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PODSTAWY CHEMII SUPRAMOLEKULARNEJ Z ELEMENTAMI

NANO – NIEKONWENCJONALNIE

SAMOORGANIZACJA SUPRAMOLEKULARNA

Marek Pietraszkiewicz, Instytut Chemii Fizycznej PAN, 01-224 Warszawa, Kasprzaka 44/52, tel: 3433416

E-mail: [email protected]

SAMOORGANIZACJA SUPRAMOLEKULARNA

samoorganizacja niekowalencyjna

SAMOORGANIZACJA KOWALENCYJNA

• KALIKSARENY

• KUKUBITURIL

• HETEROPOLIANIONY

HETEROPOLIANIONY

Heteropolianiony powstają podczas kontrolowanej (pH) polikondensacji molibdenianów, wolframianów, wanadanów e

środowisku kwaśnym.

Molecular Symmetry Breakers∫Generating Metal-Oxide-Based Nanoobject Fragments as Synthons for Complex Structures: [{Mo128Eu4O388H10(H2O)81}2]

20-- a Giant-Cluster Dimer, L. Cronin,C. Beugholt, E. Krickemeyer, M Schmidtmann, H. Boegge, P. Koegerler, T.Kim K.Luong, and Achim Mueller*, Angew. Chem. Int. Ed., 41, 2805 (2002)

Figure 1.Left:a packing diagram of the cluster units of 1a in ball-and-stick representation looking down the cavities∫(Eu III ions in green).Right:a representation of 1a with the molybdenum oxide based units displayed as polyhedra ({Mo1 }yellow;{Mo2 }red;{Mo8 }blue with central pentagonal units in cyan;Eu III coordination spheres in ball-and-stick representation).Bottom right:an expanded view of the Mo-O-Eu groups linking the two cluster rings.

Molecular Symmetry Breakers∫Generating Metal-Oxide-Based Nanoobject Fragments as Synthons for Complex Structures: [{Mo128Eu4O388H10(H2O)81}2]

20-- a Giant-Cluster Dimer, L. Cronin,C. Beugholt, E. Krickemeyer, M Schmidtmann, H. Boegge, P. Koegerler, T.Kim K.Luong, and Achim Mueller*, Angew. Chem. Int. Ed., 41, 2805 (2002)

Figure 2.Demonstration of how an {Mo128 Eu4 }ring of 1a can formally be constructed from a parent {Mo154 }-type cluster by a cutting∫process giving the two large important fragments.Top left:A side view of the {Mo154 }ring,the cutting positions are marked as large black spheres;top right:those units which have to be removed from the {Mo154 }ring and those which have to be added to the resulting two large fragments (left and right)to generate the {Mo128 Eu4 }cluster;bottom:the {Mo128 Eu4 }cluster from a side and top view (color code as in Figure 1)with the new {Mo*2 }units in brown which are shown in the side view together with the EuO9 polyhedra in ball-and-stick representation;the MoO6 octahedra of a selected {Mo7 }and a {Mo9 }group, respectively,as hatched violet polyhedra.

FORMATION OF SUPRAMOLECULAR POLYOXOANIONS

Figure 1.Polyhedral representation of [(TiP2 W15 O55 OH)2 ]14+ (1 ).The PO4 ,

WO6 ,and TiO6 polyhedra are shown in blue, red, and green, respectively.

Figure 3.Polyhedral representation of [{Ti3 P2 W15 O57.5 (OH)3 }4 ]24 + (2 )with a bird ×s-eye view along a twofold rotation axis.The color code is the same as in Figure 1.

Figure 5.Polyhedral representation of [{Ti3 P2 W15 O57.5 (OH)3 }4 ]24 (2 )with a view along a mirror plane.The color code is the same as in Figure 1.

SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ:

• WODOROWYCH

• KOORDYNACYJNYCH

• JONOWYCH

• -KWAS - -ZASADA

• HYDROFOBOWYCH

SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ WODOROWYCH

G.W. Whitesides

G.W. Whitesides

G.W. Whitesides

G.W. Whitesides

G.W. Whitesides

G.W. Whitesides

G.W. Whitesides

SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ KOORDYNACYJNYCH

Koordynacja liniowa

Koordynacja trygonalna

Koordynacja płaska kwadratowa

Koordynacja tetraedryczna

Koordynacja bipiramidy trygonalnej

Koordynacja oktaedryczna

Koordynacja bipiramidy pentagonalnej

Koordynacja sześcienna

Rodzaj anionu i rozpuszczalnika ma znaczny wpływ na architekturę molekularną powstających kompleksów koordynacyjnych


Macromolecules Containing Bipyridine and Terpyridine Metal Complexes: Towards Metallosupramolecular Polymers Ulrich S. Schubert*and Christian Eschbaumer, Angew. Chem.Int. Ed., 41, 2892 (2002)

J.-M. LEHN – MOLECULAR GRIDS



Figure 4.Distribution curves of the species 1 ,L6 Ag 9 ,( ,the t -3 form of L5 Ag ( )and al the others ( ;by difference)in the course of the titration of L by AgCF3 SO3 in CD3 Cl/CD3 NO2 25/75,determined by integration of characteristic 200 MHz 1 H NMR signals for the two complexes.The inset shows part of the distribution curves of the species containing 6 ±9 silver ions for a statistical non-cooperative Ising mode with nine independent sites.

WIELKIE METALLACYKLE

Figure 1.a)The self-assemblyof a porphyrin nonameric arrayconsisting of 30 particles is followed byb)the self-organization of these nonamers into columnar aggregates that are about 6 nm in diameter and an average of 5 nm in height.The size of these latter entities can be directed byvarious means.












Assembly of a Truncated-Tetrahedral Chiral [M12-L18]24+ Cage** Z. R. Bell, J.

C. Jeffery, J. A. McCleverty, and M. D. Ward*, Angew. Chem.Int. Ed., 41, 2515 (2002)


Assembly of a Truncated-Tetrahedral Chiral [M12-L18]24+ Cage** Z. R. Bell, J.

C. Jeffery, J. A. McCleverty, and M. D. Ward*, Angew. Chem.Int. Ed., 41, 2515 (2002)


Supramolecular Metal-Organometallic Coordination Networks Based on Quinonoid ð-Complexes Moonhyun Oh, Gene B. Carpenter, and Dwight A. Sweigart, Acc. Chem. Res., 37, 1 (2004)

In the context of coordination networks, we reasoned that the role of the spacer or linker could be provided not only by organic ligands to generate MONs, but also by appropriate organometallic ð-complexes that have the ability to function as multifunctional ligands (“organometalloligands”) to afford metal-organometallic coordination networks (MOMNs). Figure 1 illustrates the essential difference between the two types of networks for a one-dimensional system.

















FIGURE 12. Self-assembly of p-QMTC and 2,2¢-bipyridine into 1D networks that interdigitate via pi-pi stacking (blue) to generate MOMN 16, having “pi-pockets” that bind free 2,2-bipyridine (red).





FIGURE 14. Hypothetical highly porous MOMNs consisting of quinonoid 1D string polymers as infinite SBUs and appropriate organic spacers


Nanoscale Borromean Rings, STUART J. Cantrill, Kelly S. Chichak, Andrea J. Peters, and J. Fraser Stoddart*, Acc. Chem. Res., 38, 1 (2005)


Nanoscale Borromean Rings, Stuart J. Cantrill, Kelly S. Chichak, Andrea J. Peters, and J. Fraser Stoddart*, Acc. Chem. Res., 38, 1 (2005)

FIGURE 3. Generic strategies for the synthesis of Borromean-ring compounds (IV), which may also be depicted in orthogonaland Vennarrangements.



FIGURE 4. Busch’s proposed27 ring-in-ring synthesis of a Borromean-ring compound.



FIGURE 5. Conceptual advance32 from a double-threaded [3]pseudorotaxane to a ring-in-ring complex based upon the interaction between crown ethers and secondary dialkylammonium ions.





