Phase behavior of phospholipids

and other surfactants:

Morphology of lipid assemblies

Assoc. Prof. Dr. I. Tuncer DEGIM

Lipids, Oils, Amphiphilic molecules etc. have some interesting
behaviors and these have been discovered long ago.

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TECHNOLOGICAL IMPORTANCE OF POLYMER
AND SURFACTANT AND ADSORPTION
Surfactants:
• Froth floatation, foams
• Enhanced Oil Recovery
• Paints
• Stabilization
• Increasing the solubility
Polymers:
• Lubrication
• Adhesion
• Stabilization
• Flocculation
• Reducing the sedimentation
• Controling crystal growth
• Ameliorating formulation Silica dispersions with different PEO
properties (spreading, viscosity concentrations in presence.*
etc.)

Teflon
*htttp://www.chm.bris.ac.uk/pt/polymer/dongqiu.shtml
Drug delivery, targetting, liposomes,
nanosomes and so on…

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 PULMONARY SURFACTANT
Pulmonary surfactant is a surface-active lipoprotein formed by
type II alveolar cells. Their purpose is:

•To increase pulmonary compliance.

•To prevent the lung from collapsing at the end of expiration
By adsorbing to the air-
water interface of alveoli
with the hydrophilic
headgroups in the water
and the hydrophobic tails
facing towards the air, the
main lipid component of
surfactant, reduces surface
tension.

http://oac.med.jhmi.edu/res_phys/Encyclopedia/Surfactant/Surfactant.HTML
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So we need to know something
more in detail about lipids,
especially phospholipids and
surfactants…..
Phospholipids and detergents
both have head groups and the
tail parts on the molecule
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Visualisition of molecules
Some phospholipids structure

Dipalmitoylphosphotidylcholin-DPPC
• Surfactants and phospholipids are molecules
that preferentially adsorb at an interface, i.e.
solid/liquid (froth flotation, solid lipid
particles, liposomes), liquid/gas (foams),
liquid/liquid (emulsions).

• Significantly alter interfacial free energy

(work needed to create or expand
interface/unit area).

• Surface free energy of interface minimized by

reducing interfacial area.
 SURFACTANT CLASSES
Anionic (~ 60% of industrial surfactants)
SURFACTANT CLASSES (contd.)
Cationic (~ 10% of industrial surfactants)
SURFACTANT CLASSES (contd.)
Non-ionic (~ 25% of industrial surfactants)
 SURFACTANT CLASSES (contd.)
Amphoteric or zwitterionic (~ 10% of industrial
surfactants). Generally expensive “specialty chemicals”
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Structures of some bilogical membrane lipids determined by
X-ray crystallography
The most outstanding futures of these molecules are:
1- Their molecular areas are around 30-50 A2 ,

2- The polar head group is virtually parallel to the plane bilayer; the
amino group is hydrogen bonded to unesterified phosphate oxygens of
an adjacent molecule; The glyceroo group is essentially oriented
normal to the plane of the bilayer,

3- The sn2 fatty acid chain extends parallel to the plane of the bilayer
for first two carbons and then is directed down into the bilayer. The
sn1 fatty acid extends directly into the bilayer,

4- The acyl chain are directed perpendicular to the bilayer surface and,
with the exeption of the initial part of the sn-2 fatty acid, are in fully
extended, all-trans configuration.
 Detailed structure of
phosphotidyl cholin molecule
 A: PEA in crystall form, acyl groups the
same,
 B: PEA in liquid crystall form, ater or other
polar solvent bridges the gap between
neighbors and stabilizes the structures,
 C: PC in theoretical arrangement and
showing that the space between head
groups are (50 A) which larger than
required space (Actual value is 38 A),
 D: PC Arrangement in overlapping fashion,
 E: Lamellar gel phase arrangement,
accomodating larger cross sectional area
(50 A2 ) ,
 F: Arrangement in lamellar luquid
crystalline phase, PC does not require the
head group lattice to be distrupted.
 Major futures of crystall structures considering
improtance for lipid bilayers:
1-Structures all in lamellar, polar and non polar groups
organized as in bilayers,
2- PC and cerebrosides have packaging problem because of
bulky head groups, this is important for the properties of
biological and model membranes,
3-The polar headgroups essentially lie flat in the plane of the
bilayer, with intermolecular hydrogen bonding,
4- Acyl chains (saturated) are in all-trans configuration,
5- The sn-2 fatty acyl chain does not extend into the bilayer
until after C2 position.
Lipid-water mixtures:

Lamellar gel phase Lamellar luqiud

crystalline phase

Hexagonal I phase
Hexagonal II phase
Do not confuse !!!
 Lipid hydration:
Many lipids are swell in water.
Lipids which are neutral or isoelectric
(PC) show no or limitted swelling
(limitted water layers between lamellae).
In excess water two phase exist.
Charged lipids show continious
swelling with water up to certain threshold.
The stability of multilamellar or unilamellar
structures are determined by
electrostatic interactions.
Polarisation of water molecules
by lipid polar head groups results
In strong repulsive effect for bilayers.
Phase diagram of PC in water
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Video enhanced microcobe

