Redfern [4] to prove the consistence of the kinetic study.
Criado[5] mastercurves were plotted from experimental data to confirm the degradation
kinetic model assumed.
For the samples submitted to an accelerated biodegradation process, no accentuated changes
were observed at the thermal stability of the polymer. No linear trend was established for the
activation energy evolution along the degradation in soil time, evidencing an oscillating
behaviour, with an initial Ea decrease until 150 days of exposure in soil, followed by an Ea
increase until the end of the experiment.
The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the
European Regional Development Fund for the economical support through the Project CTM2004-
04977/TECNO and for the concession of the pre-doctoral grants through the programmes FPI and FPU.
Keywords: poly (lactic acid);biodegradation in soil; thermogravimetry; kinetic analysis ____________________________________
[1] DIN 53739 Testing of plastics. (1984).
[2] Broido, A .J.Polym.Sci. Part-2, 27,1768, (1969).
[3] Chang, W.L. , J. Appl. Polym. Sci, 53, 1759, (1994).
[4] AW. Coats, Redfern JP. Nature, 201, 68. (1964).
[5] Criado,J.M., Thermochimica Acta, ,24,86, (1978).
83
P-51 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Comparative Study about the Biodegradability and the Mechanical
Performance of Different Biocomposites Based on Thermoplastic
Starch Reinforced with Cotton Fibre
Rosana Moriana, L. Santonja-Blasco , J. D. Badia, and A. Ribes-Greus
Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior
de Ingeniería del Diseño. Universidad Politécnica de Valencia.
Camino de Vera s/n 46022 Valencia
The substitution of traditional polymeric-based composite materials with synthetic matrixes
(epoxy, unsaturated polyester, or phenolics) reinforced with fillers such as glass, carbon or
aramid fibres, by environmentally-friendly composites with a biodegradable matrix and
natural fibres is therefore considered critical, due to an increasing environmental
consciousness and demands of legislative authorities [1]. Recent advances in natural fibre
development and composite science allow improving materials from renewable sources. The
current challenge is to design materials with structural and functional stability during use,
together with enhanced degradability during disposal in landfills to reach to close the material
loop without environmental hazard [2]. The purpose of this work is to study different
composites reinforced with a cotton fibre in order to analyse the influence of the matrix
employed. Thermal Analysis has been performed to evaluate the potential applications of
these blends, their characterisation, as well as the study of their degradation processes.
The polymeric matrices are based on thermoplastic starch-based materials commercialized
under the Mater-Bi KE 03B1 and Mater-Bi NF01U trade marks, [Novamont North America
(USA)]. Cotton is the natural fibre employed as reinforcement [Yute S.L.(Spain)]. The
thermo-mechanical properties of Mater-Bi have been investigated to assess its suitability as a
matrix material for the fabrication of biocomposites, to guarantee the improvement of the
mechanical properties after reinforcing with the biofibres, and to investigate the viscoelastic
behaviour in the studied materials. The biodegradability of the unfilled matrix, the natural
fibres and the composite with 10% in weight of cotton, were simulated by an accelerated soil
burial test (DIN 53739) [3]. Thermogravimetric analysis was used to study the thermal
stability of the employed materials, to fully investigate their thermal decomposition process
and to monitor their degradation process in soil. A deep kinetic analysis of the decomposition
process has been performed, with the determination of the activation energies and the
discussion of the reaction mechanism.
The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the
European Regional Development Fund for the economical support through the Project CTM2004-
04977/TECNO and for the concession of the pre-doctoral grants through the programmes FPI and FPU.
Keywords: biocomposites; renewably polymers; mechanical properties; thermal analysis.
____________________________________
[1] C. Bastioli, C. Facci, Biodegradable Plastic Conference, Frankfurt. (1999).
[2] A.K. Mohanty; M. Misra; T.D. Drzal, Ed.; Natural Fibers, Biopolymers and Biocomposites, Taylor & Francis
edition, Boca Raton, (2005). [3] DIN 53739 Testing of plastics. Influence of Fungi and Bacteria. Visual Evaluation. Change in Mass and
Physical Properties, (1984).
84
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-52
Improving the Processing Ability and Mechanical Strength of Starch/PVA
Blends through Plasma and Acid Modification
Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu
Department of Materials Engineering, Tatung University,
40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.
In this investigation, maleic anhydride (MA), and citric acid (CA) used as the processing
additive and plasma treatment to improve the processing ability and mechanical strength of
biodegradable starch/PVA blends were studied. The melt flow index of starch/glycerol/PVA
(300g/60g/80g) was increased from 2.3g/10min to 32.7 g/10min by adding 3g of MA and to
130 g/10min by adding MA and plasma treatment. The mechanical strength of
starch/glycerol/PVA increases from 3.48 to 6.21 MPa by adding 1.5g of MA and 1.5g of CA,
while it increases to 6.26 MPa by plasma treatment. Esterization reaction occurred when MA
was dissolved into glycerol and glycerol grafted onto plasma pretreatment PVA. This was
caused the improved compatibility between starch and PVA. Thermogravimetric analysis, x-
ray diffraction, and scanning electron microscopy were used to study the morphology during
plasma and acid modification.
Keywords: biodegradable; maleic anhydride; citric acid; starch; thermogravimetric analysis (TGA)
85
P-53 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Biodegradation of Starch and PVA/Starch Blend Enhanced
by Rhizopus Arrhizus
Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu
Department of Materials Engineering, Tatung University,
40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.
Biodegradation of starch and PVA/starch blend improved by Rhizopus arrhizus was
examined. PVA, tapioca starch, and PVA/starch blend were buried in soil for sixteen weeks in
order to study the different biodegradation rates among these three materials. The PVA/starch
blend consisted of PVA (20%), glycerol (15%), and native tapioca starch (65%). Burial tests
were performance in three different soil conditions: (a) general compost (b) adding fungus in
compost, and (c) adding fungus in compost after sterilization. The complete biodegradation
time of PVA/starch blend were in the order as (b) test (burial time of 10 weeks) < (c) test (12
weeks) < (a) test (16 weeks). The biodegradation of starch has the same tendency among
these burial soil conditions, but degradation time was shortening to 6, 8 and 10 weeks.
Thermogravimetric analysis, x-ray diffraction, and scanning electron microscopy were used to
determine the morphology and degradation process of each material. Overall, adding
Rhizopus arrhizus in combination with other microorganisms can initiate the biodegradation
and increase the degradation rate for starch and its blend in the burial tests.
Keywords: biodegradable; fungus; starch; thermogravimetric analysis (TGA)
86
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-54
Biodegradable Blends of Polylactide and Natural Rubber
Marcin Kowalczyk and Ewa Piorkowska
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, 90-363 Lodz, Poland
Blends of polylactide (PLA) with two poly(1,4-cis-isoprene)s, differing in molecular
weight, were prepared with the aim to improve drawability through promotion of craze
plasticity. Morphology and mechanical properties of the blends were examined. Compression
moulded and quenched films of PLA and the blends containing of 5-25 wt% of rubber were
amorphous, as it followed from DSC studies. Tg of PLA, at about 55oC, remained unaffected
by the presence of rubber. SEM, TEM and DMTA studies revealed that the blends were phase
separated, with rubber particles dispersed within PLA matrix. Tensile test, performed on an
Instron at the drawing rate of 5%/min and 50%/min, demonstrated that incorporation of
rubber decreased significantly a yield stress. Significant improvement of elongation at break
and tensile impact strength was achieved in the blends with 5 wt% of rubber. SEM and SAXS
examination of deformed specimens demonstrated that at early stages of deformation crazes
were initiated, presumably by rubbery particles. Further deformation involved also shear
banding.
Such a way of modification of PLA mechanical properties is a promising alternative to
plasticization.
Keywords: polylactide ; biodegradable blends; mechanical properties
87
P-55 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Synthetic Analogues of PHA
Anionic Ring-opening Polymerization of ββββ-alkoxy Substituted ββββ-lactones
G. Adamus and M. M. Kowalczuk
Polish Academy of Sciences, Centre of Polymer and Carbon Materials,
34 M. Curie-Sklodowska St, 41-800 Zabrze, Poland
Polyhydroxyalkanoates (PHAs) are thermoplastic aliphatic polyesters produced by microorganisms as energy storage materials. They represent an interesting group of biodegradable polymers that have recently received much attention, particularly as environmentally friendly materials produced from renewable resources. Among the variety of PHAs, poly[(R)-3-hydroxybutyrate], PHB, is of particular importance.
Synthetic analogues of this biopolymer of potential industrial importance are obtainable by direct copolymerization of epoxides with carbon monoxide [1] or via ring-opening polymerization (ROP) of β-butyrolactone to isotactic, atactic (a-PHB) and syndiotactic poly-3-hydroxybutyrate. [2-6]
Recently, systematic investigations have been conducted on the catalytic synthesis of β-lactones through the carbonylation of epoxides, since epoxides are easy to synthesize, inexpensive, and readily available in an enantiomerically pure form. This specific synthetic method opens a new opportunities for exploring the utility of the β-lactones (and in particular precursors of synthetic analogues of natural poly(3-hydroxyalkanoate)s i.e. β-substituted β-lactones) as monomers for the synthesis of new polymers with desired properties. [7]
The aim of the present communication is to report the ability of novel β-alkoxy substituted β-lactones i.e.: β-(methoxymethyl)-β-propiolactone (MOMPL) and β-(ethoxymethyl)-β-propiolactone (EOMPL) to undergo anionic ROP. Polymerization was conducted in the presence of activated carboxylates i.e. supramolecular complex of potassium acetate and tetrabutylammonium acetate (Bu4N
+Ac) as well as by tetrabutylammonium hydroxide. The subtle structure of the polyesters obtained has been established on the basis of ESI-MSn experiments. Acknowledgement. This research project was supported by Polish Ministry of Science and Higher Education project No 3 T08E 022 30 and by Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD-CT-2004-509232.
Keywords:; biodegradable polymers; poly(3-hydroxy-4-methoxybutyrate), poly(3-hydroxy -4-ethoxybutyrate) ____________________________________
[1] Allmendinger, M.; Eberhardt, R.; Luinstra, G.; Rieger, B. J.Am.Chem.Soc. 2002, 124, 5646. [2] (a) Zhang, Y.; Gross, R.A.; Lenz, R.W. Macromolecules 1990, 23, 3206-3212; (b) Tanahashi, N.; Doi, Y.;
Macromolecules 1991, 24, 5732-5733; (c) Hori, Y.; Suzuki, M.; Yamaguchi, A.; Nishishita, T. Macromolecules 1993, 26, 5533-5534; (d) Abe, H.; Doi, Y. Macromolecules 1996, 29, 8683-8688.
[3] Rieth, L.R.; Moore, D.R.; Lobkovsky, E.B.; Coates, G.W. J.Am.Chem.Soc. 2002, 124, 15239-15248. [4] (a) Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651-1656; (b)
Abe, H.; Matsubara, I.; Doi, Y.; Hori, Y.; Yamaguchi, A. Macromolecules 1994, 27, 6018-6025. [5] Kurcok, P.; Śmiga, M.; Jedliński, Z.; J.Polym. Sci. Polym. Chem. 2002, 40, 2184-2189. [6] (a) Kemnitzer, J.E.; McCarthy, S.P.; Gross, R.A. Macromolecules 1993, 26, 1221-1229; (b) Kricheldorf,
H.R.; Eggerstedt, S. Macromolecules 1997, 30, 5693-5697. [7] Church, T.L.; Getzler, Y.D.Y.L.; Byrne, C.M.; Coates, G.W Chemical Communications 2007, 7, 657-674.
