ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ Профессор Н.Г. Рамбиди. - презентация

1 ФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ НАНОТЕХНОЛОГИИ Профессор Н.Г. Рамбиди

2 11. Нанохимия

3 Молекулярный дизайн

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

5 Краун эфиры Negative charge concentrated in the cavity of the molecule Negative charge concentrated in the cavity of the molecule Forms stable lewis acid / lewis base with complex Forms stable lewis acid / lewis base with complex Cs +

6 Formation of Calixarenes Phenol is reacted Formaldehyde and NaOH then heated Phenol is reacted Formaldehyde and NaOH then heated

7 Calixarene Configuration

8 Molecular binding 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. 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. 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 +

9 Фуллерены

10 Фуллерены

11 Фуллерены

12 Nontraditional Fullerenes enclosing metal atom clusters. - Three fused pentagons in the C 68 cage: Violation of the Isolated Pentagon Rule (IPR). - Strong gain of stability upon incorporation of NSc 3 in the C 68 cage Sc 3 68 Use of Fullerenes enclosing metal atom clusters as Novel Magnetic Resonance Imaging contrast agents ?

13 Fullerenes with incorporated Helium Clusters He 60 ( D 2d ) 60 (I h ) - NMR studies on noble gas atoms enclosed in fullerene shells ( M. S. Syamala et al., JACS 124, 6216, 2002 ). - He n encapsulated fullerenes of extraterestial detected in geological sediments ( L. Becker et al., Science ). He n configurations in fullerene cages?

14 С ложные молекулярные системы

15 Organic, polymer/biopolymer synthesis Building blocks with natural and synthetic components for site directed self assembly into functional nanostructure

16 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.

17 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.

18 Self-assembly of a receptor from H-bonded molecular building blocks Reinhoudt et al. Guest =

19 Электроактивные материалы

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23 Governing Equation of Dielectric Elastomers p= 0 E 2 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

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25 Искусственная рука

26 Протезы сердца

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28 Микро-насос

29 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)

30 Responsive materials

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36 Основные пути формирования сложных молекулярных систем

37 Самоорганизующиеся амфифильные системы

38 Surfactant Molecules: Oil-Water Building Blocks Monolayer formation Micelles - nano-reactors, drug delivery vehicles, and cleaning agents Oil-Water Interface Oil Water Surfactant Polar head group Non polar tail CH 2 CH 3 OSO 3 -

39 Micelles in the Bulk Solution Formation of stable aggregates at the cmc. low concentration high concentration

40 Micelles Polar water-like surface Apolar oil-like interior nm Normal in waterReversed in oil Solubilization Nanoreactors Oil Recovery Drug Delivery

41 Monolayer formation Surfactants can also adsorb at the air-water interface Adsorption at the air-water interface

42 Amphiphiles phosphatidyl choline lyso- phosphatidyl choline dodecylsulphate Polar Non-polar

43 Critical micelle conc

44 Micelles/Monolayers/Bilayers polar non-polar polar non-polar polar non-polar

45 Lamellar phase Amphiphiles PC - forms lamellar phases = bilayers of biology Get x-ray/nmr data

46 Lipid bilayers

47 Hexagonal phase Amphiphiles PE -forms hexagonal phase = fusion regions of biology

48 Пленки Ленгмюра- Блоджет

49 Langmuir Films Spread on water. Not equilibrium adsorption. Film can be compressed Water subphase Air Langmuir film

50 On Water S-Azo-C18 Isotherm Stearic Acid Isotherm Area (cm 2 ) Surface Pressure (mN/cm 2 ) Area (cm 2 ) Surface Pressure (mN/cm 2 ) Water Gas Water Liquid Water Solid

51 Langmuir-Schaeffer Films Water subphase Solid substrate

52 Langmuir-Blodgett Deposition Hydrophobic Surface (OTS ) Water Hydrophilic surface Hydrophobic Surface

53 Multilayer ~ 10 nm Head to head Tail to tail Head to tail Tail to head X Y Z

54 The Instrument

55 Хемосорбированные слои

56 Chemisorption Chemical reaction between the building block and the solid substrate X X X X X X X XXXXXXXXX Reactive site Spontaneous irreversible Functionalized surface

57 XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX XXXXXXXXXXXX 3D-Representation

58 OTS on Glass OTS– octadecyltrichlorosilane

59 OTS on Glass OTS coated substrate surface

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61 Membrane Structure

62 Types of membrane proteins

63 Membrane Protein Structure

64 Формирование заданной последовательности аминокислот в молекуле белка. Синтез Меррифилда

65 Solid phase peptide synthesis (SPPS) The Nobel Prize in Chemistry for his development of methodology for chemical synthesis on a solid matrix --for his development of methodology for chemical synthesis on a solid matrix Robert Bruce Merrifield Rockefeller University

66 Традиционный химический синтез

67 Синтез Меррифилда

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70 Easier!!

71 Prepare fully protected peptide!

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73 ABI 433A Peptide Synthesizer

74 Синтез Меррифилда

75 Coupling efficiency and final yield Yield (%) efficiency (%) 10-mer20-mer30-mer40-mer50-mer60-mer