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Polymer Chemistry RSCPublishing
Supporting Information
New Biomaterials from Renewable Resources - Amphiphilic Block Copolymers from δ-Decalactone
Kuldeep K. Bansal,a Deepak Kakde,a Laura Purdie,a Derek Irvine,b Steven M. Howdle,c Giuseppe Mantovania and Cameron Alexandera*
TABLE OF CONTENT:-
List of Figures
Figure S1 1H NMR of commercially available δ-decalactone acquired in CDCl3.. ...................................................................... 1
Figure S2 1H NMR spectra of propargyl-PDL and BZD-PDL in CDCl3. ..................................................................................... 2
Figure S3 1H NMR spectra of propargyl PDL before and after purification of polymer. ............................................................. 3
Figure S4 DSC plot of Propargyl PDL.. ........................................................................................................................................ 3
Figure S5 13C NMR of BZD-PDL and propargyl-PDL in CDCl3. ................................................................................................ 4
Figure S6 SEC traces of (A) BZD-PDL and (B) propargyl-PDL .................................................................................................. 5
Figure S7 Conversion of monomer with time for ROP of δ-decalactone using mPEG as initiator and TBD (5 mol %) as the
catalyst.. .......................................................................................................................................................................................... 6
Figure S8 1H NMR spectrum and SEC trace of mPEG-b-PDL (during kinetic study) after 9 h containing 5% of TBD as the
catalyst.. .......................................................................................................................................................................................... 6
Figure S9 Overlaid FTIR spectra of mPEG, δ-decalactone monomer and mPEG-b-PDL copolymer. ......................................... 7
Figure S10 1H NMR of mPEG-b-PDL and PDL-b-PEG-b-PDL copolymer in CDCl3 ................................................................. 8
Figure S11 13C NMR of mPEG-b-PDL and PDL-b-PEG-b-PDL copolymer in CDCl3. ............................................................... 9
Figure S12 SEC traces of PEG macroinitiator and different block copolymers of decalactone in chloroform ........................... 10
Figure S13 DSC plots of (A) mPEG-b-PDL and (B) PDL-b-PEG-b-PDL, obtained from second heating/cooling cycle .......... 11
Figure S14 1H NMR and 13C NMR spectra of mPEG-b-PDL-b-PPDL in CDCl3 ....................................................................... 12
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2015
Polymer Chemistry ARTICLE
Figure S15 DSC plots of mPEG-b-PDL-b-PPDL from second heating/cooling cycle ................................................................ 13
Figure S16 SEC trace of mPEG-b-PCL obtained using chloroform as the mobile phase. .......................................................... 13
Figure S17 1H NMR and 13C NMR of mPEG-b-PCL in CDCl3 .................................................................................................. 14
Figure S18 CMC plot for (A) mPEG-b-PDL, (B) PDL-b-PEG-b-PDL, (C) mPEG-b-PDL-b-PPDL and (D) mPEG-b-PCL
obtained by the pyrene 1:3 peak ratio method in water ................................................................................................................ 15
Figure S19 Size and Zeta potential of propargyl-PDL nano emulsion.. ...................................................................................... 16
Figure S20 Zeta potential values for (A) mPEG-b-PDL, (B) PDL-b-PEG-b-PDL, (C) mPEG-b-PCL and (D) mPEG-b-PDL-b-
PPDL micelles acquired in HEPES 10 mM buffer (pH – 7.4). .................................................................................................... 16
Figure S21 UV-Visible absorbance spectra of Nile red (NR) in acetone and micelles.. ............................................................. 17
Figure S22 Size distribution curve by intensity of (A) mPEG-b-PDL, (B) PDL-b-PEG-b-PDL and (C) mPEG-b-PDL-b-PPDL
acquired by DLS in water. (D) Appearance of micellar solutions and control (formulation without polymer) after Nile red
loading. ......................................................................................................................................................................................... 17
Figure S23 Physical appearance of micellar suspensions (obtained via nanoprecipitation method) in water (A) before and (B)
after filtration through 0.22 µm syringe filter. ............................................................................................................................. 18
Figure S24 Size distribution curves by intensity of (A) Blank mPEG-b-PCL, (B) AmpB loaded mPEG-b-PCL, and TEM
image of (C) Blank mPEG-b-PCL and (D) AmpB loaded mPEG-b-PCL micelles. The images were taken without staining.. .. 18
Figure S25 SEC trace of mPEG-b-PDL after 120 days of storage at pH 7.4 (temperature – 37°C). ........................................... 19
List of Tables
Table S1 Data obtained from the kinetics analysis of mPEG-b-PDL synthesis.. .......................................................................... 7
Polymer Chemistry ARTICLE
Page | 1
Figure S1 1H NMR of commercially available δ-decalactone acquired in CDCl3. Inset showing enlarged region of spectrum between 3.3 and 5.0 ppm.