88
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-56
Biopolymer-based Fluorescent Sensors
for Quality Control of Food Products
D. Ciechanska1, J. Wietecha
1, J. Kazimierczak
1, D. Wawro
1, and E. Grzesiak
2
1 Institute of Biopolymers and Chemical Fibres with the incorporated Pulp and Paper
Research Institute, 19/27 M. Sklodowskiej-Curie St., 90-570 Lodz, Poland 2 Institute of Dyes and Organic Products, 2/4 Chemikow St., 95-100 Zgierz, Poland
The research was aimed at development of simple and quick method for checking
microbiological quality of food, especially meat and milk products, using fluorescent
indicators.
The method consists in hydrolysis of substituted derivatives of fluorescein and rhodamine,
which, in normal conditions, show no fluorescence. Fluorescein has the absorption maximum
at 490 nm and emission maximum at 514 nm and rhodamine at 498 nm and 520nm,
respectively.
Upon the action of hydrolytic enzymes (esterases, lipases and proteases) released by active
food-deteriorating microorganisms the functional groups of fluorescein and rhodamine
derivatives will become unblocked and start emitting fluorescence. The rate of hydrolysis
reaction of various derivatives is proportional to the enzymes concentration and, therefore, to
the number and vitality of enzyme-producing microorganisms.
At the early stage of research, a wide range of fluorescent dyes derivatives such as
diacetylfluorescein, dibutyrylfluorescein, diacetyleosin, diacetylerythrosin,
dilauroylfluorescein, dibenzoylfluorescein and diacetylrhodamine has been investigated in
order to assess their suitability for sensors preparation. Based on the investigations two
selected derivatives – diacetylfluorescein (FDA) and dibutyrylfluorescein (FDB) were
deposited on surfaces of suitable polymer carriers. The progress of FDA and FDB hydrolysis
due to action of enzymes of specified activity was monitored by intensity of fluorescence
emitted by sensors under UV light source.
Fluorescein derivatives proved to be hydrolysed by both lipases and proteases but in the case
of lipases the reaction rate was significantly higher. It was also found out that
diacetylfluorescein was the most susceptible to the hydrolytic action of the above enzymes.
In vitro tests of fluorescent sensors were carried out using meat and milk samples of various
degrees of microbiological contamination, which had been previously stored for 0-5 days at
ambient temperature.
This work was carried out as part of research project Nr. 3 T09B 137 28, which has been
supported financially by the Ministry of Science and Higher Education.
89
P-57 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polyhydroxyalkanoates Production by Isolates from a Polluted Salt-lagoon
S. Povolo and S. Casella
Dipartimento di Biotecnologie Agrarie, University of Padova,
Viale dell’Università, 16, Legnaro (PD), Italy
Polyhydroxyalkanoates (PHAs) are a family of biodegradable polyesters having a
number of possible industrial applications. They are synthesised as intracellular carbon and
energy storage material by a wide variety of bacteria. The main obstacle to PHA diffusion is
its high production cost greatly depending, among others, upon the cost of the fermentation
substrate to be utilised as a carbon source. The use of agricultural waste materials could play
an important role in economic production of PHA [1]. Starch or hydrolysed starch, cellulose
and hemicellulose along with sucrose and cheese whey have been proposed as economical
sources [2]. Polymer production was studied in many bacteria and recently also in moderately
halophilic bacteria, which grow optimally with 3-15% (w/v) NaCl [3]. Nevertheless,
investigations on the phenotypic characteristics of some type strains belonging to the genus
Halomonas has revealed poly(β-hydroxybutyrate) [PHB] accumulation for several species. In
contrast to the culture requirements of extremely halophilic archaea, sodium chloride
concentrations of 0.5 and 4.5% (w/v) provided the highest cell densities and PHB
accumulation in the case of H. boliviensis [4]. The production of PHB by H. boliviensis from
hydrolyased starch and from sucrose was also described [5].
The objective of the present work was to isolate from the salt-lagoon of Sottomarina (Venice,
Italy) bacteria able to degrade different carbon sources such as glycerol and lactose and
producing PHA at the same time. Specially, we worked on the isolation of bacteria growing at
8 % (w/v) NaCl. Some isolates, were identified by 16S rDNA sequence analysis as belonging
to the genus Halomonas. Here we report preliminary results on the bacterial conversion of
glycerol and lactose to PHA by the selected isolates.
Keywords: moderate halophile; Poly(β-hydroxybutyrate) (PHB) accumulation; carbon source
____________________________________
[1] M. Koller, R. Bona, G. Braunegg, C. Hermann, P. Horvat, M. Kroutil, M. Martinz J. Neto, L. Pereira, P.
Varila. Biomacromolecules 6, 561-565 (2005).
[2] S.Y. Lee. Trends in Biotechnol. 14, 431-438 (1996).
[3] J.A. Mata, J. Martìnez-Cànovas, E. Quesada, V. Bèjar. Yt. Appl. Microbiol.25, 360-375 (2002).
[4] J. Quillaguamán, O. Delgado, B. Mattiasson, R. Hatti-Kaul Enzyme Microb. Technol. 38,148–154 (2006).
[5] J. Quillaguamàn, M. Muños, B. Mattiasson, R. Hatti-Kau. Appl. Microbiol. Biotechnol. 74, 981–986 (2007).
90
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-58
Thermal Properties for Blend of Poly[(L)-lactide]
and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate]
Michał Sobota, Henryk Janeczek, Piotr Dacko, and Marek M. Kowalczuk
Centre of Polymer and Carbon Materials, Polish Academy of Sciences,
34, Marii Sklodowskiej Curie St., 41-819 Zabrze, Poland
The field of biodegradable polymers is a fast growing area of polymer science because of
crude oil, natural gas which are sources for traditional plastics reached price level where
biodegradable polymers can be profitable at common applications instead of non-
biodegradable plastics. In addition, composting, which is used for disposal of food and yard
waste is the most suitable for the disposal of biodegradable materials. Therefore promising
oppurtiunity are appeared for packaging materials which could be prepare from biodegradable
polymers.
Polyesters such as: poly[(L)-lactide] (PLA), poly[hydroxyalkanoate] (PHA) are most popular
representants of biodegradable polymers which are applied in medical, pharmcological and
packaging industries. However biodegradable polymers are promising materials, many of
them are modified on diference ways for improve of physical properties and
processability.[1,2] One of the method modification polymer is blending of two or more
polymers, which is an attractive approach because of the low cost and simplicity.
The aim of the work is thermal investigation for melted blends of PLA and atactic poly[(R,S)-
3-hydroxybutyrate] (a-PHB) by differential scanning calorimetry (DSC). Molecular weight of
PLA (Mn= 100000, Mw/Mn= 2,0) and a-PHB (Mn= 80000, Mw/Mn= 1.2) were determined
by GPC performed in chlorofome with polystyrene standards. DSC thermograms for the
blends and pure PLA showed differences in rate of crystallization, process is accelerated by
the addition of a-PHB component. Time of isothermal (115°C) crystallization for blends after
processing decreased compare to neat PLA, even in sample which is 5% w/w a-PHB content.
Acknowledgment This work was supported by:
- Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth
Framework Programme under the contract number MTKD-CT-2004-509232.
- Polish Ministry of Science and Higher Education: R&D project no. R05 055 02.
- Regional Fund for PhD Students (Regionalny Fundusz Stypendiów Doktoranckich) of the
European Social Fund.
____________________________________
[1] Jedliński Z, Kurcok P, Lenz RW. J Macromol Sci Pure Appl Chem 1995;A32:797.
[2] Datta R, Tsai S-P, Bonsignore P, Moon S-H, Frank JR. FEMS Microbiol Rev 1995;16:221.
91
P-59 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Synthesis of Poly(aspartic acid)-b-Polylactide Block Copolymer
Ida Poljanšek, Blaž Brulc, Maja Gričar, Ema Žagar, Andrej Kržan, and Majda Žigon
National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
The aim of our work is the preparation and study of novel functional polymers and
polymeric materials with tailored properties for application in drug delivery systems. The
research on functional polymers is oriented towards synthesis and characterization of
biodegradable and biocompatible polyesteramides as carriers for controlled drug release based
on natural monomers lactic and aspartic acids [1,2]. The current synthetic work is focused on
the block copolymers made of these two monomers because side-chain carboxylic groups
enable the formation of complexes of the copolymer with metal ions.
In this study poly(β-benzyl L-aspartate)s and their block copolymers with L,L-lactide
with varying molar mass averages and low polydispersity indices (PDI = 1.00–1.09) were
prepared. NMR and FT-IR spectroscopy was used to elucidate the products chemical
composition, and size-exclusion chromatography coupled to multi-angle laser photometer
(SEC-MALLS) was used for the determination of the absolute molar mass averages of the
products.
The benzylic protected aspartic acid N-carboxyanhydride (Asp-NCA) was chosen as
the monomer for the preparation of the polyamide block. Benzylic protection prevented side
reaction leading to branched polymers whose degree of branching could not be controlled.
Polymerization of aspartic acid NCAs was carried out in dry N,N-dimethylformamide
at room temperature and at slightly elevated temperatures (up to 40 °C) in a dry argon
atmosphere using triethylamine or n-pentylamine as the initiator. The polymerization
mechanism is strongly dependent on the initiator used since triethylamine exhibits a basic and
n-pentylamine a more nucleophilic character [3]. Molar mass averages of poly(β-benzyl L-
aspartate)s were in both cases in the order of 103–10
4 g mol
-1 (depending on the ratio of
monomer to initiator used), while polymers were practically monodisperse (PDI = 1.00–1.05).
The next step was the copolymerization of poly(β-benzyl L-aspartate) and L,L-lactide
using stannous(II) octoate as the catalyst [4]. The reactive amino end group of protected
poly(aspartate) block acts as a co-initiator. The linear block copolymers of well defined
structures were synthesized in solution in a dry nitrogen atmosphere and at temperatures
between 50 and 75°C by lactide ring-opening polymerization. The chemical composition of
the block copolymers i.e., the length of lactide block depends on the feed ratio, temperature
and time of reaction. The copolymers synthesized in this manner were linear, but those
prepared at temperatures at 65 °C and above exhibited some degree of branching due to
partial hydrolysis of pendant benzylic ester groups.
Keywords: biodegradable polymers; block-copolymers; characterization
____________________________________
[1] K. Uhrich, S. Cannizzaro, R. Langer, K. Shakesheff, Chem. Rev. 99, 3181 (1999).
[2] C. S. Ha, J. A. Gardella, Chem. Rev. 105, 4205 (2005).
[3] H. Sekiguchi, Pure Appl. Chem. 53, 1689 (1981).
[4] A. Kowalski, J. Libiszowski, R. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38, 8170 (2005).
92
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-60
Compostability of Aliphatic-aromatic Copolyester and their Blends
under Natural Weather Depending Conditions
Katarzyna Krasowska1, Maria Rutkowska
1, and Marek M. Kowalczuk
2
1Gdynia Maritime University, Department of Chemistry and Industrial Commodity Science,
81-87 Morska Str., Gdynia, Poland 2Polish Academy of Sciences, 34 M. Sklodowskiej-Curie Str., Zabrze, Poland
Recently, there is growing demand of biodegradable polymers. They have acquired an
important place in modern life. Products from biodegradable polymers have been
implemented in the medical field, pharmacy, gardening, agriculture and packaging. Selective
use of biodegradable polymers in certain applications might help to reduce the environmental
impact of plastic wastes.