FIGURE 7. Synthesis36 of Siegel’s ring-in-ring complex, in which two endo bipyridyl ligands await the threading of the components necessary for construction of the final ring of a molecular Borromean link.



FIGURE 8. (Top) Translation and deformation of the VennBorromean link into a 3Dstructure with double-helical regions. (Bottom) Synthetic approach38 for the formation of a DNA Borromean-ring compound from the ligation of two three-arm junctions.



FIGURE 9. (Top) Schematic assembly of a Borromean link from a combination of endo-tridentateand exo-bidentateligands around metal ion templates. (Bottom) Reversible reaction of 2,6-diformylpyridine with a diamine, containing a dipyridyl binding site, in the presence of zinc acetate affords42 a molecular Borromean link


Discrete Stacking of Large Aromatic Molecules within Organic-Pillared Coordination Cages, M. Yoshizawa, J. Nakagawa, K. Kumazawa, M. Nagao, M. Kawano, T. Ozeki, and M. Fujita, Angew. Chem. Int. Ed., 44, 1810, 2005








Anion Control over Interpenetration and Framework Topology in Coordination Networks Based on Homoleptic Six-Connected Scandium Nodes De-Liang Long, Robert J. Hill, Alexander J. Blake, Neil R. Champness,* Peter Hubberstey,* Claire Wilson, and Martin Schrçder, Chem. Eur. J., 11, 1384 (2005)

L = 4.4’-bipyridine



Figure 1. The coordination geometries at ScIII in a) 1, b) 2, c) 3 and d) 4. Hydrogen atoms are omitted for clarity.





Figure 4. View of 2 parallel to the crystallographic a axis (a)


Readily Prepared Metallo-Supramolecular Triple Helicates Designed to Exhibit Spin-Crossover Behaviour Floriana Tuna,[a] Martin R. Lees,[b] Guy J. Clarkson,[a] and Michael J. Hannon, Chem. Eur. J., 10, 5737 (2004)


Ruthenium(ii) as a Novel Labile Partner in Thermodynamic Self-Assembly of Heterobimetallic d±f Triple-Stranded Helicates Stÿphane Torelli, Sandra Delahaye, Andreas Hauser, Gÿrald Bernardinelli, and Claude Piguet, Chem. Eur. J., 10, 3503 (2004)

M = Cr(III), Co(III)


Ruthenium(ii) as a Novel Labile Partner in Thermodynamic Self-Assembly of Heterobimetallic d,f Triple-Stranded Helicates Stÿphane Torelli, Sandra Delahaye, Andreas Hauser, Gÿrald Bernardinelli, and Claude Piguet, Chem. Eur. J., 10, 3503 (2004)

Figure 9. a) Perspective view of HHH [RuLu(L1)3]5+ perpendicular to the pseudo-C3 axis in the crystal structure of 6, and b) atomic numbering scheme of strand a (ellipsoids are represented at the 40% probability level).


Programming Heteropolymetallic Lanthanide Helicates: ThermodynamicRecognition of Different Metal Ions Along the Strands, S. Floquet, M. Borkovec, G. Bernardinelli, A. Pinto,[c] L.-A. Leuthold, G. Hopfgar tner, D. Imbert, J.-C. G. Buenzli, andC. Piguet, Chem. Eur. J., 10, 1091 (2004)


Programming Heteropolymetallic Lanthanide Helicates: ThermodynamicRecognition of Different Metal Ions Along the Strands, S. Floquet, M. Borkovec, G. Bernardinelli, A. Pinto,[c] L.-A. Leuthold, G. Hopfgar tner, D. Imbert, J.-C. G. Buenzli, andC. Piguet, Chem. Eur. J., 10, 1091 (2004)


Supramolecular Spintronic Devices: Spin Transitions and Magnetostructural Correlations in [Fe4

IIL4]8+ [2 2] Grid-Type Complexes, M. Ruben, E. Breuning, J.-M. Lehn, V.