e
e
b
b
c
d f
g
h
i
j
c
d
j g,h,i
f,g
d
b
k l
k l
e
l k
4.9 4.7 4.5 4.3 4.1 3.9 3.7 3.5 3.3
a
Polymer Chemistry ARTICLE
Page | 2
Figure S2 1H NMR spectra of propargyl-PDL and BZD-PDL in CDCl3. Inset showing enlarged area of 1HNMR to aid visualisation of diagnostic proton peaks. Lettering adjacent to positions on the chemical structures refer to protons labelled on the NMR spectra
a, a’
d’, l j
d
f, f’, g, g’, h’, h’
b, b’, c, c’, e’, e’
i, i’
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a a’ d’
e’
i’
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l c’
b’
d
j b
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4.7 4.5 4.3 4.1 3.9 3.7 3.3 2.9 2.7 3.5 3.1 2.5
q, r, s
p, t o
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l k, m d’, j
i’
f’ e’
b’ c’
g’ h’
a’ j d’
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m’
l d
o q
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o
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l k, m d’, j
7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2
a, a’
f, f’, g, g’, h’, h’
b, b’, c, c’, e’, e’
i, i’
p, t
q, r, s
Po
Figrea
Fig
lymer Chemis
gure S3 1H Naction mixture
gure S4. DSC
stry
NMR spectraes in cold me
C plot of Prop
-0.4
-0.2
0.0
0.2
0.4
Heat F
low
(W
/g)
-100
Exo Up
a of propargyethanol.
pargyl PDL. T
-54.20
-56.00°C
-51.91°C
-50
yl PDL befor
The presented
°C(I)
C
0
re and after
d trace was a
50
Temperatur
purification o
acquired from
100
re (°C)
of polymer b
m the second
150
by precipitatio
heating/coo
0 20
Universal V3.9A
ARTI
Page
on of quench
ling cycle.
00
TA
ICLE
| 3
hed
Polymer Chemistry ARTICLE
Page | 4
Figure S5. 13C NMR of BZD-PDL and propargyl-PDL in CDCl3.
172.98
73.62
13.94
20.77
31.60 24.89
34.14
33.43
22.48
33.91
69.04
125.97
173.04
73.69
13.98
20.79
31.64
24.93
34.19
33.46
22.52
33.94
52.30
77.23
75.86
Po
Figpha
lymer Chemis
gure S6. SECase. Average
stry
C traces of (Ae molecular w
A) BZD-PDL weights were
and (B) procalculated a
pargyl-PDL, against polyst
which were tyrene as the
acquired usin molar mass
ng chloroformstandard.
ARTI
Page
m as the mo
ICLE
| 5
bile
Po
Figthe
Figthesta
lymer Chemis
gure S7. Cone catalyst.
gure S8. 1H Ne catalyst. Sandard. For 1H
stry
nversion of m
NMR spectruSEC traces wH NMR analy
%C
i
onomer with
m and SEC twere obtaineysis the samp
0
10
20
30
40
50
60
70
80
0
% C
on
vers
ion
time for ROP
trace of mPEed using chlple was disso
100 2
P of δ-decala
EG-b-PDL (duoroform as olved in CDC
200 300
Time (m
actone using
uring kinetic the mobile
Cl3.