Generally three categories of biodegradable polymers can be distinguished: (1) natural
polymers produced by plants, animals, and microorganisms such as cellulose, starch, chitin
and polyhydroxyalkanotes, (2) synthetic polymers such as polylactide, polycaprolactone, (3)
convenient blends of natural and synthetic polymers.
Among these biodegradable polymers, polyesters are the most promising materials. On the
one hand aliphatic polyesters constitute the most attractive class of artificial polymers, which
can degrade in contact with living organisms but on the other hand aromatic polyesters exhibit
excellent material properties but proved to be almost resistant to microbial attack.
To combine good material properties with biodegradability, a new group of copolyesters have
been developed as biodegradable polymers. This group includes the aliphatic-aromatic
copolyester of 1,4-butandiol with adipic and terephtalic acids. According to DIN and ASTM
standards this polymer is biodegradable, atoxic and useful in composting process.
The development of these group of the aliphatic-aromatic copolyesters biodegradable in
natural environments is the key to solving problems caused by plastic wastes. But very often
environmental degradation can only occur in favourable environments, where the
biodegradation is expected to happen.
In this way the aim of the present study was an examination of the compostability of
copolyester of 1,4-butandiol with adipic and terephtalic acids (Ecoflex, BASF) and their
blends under natural weather depending conditions.
Environmental degradation of pure Ecoflex and and their blends such as Ecoflex/
copolyester of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV) and Ecoflex/ Ramie
woven fabric took place in the compost pile consisted of the activated sludge, burnt lime and
straw preapared under natural conditions of sewage farm
The compostability of investigated polymers under natural conditions was based on the
examination of the changes of surface and weight of polymers after degradation.
The characteristic parameters of compost were also investigated and their influence on the
rate of composting process was discussed.
The results of the present study revealed that Ecoflex and their blends are degraded in
compost with activated sludge under natural conditions. The rate of composting process
depends on the nature of environment and the kind of degraded polymer. Generally the
biodegradation rates of investigated polymers in compost with activated sludge decreased in
order: Ecoflex/PHBV>Ecoflex>Ecoflex/Ramie woven fabric.
Keywords: copolyester of 1,4-butandiol with adipic and terephtalic acids, PHBV, Ramie woven fabric, compost
with activated sludge
93
P-61 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Illumination of Cellulose with Linearly Polarized Visible Light
A. Konieczna-Molenda1, M. Molenda
2, M. Fiedorowicz
1, and P. Tomasik
1
1Department of Chemistry, University of Agriculture,
Balicka 122 Str., 30-149 Cracow, Poland 2Faculty of Chemistry, Jagiellonian University,
Ingardena 3 Str., 30-060 Cracow, Poland
Cells and plants react to the polarized light [1,2]. Reports on effects of the polarized
light upon the activation of enzymes [3], enhancement rate of enzymatic hydrolysis of starch
polysaccharides [4] and rearrangement of the molecular structure of starch polysaccharides [5]
were published recently. This work provides results of our study on the changes in
physicochemical properties of cellulose induced by illumination with the polarized light.
Water suspensions of commercially available cellulose, containing long polysaccharide
chains, were illuminated with visible polarized light for 20 and 50 hrs. Another cellulose
samples suspended in water and kept in the dark served as reference. After termination of
illumination, cellulose was filtered off and dried. Crystalline structure [6], thermal properties
(DSC) [7], susceptibility to oxidation [8] and degree of polymerization (DP by viscometry) [9]
of the samples were determined. Additionally, kinetic of enzymatic as well as acid hydrolysis
of cellulose was estimated.
Illumination of cellulose with linearly polarized light (50 hrs) increased degree of
polymerization of 15%. Such effect was not observed for illuminated at shorter time as well as
for non illuminated samples. The DSC measurements indicated different water content in the
samples of illuminated and nonilluminated cellulose prepared under the same conditions. The illuminated cellulose incorporated the highest, about 18%, water content. Only for that sample
the heat effect related to water freezing was observed.
X-ray diffraction patterns demonstrated that the illumination resulted in an increase in
the cellulose crystallinity. After prolonged illumination, the cellulose was resistant to the
oxidation. Illuminated cellulose revealed lower susceptibility to enzymatic and acid-catalysed
hydrolysis
____________________________________
[1] T.Kubasowa, M.Fenyo, Z.Somosy, L.Gazso, I.Kertesz; Photochem. and Photobiol., Vol.48, No. 4, 1988,
pp. 505–509.
[2] K.M.Hartmann, A.Mollwo; Proc. Symp. Biologic Effects of Light, Basel, Switzerland, 1-3.11.1998.
[3] M.Fiedorowicz, A.Konieczna–Molenda and G.Khachatryan; Starch: – Progress in structural studies,
modifications and applications. Eds P.Tomasik, V.Yuryev, E.Bertoft, Polish Society of Food Technologist’
Małopolska Branch, 2007.
[4] M.Fiedorowicz, G.Khachatryan, A.Konieczna-Molenda, V.P.Yuryev, L.A. Wassermann; Starch:
Achievements in Understanding of Structure and Functionality. Edts.: Vladimir Yuryev, Piotr Tomasik and
Eric Bertoft . Nova Science Publishers, New York, 2006.
[5] M.Fiedorowicz, G.Chaczatrian; J. Sci. Food Agric., 2004, 84 (1), 36-42.
[6] K.Choo-Won, K.Dae-Sik, K.Seung-Yeon, M.Marquez, Yong L.J; Polymer 47 (2006) 5097-5107.
[7] A.Kochanowski, R.Dziembaj, M.Molenda, A.Izak, E.Bortel; J. Therm. Anal. Cal. 88(2) (2007) 499-502.
[8] L.M.Proniewicz, C.Paluszkiewicz, A.Wesełucha-Birczyńska, H.Majcherczyk, A.Barański, A.Konieczna;
J. Molec. Struc. 596 (2001) 163-169.
[9] A.Barański, A.Konieczna–Molenda, J.M. Łagan, L.M. Proniewicz; Restaurator 24 (2003) 36-45.
94
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-62
Poly(L-lactide) Nano- and Micro-fibers by Electrospinning:
Influence of Poly(L-lactide) Molecular Weight
W. Tomaszewski1, A. Duda
2, M. Szadkowski
1, J. Libiszowski
2, and D. Ciechańska
1
1Institute of Biopolymers and Chemical Fibres,
Sklodowskiej-Curie 19/27, 90-570 Lodz, Poland 2 Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, 90-363 Lodz, Poland
Aim of the work
The present contribution aims at reporting on studies of nanofibers and nanofibrous mats
parameters obtained from poly(L-lactide)s (PLA’s) of various molecular weights.
Materials
PLA’s were prepared by the controlled ring-opening polymerization of the L.L-dilactide (LA)
monomer. The polymerization was carried out in THF as a solvent at 80°C with tin(II) bis-
octanoate (2-ethylhexanoate) as a coinitiator. For the resulting, isolated by precipitation into
methanol PLA’s, the following molecular weights (Mn, SEC, LLS detector) were determined:
22×103, 62×10
3, 132×10
3.
Preparation of fibrous mats by electrospinning
The spinning solutions contained from 1 to 12 wt-% of PLA in a solvent composed of 90/10
wt% CHCl3/DMSO mixture. The electrospinning apparatus was equipped with 12 points
spinning head sliding along a rotating tube, with diameter of about 8 cm, as collecting
electrode. The air gap and voltage were 15 cm and 20 kV, respectively. The electrospun
products were flat fibrous sheets, about 0.1 mm thick.
Analytical methods
Microscopy. The electrospun products were observed by a scanning electron microscope
Quanta 200(W), FEI Co., USA.
Thermal characterization. The thermal transitions were measured by a differential scanning
calorimeter DSC-2, Perkin-Elmer, USA.
Viscometry. The viscosity of the spinning solutions were measured by a Brookfield
viscometer
Tensile tests. The tensile properties were measured by classic (tensile tester, Instron 5544,
USA) and special ball piercing (modified Instron apparatus) methods.
Results
The nano- and micro-fibrous mats with diameters of fibers in the range from 0.1 to 1.7 µm
were manufactured by electrospinnig from solution. Molecular weights of the applied PLA’s,
viscosities of the spinning solutions, and the fibers thickness were correlated. The
microscopic, thermal and tensile characteristics of the resulting mats were examined.
This work was carried out as a part of the research project no. 3 T08E 036 29 supported by
the Ministry of Science and Higher Education, Poland
Keywords: poly(L-lactide); nanofibrous mats; electrospinning; mechanical properties
95
P-63 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Biomedical Applications of Maleic Anhydride Copolymers
and Their Derivatives
Gabrielle C. Chitanu1, Irina Popescu
1,
Adina G. Anghelescu-Dogaru1, and Irina Dumistracel
2
1“Petru Poni” Institute of Macromolecular Chemistry,
Aleea Grigore Ghica Voda 41A, 700487, Iasi, Romania 2S. C. Antibiotice S.A. - Iasi, Valea Lupului 1, Iasi, Romania
The use of maleic anhydride copolymers or their derivatives for medical or
pharmaceutical purposes is already known, some of such applications being of current use. An
important research effort was dedicated to this topic, the pioneering results of Breslow [1] and
Maeda [2] are worthy to be mentioned as well as the contributions of Hirano and co-workers
[3], Hodnett et al. [4], Azori, Pato and co-workers [5], Rubessa and co-workers [6], Heller et
al. [7], A. Urtti and his group [8]. The application of maleic anhydride copolymers in the
biomedical and pharmaceutical topic is promoted by several advantages from which can be
mentioned their regular, reproducible chemical structure, their variable
hydrophobicity/hydrophilicity, that can be tailored by choosing the suitable comonomer, and
their chemical versatility, due to the anhydride cycle, which allows to attach different low
molecular compounds by mild reactions. Not on the last place is the pH dependent solubility
of the conjugates based on maleic anhydride copolymers, which is particularly suitable for the
controlled delivery of drugs in different segments of the gastrointestinal tract. In the first
section of our contribution all these aspects are reviewed in a systematical and organized
manner.
The second part of our work presents several of our results aiming the obtaining of
maleic anhydride (MA) copolymers based derivatives or systems for biomedical purpose.
They are described:
- Synthesis and characterization of macromolecular disinfecting systems from MA
copolymers and OH- containing disinfectants such as thymol or eugenol
- Synthesis and characterization of menthol-containing polymers for dental use
- Synthesis and characterization of amidic derivatives of MA copolymers and preparation of
microparticles loaded with bioactive molecules
- Some data on the polymer degradation in aqueous solution.
Acknowledgement The financial support of Romanian National Authority for Scientific Research, CEEX
projects no. 14/2005 and 277/2006 is gratefully acknowledged.
Keywords: bioactive polymers; polymer degradation; maleic anhydride copolymers; polymer-drug conjugates
____________________________________
[1] D. S. Breslow, Pure Appl. Chem., 46, 103 (1976).
[2] H.Maeda, Adv. Drug Delivery Rev., 6, 181 (1991).
[3] Hirano, T.; Ohashi, S.; Morimoto, S; Tsuda, K. Makromol. Chem., 187, 2815 (1986); Hirano, T.; Todoroki,
T.; Kato, S; Yamamoto, H.; Calicetti, P.; Veronese, F.; Maeda H.; Ohashi, S. J. Control. Release, 28, 203
(1994); Hirano, T.; Todoroki, T.; Morita, R.; Kato, S; Ito, Y.; Kim, K.-H.; Shukla, P. G.; Veronese, F.; Maeda
H.; Ohashi, S. J. Control. Release, 48, 131 (1997).