Ksenofontov, F. Renz, Philip Goetlich, and G. B. M. Vaughan, Chem. Eur. J., 9, 4422 (2003)





Figure 3. Top (a) and side view (b) of the single-crystal X-ray investigation of complex 7; some of the S-n-propyl chains are disordered (anions, solvent molecules, and hydrogen atoms are omitted for clarity).






Hexacyanometalate

Molecular chemistry


Hexacyanometalate Molecular Chemistry: Heptanuclear Heterobimetallic Complexes; Control of the Ground Spin State, V. Marvaud, C. Decroix, A. Scuiller, C. Guyard-Duhayon, J. Vaissermann, F. Gonnet, and M. Verdaguer, Chem. Eur. J., 9, 1677 (2003)

Figure 2. Synthetic strategy scheme.







SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ JONOWYCH

PODOBNIE, JAK W KOMPLEKSACH KOORDYNACYJNYCH

SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ -KWAS - -ZASADA

Amphiphilic Bistable Rotaxanes, Jan O. Jeppesen,*[a, b] Kent A. Nielsen,[a, b] Julie Perkins, Scott A. Vignon, Alberto Di Fabio, Roberto Ballardini, M. Teresa Gandolfi, Margherita Venturi, Vincenzo Balzani, Jan Becher, and J. Fraser Stoddart, Chem. Eur. J., 9, 2982 (2003)

Figure 1. Molecular formulas of the single-station [2]rotaxane 1 ¥ 4PF6 , the slow two-station [2]rotaxane 2 ¥ 4PF6 , and the fast two-station [2]rotaxane 3 ¥ 4PF6 (only one translational isomer is shown in each case).



Figure 1. Molecular formulas of the single-station [2]rotaxane 1 ¥ 4PF6 , the slow two-station [2]rotaxane 2 ¥ 4PF6 , and the fast two-station [2]rotaxane 3 ¥ 4PF6 (only one translational isomer is shown in each case).



SAMOORGANIZACJA NIEKOWALENCYJNA – WYKORZYSTANIE WIĄZAŃ HYDROFOBOWYCH

FORMOWANIE WARSTWA Z BOLA-AMFIFILAMI

WYTWARZANIE ZEWNĘTRZNEJ WARSTWY POLIMERYCZNEJ

MICELLE

Schematyczna reprezentacja powstawania membrany pęcherzykowej

Supra-organizacja micellarna dyskotyczna

Schematyczna reprezentacja micelli

Hydrofobowe substraty tworzą heterogeniczny dimer w micelli SDS.

Sposób formownia rurek lipidowych

Obraz mikroskopowy nanorurek otrzymanych w wyniku samoorganizacji micellarnej

Model 3D z rozciągniętymi konformacjami 72 cząsteczek

MEZOFAZY

Liquid crystal state and History

• 1888 Freidrick Reinitzer,cholesteryl benzoate

• 1968 RCA-first experimental LCD

What are Liquid Crystals?

Liquid Crystal – a thermodynamic stable phase without the existence of a 3-dimensional crystal lattice – generally lying between the solid and isotropic(“liquid”) phase.

Classes of liquid Crystals

• Thermotropic:nematic and isotropic

Nematic

• Smectic and Chiral Nematic

Transitions

LCDs

• Nematic crystals between to pieces of polarized glass at right angles.

• Microscopic grooves in glass align closest layer of LC, creating twisting.

• Twisted layers guide light through LCD.

• Electric current causes LCs to untwist causing black appearance

• Backlit and reflective

• Active and passive matrices

Lyotropic Liquid Crystals

– Induced by the influence of solvent

– Rod-like in shape

– Amphiphilic in nature• Lyophilic (solvent-attracting) part

• Lyophobic (solvent-repelling) part

– When concentration of mesogens increases, solvent induced aggregation of the constituent mesogens leads to micellar structures


– In the presence of solvent, the lyopobic ends will stay together and the lyophilic ends extend outward toward the solution. When concentration of mesogens increases, micelles become large and swollen.