400
min)
mPEG as ini
study) after 9phase and p
500 60
itiator and TB
9 h containinpolystyrene
00
ARTI
Page
BD (5 mol %)
g 5% of TBDas molar m
ICLE
| 6
) as
D as ass
Polymer Chemistry ARTICLE
Page | 7
Table S1. Data obtained from the kinetics analysis of mPEG-b-PDL synthesis. As shown in figure S8, peaks 1 and 2 correspond to copolymer and homopolymer respectively. (PD-Polydispersity Index)
Time Conversion by NMR (%)
Mn,SEC Peak 1 (kDa)
PD Peak1
Mn,SEC Peak 2 (kDa)
PD Peak 2
15 min 15 12.6 1.02 1.2 1.36
30 min 21 13.7 1.02 1.7 1.37
1 h 35 15.2 1.02 2.8 1.23
1.5 h 45 15.8 1.02 3.3 1.21
2 h 52 16.4 1.02 3.9 1.16
3 h 62 17.2 1.02 4.5 1.14
4 h 69 17.3 1.02 4.6 1.13
5.5 h 70 17.6 1.02 4.7 1.13
9 h 70 17.6 1.02 4.7 1.12
Figure S9 Overlaid FTIR spectra of mPEG, δ-decalactone monomer and mPEG-b-PDL copolymer.
0
20
40
60
80
100
120
648114816482148264831483648
Tra
nsm
ittan
ce
Wavenumber cm-1
mPEG decalactone mPEG-b-PDL
Polymer Chemistry ARTICLE
Page | 8
Figure S10. 1H NMR of mPEG-b-PDL and PDL-b-PEG-b-PDL copolymer in CDCl3
h
d
p
o
l k
j
a
b
c
e f
g i
d
p
k, l, o
j
a
f, g, h
b, c, e
i
d
p
k, l, o
f, g, h
b, c, e
i
a
a
h
d b
c
e f
g i
p
o l
k
Polymer Chemistry ARTICLE
Page | 9
Figure S11. 13C NMR of mPEG-b-PDL and PDL-b-PEG-b-PDL copolymer in CDCl3.
a b
c
d e f
g
h
i k
j
a c
c
c
f
f
d e
h
i
j
g
b f
k
a b
c
f
g
h
i
j
k
d
d
a
k
Polymer Chemistry ARTICLE
Page | 10
Figure S12. SEC traces of PEG macroinitiators and different block copolymers of decalactone, which were obtained using chloroform as the mobile phase. Polystyrene standards were used to calibrate the SEC.
11 12 13 14 15 16 17
Retention Time (Min.)
PEG4K mPEG5K PDL-b-PEG-b-PDL mPEG-b-PDL mPEG-b-PDL-b-PPDL
Polymer Chemistry ARTICLE
Page | 11
Figure S13. DSC plots of (A) mPEG-b-PDL and (B) PDL-b-PEG-b-PDL, obtained from second heating/cooling cycle.
-54.65°C(I)
-56.78°C
-52.69°C
54.60°C
50.97°C70.28J/g
-4
-2
0
2
4
He
at F
low
(W
/g)
-100 -50 0 50 100 150 200
Temperature (°C)Exo Up Universal V3.9A TA In
50.91°C 70.28 J/g
-56.78°C -54.65°C (I)
-52.69°C
54.60°C
-100 -50 0 50 100 150 200
A
-53.36°C(I)
-55.50°C
-51.17°C
47.02°C
43.45°C61.67J/g
-4
-2
0
2
4
Hea
t F
low
(W
/g)
-100 -50 0 50 100 150 200
Temperature (°C)Exo Up Universal V3.9A TA
43.45°C 61.67J/g
-55.50°C -53.36°C (I)
-51.17°C
47.02°C
-100 -50 0 50 100 150 200
B
-55.50°C -53.36°C (I)
-51.17°C
43.45°C 61.67 J/g
47.02°C
Po
Fig
lymer Chemis
gure S14. 1H
kj
stry
NMR and 13C
p o l
k
C NMR spect
h
da
b
c
f
g i
tra of mPEG-
d
d
e
q
r s
-b-PDL-b-PP
p
u
k, l, o
t u
PDL in CDCl3
j
.
a, q
f, g, h, s, t
b, c, e, r
ARTI
Page |
i
ICLE
12
Po
Fig
Figuse
lymer Chemis
gure S15 DSC
gure S16. SEed to calibrat
stry
C plots of mP
EC trace of mte the SEC.
