self assembling · evolution from divided to condensed and to organized, living and thinking matter...

SELF – ASSEMBLING

a step in the development of complex organized matter

Academia Romana

Valeria Harabagiu ([email protected])“Petru Poni” Institute of Macromolecular Chimistry41A, Aleea Grigore Ghica Voda, 700487 Iasi

Dynamic Nano Systems: Concepts and Application Bucuresti, September 23-24, 2010

mailto:[email protected]

TOPICS

Concepts, definitions

Self-assembling systemsChemistry laboratory

Drug loaded nanoparticles(Poly)rotaxanesLB films of modified cyclodextrins

Nature

Perspectives


CONCEPTS

THERMODYNAMICS

equilibrium spontaneous

self-assembly self-organization

Collective, nonlinear interactions

Dissipative, nonequilibrium order Interplay between intrinsic/

extrinsic factors Decay upon removal of the

energy source

Halley and Winkler, Complexity, 2008

Collective interactions

Nondissipative, equilibrium order Thermodynamically controlled

Stable at equilibrium, no need for energy input


WHAT CHEMISTS KNOW TO DO ?

« Petru Poni » Institute of

Macromolecular Chemistry


Drug loaded nanoparticles

Controlled structures of poly(siloxane – caprolactone) copolymers

Controlled morphology (reduced crystallinity of polycaprolactone

rich domain)

(co)nanoprecipitation drug loaded nanoparticles

Nanoparticle functionalization application


C. Iojoiu et al.,

J. Polym. Sci.: Part A: Polym. Chem. 42(3), 689-700 (2004)

C. Racles, Macromol. Chem. Phys. 206, 1757-1768 (2005)

Siloxane-caprolactone copolymers Controlled coordinating anionic polymerization

- Molecular weight- Morphology

3012.5

3583.42555.8

3811.9

2099.04154.3

1756.94725.4

Maldi tof spectra

-Si-O-Si-(CH2)3-O-(CH2)3-OH + caprolactone


C. Iojoiu et al., J. Polym. Sci.: Part A: Polym. Chem. 42(3), 689-700 (2004)

Copolymer morphology (polarized optical micrographs)

CL2000-SiO1000-CL2000 CL6000-SiO1000-CL6000


Organic solution

0.2 g PDMS-PCL

1 g vitamin E

20 ml acetone

Aqueous Solution

0.4 g pluronic F-68

40 ml water

1. Precipitation2. Evaporation of solvent

Nanoparticle SuspensionStableDimensions: around 200 nm

Pluronic F-68 = PEO/PPO/PEO 76/30/76

Hydrophobic polymer(PDMS-PCL)

Hydrophilicpolymer(pluronic F-68)

Active principle(vitamin E)


Nanoprecipitation

Application

- Controlled release

- Catalysis

Activeprinciple

matrix

PolymerNanosphere

Galactose

Nanocapsule

Nanoparticle


Si O Si

CH3

R

glycoside

CH3

CH3

On

m

Si

CH3

CH3

O Rn

Rglycoside glycoside

Si O

Si

O

O

Si

O Si

CH3Rglycoside

CH3

Rglycoside

CH3

CH3

R glycoside

R glycoside

C. Racles, Macromol. Chem. Phys. 206, 1757-1768 (2005)

Polysiloxanes / cyclodextrins

Fullerene C60 / carboxyester modified cyclodextrin

(Poly)rotaxanes

Cyclodextrin macrocycles


typical example of non-covalent association of non-identical molecules

macrocycle + organic/inorganic compound/polymer

Preparation

Polymerization of inclusion complexes

k1 >> k2


Inclusion of pre-synthesized polymers

Epoxy-terminated polydimethylsiloxane/cyclodextrinpolyrotaxanes

Polyrotaxane+freeβCD

Polyrotaxane

βCD

Prot+ βCD

Prot

Marangoci et al.