[4] E.M. Hodnett, A. Wai Wu, and F.A. French, Eur. J. Med. Chem., 13, 577 (1978) and subsequent papers.
[5] See for example: M. Azori, in: “Polymers in Medicine III”, ed. by C. Migliaresi, Elsevier Sci. Publishers,
B.V., Amsterdam, 1988, p. 189-199.
[6] C. Flego, M. Lovrecich, and F. Rubessa, Drug. Develop. Ind. Pharm., 14, 1185 (1988) and subsequent papers
[7] J. Heller, R.W. Baker, R.M. Gale, J.O. Rodin, J. Appl. Polym. Sci. 22, 1991 (1978).
[8] U. Finne, K. Kyyrönen, A. Urtti, J. Control. Release 10, 189 (1989).
96
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-64
Complexation of Phosphorylated Cellulose with Collagen
Dana M. Suflet1, Gabrielle C. Chitanu
1, and Viorica Trandafir
2
1“Petru Poni” Institute of Macromolecular Chemistry,
Aleea Grigore Ghica Voda 41A, 700487, Iasi, Romania 2National Research and Development Institute for Textile and Leather,
str. Ion Minulescu 93, sector 3, Bucuresti, Romania
Polysaccharides are of the most abundant biopolymers possessing structural diversity
and functional versatility. They are polyglucans type polymers, containing glucose repeating
units only; however a broad variety of structures appears, resulting from the stereochemistry
of the anomeric C-atom, from the regiochemistry of the glycosidic linkage and from the
pattern of branching. Chemical derivatization of polysaccharides has a determinant effect on
their macroscopic properties, such as solubility, stability, and viscosity characteristics. If the
functionalization leads to polysaccharide derivatives bearing ionic or ionizable groups they
will behave as polyelectrolytes. Among these, the strong polyelectrolytes containing
phosphoric groups can be obtained mainly by derivatization [1, 2].
Collagen is the most abundant protein in higher animals, and its function has been
considered to maintain the body skeleton. Collagen is usually employed in drug delivery
systems or as material for constructing artificial organs. The interaction of collagen with other
natural or synthetic polyelectrolytes is interesting at least from two points of view. The first
concerns the way in which the polymers interact with nonflexible protein molecules, an
understanding of which could provide a better explanation of the interaction mechanism of
polyelectrolytes with ionic colloidal particles. The second concerns the extent to which
biochemical activity is maintained in the resulting complexes, the answer to which is central
to the molecular design of composite collagen-polymer systems [3].
In this work we report original results regarding the interaction of phosphorylated
cellulose [4] with collagen in aqueous salt-free or added salt containing systems. The
collagen-phosphorylated cellulose systems were investigated firstly in aqueous solution, by
potentiometric, conductometric and turbidimetric titration, according to the recommended
procedures [2, 5, 6]. The elemental analysis, FT-IR spectra, electron microscopy and
termogravimetric method were used in characterization of complexes formed in different
conditions.
Acknowledgement: The financial support of Romanian National Authority for Scientific Research, CEEX project
no. 16/2005 is gratefully acknowledged.
Keywords: natural polymers; polysaccharides; collagen; intermacromolecular complexes
____________________________________
[1] D. Klemm, B. Philipp, T. Heinze, U. Heinze, W. Wagenknecht, Comprehensive Cellulose Chemistry, Wiley
Verlag GmbH, D-69469 Weinheim (F.R.G.), 2, 1998.
[2] H. Dautzenbeg, W. Jaeger, J. Köetz, B. Philipp, Ch. Seidel, D. Stscherbina, in Polyelectrolytes. Formation,
Characterization and Application, Hansel Publishers, Munich, 1994.
[3] A. Tsuboi, T. Izumi, M. Hirata, J. Xia, P.L. Dubin, E. Kokufuta, Langmuir, 12, 6295 (1996).
[4] M.D. Suflet, G.C. Chitanu, V.I. Popa, React. Funct. Polym., 66(11), 1240 (2006).
[5] Y. Li, P.L. Dubin, H.A. Havel, S.L. Edwards, H. Dautzenberg, Macromolecules, 28, 3098 (1995).
[6] Y.-P. Wen, P.L. Dubin, Macromolecules, 30, 7856 (1997).
97
P-65 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Effect of Collagen on Sparingly Soluble Inorganic Salts Separation
Irina M. Pelin1, Gabrielle C. Chitanu
1, Viorica Trandafir
2, and Zina Vuluga
3
1“Petru Poni” Institute of Macromolecular Chemistry,
aleea Grigore Ghica Voda 41A, Iasi 700487, Romania 2National Research and Development Institute for Textile and Leather,
str. Ion Minulescu 93, sector 3, Bucuresti, Romania 3National Research and Development Institute for Chemistry and Petrochemistry –
ICECHIM, Splaiul IndependenŃei 202, Bucuresti, Romania
Collagen is a natural polyelectrolyte (polyampholyte) obtained by extraction from
different animal sources. It proves good properties, from which it should be mentioned
biocompatibility, bioabsorbability and hipoimmunogenicity, that make it proper in many
biomedical applications as hemostats, sealants, implant coatings, artificial skin, bone graft
substitutes, corneal shields and injectables for plastic surgery [1].
The interest in developing bone substitutes has been growing and numerous papers
describe new methods of preparation. The bones contain a carbonated and partially
substituted apatite, based on nanocrystal aggregates associated with collagen. In most cases,
collagen processing involves aqueous preparations, and the obtaining of hydroxyapatite
(HAp) takes place also in water.
In our paper we investigated the interaction in aqueous solutions between the
precursors of HAp: ammonium dihydrogen phosphate and calcium nitrate tetrahydrate, in
presence of various amounts of collagen as crystallization regulator. As mineralizing agent a
12.5% ammonium hydroxide solution was used. The influence of collagen was followed by
potentiometric, conductometric and turbidimetric titration. The particles of HAp were
characterized by FTIR spectroscopy, X-ray diffraction and scanning or transmission electron
microscopy.
Acknowledgement: The financial support of Romanian National Authority for Scientific Research, CEEX project
no. 16/2005 is gratefully acknowledged.
Keywords: collagen, hydroxyapatite, crystallization regulators, biomaterials ____________________________________
[1] W. Friess, M. Schlapp, Eur. J. Pharm. Biopharm. 51, 259 (2001).
98
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-66
Supramolecular Systems from Natural Polymers
and Maleic Polyelectrolytes
Irina Popescu1, Marcel I. Popa
2, and Gabrielle C. Chitanu
1
1“Petru Poni” Institute of Macromolecular Chemistry,
Aleea Grigore Ghica Voda nr. 41-A, 700487, Iasi, Romania 2“Gh. Asachi” Technical University, Faculty of Chemical Engineering
and Environment Protection, Bd. D. Mangeron 71, Iasi, Romania
Polyelectrolyte complexes (PEC) result from the interaction of macromolecules
carrying opposite charged groups. They have been proposed for several purposes, from which
we mention the design of drug delivery systems, anticoagulant coatings, and membranes or
even as skin substitutes. The preparation of PEC from natural polymers, such as
polysaccharide or polypeptides has the additional advantage of being non-toxic,
biocompatible, and bioabsorbable.
Chitosan is a cationic polysaccharide obtained by deacetylation of chitin, which is the
major constituent of the shells of crustacean and insects. As the other natural polymers it is
renewable, highly biocompatible, very low toxic in the oral and implant administrations and
biodegradable. By derivatization or complexation of chitosan a variety of new functional
materials can be obtained.
In our work the formation of PEC by interaction between chitosan and maleic acid
copolymers (MP) as strong/weak dibasic polyanions was investigated. The salt form of maleic
acid copolymers with: vinyl acetate, N-vinylpyrrolidone, styrene and methyl methachrylate
and the hydrochloride form of chitosan were used, all macromolecular partners being
carefully purified by diafiltration and freeze-drying. The interaction of chitosan with MP in
aqueous solution was followed by potentiometric, conductometric and turbidimetric titration
by varying the polyelectrolytes concentration and the mixing order [1, 2]. The effect of the
added low molecular salt on the complex formation was also investigated. The precipitated
complexes were analysed by FT infrared spectroscopy, thermogravimetric analysis and
differential scanning calorimetry. Preliminary layer-by-layer experiments were performed to
obtain thin films from maleic polyelectrolytes and chitosan [3].
Chitosan behavior in the interaction with maleic polyelectrolytes was compared with
other natural polymers such as collagen.
Acknowledgement: The financial support of Romanian National Authority for Scientific Research, CEEX project
no. 16/2005 is gratefully acknowledged.
Keywords: chitosan; maleic polyelectrolytes; intermacromolecular complexes; supramolecular systems
____________________________________
[1] B. Philipp, H. Dautzenberg, K.-J. Linow, J. Kötz, W. Dawydoff, Prog. Polym. Sci. 14, 91 (1989).
[2] A. F. Thünemann, M. Müller, H. Dautzenberg, J.-F. Joanny, H. Löwen, Adv. Polym. Sci. 166, 113 (2004).
[3] O. N. Oliveira, J.-A. He, V. Zucolotto, S. Balasubramanian, L. Li, H. S. Nalwa, J. Kumar, S. K. Tripathy,
“Layer by layer polyelectrolyte-based thin films for optoelectronic and photonic applications”, chapter in
“Handbook of polyelectrolytes and their applications”, Ed. By S. K. Tripathy, J. Kumar and H. S. Nalwa,
American Scientific Publishers, 2002, USA.
99
P-67 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Polylactide-polyglycidol Block Copolymer as a New
Nanoparticles Forming Material
Mariusz Gadzinowski, Beata Miksa, and Stanislaw Slomkowski
Center of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, 90-363 Lodz, Poland
A novel kind of block copolymer: polyglycidol-b-polylactide was synthesized by living
anionic polymerization and used for the nanoparticles preparation. The main advantage of
using polyglycidol is presence of functional hydroxyl groups in the hydrophilic polyglycidol
chain. Synthesis includes four main steps: a) protection of glycidol hydroxyl group, b)
polymerization of protected monomer, c) extension of polyether chain by polymerization of
L-lactide initiated by active centers on the living polyglycidol chain and d) deprotection of
glycidol hydroxyl groups. Potassium tert-buthoxide has been used as an intiator.
Polymerizations were carried on in THF. Copolymer blocks lengths were determined by 1H-NMR spectroscopy and a very good agreement between calculated (assuming quantitative
initiation and complete monomer conversion) and measured molecular weight of blocks was
observed. In water macromolecules of all synthesized polyglycidol-b-polylactides (with
various molecular weight: PGL4000-PLA3000, PGL2000–PLA3000, PGL4000-PDLA3000)
did self-assembly into nanoparticles with diameters ranging from 22 to 31 nm. There was
developed a method for preparation of polyglycidol-b-polylactide loaded with ovalbumin
(OVA). This method consists on dialysis of copolymer and ovalbumin solution in DMSO
carried on against water. Diameter of nanoparticles with OVA was equal 31 nm. The high
loading with OVA (from 77-200 mg protein per gram of nanoparticles, depending on the
PGL/PLA ratio in the copolymer chain) has been achieved.