Lyotropic liquid crystal bilayer

Lyotropic liquid crystal micelle


– Mesophase is temperature sensitive

∵ Conformation of mesogen is temperature

sensitive

– Also solvent and concentration dependent

∵ principal interaction is the solute-solvent

interaction

e.g. polypeptides in water, DNA

Liquid Crystalline Phases of Disc-like Compounds

Characterization of columar arrangement

dependent of

I. The order or disorder of the molecular stacking in the

column

II. The two-dimensional lattice symmetry such as

hexagonal : Dh, rectangular: Dr

Examples of Discotic Liquid Crystals

R

R

RR

R

RO

O

R

R

R

R

R

R

COOH17C8O

O O

C12 H

25

C 12H 25

C 12H 25

C12 H

25

H3 C

OO

OO

CH 3

OOCH3

OO

CH

3H 3C

OO

H3COO

N

N

N

NH

HN

N

N

N

R

R

R

R

RR

RRR R R

RR

R

COOR = C7H15 COOR = C7H15

R =C8 H19COOCH2OC12H25R =

213

4 5

6 71 hexa-n-alkanoates of benzene; 2 hexa-substituted anthraquinones; 3 tri-

substituted benzenes; 4 bipyrene derivates; 5 scyllo-inosithe hexa-acetate; 6 octa-substituted phthalocyanine derivates; 7 hexa-substituted tribenzocyclononene.

Polymorphism and Phase Sequences

• Generalized sequence rule:Solid Smectic B Smectic C Smectic A

Nematic Isotropic

• No single compound show complete sequence

• It is possible to have “re-entrant” phase sequencee.g. Nre – SA – N

e.g. SA re – Nre – SA – N

• No generalized sequence rule for disc-like molecules

General Structural Requirements for Rod-like Mesogens

A. Anisotropic Geometry– Elongated in shape

B. Rigidity– Rigid along the molecular axis

e.g.O

H

H

RR VS

Alka-2,4-dienoic Acids Alkanoic Acids

O CH2

CH2

RR

Structure-Property Relationships in Thermotropic Liquid Crystals

• Typical molecular structure of rod-shaped liquid crystal

AB B’X Y

Z Z’

A – linking group

B, B’ – ring systems

X, Y – terminal groups

Z, Z’ – lateral substituents

CH CHOlefin

C CAcetylene

CH NAzomethine

(schiff’s base)

CH N

ONitrone

O C

OEster

N N

OAzoxy

N N

Azo

CH3

CH3

△5-Steroid

CO

OHC

O

OH....

....Acid dimer

Common Central Linkages of Mesogens

Roles of Central Linking Group

• Most of the linkages are highly polarizable

with the exception of △5 steroid ring system

and acid dimer (but still rigid and linear.

• In general, the stronger the dipole or the easier

the polarizability of the central group, the

better the thermal stabilibities of the

mesophases are.


e.g.

RO COOH RO COOHVS

Form more stable mesophase

Esters of cholesterol VS Esters of cholestanol

CH3

CH3 R

O

H

C

O

R'

R

O

H

C

O

R'


• The more extended the conjugated central linkage, the more lathlike the molecule and the more enhanced the mesophase-forming properties will be.

e.g. C4H9O CH N OC4H9

N I 121 C

N I 297.5 C

C4H9O CH N N CH OC4H9


• The more polar the linking group, the higher is the viscosity.

e.g.C3H7 X C3H7

X CH2 CH2

CH2O C

O

O O C

O

N-I (C )Visc. 20°C

(mm2/s)

13117

14048

19044.2

158103


• Azomethoxy system (schiff’s base) shows a good liquid crystal phase stability but poor stability to water.

• In term of stability, the weakest part of most liquid crystal molecules is the linking group.

