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ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ PowerPoint PPT Presentation


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

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ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ

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Cs+

  • Negative charge concentrated in the cavity of the molecule

  • Forms stable lewis acid / lewis base with complex


Formation of Calixarenes

  • Phenol is reacted Formaldehyde and NaOH then heated


Calixarene Configuration


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+





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

  • 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?

He2@C60 (D2d)

He@He20@C60 (Ih)



Organic, polymer/biopolymer synthesis

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.


Guest =

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

Reinhoudt et al.




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




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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 materials




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

Formation of stable aggregates at the cmc.

low concentration

high concentration


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

Surfactants can also adsorb at the air-water interface

Adsorption at the air-water interface


Amphiphiles

Polar

Non-polar

dodecylsulphate

phosphatidyl choline lyso- phosphatidyl choline


Critical micelle conc


Micelles/Monolayers/Bilayers

polar

polar

non-polar

non-polar

non-polar

polar


Lamellar phase Amphiphiles

Get x-ray/nmr data

PC - forms lamellar phases = bilayers of biology


Lipid bilayers


Hexagonal phase Amphiphiles

PE -forms hexagonal phase = fusion regions of biology


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Langmuir Films

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

Air

Water subphase

Langmuir film


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

Solid substrate

Water subphase

Water subphase


Langmuir-Blodgett Deposition

Hydrophobic

Surface (OTS)

Hydrophobic

Surface

Water

Hydrophilic

surface


Multilayer

~ 10 nm

X

Z

Y

Head to head

Tail to tail

Head to tail

Tail to head


The Instrument



X

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Chemisorption

Chemical reaction between the building block and the solid substrate

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Spontaneous

irreversible

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Functionalized surface

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Reactive

site


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3D-Representation


OTS on Glass

OTS octadecyltrichlorosilane


OTS on Glass

OTS coated substrate surface


Membrane Structure


Types of membrane proteins


Membrane Protein Structure


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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




Easier!!


Prepare fully protected peptide!


ABI 433A Peptide Synthesizer



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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