High Perform. Polym. 20, 251 (2008)

J. Incl. Phenom. Macrocycl. Chem. 63,

355 (2009)

Polydimethylsiloxane (E-PDMS): Mn = 1000, 2000, 3000

Cyclodextrins: βCD or γCD

Polyrotaxanes: crystallinity and morphology depending on

PDMS molecular weight CD dimension and content

βCD: 2 molecules threadedon each organicchain end

γCD: the content/polymerchain increases withchain length


C60 / carboxyester modified γCD

CD

CDSA

CDSA

A. Fifere et al.

J. Incl. Phenom. Macrocycl. Chem. 64, 83 (2009) Dynamic Nano Systems: Concepts and Application Bucuresti, September 23-24, 2010

LB films

Axis of rotation

Secondary rim

Primaryrim

n

6

3

2

3

6n Modification

6 R2=R3=R6=Si(CH3)3

7 R2=R3=R6=Si(CH3)3

8 R2=R3=R6=Si(CH3)3

7 R2=R3=Si(CH3)3;

R6=SH

To synthesize well defined modified cyclodextrins with an appropriate

hydrophobic-hydrophylic balance

To demonstrate their LB film forming ability

To check for possible application of LB films


O

OO

ORR O

OR OR

OR OR 6

23

23

6

P r i m a r y r i m

S e c o n d a r y r i m

A x i s o f r o t a t i o n

n

23

O

OOHOH

OH

N-Si(CH3)3

N

O

OO-RR-O

O-R

R = Si(CH3)3

(

)n

n = 6, 7, 8

+

-

(

)n

Persilylated cyclodextrins (CD-Si3xn)

Preparation

V. Harabagiu et al., Carbohydrate Polymers 56, 301 (2004)

Room temperature

DMF/chloroform solvent mixture

100 % yield


1H- and 13C-NMR spectra of -CD-Si3x6

Si-CH3

H1

H2-6

C2-6

C1

Si-CH3

Structural characterisation


MALDI-TOF mass spectrum of γ-CD-Si24

m/z = 3066: γ-CD-Si24 + K+

m/z = 3050: γ-CD-Si24 + Na+

m/z = 2993: γ-CD-Si24 – Si(CH3)3 + K+

11th European Conference on Organized FilmsPotsdam, July 9-11, 2008

obtained with 2-nitrophenyloctyl ether as matrix (5·10−3 M in THF) (reflected mode)

LB filmsStructure of modified cyclodextrins

O

OO

ORR O

OR OR

OR OR 6

23

23

6

P r i m a r y r i m

S e c o n d a r y r i m

A x i s o f r o t a t i o n

n

Axis of rotation

Secondary rim

Primaryrim

n

6

2

3 2

3

6

n Modification

6 R2=R3=R6=Si(CH3)3

7 R2=R3=R6=Si(CH3)3

8 R2=R3=R6=Si(CH3)3

7 R2=R3=Si(CH3)3;

R6=SH

O. Fichet et al., Thin Solid Films (2008)

Pressure surface isotherms

recorded on a water

subphase

temperature 20 °C;

compression rate,

20 Å2 molecule−1 min−1

(a) αCD-Si3x6 (b) βCD-Si3x7 (c) γCD-Si3x8 (○) βCD-7S-14Si

A0 346 400 470 412

ACOLL 208 295 356 330

A0 ACOLL πCOLL

pC8-βCD 455 428 12

6SiMe2tBu-βCD 380 278 47


FTIR spectra films in the range 3100–2750 cm−1 of 1 to 21 layered LB films

Inserted picture: 2956 cm−1 absorbance of pTMS-βCD-Si3x7

measured as a function of the number of LB layers

Multilayered LB films – chemical structure


LB films – chemical structure

Infrared spectra (10 scans) of

(a) βCD-Si3x7 powder (KBr pellet—resolution: 1 cm−1)

(b) 21 layers of pTMS-βCD LB film (CaF2—resolution: 4 cm−1)