4-alkyl-4’-cyanobiphenyl, the first series stable room temp. L. C. invented at Hull University, England

Roles of Terminal Groups

• Usually extending the molecular axis (long axis increasing liquid crystal thermal stability

• The presence of the dipolar terminal gives higher thermal stability of the mesogen.

e.g.C8H17O COOH VS C9H19 COOH

N-I is 40 C higher

Common Terminal Groups of Mesogens

CH3 (CH2)

RO

CRO

O

CR

O

O

F, Cl, Br, I

CN

NO2

R2N

ALKYL- may be branched

ALKYLOXY; also internal ETHERS

ALKYLCARBOXY

ALKYLCARBONATO

HALOGEN

CYANO

NITRO

AMINO

R may be H

Roles of Terminal Groups

• Terminal carboxylic acid group may induce a much high L.C. thermal stability.e.g.

∵ the carboxylic acid forms a dimer, doubling the overall length of the molecule without broadening it.

CC6H13O

O

O C3H7C6H13O COOHVS

C-S = 67.5 C, S-I = 107 C C-Sc = 213 C, Sc-N = 243 C

N-I = 272.5 C

Roles of Lateral Substituents

• In general, it will broaden the molecule thus reducing lateral attractions and lowering stabilities of nematic and smectic phases.

• The substitution effect depends on– The position of the group

– The nature of the group

– The polarity of the group

– The size of the group

Roles of Lateral Substituents

• With an addition of a substituent ortho to the polar terminal group, it can hinder the molecular association leads to a higher △.

e.g.C5H11 C

O

O

X Y

CN

X Y C-N/C N-I/C △H H 56.8 63.4 20.7

H F 20 30 48.9

Applications of Liquid Crystals

1. Liquid Crystal Displays (LCDs)

2. Liquid Crystal Thermometers/Pressure

Sensors

3. Switchable Windows

SAMOORGANIZACJA NA POWIERZCHNIACH

POWIERZCHNIE STAŁE

3D SURFACES

• ELEMENTS: Ag, Au, Cu, platinum metals, C, Si,

• SEMICONDUCTORS: CdS, CdSe, HgTe, TiO2, ZrO2, PbS, ZnSe, GaN

• INSULATORS: SiO2

2D SURFACES

• ELEMENTS: Ag, Au, Cu, platinum metals, C, Si

ANCHORING FUNCTIONAL GROUPS:

COVALENT BINDING

Si(OMe)3, NCS, NCO, COCl, for surfaces with OH groups:

SiO2, C, Si, TiO2, ZrO2, In-Sn-oxide (ITO), metal oxides of:

Al, Zr, Ti, Si, B, Ge, Hf, Ta, Nb, V, Ge, Sn, In, Y

NON-COVALENT BINDING

RS, RSSR, RNHCS2, RS2O3-, thiophene, RSe, RSeSeR, for surfaces: Au,

Ag, Cu, platinum metals, CdS, ZnSe, HgTe

RCOO, for Ag

RPO32-, for Al2O3, TiO2, ZrO2

SURFACE PREPARATION AND TSF BUILD-UP

• SURFACE CLEANING/HYDROPHILISATION

• CONDITIONING IN THE PRESENCE OF TRANSITION METAL ALKOXIDES

• HYDROLYIS, WASHING, DRYING

• CONDITIONING IN THE PRESENCE OF TRANSITION METAL ALKOXIDES

• HYDROLYIS, WASHING, DRYING, etc.