-4
-2
0
2
4
Hea
t Flo
w (
W/g
)
-100
Exo Up
-100
PEG-b-PDL-b
mPEG-b-PCL
-52.76
-55.32°
-51.81°C
-50
-55.32°C-52.76°C
-51.81°C
-50
1
b-PPDL from
L obtained us
6°C(I)
°C
0
C C (I)
0
second heat
sing chlorofor
54.75°C
51.58°C51.49J/g
50
Temperature
51.58°C 51.49J/g
54.75°C
50
ting/cooling c
rm as the mo
C
88.06°C83.505.489
100
(°C)
C
100
83.5.488.06°C
cycle.
obile phase.
0°C9J/g
150150
50°C 489J/g
Polystyrene
200
Universal V3.9A TA
200
ARTI
Page |
standards w
ICLE
13
were
Polymer Chemistry ARTICLE
Page | 14
Figure S17. 1H NMR and 13C NMR of mPEG-b-PCL in CDCl3.
e
j b, c, d
a
f g, i
h
e
j
b
a f
g
h
i
c d
a
b
c
d
e f g
h
a
b
c
d
e
f
g
h b
b
Polymer Chemistry ARTICLE
Page | 15
Figure S18. CMC plot for (A) mPEG-b-PDL, (B) PDL-b-PEG-b-PDL, (C) mPEG-b-PDL-b-PPDL and (D) mPEG-b-PCL obtained by the pyrene 1:3 peak ratio method in water.
Inte
nsi
ty R
atio
(3
73/3
84) A B
Polymer Concentration µg/mL(Log10 Scale)
Polymer Concentration µg/mL(Log10 Scale)
Inte
nsi
ty R
ati
o (
373/
384
)
C D
Po
Figwh
FigmP
lymer Chemis
gure S19. Sizhereas zeta p
gure S20. ZePEG-b-PDL-b
stry
ze and Zeta potential was
eta potential b-PPDL mice
potentials omeasured in
measuremeelles acquired
of propargyl-P 10 mM HEP
nts of (A) md in HEPES 1
PDL nano emPES buffer.
mPEG-b-PDL10 mM buffer
mulsion. Size
, (B) PDL-b-r (pH 7.4).
e was determ
-PEG-b-PDL,
mined in HP
, (C) mPEG
ARTI
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LC grade wa
-b-PCL and
ICLE
16
ater
(D)
Po
Figen
FigPPNil
lymer Chemis
gure S21. UVcapsulated N
gure S22. SizPDL acquirede red loading
stry
V-Visible absNR in mPEG-
ze distributiod by DLS in wg.
4500.0
0.5
1.0
Ab
so
rba
nc
e (
no
rmal
ised
)
sorbance sp-b-PDL micel
n curve by inwater. (D) Ap
50
W
NR in a
ectra of Nileles dispersed
ntensity of (Appearance of
00
Wavelength
acetone
e red (NR) id in water.
A) mPEG-b-Pf micellar sol
550
(nm)
NR in m
n acetone a
PDL, (B) PDLutions and co
600
micelles
nd micelles.
L-b-PEG-b-PDontrol (formu
Micelle sam
DL and (C) mulation withou
ARTI
Page |
mples contain
mPEG-b-PDLut polymer) a
ICLE
17
ned
L-b-after
Po
Figand
Figimasta
lymer Chemis
gure S23. Phd (B) after filt
gure S24. Sizage of (C) B
aining. Scale
stry
hysical appeatration throug
ze distributionBlank mPEG-
bar – 500 nm
arance of micgh 0.22 µm sy
n curves by i-b-PCL and (m.
cellar suspenyringe filter.
ntensity of (A(D) AmpB lo
nsion (obtain
A) Blank mPEaded mPEG
ed via nanop
EG-b-PCL, (B-b-PCL mice
precipitation
B) AmpB loadelles. The ima
method) in w
ded mPEG-bages were re
ARTI
Page |
water (A) bef
b-PCL, and Tecorded with
ICLE
18
fore
TEM hout
Po
Figwa
lymer Chemis
gure S25. SEas calibrated
stry
EC trace of musing polysty
PEG-b-PDL yrene standa
after 120 dayrds and chlor
ys of storageroform was u
e at pH 7.4 (teused as the m
emperature –mobile phase.
– 37°C). The .
ARTI
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SEC instrum
ICLE
19
ment