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ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ. Профессор Н.Г. Рамбиди. 11. Нанохимия. Молекулярный дизайн. - PowerPoint PPT Presentation
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ФИЗИКО-ХИМИЧЕСКИЕФИЗИКО-ХИМИЧЕСКИЕОСНОВЫОСНОВЫ
НАНОТЕХНОЛОГИИНАНОТЕХНОЛОГИИ
Профессор Н.Г. Профессор Н.Г. РамбидиРамбиди
11. Нанохимия11. Нанохимия
Молекулярный дизайнМолекулярный дизайн
Были подробно рассмотрены:Были подробно рассмотрены:-молекулярные аспекты -молекулярные аспекты синтеза природного каучука,синтеза природного каучука,-принципы конструирования -принципы конструирования молекулы хироптицена – молекулы хироптицена – переключающегося переключающегося молекулярного элемента,молекулярного элемента,-молекулярная память на -молекулярная память на основе молекул ротаксанов.основе молекул ротаксанов.
Краун эфирыКраун эфиры
Negative charge concentrated in the cavity of the Negative charge concentrated in the cavity of the moleculemolecule
Forms stable lewis acid / lewis base with complexForms stable lewis acid / lewis base with complex
O
O
O
O
O
O
Cs+
Formation of CalixarenesFormation of Calixarenes
Phenol is reacted Formaldehyde and NaOH then Phenol is reacted Formaldehyde and NaOH then heatedheated
OHHO
HOOH
CH2
O
+
HO
Calixarene ConfigurationCalixarene Configuration
Molecular bindingMolecular binding The facing pairs of aromatic rings of The facing pairs of aromatic rings of
the calixarene in this conformation the calixarene in this conformation form two cavities that are each pre-form two cavities that are each pre-organized for partial organized for partial insertion of a insertion of a Cs+ ion. Cs+ ion.
Crystal structures of model Crystal structures of model complexes with cesium salts havecomplexes with cesium salts have demonstrated a significant dual pi-demonstrated a significant dual pi-interaction between the facing interaction between the facing aromatic rings and the guest Cs+ ion.aromatic rings and the guest Cs+ ion.
Cs+
OH
OH
HO
HO
Cs+
ФуллереныФуллерены
ФуллереныФуллерены
ФуллереныФуллерены
Nontraditional Fullerenes enclosing metal atom clusters.
- Three fused pentagons in the C68 cage: Violation of the Isolated Pentagon Rule (IPR).- Strong gain of stability upon incorporation of NSc3 in the C68 cage
Sc3N@C68
Use of Fullerenes enclosing metal atom clusters as Novel Magnetic Resonance Imaging contrast agents ?
Fullerenes with incorporated Helium Clusters
He2@C60 ( D2d)
He@He20@C60 (Ih)
- NMR studies on noble gas atoms enclosed in fullerene shells ( M. S. Syamala et al., JACS 124, 6216, 2002 ).- Hen encapsulated fullerenes of extraterestial detected in geological sediments ( L. Becker et al., Science 291 1530 2001 ).
Hen configurations in fullerene cages?
ССложные ложные молекулярные системымолекулярные системы
Organic, polymer/biopolymer
synthesis
O O
O
OO
O OO O OO OO
O
S
O
S
O
S
O
S
O
S
O
S
O
S
O
S
PO
O
O O
O
OO
O OO O OO OO
O
S
O
S
O
S
O
S
O
S
O
S
O
S
O
S
PO
O
Building blocks with natural and synthetic components for site directed self assembly into functional nanostructure
Organic synthesis: from single molecules to molecular assemblies, building block libraries, self-assembling components, liquid crystals, electroactive materials, photonic materials, chromophores, sensor elements… Combinatorial synthesis: libraries of ligands or catalysts, lead discovery and exploitation. Polymer synthesis: polymers with controlled sequence and/or architecture, dendrimers, porous and reactive media, surface coatings. Hybrid materials: organic-inorganic, biological-artificial.
Light harvesting: natural and synthetic ring antennae
Rings of chlorophylls and carotenoids funnel harvested energy to reaction center (RC). Subsequent energy transfer steps
lead to the production of ATP.
Self-assembly of a receptor from H-bonded molecular building blocks
Reinhoudt et al.