• FINAL SURFACE MODIFICATION WITH POLYFUNCTIONAL MATERIALS POSESSING ANCHORING GROUPS

VARIOUS METAL ALKOXIDES CAN BE USED IN EVERY SINGLE STEP

O O O

O O

O O O O

OOO

M

MM M

MM

O H

SUBSTRATE

O H

SUBSTRATE

RSRSRSRSRSRS

SURFACE MODIFICATION WITH METAL OXIDES AND THIOLS

M(OR)n conditioning M = Al, Zr, Ti, Si, B, Ge, Hf, Ta, Nb, V, Ge, Sn, In, Y

hydrolysis, drying, conditioning

surface conditioning with thiols

O O O O O O O O

TiTiTiTi

O O O O O O OO

O OO O O O

ZrZrZr

YYYY

OOOOOOOO

OO

SOLID SUBSTRATE

HETEROMETALLIC OXIDE TSF BUILD-UP

Ph2P(O)NCO

N

H

Si(OEt)3

H2N Si(OEt)3

P

N

NNP N

O O

O

N

PO

O

OPh

Ph

Ph

Ph

Ph

H

H

H

Ph

Ph2P(O)NCO

NN

H

Si(OEt)3

H

H2N

Si(OEt)3

N

PO

O

N

P

OPN

N

P

N

NN

O

O

O

OPh

Ph

Ph

Ph

Ph

H

H H

O

Ph

PhPh

H

Ligands with triethoxysilyl anchoring groups from commercially available di-, and triamines

SILANE ANCHORING GROUPS

ligand 2

ligand 3

SILICA IMPREGNATED WITH Zr SOL

300 400 500 600 7000

2000

4000

6000

8000

10000

Co

un

ts [a

.u.]

Wavelength [nm]300 400 500 600 700

0

2000

4000

6000

8000

10000

Co

un

ts [a

.u.]

Wavelength [nm]

ligand 2 ligand 3

exc = 275 nm

Tb emission

Tb emission

light scattering from silica

N

S

R

N

R

R = (CH2)3PO(OH)2, or (CH2)3Si(OEt)3

NN

S

MOx SUBSTRATE

O O O O

PO PO

N

S

SiO2 SUBSTRATE

O O O O

Si

Adsorpcja nanocząstek siarczku kadmu na monowarstwie osadzonej na złocie

SAMOORGANIZACJA NA POWIERZCHNI CIECZY: GRANICA FAZ – CIECZ-POWIETRZE. FILMY LANGMUIRA I LANGMUIRA-BLODGETT

Izotermy Langmuira dla filmów krystalicznych i amorficznych

SAMOORGANIZACJA NA POWIERZCHNI CIECZY: GRANICA FAZ – CIECZ-POWIETRZE. FILMY LANGMUIRA I LANGMUIRA-BLODGETT

Cząsteczki tworzące filmy molekularne na granicy faz woda-powietrze składają się z cząsteczek posiadających grupę hydrofilową i hydrofobową. Grupa hydrofilowa zanurzona jest w wodzie, hydrofobowa – wystaje ponad powierzchnie wody.

What are Langmuir-Blodgett Films?

Solid substrate

1 2

3

Within liquid media

Langmuir-Blodgett Films

• LB technique provides a window to nanotechnology: manufacture of nanoscale structures with relatively conventional equipment.

• LB films configure a path to nanotechnology: first step in the manufacture of nanosensors and nanoparticles.

Langmuir-Blodgett Films: Applications

• Manufacturing of nano-particles– Limited growth in 2-D

• Bio-mimetics– Phospho-lipids films with protein inclusions

• Nonlinear optics– Hundred of layers!

• Ultra dense magnetic storage media– Magnetic nano-particles and nano-films

• Nano-sensors– Combination of MEMS and NEMS

• Many nano-technology applications• In Nature function and order go together!

Applications: Carbon nanotubes for energy storage

Use of LB films as precursors

to make collections of highly

ordered nanotubes.

(NSF-NIRT * UToledo-UAH)

Applications: Nanosensors

Vibrating cantilevered wires

coated with LB films,

modified with antibodies.

(Michael George, Chemistry)

Sketch of Experimental Setup

LANGMUIR-BLODGETT (LB) TECHNIQUE

Multilayer Deposition: Y TO X and Y to Z Transitions

Y to Z transition

Y to X transition

X, Y AND Z-TYPE DEPOSITION AND TRANSFER RATIO

Transfer ratio

100L

S

Aτ

A

Oddziaływanie hydrofobowe łańcuchów węglowodorowych nad powierzchnią cieczy i oddziaływanie grup polarnych w subfazie wodnej

Gęsto upakowana warstwa potrójna

Rozpoznanie molekularne w subfazie wodnej, zawierającej analit