100
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-68
Structure Evolution in Amorphous Poly(L/DL-lactide)
upon Plain Strain Compression
Miroslaw Pluta and Andrzej Galeski
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, 90-363 Lodz, Poland
Plastic deformation of amorphous, thermally non-crystallizable poly(L/DL-lactide) 70/30 (P(L/DL)LA) was induced by a plain strain compression in a channel-die at different temperatures, above Tg from 60
oC to 90oC. Samples undeformed (reference) and deformed to different compression ratios (CR), from 4.6 to 23.0, were studied by an X-ray diffraction, thermally modulated differential scanning calorimetry, light microscopy and mechanical methods – viscoelastic and tensile tests. The effects of the compression ratios and deformation temperatures on the final structure and properties of the P(L/DL)LA were evaluated. It was revealed that plastic deformation transformed of an amorphous P(L/DL)LA (thermally non-crystallizable), to a crystalline fibrillar texture oriented in the flow direction. Fibrillar texture was formed in spite of the tendency of the plane strain compression to form single crystal-like texture. The crystallite size in the transverse direction was small, up to 90 Å at the highest CR. No evidence of lamellar organization and features of supermolecular structure were detected by SAXS and light microscopy, respectively. The oriented samples exhibited low crystallinity degree at the level of 6-9% at the highest CR. The main transformation mechanism was shear and orientation induced crystallization. The crystalline phase was in the α crystallographic modification of poly(lactide) typically formed in more stereoregular poly(lactide) by thermal treatment. The glass transition increased with the increase of CR reflecting the increase of orientation of the polymer chains. Tensile strength of deformed samples were improved considerably in comparison to the reference sample.
101
P-69 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Structure and Physical Properties of PLA/Calcium Sulfate Composites
Miroslaw Pluta
1, Marius Murariu
2, Amália Da Silva Ferreira
3,
Michaël Alexandre2, Andrzej Galeski
1, and Philippe Dubois
3
1Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112, 90-363 Lodz, Poland 2Materia Nova asbl, Parc Initialis, Av. Nicolas Copernic 1, B-7000 Mons, Belgium
3Centre of Innovation and Research in Materials & Polymers (CIRMAP), Laboratory of Polymeric
and Composite Materials (LPCM), University of Mons-Hainaut, Académie Universitaire Wallonie-
Bruxelles, Place du Parc 20, B-7000 Mons, Belgium
Starting from calcium sulfate (gypsum) as fermentation by-product of lactic acid production
process, high performance composites have been produced by melt-blending polylactide
(PLA, L/D isomer ratio of 96 : 4) and beta - anhydrite II (AII) filler i.e., calcium sulfate
hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and
thermal properties due to good filler dispersion throughout the polyester matrix, these
composites are interesting for potential use as biodegradable rigid packaging. Physical
characterization of selected composites filled with 20 and 40 wt% AII has been performed
and compared to processed unfilled PLA with similar amorphous structure. State of dispersion
of the filler particles and interphase characteristic features have been investigated using light
microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease
PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching
a slight increase of PLA crystallizability during melt-crystallization and upon heating from
the glassy, amorphous state (DSC). It was found by thermo-mechanical measurements
(DMTA) that the AII filler increased pronouncedly storage modulus (E’) of the composites in
comparison with PLA in a broad temperature range: e.g. addition of 40 wt% AII increased E’
more than 90% at 25 °C, and surprisingly, more than 200% at 80 °C. The X-ray investigations
showed stable/unchanged crystallographic structure of AII during processing with molten
PLA and in the composite system. The notable thermal and mechanical properties of PLA–
AII composites are accounted for by the good filler dispersion throughout the polyester matrix
confirmed by morphological studies, system stability and favourable interactions between
components.
102
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-70
Materials of Functional Properties Based on Biodegradable Polymers
M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak
Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
Modern plastic materials constitute frequently polymer blends and composites obtained
by mixing polymers with fillers, adhesion promoters, processing aids etc. Incorporation of
such additives brings about a novel properties to a matrix polymer, thus broadening a field of
possible applications. Recent shortages in the petrochemical products delivery and high oil
prices caused a revival of renewable resources, which is higly advantageous for a sustainable
development. Polymers and fillers deriving from agriculture recently have focused substantial
interest of the research teams and industry. Thermoplastic composites with natural fibers
(biocomposites) have been increasingly used in automotive industry, insulating materials and
in constructions. Further modification may be obtained by addition of functional fillers.
Properties of biodegradable polymers filled with natural fibers and flame retardants have been
presented in this paper.
Polylactic acid (PLA) and poly(hydroxybutyrate) (PHB) were used as matrix polymers,
whereas flax (F) and hemp fibers (H) were used for reinforcement. Different flame retardants
(FR) were used for modification of the fire resistance of biocomposites. Flammability was
evaluated by UL 94 horizontal and vertical Bunsen burner tests according to IEC 6007 and
IEC 60695. Mechanical properties of biocomposites were tested by means of the tensile and
bending methods. Selected results have been presented in Table 1 and Table 2.
Table 1. Horizontal burn method
Material Burning time
(0-25 mm), min
Behaviour Class
PLA
PLA/F30/20FR
PLA/H30/20FR
PLA/H30/20FR/10M
PLA/H30/20FR/20M
PLA/H30/20FR/30M
0:16
1:45
0:02
1:00
2:20
1:20
burning, flaming drips, cotton ignition
burning stops, no flaming drips
burning stops, no flaming drips
burning stops, no flaming drips
burning stops, no flaming drips
burning stops, no flaming drips
HB
HB
HB
HB
HB
Table 2. Vertical burn method
Material Burning time
(50 mm), sec
Behaviour Class
PLA
PLA/F30/20FR
PLA/H30/20FR
PLA/H30/20FR/10M
PLA/H30/20FR/20M
PLA/H30/20FR/30M
5
0
0
20
15
40
buring intensively, flaming drips, cotton ignition
no flaming drips
no flaming drips
no flaming drips
no flaming drips
no flaming drips
-
V-0
V-0
V-1
V-1
V-1
Acknowledgements
This research was financially supported by FP6-IP-SME Project 515769-2 BIOCOMP.
Keywords: biodegradable polymers; fire resistance; mechanical properties
103
P-71 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Influence of Gamma-radiation on PCL/PHB Blends
D. Babic1, Z. Kacarevic-Popovic
1, G. Mikova
2, and I. Chodak
2
1Institute of Nuclear Sciences Vinca, Laboratory Gamma, Belgrade, Serbia 2Polymer Institute of the Slovak Academy of Sciences, Bratislava, Slovakia
The influence of high energy radiation to polymer blend made of polycaprolactone (PCL) and
polyhydroxybutyrate (PHB) was studied.
The PCL/PHB blend was prepared in 50:50 component ratio with different amounts of
triallylcyanurate (TAC) up to 5%.
The samples have been irradiated with the radiation doses of 25 and 50 kGy with the Co-60
gamma rays.
Mechanical properties were studied by stress-strain measurements. Heat properties and
supermolecular structure were followed by thermal characterization with DSC method.
Molecular structure was characterized by FTIR. Changes in structural and mechanical
properties are correlated with the influence of TAC content and absorbed radiation dose. The
effects to end-use properties of this material were discussed. As this material is of interest for
use in biodegradable application the changes of biodegradability of the radiation treated
blends has been followed as well.
104
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-72
Synthesis and Properties Evaluation of a New Class
of Degradable Polymers: Poly(vinyl-co-ester)s
Seema Agarwal and Liqun Ren
Philipps Universitaet Marburg,
Hans-Meerwein Strasse, 35032 Marburg, Germany
Generally, a high molecular weight polymer based on the C-C backbone like vinyl polymers
tends to be resistant to hydrolysis, oxidative cleavage, resistant to the enzymatic attack etc.
and are therefore not (bio)degradable, whereas heteroatom-containing polymer backbones
confer (bio)degradability. In this work efforts have been made to bring degradable ester
linkages onto the poly vinyl polymer backbones like poly (methyl methacrylate)(PMMA)
and poly(N-isopropyl acrylamide)(PNIPAAM) for the generation of new class of degradable
materials poly(vinyl-co-ester)s. A combination of radical ring-opening polymerisation of
cyclic ketene acetals and conventional free-radical polymerisation of vinyl monomers have
been utilised for bringing ester linkages onto the C-C backbones. An in sight into the
microstructure of the resulting materials is achieved using different 1D and 2D NMR
techniques. The introduction of ester linkages generated different new materials with a range
of properties like varied lower critical solution temperatures (LCSTs), improved thermal
stability, elasticity etc. besides making them degradable thereby increasing their utility areas
for various biomedical applications. Synthesis, characterization and properties of some new
materials like (poly(MMA-co-ester)s and poly(NIPAAM-co-ester)s will be presented.
105
P-73 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Dynamic-Mechanical and Thermal Properties of Biodegradable Composites
from Polylactic Acid (PLA) Reinforced with Wood Fibres
A. Gregorova and R. Wimmer
Green Composites Group, Universität für Bodenkultur Wien,
Peter Jordanstrasse 82, 1190 Vienna, Austria
Biodegradable polymers have received an increased interest for utilization due to
increasing environmentally aware consumers, increased price of crude oil and global
warming. Nowadays, biodegradable polymers are used with a number of applications, such as
therapeutic aids, medicines, coatings, food products and packaging materials. Poly(lactic acid)
(PLA) is a biodegradable hydrolysable aliphatic polyester of lactic acid, which can be
obtained from renewable resources. PLA is becoming increasingly popular as a biodegradable
engineering plastic due to its high mechanical strength, and easy to process compared to other
biopolymers. However, the addition of plasticizers is necessary because of rigidity and
brittleness f PLA.
The goal of this work was to compare the dynamic-mechanical and thermal properties
of 5% softwood and hardwood filled PLA films prepared by solution casting method in
chloroform. Softwood and hardwood fibres with particles from 100-500 µm were modified by
various methods such as hydrolysis, esterification, oligoesterification, NaOH impregnation,
and silane impregnation.
Dynamic-mechanical-analysis (DMA) and differential-scanning-calorimetry (DSC)
showed that different types of wood fibres modification have a tremendous effect on the
results in terms of changes in storage and loss moduli, as well as crystallinity.
Keywords: biodegradable polymers; wood fibres, dynamic-mechanical properties, differential scanning
calorimetry
106
(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-74
New Derivatives of Methyl Oleate
Tarik Eren and Banu Taslica
Department of Chemistry, Bogazici University, Bebek, Istanbul, 34342, Turkey
Abstract: The purpose of this work is to synthesize new free radically polymerizable
monomers based on methyl oleate. The chemistry consists of reaction of the unsaturated fatty
ester with N-bromosuccinimide (NBS) in the presence of excess amount of a nucleophile. The
nucleophiles used were acrylic acid (1), methacrylic acid (2), methacrylamide (3) and maleic
acid-mono(dibutylamine) salt (4). Monomers are the addition products of bromine and the
nucleophile to the oleate double bond. These new monomers were characterized by
spectroscopic techniques. New phosphonate derivative of methyl oleate was also synthesized.
Bromoacrylated methyl oleate was reacted with trimethyl phosphite (TMP) by Arbuzov
reaction to produce the phosphonate (5) derivative. 1,4- addition of TMP to the acrylate
double bonds of bromoacrylated methyl oleate was observed as main product instead of the
expected Michaelis-Arbuzov product.
COOCH3
OH
O
O
OH
O
NH2
HO
O
O
O
H3N C4H9 2
NBS, RT, 1 day
NBS, RT, 1 day
NBS, RT, 6 h, Acetone
1. NBS, RT,
1 day, CH2Cl2
2. H
[1]
[2]
[3]
[4]
COOCH3
Br
X
O
CO
HC CH2
O
CO
C CH2
CH3
NH
CO
C CH2
CH3
O
CO
HC CHC OH
O
[1] [2] [3] [4]
X
Fig. Synthesis of new derivatives of 10-bromo, 9-acrylate methyl stearate (1); 10-bromo, 9-
methacryloxy methyl stearate (2); 10-bromo, 9-methacrylamido methyl stearate (3); mono-9-
(10-bromo methyl stearate)yl ester (4) (corresponding regioisomers are not shown).