Guest =
Электроактивные материалыЭлектроактивные материалы
Электроактивные материалы
Governing Equation of Dielectric Elastomers
p=0E2
• Where: – p is effective compressive stress– is relative dielectric constant
– 0 is permittivity of free space (a constant)
– E is strength of electric field between diodes
Искусственная рука
Протезы сердца
Микро-насос
Applications: Heel-Strike Generator
• DoD is using dielectric elastomers to develop a heel-strike generator to go in soldiers boots that would generate electricity just from walking
• A dielectric elastomer generator works like an actuator in reverse (mechanical-to-electrical instead of electrical-to-mechanical energy)
Responsive materialsResponsive materials
Основные пути формирования Основные пути формирования сложных молекулярных системсложных молекулярных систем
СамоорганизующиесяСамоорганизующиесяамфифильныеамфифильные
системысистемы
Surfactant Molecules: Oil-Water Building Blocks
Monolayer formationMicelles - nano-reactors, drug delivery vehicles, and cleaning agents
Oil-Water Interface
Oil
Water
Surfactant
Polar head group
Non polar tail
CH2
CH2
CH2
CH2
CH2
CH3
OSO3-
Micelles in the Bulk Solution
Formation of stable aggregates at the cmc.
low concentration high concentration
Micelles
“Polar” water-like surface
“Apolar” oil-like interior
10-100 nm
Normal in water Reversed in oil SolubilizationNanoreactorsOil RecoveryDrug Delivery
Monolayer formationSurfactants can also adsorb at the air-water interface
Adsorption at the air-water interface
Amphiphiles
phosphatidyl choline lyso- phosphatidyl choline
dodecylsulphate
Polar
Non-polar
Critical micelle conc
Micelles/Monolayers/Bilayers
polar
non-polar
polarnon-polar
polar
non-polar
Lamellar phase Amphiphiles
PC - forms lamellar phases = bilayers of biology
Get x-ray/nmr data
Lipid bilayersLipid bilayers
Hexagonal phase Amphiphiles
PE -forms hexagonal phase = fusion regions of biology
Пленки Ленгмюра-Пленки Ленгмюра-БлоджетБлоджет
Langmuir Films
Spread on water. Not equilibrium adsorption. Film can be compressed
Water subphase
Air
Langmuir film
On Water
0
10
20
30
40
50
200 220 240 260 280 300
0
10
20
30
40
50
0 100 200 300 400 500 600
S-Azo-C18 Isotherm
Stearic Acid Isotherm
Area (cm2 )
Su
rfac
e P
ress
ure
(m
N/c
m2 )
Area (cm2 )
Su
rfac
e P
ress
ure
(m
N/c
m2 )
Water
Gas
Gas
Water
Liquid
Liquid
Water
Solid
Solid
Langmuir-Schaeffer Films
Water subphaseWater subphase
Solid substrate
Langmuir-Blodgett DepositionHydrophobic Surface (OTS)
Water
Hydrophilicsurface
Hydrophobic Surface
Multilayer
~ 10 nm
Head to headTail to tail
Head to tailTail to head
XY Z
The InstrumentThe Instrument
Хемосорбированные слоиХемосорбированные слои
ChemisorptionChemical reaction between the building block and the solid substrate
X
X
X
X
X
X
X
X X X X X X X X XReactive site
Spontaneousirreversible Functionalized surface
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
X X X X X X X X X X X XX X X X X X X X X X X X
3D-Representation
OTS on Glass
Si
ClClCl
Si
ClClCl
Si
ClClCl
Si
ClClCl
OTS– octadecyltrichlorosilane
OHOH OHOH
OTS on Glass
Si
ClClCl
Si
ClClCl
Si
ClClCl
Si
ClClCl
OHOH OHOH
OTS coated substrate surface
Membrane Structure
Types of membrane proteins
Membrane Protein Structure
Формирование Формирование заданной заданной
последовательности последовательности аминокислот в аминокислот в
молекуле белка.молекуле белка.Синтез МеррифилдаСинтез Меррифилда
Solid phase peptide Solid phase peptide synthesis (SPPS)synthesis (SPPS)
The Nobel Prize in Chemistry 1984The Nobel Prize in Chemistry 1984 --for his development of methodology for --for his development of methodology for
chemical synthesis on a solid matrix chemical synthesis on a solid matrix
Robert Bruce MerrifieldRockefeller University
Традиционный химический синтез
Синтез Меррифилда
Easier!!
Prepare fully protected peptide!
ABI 433A Peptide Synthesizer
Синтез Меррифилда
Coupling efficiency and final Coupling efficiency and final yieldyield
Yield (%)
efficiency (%)
10-mer 20-mer 30-mer 40-mer 50-mer 60-mer
99 90 82 74 67 61 55
98 82 67 55 45 36 30
95 60 36 21 13 8 5
80 11 1 0 0 0 0