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ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ. Профессор Н.Г. Рамбиди. 11. Нанохимия. Молекулярный дизайн.

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slide1

ФИЗИКО-ХИМИЧЕСКИЕОСНОВЫНАНОТЕХНОЛОГИИФИЗИКО-ХИМИЧЕСКИЕОСНОВЫНАНОТЕХНОЛОГИИ

Профессор Н.Г. Рамбиди

slide4

Были подробно рассмотрены:-молекулярные аспекты синтеза природного каучука,-принципы конструирования молекулы хироптицена – переключающегося молекулярного элемента,-молекулярная память на основе молекул ротаксанов.

slide5
Краун эфиры

Cs+

  • Negative charge concentrated in the cavity of the molecule
  • Forms stable lewis acid / lewis base with complex
formation of calixarenes
Formation of Calixarenes
  • Phenol is reacted Formaldehyde and NaOH then heated
molecular binding
Molecular binding

Cs+

  • The facing pairs of aromatic rings of the calixarene in this conformation form two cavities that are each pre-organized for partial insertion of a Cs+ ion.
  • Crystal structures of model complexes with cesium salts have demonstrated a significant dual pi-interaction between the facing aromatic rings and the guest Cs+ ion.

Cs+

slide12

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

[email protected]

Use of Fullerenes enclosing metal atom clusters as

Novel Magnetic Resonance Imaging contrast agents ?

slide13

Fullerenes with incorporated Helium Clusters

  • 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?

[email protected] (D2d)

[email protected]@C60 (Ih)

slide15

Organic, polymer/biopolymer synthesis

Building blocks with natural and synthetic components for site directed self assembly into functional nanostructure

slide16

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.

slide17

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.

slide18

Guest =

Self-assembly of a receptor from H-bonded molecular building blocks

Reinhoudt et al.

governing equation of dielectric elastomers
Governing Equation of Dielectric Elastomers

p=e*e0*E2

  • Where:
    • p is effective compressive stress
    • e is relative dielectric constant
    • e0 is permittivity of free space (a constant)
    • E is strength of electric field between diodes
applications heel strike generator
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)
slide36
Основные пути формирования сложных молекулярных систем
slide37
СамоорганизующиесяамфифильныесистемыСамоорганизующиесяамфифильныесистемы
surfactant molecules oil water building blocks

CH2

CH2

CH2

CH2

CH2

CH3

OSO3-

Surfactant Molecules: Oil-Water Building Blocks

Surfactant

Oil

Non polar tail

Oil-Water Interface

Water

Polar head group

Monolayer formation

Micelles - nano-reactors, drug delivery vehicles, and cleaning agents

micelles in the bulk solution
Micelles in the Bulk Solution

Formation of stable aggregates at the cmc.

low concentration

high concentration

micelles
Micelles

“Polar” water-like surface

10-100 nm

“Apolar” oil-like interior

Normal in water

Reversed in oil

Solubilization

Nanoreactors

Oil Recovery

Drug Delivery

monolayer formation
Monolayer formation

Surfactants can also adsorb at the air-water interface

Adsorption at the air-water interface

amphiphiles
Amphiphiles

Polar

Non-polar

dodecylsulphate

phosphatidyl choline lyso- phosphatidyl choline

micelles monolayers bilayers
Micelles/Monolayers/Bilayers

polar

polar

non-polar

non-polar

non-polar

polar

lamellar phase amphiphiles
Lamellar phase Amphiphiles

Get x-ray/nmr data

PC - forms lamellar phases = bilayers of biology

slide47

Hexagonal phase Amphiphiles

PE -forms hexagonal phase = fusion regions of biology

langmuir films
Langmuir Films

Spread on water. Not equilibrium adsorption. Film can be compressed

Air

Water subphase

Langmuir film

on water
On Water

Stearic Acid Isotherm

Solid

Liquid

Surface Pressure (mN/cm2)

Gas

Water

Area (cm2 )

S-Azo-C18 Isotherm

Water

Solid

Surface Pressure (mN/cm2)

Liquid

Gas

Water

Area (cm2 )

langmuir schaeffer films
Langmuir-Schaeffer Films

Solid substrate

Water subphase

Water subphase

langmuir blodgett deposition
Langmuir-Blodgett Deposition

Hydrophobic

Surface (OTS)

Hydrophobic

Surface

Water

Hydrophilic

surface

multilayer
Multilayer

~ 10 nm

X

Z

Y

Head to head

Tail to tail

Head to tail

Tail to head

chemisorption

X

X

X

X

X

X

X

X

X

Chemisorption

Chemical reaction between the building block and the solid substrate

X

Spontaneous

irreversible

X

Functionalized surface

X

X

X

X

X

Reactive

site

3d representation

X

X

X

X

X

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X

3D-Representation
ots on glass
OTS on Glass

OTS– octadecyltrichlorosilane

ots on glass1
OTS on Glass

OTS coated substrate surface

slide64
Формирование заданной последовательности аминокислот в молекуле белка.Синтез Меррифилда
solid phase peptide synthesis spps
Solid phase peptide synthesis (SPPS)

The Nobel Prize in Chemistry 1984

--for his development of methodology for chemical synthesis on a solid matrix

Robert Bruce Merrifield

Rockefeller University

coupling efficiency and final yield

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

Coupling efficiency and final yield
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