CD-nSi(CH3)3

+ H2O- m(CH3)3SiOH

CD-(n-m)Si(CH3)3(OH)m

HYDROLYSIS


Frequency change of the quartz crystal microbalance as a

function of the number of deposited layers at 30 mN.m−1

(⋄) αCD-Si3x6

(×) βCD-Si3x7

(○) γCD-Si3x8


(•) theoretical and

(▪) measured

values

of the different

CD-Si3xn

(○) theoretical and

(□) measured

values

of βCD-6S-14Si

Molar masses versus D-glucopyranose unit number


Arrays for non polar gas sensors

* LB films (20 layers) of βCD-Si3x7

exposed to benzene vapours

* at t = 1200 s, LB films were removed in air

Benzene vapors up-take

APPLICATION of modified CDs LB films

CD-7S-14Si ionic channels

in lipid membranes

O. Fichet et al., Thin Solid Films (2008)

L. Bacri et al., Langmuir 21,

5842 (2005)

Asolectin + CD-7S-14Si

ΔV = 150 mV


WHAT NATURE KNOWS TO DO ?


Scheletul unui burete de mare

Virusii- bio-nano-coloizi

- prezinta, in general, doua forme:

icosaedrica

helicoidala


Virusul mozaicul tutunului (TMV)

2,130 unitati, Mw 40,000,000A. Klug, Angew. Chem. Int. Ed. Engl. 1983, 22, 565

ARN

Lungime ~ 300 nm

Intindere ~ 18 nm

Agregate liotrope de tipul baghetelor

Rice Yellow Mottle VirusCowpea Chlorotic Mottle Virus

(CCMV)

Platforma de asamblare pentru CCMV

Redrawn from Johnson and Speir, J. Mol. Biol. 269, 665.

Stuctura icosaedrica

180 subunitati identice

(20kD)

Diametru 30 nm

Cavitate interna 18 nm

Virus SARS (sindrom respirator sever acut)

? ? ? ! ! !

evolution from divided to condensed and to organized, living and

thinking matter

increase in complexity through self-organization

Ontogenetic questions: how the matter became complex (thinking

organisms) starting from elementary particles?

Epigenetic questions: what other complex matter does exists or

is to be created?


ABIOTIC SYNTHESIS OF ORGANIC COMPOUNDS “cold theory”

simple inorganic compounds = primordial reducing atmosphere

SYNTHESE ABIOTIQUE DES PORPHIRINES: C.I. Simionescu et al., 1977BIOGENESE: C.I. Simionescu et al., 1978

highly energeticchemistry

H2 CH4 ?CO NH3 ?CO2

H2O

organic compounds

adsorption on the frozen surface of primary ocean

(prevention of the destructive action of high energy sources)

slow thaw of frozen oceanformation of “primordial soup”

organic compoundsinorganic salts

diverse and morecomplex compounds

? • dilution: Hull, Nature, 1960• incompatibility: amino acids and sugars

destroy each other

?• with O2:

no amino acidsno life possible

• no O2: no ozoneno life possible

lifeless coarcevates


COMPLEX ORGANIZED MATTER – evolution to lifeother mysteries

Building proteins and nucleic acids

other necessary components of life: lipids, carbohydrates etc.

?• some components are not available in appropriate state

ex.: phosphoric acid required for DNA reacts with Ca2+ - insoluble salt• polymerisation

through what mechanism the amino acids were transformed into proteins?• sequences

F. Hoyle (astronomer): “the probability of life evolving anywhere in the universe is likely a tornado sweeping through a junkyard and assembling a Boeing 747”

• optical isomershow the optical isomers were produced?

Building biological systems from biological components

?• mechanism of the controlled building of the systems (how a biological system

could arise) ?


snowflakes

WATER AND LIFE

- solvent for vital organic andinorganic compounds

- metabolism component- photosynthesis and respiration

- capillary action

WATER

- dipolar molecule- hydrogen bonding

- self-assembling (crystallization)

PROPERTIES


http://upload.wikimedia.org/wikipedia/commons/c/c2/SnowflakesWilsonBentley.jpg

http://upload.wikimedia.org/wikipedia/commons/6/64/Capillarity.svg

http://upload.wikimedia.org/wikipedia/commons/2/2f/Auto-and_heterotrophs.svg

SILICATES AND LIFE

IN THE PRIMARY AGE OF EARTH

- were they one of the promoters in the synthesis of organic molecules?