107
AUTHOR INDEX
Aa van der L. J. 25 (I-10)Adamus G. 35 (P-02), 54 (P-21), 56 (P-23),
88 (P-55)Agarwal S. 30 (I-15), 105 (P-72)Albertsson A.-C. 15 (I-02)Alexandre M. 17 (I-04), 102 (P-69)Anghel N. 61 (P-28)Anghelescu-Dogaru A. G. 96 (P-63)Atlic A. 28 (I-13), 78 (P-45), 80 (P-47)Avella M. 66 (P-33)Babic D. 104 (P-71)Badia J. D. 82 (P-49), 83 (P-50), 84 (P-51)Bawa S. S. 42 (P-09)Bertoldo M. 21 (I-07), 52 (P-19)Błasinska A. 67 (P-34)Bobalova J. 51 (P-18)Bogoeva-Gaceva G. 66 (P-33)Bonnaud L. 17 (I-04)Borsali R. 22 (I-08)Bourdiot U. 30 (I-15)Braunegg G. 28 (I-13), 78 (P-45), 80 (P-47)Bronco S. 21 (I-07), 52 (P-19), 53 (P-20)Brulc B. 92 (P-59)Buzarovska A. 66 (P-33)Cardamone J. M. 72 (P-39)Casella S. 90 (P-57)Chardhuri J. B. 38 (P-05)Chen Y. 30 (I-15)Chiellini E. 27 (I-12)Chitanu G. C. 96 (P-63), 97 (P-64), 98 (P-65),
99 (P-66)Chodak I. 104 (P-71)Ciardelli F. 21 (I-07), 52 (P-19), 53 (P-20)Ciechanska D. 89 (P-56), 95 (P-62)Ciolacu D. 55 (P-22)Ciolacu F. 55 (P-22)Cognigni F. 52 (P-19)Coltelli M.-B. 21 (I-07), 53 (P-20)Cosutchi A. I. 60 (P-27)Cuart M. 64 (P-31)Czarny A. 74 (P-41)Da Silva Ferreira A. 17 (I-04), 102 (P-69)Dacko P. 48 (P-15), 50 (P-17), 91 (P-58)Davidson M. G. 38 (P-05)Dersch R. 30 (I-15)Dijkstra P. J. 25 (I-10)Dobrzynski P. 65 (P-32), 71 (P-38), 70 (P-37)Drobnik J. 67 (P-34)Dubois P. 17 (I-04), 102 (P-69)Duda A. 16 (I-03), 62 (P-29), 95 (P-62)
Dumistracel I. 96 (P-63)Dumitriu R. P. 57 (P-24)Duncianu C. 45 (P-12)Dzwonkowski J. 50 (P-17)El Fray M. 34 (P-01)Ellis M. J. 38 (P-05)Erberich M. 26 (I-11)Eren T. 107 (P-74)Errico M. E. 66 (P-33)Faÿ F. 47 (P-14)Feijen J. 25 (I-10)Fiedorowicz M. 32 (I-17), 94 (P-61)Filip D. 49 (P-16), 60 (P-27)Florczak M. 62 (P-29)Focarete M. L. 69 (P-36), 71 (P-38)Frackowiak S. 103 (P-70)Gadzinowski M. 100 (P-67)Galeski A. 18 (I-05), 101 (P-68), 102 (P-69)Gamian A. 76 (P-43)Garnaik B. 46 (P-13)Gensheimer M. 30 (I-15)Gentile G. 66 (P-33)Gebarowska K. 70 (P-37)Gnanou Y. 22 (I-08)Gołebiewski J. 50 (P-17)Gregorova A. 106 (P-73)Greiner A. 30 (I-15)Gricar M. 92 (P-59)Gross R. A. 20 (I-06)Grozdanov A. 66 (P-33)Grzesiak E. 89 (P-56)Gualandi C. 71 (P-38)Hans M. 26 (I-11)Harabagiu V. 54 (P-21)Haznar D. 75 (P-42), 76 (P-43)Hermann-Krauss C. 78 (P-45), 80 (P-47)Hesse P. 78 (P-45), 80 (P-47)Hicks K. B. 73 (P-40)Hiemstra C. 25 (I-10)Houga C. 22 (I-08)Höcker H. 37 (P-04)Hu Y. 65 (P-32)Huang C.-Y. 63 (P-30), 81 (P-48), 85 (P-52),
86 (P-53)Hulubei C. 60 (P-27)Ichim M. 61 (P-28)Imaz N. 59 (P-26)Ioan S. 60 (P-27)Iversen T. 39 (P-06)Iwanczuk A. 103 (P-70)
108
Janeczek H. 50 (P-17), 56 (P-23), 91 (P-58)Janèiauskaite U. 79 (P-46)Jaworska J. 65 (P-32)Jin R. 25 (I-10)Jones M. D. 38 (P-05)Kacarevic-Popovic Z. 104 (P-71)Karas J. 74 (P-41)Kasperczyk J. 65 (P-32), 70 (P-37)Kavaliauskaite R. 41 (P-08)Kawalec M. 56 (P-23), 58 (P-25), 71 (P-38)Kazimierczak J. 89 (P-56)Keul H. 26 (I-11)Klee D. 37 (P-04)Klimaviciute R. 41 (P-08)Koller M. 28 (I-13), 78 (P-45), 80 (P-47)Konieczna-Molenda A. 94 (P-61)Kowalczuk M. M. 29 (I-14), 35 (P-02), 48 (P-15),
50 (P-17), 54 (P-21), 56 (P-23), 58 (P-25),68 (P-35), 88 (P-55), 91 (P-58), 93 (P-60)
Kowalczyk M. 87 (P-54)Kowalski W. J. 68 (P-35)Kozlowska A. 103 (P-70)Kozlowski M. 103 (P-70)Krasowska K. 93 (P-60)Kržan A. 92 (P-59)Kulbokaitë R. 77 (P-44)Kurcok P. 56 (P-23), 58 (P-25)Kutschera C. 28 (I-13), 78 (P-45), 80 (P-47)Langlois V. 64 (P-31)Lao H.-K. 64 (P-31)Lemeins J.-F. 22 (I-08)Lemstra P. J. 24 (I-09)Li S. 65 (P-32)Libiszowski J. 95 (P-62)Lindström M. 39 (P-06)Linossier I. 47 (P-14), 64 (P-31)Liu C.-I. 63 (P-30), 81 (P-48)López-Arraiza A. 59 (P-26)Lu W.-L. 81 (P-48)Macocinschi D. 49 (P-16)Makuška R. 77 (P-44), 79 (P-46)Malhotra B. D. 42 (P-09)Marcinkowska A. 76 (P-43)Meaurio E. 59 (P-26)Meyer J. 26 (I-11)Michalak M. 58 (P-25)Mikkonen K. S. 73 (P-40)Mikova G. 104 (P-71)Miksa B. 100 (P-67)Mishra A. P. 40 (P-07)Moczek Ł. 31 (I-16)Moeller M. 26 (I-11)
Molenda M. 94 (P-61)Molenda-Konieczny A. 32 (I-17)Moriana R. 82 (P-49), 83 (P-50), 84 (P-51)Murariu M. 17 (I-04), 102 (P-69)Musioł M. 48 (P-15), 68 (P-35)Narayan R. 14 (I-01)Nilsson H. 39 (P-06)Nowakowska M. 31 (I-16)Olsson A. 39 (P-06)Pandey A. 46 (P-13)Pelin I. M. 98 (P-65)Pennanec X. 64 (P-31)Peptu C. 54 (P-21), 58 (P-25)Piegat A. 34 (P-01)Pielka S. 74 (P-41), 75 (P-42), 76 (P-43)Piorkowska E. 18 (I-05), 87 (P-54)Pluta J. 75 (P-42), 76 (P-43)Pluta M. 17 (I-04), 18 (I-05), 101 (P-68),
102 (P-69)Poljanšek I. 92 (P-59)Popa M. I. 99 (P-66)Popescu I. 96 (P-63), 99 (P-66)Povolo S. 90 (P-57)Ren L. 105 (P-72)Renard E. 64 (P-31)Ribes-Greus A. 82 (P-49), 83 (P-50), 84 (P-51)Rondán C. E. 53 (P-20)Rutkowska M. 93 (P-60)Rychter P. 35 (P-02)Rydz J. 48 (P-15)Saha N. 51 (P-18)Saha P. 51 (P-18)Santonja-Blasco L. 82 (P-49), 83 (P-50),
84 (P-51)Sarasua J.-R. 59 (P-26)Scandola M. 56 (P-23), 69 (P-36), 70 (P-37),
71 (P-38)Sedlarik V. 51 (P-18)Signori F. 21 (I-07), 52 (P-19), 53 (P-20)Sikorska W. 48 (P-15), 68 (P-35)Simionescu B. C. 54 (P-21)Singh S. P. 42 (P-09)Slomkowski S. 36 (P-03), 100 (P-67)Sobota M. 48 (P-15), 50 (P-17), 91 (P-58)Socka M. 62 (P-29)Solski L. 75 (P-42)Sosnowski S. 36 (P-03)Spiridon I. 61 (P-28)Spychaj S. 43 (P-10)Spychaj T. 43 (P-10), 44 (P-11)Srebrenkoska V. 66 (P-33)Suflet D. M. 97 (P-64)Szadkowski M. 95 (P-62)
109
Szczubiałka K. 31 (I-16)Szymonowicz M. 74 (P-41), 75 (P-42), 76 (P-43)Šišková A. 68 (P-35)Taslica B. 107 (P-74)Taton D. 22 (I-08)Tenkanen M. 73 (P-40)Tiwari A. 40 (P-07), 42 (P-09)Tomasik P. 32 (I-17), 94 (P-61)Tomaszewski W. 95 (P-62)Toncelli C. 53 (P-20)Trandafir V. 97 (P-64), 98 (P-65)Vallee-Rehel K. 64 (P-31)Vallée-Réhel K. 47 (P-14)Vasile C. 45 (P-12), 57 (P-24)Vidovic E. 37 (P-04)Vlad S. 49 (P-16)Vuluga Z. 98 (P-65)Wawro D. 89 (P-56)Wei J. 65 (P-32)Wendorff J. H. 30 (I-15)Wietecha J. 89 (P-56)
Wilczek P. 71 (P-38)Willför S. 73 (P-40)Wilpiszewska K. 43 (P-10), 44 (P-11)Wimmer R. 106 (P-73)Wozniak P. 36 (P-03)Wu J.-Y. 85 (P-52), 86 (P-53)Wu X. 38 (P-05)Yadav M. P. 73 (P-40)Yang S.-Y. 85 (P-52), 86 (P-53)Zaczynska E. 74 (P-41)Zampano G. 21 (I-07)Zapotoczny S. 31 (I-16)Zemaitatitis A. 41 (P-08)Zhong Z. 25 (I-10)Zhou W. 25 (I-10)Zini E. 69 (P-36), 70 (P-37)Zuza E. 59 (P-26)Zywicka B. 74 (P-41), 75 (P-42), 76 (P-43)Žagar E. 92 (P-59)Žigon M. 92 (P-59)
110
LIST OF PARTICIPANTS
Adamus Grazyna, Dr.Polish Academy of Sciences, Centre of Polymer and CarbonMaterials34 M. Curie-Sklodowska St; 41-800 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077; Fax: +48-32-2712969Agarwal Seema, Dr.Philipps universitaet Marburg; Department of ChemistryHans-Meerwein Strasse; 35032 Marburg; GERMANYE-mail: [email protected]: +49-6421-2825755; Fax: +49-6421-2825785Albertsson Ann-Christine, Prof.KTH, Royal Institute of Technology; Department of PolymerTechnologyS-100 44 Stockholm; SWEDENE-mail: [email protected]: +46-8-7908274; Fax: +46-8-7908274Babic Dragan, Dr.Institute of Nuclear Sciences Vinca; Laboratory of RadiationChemistry and PhysicsMike Petrovica Alasa 12-14; 11001 Belgrade; SERBIAE-mail: [email protected]: +381-11-2453986; Fax: +381-11-3440100Blasinska Anna, Dr.Technical University of Lodz; Department of Fiber Physics andTextile MetrologyZeromskiego 116; 90-924 Lodz; POLANDE-mail: [email protected] Gerhard, Prof.Technische Universität Graz; Institut für BiotechnologiePetersgasse 12; 8010 Graz; AUSTRIAE-mail: [email protected]: +43-316-8738412; Fax: +43-316-8738412Brulc Blaž, Mr.National Institute of Chemistry; Laboratory of PolymerChemistry and TechnologyHajdrihova 19; 1000 Ljubljana; SLOVENIAE-mail: [email protected]: +386-1-4760207Cardamone Jeanette M, Dr.U.S. Department of Agriculture; Fats, Oils and AnimalCoproducts Research Unit600 E. Mermaid Lane; 19038 Wyndmoor; UNITED STATESE-mail: [email protected]: +215-2336680; Fax: +215-2336795Chen Su-Chen, Ms.Taiwan Textile Research Institute; Department of Raw Materialsand Yarn FormationNo.6, Chengtian Rd., Tucheng; 23674 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected]: +886-22670321 ext.223Chiellini Emo, Prof.Universita di Pisa; Dip. Chimica e Chimica IndustrialeVia Risorgimento 35; 56126 Pisa; ITALYE-mail: [email protected]: +39-50-2219299; Fax: +39-50-2219299Chitanu Gabrielle Charlotte, Dr.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299
Chodak Ivan, Prof.Polymer Institute, Slovak Academy of Sciences; ComositeThermoplasticsDubravska 9; 84236 Bratislava; SLOVAKIAE-mail: [email protected]: +421-2-54771603
Ciardelli Francesco, Prof.University of Pisa; Department of Chemistry and IndustrialChemistryvia Risorgimento, 35; 56126 Pisa; ITALYE-mail: [email protected]: +39-050-2219229; Fax: +39-050-2219229
Ciechanska Danuta, Dr.Institute of Biopolymers and Chemical Fibres with theIncorporated Pulp and Paper Research InstituteSklodowskiej-Curie 19/27; 90-570 Lodz; POLANDE-mail: [email protected]: +48-42-6376510; Fax: +48-42-6376501
