ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ

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