lundi

11h-12h20

mardi

8h-9h20

9h30-10h50

11h-12h202

13/09/2010

Oda

14/09/2010

20/09/2010

Oda

21/09/2010

Oda (Petrus)

Oda(Petrus)

27/09/2010

Dufourc

28/09/2010

Dufourc(Petrus)

Dufourc(Petrus)

04/10/2010 11/10/2010 Rayner

05/10/2010 12/10/2010 Barthlmy

Rayner Oda

Rayner Dufourc

18/10/2010 25/10/2010

Schmitter Vacances Bdx 1

19/10/2010 26/10/2010 Vacances Bdx 1

Schmitter Vacances Bdx 1 Vacances Bdx 1

01/11/2010 08/11/2010

FERIE Di Primo

02/11/2010 09/11/2010 Di Primo

Schmitter Schmitter

barthlmy Schmitter

15/11/2010

barthlmy

16/11/2010

Barthlmy

Schmitter

22/11/2010

barthlmy

23/11/2010

Dufourc

Dufourc

First class, September 13, 2010

Reiko Oda, IECB, CNRS r.oda@iecb.u-bordeaux.fr

The objectives
Introduction to the Richness of the world of amphiphilic molecules in terms of morphologies, dynamics and utilities of their assemblies

Membranes and Molecular Assemblies: The Synkinetic Approach

Jrgen-Hinrich Fuhrhop and Jrgen Kning RSC, Monographs in Supramolecular Chemistry Series Editor: J. Fraser Stoddart, FRS

Intermolecular and surface forces

Jacob Israelachvili, 2nd ed.; Academic Press: London, 1992; part III.

Planning of the courses - Oda, Barthlemy

Formation of hierarchical nano-to microstructures What is an amphiphilic molecule? Structure of differents synthetic amphiphiles Assemblies of amphiphiles, structures, dynamics and interactions Physico-chemical measurements for the proprieties of assemblies Functionalisation of lipidic molecules (natural and synthetic): necleolipids, glycolipids, peptidolipids
Transport and/or vectorisation of active agent (therapy, nucleic acid).

different sizes
the earth ~ 13 106 meters in diameter the moon ~3.5 106 meters in diameter

Renne Bordeaux ~ 5 105 meters lestuaire de la Gironde ~104 meters a whale a man a hair a cell up to ~30 meters ~1 meter ~ 10-4 meter (100 m) ~ 10-5 meter (10 m)

a molecule ~ 10-9 meter (nm)

a man a hair a cell

~1 meter ~ 10-4 meter (100 m) ~ 10-5 meter (10 m)

a molecule ~ 10-9 meter (nm)

In living systems, molecules self-assemble in a well defined way and these assemblies have collective properties and functions
Living cells self-assemble, and understanding life will therefore require understanding self-assembly. - George Whitesides

Intra and Inter-molecular self assemblies and their functions

hierarchical construction
Microtubule

proteins
From 20 amino acide

DNA double helix

20 nm
from 4 nucleotides

2 nm

a lady bug

a cell 10 m 5 mm a stem of a plant

10 cm

Studying Amphiphilic/lipidic molecules allows connecting angstrom scale objects to visible and observable world

O (H3C)3+N O
-

O P O

O O O

CnH2n CnH2n

Nature has a lot of imagination in terms of morphologies and functions of self assembled structures

understand how and why they are made like that

Can we make systems which mimic those structures and functions?

natural object
VIRUS

synthetic structure

icosahedron The 20 faces of a regular icosahedron are equilateral triangles

natural object
microtubule

synthetic structure

30 nm VIRUS

up to a certain level, we can mimic the morphologies of nano-micro structures based on molecular assembly which exist in nature

For designing such objects, we have to well control the properties of molecular building blocks at atomic scale ("bottom-up" approach)

Amphiphilic molecules
Amphi (on both sides) phile (like)

Any molecules which have two sides which like two media respectively which are otherwise non-miscible are theoretically amphiphilic
Water vs oil (99% of the cases, hydrophilic and phobic at the same time)
Fluorocarbon vs hydrocarbon

Molecules which can have hydrophobic and hydrophilic parts at the same time are,
Detergents

low molecular weight e1000 g/mol

Surfactants surface active agents (tensio-active) Lipids

~2 nm

high molecular weight >>1000 g/mol

Proteins peptides polymers

10~100 nm

synonym : amphipathic

Low molecular weight amphiphiles

molecules which Have hydrophilic and hydrophobic parts at the same time Soluble (or dispersible) in at least one of the liquids Go selectively to the interface, and lower the surface tension of the liquid

Such molecules are also called as : Detergent (washing) Lipid (natural molecules, constituent of cell membrane) surfactant or surface active agent (lowers surface tension) No real rule for definition, rather defined by the utility They dont overlap with each other exactly

Utilities of surfactants (by lowering surface tention)

Cleaning (soaps, shampoo,..) Emulsifier (skin cream, medical creams, mayonnaise) Viscosity increase (shampoo, liquid soap..)
water grease water

separation

emulsion
thermodynamically unstable

oil
>400 nm

water
microemulsion (thermodynamically stable) 10~100 nm

increase in the interface area does not cost much energy

Utilities of surfactants
Bubbles, humidifier (Shaving cream) Bubbles, volume increase (cheap ice cream and sherbet) Solubilizer, stabilizer (painting, food)
~10 nm 1m
air

water

colorful bubbles to invisible bubbles (black film)

vesicles cells

Structure of amphiphilic molecules

Both Hydrophobicity and hydrophilicity have to be strong enough

Hydrophobic part ~ 6-20 carbons saturated or non-saturated Hydrophilic part, charged groups, COO-, SO4-,PO4- ,NMe3+ ,NH3+ non ionic groups ((CH2)2O)n, sugar -OH,-COOH are often not enough hydrophilic Alcohols, carboxylic acids are not surfactants strictly speaking, even if they are amphiphilic

various natural lipid structures

Courses by E. Dufourc P. Barthlemy

Many examples are found in the literature for synthetic amphiphiles Some examples, their characteristics and classifications Why do we make new types of amphiphilic molecules? Logic behind design

STRUCTURE of Surfactant molecules

a)

b)

c)

d)

e)

+ -

monomeric

two chains lipid-like

catanionic

gemini

bola

They can be charged (cationic, anionic) or non-ionic (neutral) or zwitterionic (cation and anion in the same molecule)

 Most simple or commercial molecules photoactive surfactant Bola amphiphiles Gemini, or oligomeric surfactants Molecules with functional (biological) headgroups

Most simple or commercial molecules Charged amphiphiles cationic

Br- N

anionic

DAAB ATAB

O Na
+

O O O O

O- S O

AOT

Br-

O Na+ O- S O O

SDS carboxylic

catanionic
N O O- S O

Na+

OO

formed with two amphiphiles with opposite charges

non-ionic
HO O
m CnH2n+1

CnEm Sugar

HO

OH OH H N OH OH O
OH O

HO HO

zwitterionic phosphocholine
(ethanolamine)
-

O O
-

(H3C)3+N

O P O

O O O

CnH2n CnH2n

O O P O O N+

Bola amphiphiles

O O S O O S O O

symmetric

HO HO

OH O

O O O

H N

N+

dissymmetric

often associated to vesicle formation

water

water

photosensitive amphiphiles
photoisomerisation (conformation change) or photolysis

irradiation ?

Gemini, or oligomeric surfactants

Lowers cmc with high solubility (cmc ~hydrophobicity, solubility ~head groups) Possibility to have molecular structures with richer varieties

a b

a e c b d

Gemini, or oligomeric surfactants