Ciolacu Diana Elena, Dr.Petru Poni Institute of Macromolecular Chemistry; Chemistry -Physics of PolymersGrigore-ghica Voda Alley, 41A; 700487 Iasi; ROMANIAE-mail: [email protected]
Dacko Piotr, Dr.Centre of Polymer and Carbon MaterialsM. Curie-Skłodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]
Davidson Matthew G, Prof.University of Bath; Department of ChemistryClaverton Down; BA27AY Bath; UNITED KINGDOME-mail: [email protected]: +44-1225-386443
Dubois Philippe, Prof.Université de Mons-HainautPlace du Parc, 20; B-7000 Mons; BELGIUME-mail: [email protected]: +32-65-373480; Fax: +32-65-373480
Duda Andrzej, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer ChemistrySienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6819815; Fax: +48-42-6847126
Dumitriu Raluca Petronela, Ms.Romanian Academy, "Petru Poni" Institute of MacromolecularChemistry; Physical Chemistry of PolymersGr. Ghica Voda Alley, 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299
Duncianu Catalina Natalia, Ms.Institute of Macromolecular Chemistry Petru Poni; Departmentof Physical Chemistry of PolymersGr. Ghica Voda Alley 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299
Dworak Andrzej, Prof.Polish Academy of Sciences; Institute of Coal ChemistrySowinskiego 5; 44-121 Gliwice; POLANDE-mail: [email protected]: +48-32-2380780; Fax: +48-32-2380780
111
El Fray Miroslawa, Prof.Szczecin University of Technology; Polymer InstitutePulskiego 10; 70-322 Szczecin; POLANDE-mail: [email protected]: +48-91-4494828; Fax: +48-91-4494098
Fay Fabienne, Dr.Université Bretagne Sud; Laboratoire de Biotechnologie etchimie MarineCentre de Recherche BP92116; 56321 Lorient; FRANCEE-mail: [email protected]
Feijen Jan, Prof.University of Twente; Institute for BioMedical TechnologyP.O. Box 217;; 7500 AE Enschede; NETHERLANDSE-mail: [email protected]: +31-53-4893367; Fax: +31-53-4893367
Filip Daniela, Dr.Institute of Macromolecular Chemistry; Physical Chemistry ofPolymersAleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIAE-mail: [email protected]
Florjanczyk Zbigniew, Prof.Warsaw University of Technology; Department of PolymerChemistry and Technology, Faculty of ChemistryNoakowskiego 3; 00-664 Warsaw; POLANDE-mail: [email protected]: +48-22-2347303; Fax: +48-22-2347303
Forstner Reinhard, Dr.Upper Austrian Research G.m.b.HFranz-Fritsch-Strasse 11; 4600 Wels; AUSTRIAE-mail: [email protected]: +43-7242-20881022; Fax: +43-7242-20881020
Gadzinowski Mariusz, Dr.Center of Molecular and Macromolecular Studies PolishAcademy of Sciences; Department of Engineering of PolymerMaterialsSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803235
Galeski Andrzej, Prof.Centre of Molecular and Macromolecular Studies; olymerPhysics DepartmentSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803250; Fax: +48-42-6803261
Garnaik Baijayantimala, Dr.National Chemical Laboratory; Polymer Science andEngineering DivisionDr.Homi Bhabha Road; 411008 Pune; INDIAE-mail: [email protected]: +91-20-25902071 ext.2071; Fax: +91-20-25902615ext.2615
Gebarowska Katarzyna, Ms.Centre of Polymer and Carbon Materials Polish Academy ofSciencesSkłodowskiej-Curie 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-60983359
Gnanou Yves, Dr.Université Bordeaux I; Laboratoire de Chimie des PolymèresOrganiques (LCPO-CNRS)16, ave Pey-Berland; 33607 Pessac; FRANCEE-mail: [email protected], [email protected]: +33-5-40006987; Fax: +33-5-40006987
Gregorova Adriana, Dr.Universität für Bodenkultur Wien; Institut für HolzforschungPeter-Jordan-Straße 82; A-1190 Wien; AUSTRIAE-mail: [email protected]
Greiner Andreas, Prof.Universitat Marburg; Materials Science CenterHans-Meerwein-Strasse, Gebäude H; D-35032 Marburg;GERMANYE-mail: [email protected]: +49-6421-2825573; Fax: +49-6421-2825573
Gross Richard A., Prof.The Polytechnic University; Department of Chemical andBiological SciencesSix Metrotech Center; NY 11201 Brooklyn; UNITED STATESE-mail: [email protected]: +718-2603984; Fax: +718-2603984
Grozdanov Anita, Dr.Faculty of Technology and Metallurgy; Department of PolymerEngineeringRugjer Boskovic 16; 1000 Skopje; MACEDONIAE-mail: [email protected]: +389-2-3064588 ext.237; Fax: +389-2-3065389
Gulle Heinz, Dr.Baxer Aktiengesellschaft; R&D Biosurgery Fibrin PlatformIndustriestrasse 67; 1220 Vienna; AUSTRIAE-mail: [email protected]: +43-1-20100259Haan Robert, Mr.Purac Biochem bv; Process TechnologyArkelsedijk 46; 4206AC Gorinchem; NETHERLANDSE-mail: [email protected]: +31-183-695695; Fax: +31-183-695607
Ichim Maria, Dr.Institutul De Inginerie, Biotehnologie Si Protectia MediuluiProf. Ion Bogdan nr.10; 010539 Bucuresti; ROMANIAE-mail: [email protected]: +40-21-2113754; Fax: +40-21-2102659
Iversen Tommy, Dr.STFI-PackforskDrottning Kristinas väg 61; SE-11486 Stockholm; SWEDENE-mail: [email protected]: +46-8-6767000 ext.210; Fax: +46-8-4115518
Janciauskaite Ugne, Ms.Vilnius University; Polymer ChemistryNaugarduko 24; LT-03225 Vilnius; LITHUANIAE-mail: [email protected]: +370-5-2337811; Fax: +370-5-2330987
Jaworska Joanna, Ms.Polish Academy of Sciences; Centre of Polymer and CarbonMaterialsSklodowskiej-Curie 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2712214 ext.164Kawalec Michal, M.Sc.Centre of Polymer and Carbon Materials Polish Academy ofSciences34, Marii Skłodowskiej-Curie St.; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077 ext.121Klimaviciute Rima, Dr.Kaunas University of Technology; Organic TechnologyRadvilenu 19; LT-50524 Kaunas; LITHUANIAE-mail: [email protected]: +370-37-456081; Fax: +370-37-456081
112
Koller Martin, Dr.Graz University of Technology; Institute of Biotechnology andBiochemical EngineeringPetersgasse 12; 8010 Graz; AUSTRIAE-mail: [email protected]: +43-316-8738905
Konieczna-Molenda Anna, Dr.University of Agriculture; Department of ChemistryBalicka 122; 30-149 Cracow; POLANDE-mail: [email protected]
Kowalczuk Marek M., Prof.Centre of Polymer and Carbon Materials, Polish Academy ofSciencesM. Curie-Sklodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077; Fax: +48-32-2716077
Kowalczyk Marcin, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Polymer PhysicsSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803237
Kowalski Witold J., Prof.Jan Długosz University, Faculty of Mathematics and NaturalSciences; Institute of Chemistry and Enivironmental ProtectionArmii Krajowej 13/15; PL-42-200 Czestochowa; POLANDE-mail: [email protected]: +48-502-616458
Kozlowska Anna, Dr.Wroclaw University of TechnologyWybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3206216
Kozlowski Marek, Prof.Wroclaw University of Technology; Faculty of EnvironmentalEngineeringWybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3206538; Fax: +48-71-3282980
Krasowska Katarzyna, Dr.Gdynia Maritime University; Department of Chemistry andIndustrial Commodity ScienceMorska 81-87; 81-225 Gdynia; POLANDE-mail: [email protected]: +48-58-6901367; Fax: +48-58-6206701
Krucinska Izabella, Prof.Technical University of Lodz; Textile Engineering and MarketingZeromskiego 116; 90-924 Lodz; POLANDE-mail: [email protected], [email protected]: +48-42-6313300; Fax: +48-42-6313300
Krzan Andrej, Dr.National Institute of Chemistry; Laboratory for PolymerChemistry and Technology;Hajdrihova 19, POB 660; 1001 Ljubljana; SLOVENIAE-mail: [email protected]: +386-1-4760204; Fax: +386-1-4760204
Kurcok Piotr, Dr.Centre of Polymer and Carbon Materials, Polish AcademySciences34, Marii Sklodowskiej Curie St.; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077 ext.261; Fax: +48-32-2712969
Lao Hoi-Kuan, Dr.LBCM - Laboratoire de Biotechnologie et Chimie Marine;Universite de Bretagne SudRue Saint Maude; 56321 Lorient; FRANCEE-mail: [email protected]: +33-2-97874594Lee Chia, Ms.Tatung UniversityNo. 40, Cung-Shan N. RD., Sec. 3; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Piet J., Prof.Eindhoven University of Technology; Polymer TechnologyPO Box 513, Helix STO 0.37; 5600 MB Eindhoven;NETHERLANDSE-mail: [email protected]: +31-40-2473650; Fax: +31-40-2473650Liu Chia-I, Ms.Tatung University; Department of Materials Engineering40, Chung-Shan N. Rd.,3rd Sec.; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Wan-Ling, Dr.Taiwan Textile Research Institute; Raw Materials and YarnFormationNo.6 Chengtian Rd.; 23674 Tucheng; TAIWAN, PROVINCE OFCHINAE-mail: [email protected]: +886-2-22670321 ext.245Macocinschi Doina, Dr.Institute of Macromolecular Chemistry; Physical Chemistry ofPolymersAleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIAE-mail: [email protected] Ricardas, Prof.Vilnius University; Polymer ChemistryNaugarduko 24; LT-03225 Vilnius; LITHUANIAE-mail: [email protected]: +370-5-2337811; Fax: +370-5-2330987Meyer Sibylle, Ms.Wiley-VCH VerlagBoschstrasse 12; 69469 Weinheim; GERMANYE-mail: [email protected] Kirsi, M.Sc.University of Helsinki; Department of Applied Chemistry andMicrobiologyLatokartanonkaari 11; 00014 Helsinki; FINLANDE-mail: [email protected]: +358-9-19158417; Fax: +358-9-19158475Mishra Astbhuja Prasad, Dr.Ministry of Science and Technology; Department of Scienceand TechnologyTechnology Bhawan, New Maharauli Road; 110016 New Delhi;INDIAE-mail: [email protected]: +91-11-26590325Moeller Martin, Prof.DWI an der RWTH Aachen e. V.Pauwelsstrasse 8; 52074 Aachen; GERMANYE-mail: [email protected]: +49-241-8023300; Fax: +49-241-8023301Nadolny Andrzej J., Dr.Scientific Centre of the Pol. Acad. Sci. in ViennaBoerhaavegasse 25; 1030 Wien; AUSTRIAE-mail: [email protected]: +43-1-7135929 ext.303
