Self-assembly and Bio-Liquid Crystals

Chapter 3

Structural change of micelles

and surfactant packing parameter, g

Presented by Le Huu Tuan

Advisor: Prof. Kang Shin Woong
 Change of Micelle Structures:
- Any change that can be effected either attractive or repulsive or Both force can
change the force balance between them.
- The change of binding degree of anionic counterion affect effective density of charge
d head groups on the surface alter the repulsive force attractive hydrophobic force
will respond toward the new force balance
usually results in structural change of micelle.
- Other factors also effect to structural transition.
Change of Micelle Structures:
- The typical evolution of micelle structures in aqueous solution:

spherical (ellipsoidal) rod-shaped worm-like various liquid crystals

larger, more ordered, less symmetric

This change usually occurs by:

the increase of surfactant concentration (increasing attractive force)
increase of counterion concentration (decreasing repulsive force)
 General Scheme of Micellization:

- Surfactant monomer correspond to primary building unit.

- Spherical micelle: primary self-aggregate
- Structural change due to the shift of force balance
- Spherical/ellipsoidal/rod-shaped/worm-like LC Phases
micelles: secondly building units
- Hexagonal/cubic/lamellar liquid crystal phases:
secondary self-aggregates
- Delicate shift of force balance may induce
phase transitions between mesophases (LCs).

Nu
LC Phases
Ch
Concept of Force Balance and Surfactant Packing Parameter:

- Surfactant/micelle packing parameter, g: dimensionless parameter

: volume of hydrocarbon chain of monomer in the micelle
ao : area occupied by the head group on the micelle surface
lc : apparent length of the hydrocarbon chain of monomer in the micelle
c
- For primary self-assembly, the total free energ
: free energy at the oil-water interface
y is expressed as follows:
A : total area of micelle surface
a : surface area occupied by monomer
- Attractive contribution, UA,P (x) = A K : constant
(hydrophobic interaction)
- Dividing this term by aggregation number, n
A/n = a c

- Repulsive contribution, UR,P (x) = K/a

(electrostatic repulsion, hydration and steric
interactions (All are inversely proportional to
the area of head group, a)
- Total interfacial free energy per monomer
at the micelle surface:

- a for the minimum energy U dU/da = 0

ao
- With the assumption of compact micelle (i.e., no water penetration on the surface)
= 27.4 + 26.9 nhc in 3
nhc : number of carbons in HC chain
lmax = 1.54 + 1.265 nhc in lmax : max. possible extension of HC chain
l lmax
( /l 21 2 constant for large nhc )
- The number of C-C kink configuration is the main factor in estimating l
- One kink can reduce the chain length ~ 1.25
- Typical surfactant chains have 1.5 2.5 kinks (~1.8 3.2 )
depending on their length and dynamic state
- The most favorable micelle structure can be determined by using surfactant packing
parameter (g) without knowing complex relation between forces.

g 1/3 ------> cone type monomer ------ spherical micelles Cylin

g 1/2 ------> truncated cone t ------ drical micelles flexible
g 1/2 ~ 1 ------> runcated cone c ------ bilayers, vesicles bilaye
g 1 ------> ylinder type ------ r-type micelles reverse
g > 1 ------> inverted (truncated) cone ---- micelles
-->
 Various forces acting laterally between head groups and HC-chains

c
HLB number:
Hydrophile-Liphophile
Balance number
 Hydrophile Lipophile Balance
The fractional of hydrophobic part to hydrophilic part of surfactant

The value of HLB can be calculated by equation below:

The HLB value can be used to predict the surfactant properties of a molecule.

The dissolve of a matter in water.

Different types of structures and mesophases formed by amphiphiles in water
Ellipsoidal micelles

First order phase transitions

process
 3.5 Multicomponent Micelles
Mixed micelles:
- Micelle that is formed through the self-assembly of more than two different kinds of
surfactant molecules
- Composition of monomers is directly related to the composition in the mixed micelle.
- Pseudo-phase separation model is more suitable for describing the formation of
mixed micelles.

When both surfactant 1 and 2 coexist

- there are more than one molecular
interactions
Three molecular interactions: b
etween 1 and 1
between 2 and 2
between 1 and 2
Multicomponent Micelles: mixed micelles

- For the formation of ideal or close to ideal mixed micelle, all three interactions
should be the same or similar.

- cmc of surfactant mixture 1 and 2 becomes cmc1, cmc2 : cmc of each surfactant
x1, x2 : mole ratio of each surfactant
1/cmc = x1/cmc1 + x2/cmc2 x1 + x2 = 1

- Example: surfactants with the same or similar

head group homolog series of surfactants
For ionic-nonionic surfactant systems
- Negative deviation from ideality: net attractive interaction between surfactants
(attractive between surfactants 1 and 2)
- The repulsive force between ionic head groups can be shielded by nonionic group.
- Possible additional attractive force between ionic and nonionic head groups (charge-
dipole interaction).
 Multicomponent Micelles: synergism
Mixed micelle with large negative deviation:
- The largest negative deviation from ideality comes from cationic-anionic surfactants.
- Strong electrostatic attraction between head groups is responsible for this.
- Usually, the systems with negative deviation from ideality show synergism in many physico-
chemical properties.
Synergism: property/performance of mixed micelle system is better than any of single
component systems.
- In this case, cmc of the mixed micelle is smaller than that of single component system.
- This changes the concentration of monomer in solution, structure of micell,
aggregation number, and phase diagram.
- A small addition of the second component can dramatically change the micellization process
itself.
- Cationic-anionic surfactants form a vesicle at a relatively low
concentration.
 Antagonism:
Multicomponent Micelles: antagonism - An opposing force, principle, or tendency
- The opposing action of substances, as drugs
When the interaction 1-1 and 2-2 is stronger than interaction 1-2
- The system shows a positive deviation from ideality.
- Antagonism is found in this case: cmc of mixed micelle increases and
aggregation number (n) decreases.
- For the extreme case of the mixture of HC and per-FC surfactants, two different
micelles (HC-rich and per-FC-rich micelles) can coexist in solution.
The third type of mixed micelle
Amine oxide
- This forms a micelle with cmc range
of 1 ~ 200 mM in aq. solution at RT.
- Depending on the solution pH, the head group can be either cationic or nonionic.
cationic (protonated form) at low pH
coexisting cationic/nonionic form at medium pH
nonionic (deprotonated form) at high pH
Mixed micelle systems
- Important for industrial applications.
- For many practical reasons, the micellar systems that are used in industry
are multicomponent system.

On nanotechnology side
- The concept of mixed micelle provides an important insights.
- The synergism and antagonism of mixed micelle play an important role in determining
/controlling the structure and quality
Formation of mixed monolayer/multilayer and their phase behavior can be critical issue f
or nanofablication or nanopatterning processes
- It provides good insight into development of heterogeneous self-assembly for progress
in nanodevice.