- did they represent the template for the structuring (ordering) of organic molecules?

N. Oita, CICATROL, „80

SILICATES

- large diversity- crystallized or amorphous

PROPERTIES

(Si-O)m (O-Metal+)n


http://www.google.ro/imgres?imgurl=http://www.galleries.com/minerals/silicate/labrador/labrador.jpg&imgrefurl=http://www.galleries.com/minerals/silicate/labrador/labrador.htm&h=360&w=480&sz=36&tbnid=lQ5PzQtpncBNaM:&tbnh=97&tbnw=129&prev=/images%3Fq%3Dsilicates&usg=__3NeEOV5L6_EsghMdxO2PGc9rwE0=&sa=X&ei=cv8YTMfpCKCWOI22_PwP&ved=0CDQQ9QEwBA

http://www.google.ro/imgres?imgurl=http://www.suu.edu/faculty/colberg/Hazards/silicates.jpg&imgrefurl=http://www.suu.edu/faculty/colberg/Hazards/Append2.html&h=627&w=600&sz=83&tbnid=Jw8Njd4RSB69jM:&tbnh=136&tbnw=130&prev=/images%3Fq%3Dsilicates&usg=__Q_6Lz5ZSxXbaAWeZ5Ykn7CRsx4Y=&sa=X&ei=cv8YTMfpCKCWOI22_PwP&ved=0CDYQ9QEwBQ

http://www.google.ro/imgres?imgurl=http://media-2.web.britannica.com/eb-media/42/2642-004-ECDAC0A8.gif&imgrefurl=http://www.britannica.com/EBchecked/topic-art/544227/2492/Various-structural-linkage-schemes-in-silicates&h=1036&w=494&sz=42&tbnid=0sx3RHcZ7Kw_PM:&tbnh=150&tbnw=72&prev=/images%3Fq%3Dsilicates&usg=__cV2W2P6zVnjC3Pv_IytLDqbu__M=&sa=X&ei=cv8YTMfpCKCWOI22_PwP&ved=0CDgQ9QEwBg

http://www.google.ro/imgres?imgurl=http://www.geo.wvu.edu/~jtoro/geol101/minerals/silicates.jpg&imgrefurl=http://www.geo.wvu.edu/~jtoro/geol101/Outlines-1.html&h=733&w=1000&sz=271&tbnid=4owUu99I3pD27M:&tbnh=109&tbnw=149&prev=/images%3Fq%3Dsilicates&usg=__4RrYK8kC3zHcKqo9PIFU-ZFpEJo=&sa=X&ei=cv8YTMfpCKCWOI22_PwP&ved=0CDoQ9QEwBw

http://www.google.ro/imgres?imgurl=http://alex.state.al.us/uploads/24065/silicates.bmp&imgrefurl=http://alex.state.al.us/lesson_view.php%3Fid%3D24065&h=393&w=432&sz=498&tbnid=6Nn30HKQJltKwM:&tbnh=115&tbnw=126&prev=/images%3Fq%3Dsilicates&usg=__sfVy4XXaXhqVU5C65-bQrlYbW88=&sa=X&ei=cv8YTMfpCKCWOI22_PwP&ved=0CDIQ9QEwAw
















WHERE CHEMISTS ARE?

SUPRAMOLECULAR CHEMISTRY – SCOPE AND PERSPECTIVES

MOLECULES – SUPERMOLECULES – MOLECULAR DEVICES

Nobel lecture, December 8, 1987

JEAN-MARIE LEHN

Institut Le Bel, Université Louis Pasteur, Strasbourg

and Collège de France, Paris

combinatorial dynamic chemistry (CDC)

adaptive and evolutive chemistry

CDC

Conclusions

Thank you!

Chemists are able to

investigate the past, to

create the present and to

provide links to the future

N

N

N

N

N

N N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N

N N

N NNN

F e2 +

NN

NN N N

F e2 +

F e2 +

F e2 +

F e2 +

F e2 +

There is still a long way

for human intelligence

to mach NATURE abilities

self assembling · evolution from divided to condensed and to organized, living and thinking matter...

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