113
Narayan Ramani, Prof.Michigan State University; Chemical Engineering Division2527 Engineering Building; MI 48824-122 East Lansing;UNITED STATESE-mail: [email protected]: +517-4320775; Fax: +517-4320775
Nilsson Helena, M.Sc.STFI-Packforsk; Packaging and LogisticsDrottning Kristinas väg 61; 11486 Stockholm; SWEDENE-mail: [email protected]: +46-8-6767253
Nowakowska Maria, Prof.Jagiellonian University; Department of Physical Chemistry andElectrochemistry, Faculty of ChemistryIngardena 3; 30-060 Krakow; POLANDE-mail: [email protected]: +48-12-6632050; Fax: +48-12-6632050
Pandey Asutosh Kumar, Mr.National Chemical Laboratory; Polymer ChemistryDr.Homi Bhabha Road; 411008 Pune; INDIAE-mail: [email protected]: +91-20-25902071 ext.2071
Pelin Irina Mihaela, Ms.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299
Penczek Stanislaw, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of SciencesSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6819815; Fax: +48-42-6819815
Peptu Cristian, M.Sc.Institute of Chemistry and Environmental Protection JanDlugosz Czestochowa13/15 Armii Krajowej Av.; 42-200 Czestochowa; POLANDE-mail: [email protected]
Piorkowska Ewa Malgorzata, Prof.Centre of Molecular and Macromolecular Studies; PolymerPhysics DepartmentSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803223; Fax: +48-42-6803261
Pluta Miroslaw, Dr.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer PhysicsSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803237; Fax: +48-42-6847126
Popescu Irina, Ms.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299
Povolo Silvana, Dr.Universita degli Studi di Padova; Biotechnologie AgrarieViale dell’Universita, 16; 35020 Legnaro; ITALYE-mail: [email protected]: +39-49-8272926; Fax: +39-49-8272929
Rapa Maria, Ms.Commercial Society Incerplast S.A.; Research DevelopmentZiduri Mosi 23; 021203 Bucuresti; ROMANIAE-mail: [email protected]: +40-21-2525250Raquez Jean-Marie, Dr.University of Mons-Hainaut/Materia Nova; Laboratory ofPolymeric Composites and MaterialsPlace du Parc 20; 7000 Mons; BELGIUME-mail: [email protected]: +32-65-373771Rokicki Gabriel, Prof.Warsaw University of Technology; Department of PolymerChemistry and Technology, Faculty of Chemistryul. Noakowskiego 3; 00-664 Warszawa; POLANDE-mail: [email protected]: +48-22-2347562; Fax: +48-22-2347562
Rutkowska Maria, Prof.Gdynia Maritime University; Department of ChemistryMorska 83; 81-225 Gdynia; POLANDE-mail: [email protected]: +48-58-6901585; Fax: +48-58-6206701
Rychter Piotr, M.Sc.Chemistry and Environmental Protection; Mathematics andEnvironmentArmii Krajowej Av., 13/15; 42-200 Czestochowa; POLANDE-mail: [email protected]: +48-34-3615154; Fax: +48-34-3665322
Sahli Stefan, Dr.Sika Technology AG; Corporate Research and AnalyticsTüffenwies 16; 8048 Zürich; SWITZERLANDE-mail: [email protected]: +41-44-4365827; Fax: +41-44-4365850
Santonja-Blasco Laura, Ms.Universidad Politecnica ValenciaCamino De Vera S/n; 46022 Valencia; SPAINE-mail: [email protected]: +34-96-3879817 ext.71806Sarasua Jose-Ramon, Prof.University of the Basque Country; Materials ScienceETS Ingenieria Bilbao, Alameda de Urquijo s/n; 48013 Bilbao;SPAINE-mail: [email protected]: +34-94601427; Fax: +34-94601418
Scandola Mariastella, Prof.University of Bologna; G. Ciamician Chemistry DepartmentVia Selmi 2; 40126 Bologna; ITALYE-mail: [email protected] Vladimir, Dr.Faculty of Technology, Tomas Bata University in Zlín; PolymerCentreT.G. Masaryka 275; 76272 Zlín; CZECH REPUBLICE-mail: [email protected]: +420-57603801; Fax: +420-57603144
Signori Francesca, Dr.University of Pisa; Dipartimento di Chimica e ChimicaIndustrialevia Risorgimento 35; I-56126 Pisa; ITALYE-mail: [email protected]: +390-50-2219212; Fax: +390-50-2219320
Sikorska Wanda, Dr.Centre of Polymer and Carbon MaterialsM.C.-Skłodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]
114
Slomkowski Stanislaw, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of SciencesSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6826537; Fax: +48-42-6826537Sobota Michal, M.Sc.Centre of Polymer and Carbon Materials, Polish Academy ofSciences34, Marii Sklodowskiej Curie St. Poland; 41-819 Zabrze;POLANDE-mail: [email protected]: +48-32-2716077 ext.121Socka Marta, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer ChemistrySienkiewicza, 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803219 ext.219Spiridon Iuliana, Dr.Petru Poni Institute of Macromolecular Chemistry; NaturalPolymersAleea Gr. Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299Spychaj Tadeusz, Prof.Szczecin University of Technology; Polymer InstitutePulaskiego 10; 70-322 Szczecin; POLANDE-mail: [email protected]: +48-91-4494684; Fax: +48-91-4494685Stanford John L., Prof.University of Manchester; School of MaterialsGrosvenor Street; m17hs Manchester; UNITED KINGDOME-mail: [email protected]: +44-161-2003573Stepto Robert F., Prof.University of Manchester and UMIST; Polymer Science andTechnology GroupGroswenor St.; M1 7HS Manchester; UNITED KINGDOME-mail: [email protected] Dana Mihaela, Dr.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299Szymonowicz Maria, Dr.Wrocław Medical University; Department of ExperimentalSurgery and Biomaterials ResearchPoniatowskiego 2; 50-326 Wroclaw; POLANDE-mail: [email protected]: +48-71-7840135Šišková Alena, M.Sc.Jan Dlugosz University, Faculty of Mathematiscs and NaturalSciences; Institute of Chemistry and Environmental ProtectionArmii Krajowej 13/15; PL-42-200 Czestochowa; POLANDE-mail: [email protected] Banu, M.Sc.Bogazici University; Department of ChemistryBebek; 34342 Istanbul; TURKEYE-mail: [email protected]: +90-212-3587572; Fax: +90-212-2872467Tiwari Ashutosh, Dr.National Physical Laboratory; Division of Engineering MaterialsDr. K. S. Krishnan Road; 110012 New Delhi; INDIAE-mail: [email protected]: +91-11-32507819
Tomasik Piotr, Prof.Agricultural University in Krakow; Department of ChemistryBalicka 122; 30-149 Krakow; POLANDE-mail: [email protected]: +48-12-6624335; Fax: +48-12-6624335Vairon Jean-Pierre, Prof.Université Pierre et Marie Curie; UMR 7610 - Chimie DesPolymeresCase 185, 4 Place Jussieu; F-75252 Paris Cédex 05; FRANCEE-mail: [email protected]: +33-1-44275502; Fax: +33-1-44275502Vidovic Elvira, Dr.University of Zagreb; Faculty of Chemical EngineeringMarulicev trg, 19; 10000 Zagreb; CROATIAE-mail: [email protected]: +385-1-4597128; Fax: +385-1-4597142Weber Hedda, Dr.Competence Centre Wood; Wood and Pulp ChemistryWerkstrasse 2; 4860 Lenzing; AUSTRIAE-mail: [email protected]: +43-7672-7013181; Fax: +43-7672-9183181Woldum Henriette Sie, M.Sc.Chew Tech I/SDandyvej 19; DK-7100 Vejle; DENMARKE-mail: [email protected] Pawel, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Science; Department of Engineering of PolymerMaterialsSienkiewicza, 112; 90-363 Lodz; POLANDE-mail: [email protected] Xujun, Mr.University of Bath; Center for Regenerative Medicine,Department of Chemical Engineering& Department ofChemistryClaverton Down; BA27AY Bath; UNITED KINGDOME-mail: [email protected] Jing-Yi, Ms.Tatung University; Department of Materials EngineeringChung-Shan N. Rd., 3rd Sec.; 10452 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected]: +886-2-25925252; Fax: +886-2-25866050Yang Sung-Yeng, Mr.Tatung University40, Chung-Shan N. Rd., 3rd Sec.; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Boris, Mr.Postnova Analytics GmbHMax-Planck-Str. 14; 86899 Landsberg am Lech; GERMANYE-mail: [email protected]: +49-8191-428181; Fax: +49-8191-428175
Zuchowska Danuta, Prof.Wroclaw University of Technology; Faculty of ChemistryWybrzeze S. Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3203633; Fax: +48-71-3203633
Zywicka Bogusława, Dr.Wroclaw Medical University; Department of ExperimentalSurgery and Biomaterials ResearchPoniatowskiego 2; 53-326 Wrocław; POLANDE-mail: [email protected]: +48-71-7840136
115