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 Micelles
• If concentration is sufficiently high, surfactants can form
aggregates in aqueous solution  micelles.
• Typically spheroidal particles of 2.5-6 nm diameter.
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 Manifestations of Micelle Formation -- CMC --
Onset of micellization observed by sudden change in
measured properties of solution at characteristic surfactant
concentration  critical micelle concentration (CMC).
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 CMC - Sodium Octanoate CMC - Sodium Octanoate

30 2.5
y = 1.708x + 6.92
25 R2 = 1
2

20
1.5
y = 0.0056x + 0.6381
15
R2 = 1

k(S/m) 1
10
Heighty(cm)
= -0.1826x + 1.9626
y = 2.9683x + 0.1809 0.5
5 R2 = 0.8433
R2 = 0.9936
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12

C (%w /v) C (%w /v)

CMC - Sodium Decanoate CMC - Sodium Decanoate

10 2.5
y = 1.324x + 2.7617
9
R2 = 0.9999 2
8
y = 0.042x + 0.9801
7
R2 = 0.75
6 1.5

5
1
k(S/m)
4
3 Height (cm)
y = 2.7549x + 0.0378 0.5
2
R2 = 0.998 y = -0.8206x + 2.0106
1
R2 = 0.9807
0
0
0 1 2 3 4 5 6
0 1 2 3 4 5 6

C (%w /v) C (%w /v)

Conductivity and Capillary Rise Graphs for Sodium Octonate

and Decanoate
 CMC - Sodium Dodecanoate CMC - Sodium Dodecanoate

2.5 2.5
y = 1.42x + 0.575
R2 = 0.9853 y = -3.6028x + 2.0119
2 2
R2 = 0.9501

1.5 1.5

k(S/m)
1 1

Height (cm) y = 0.8845

0.5
y = 2.6477x + 0.0037 0.5
R2 = 0
R2 = 0.994
0
0
0 0.2 0.4 0.6 0.8 1 1.2
0 0.2 0.4 0.6 0.8 1 1.2
C (%w /v) C (%w /v)

CMC - Sodium Dodecyl Sulfate CMC - Sodium Dodecyl Sulfate

1.2 2.5

1
y = -0.0407x + 1.2914
y = 0.8x + 0.335 2
R2 = 0.0211
0.8
R2 = 0.9995
1.5
0.6

k(S/m) 1
0.4
Height y(cm)
= -6.4983x + 1.9728
y = 2.21x + 0.0033
0.2 0.5
R2 = 0.9974 R2 = 0.8234
0
0
0 0.2 0.4 0.6 0.8 1 1.2
0 0.2 0.4 0.6 0.8 1 1.2
C (%w /v) C (%w /v)

Conductivity and Capillary Rise Graphs for Sodium Dodecanoate

and Dodecyl Sulfate
 MICELLES
-- Driving Force --

Hydrophobic groups can perturb solvent structure and

increase free energy of system. Surfactant will 
concentrate at S/G interface to remove hydrophobic groups
from solution and lower Go.

AIR

WATER
 MICELLES
-- Driving Force --
Beyond a surfactant concentration (CMC)

Go can also be decreased by aggregation into micelles such

that hydrophobic groups are directed into interior of structure
and hydrophilic groups face solvent.

Decrease in Go for removal of hydrophobic groups from

solvent contact by micellization may be opposed by:
(i) loss in entropy
(ii) electrostatic repulsion for charged headgroups

Micellization is  a balance between various forces which

can be influenced by certain phenomena
 MICELLES
--Headgroup and Chain Length--
Surfactant Temp (°C) b0 b1

Na carboxylates 20 2.41 0.341

K carboxylates 25 1.92 0.290
alkylsulfonates 40 1.59 0.294
alkylsulfates 45 1.42 0.295
alkylam m onium chlorides 25 1.25 0.265

• Branching or addition of double bonds or polar groups to alkyl chain

generally increases CMC.
• Addition of benzene ring equivalent to addition of ~ 3.5 carbons
(methylene groups).
• Replacement of hydrogens in alkyl chain with fluorine initially
increases CMC, followed by marked decrease as fluorine substitution
goes to saturation.

(Hunter, Foundations of Colloid Science, p. 569, 1993, Fig 10.2.1)

 MICELLES
--Headgroup and Chain Length--
• Klevens (1953): surfactants with linear alkyl chains, CMC is related
to number of carbons by;
log10CMC = b0 - b1mc
Where:
mc is number of carbons in chain
b0 and b1 are constants

(Hunter, Foundations of Colloid Science, p. 569, 1993, Fig 10.2.1)

 CMC
-- Effect of Added Electrolyte --
• Addition of electrolyte significantly affects CMC,
particularly for ionic surfactants

• For non-ionic and zwitterionic surfactants;

log10CMC = b2 + b3Cs
where Cs is salt concentration (M), b2 and b3 are constants for
specific surfactant, salt and temperature

• Change in CMC attributed to “salting in” or “salting out”

effects. Energy required to create volume to accommodate
hydrophobic solute is changed in electrolyte solution due to
water-ion interactions  change in activity coefficient.
 CMC Values
- General Trends -
(1) For the same head group, CMC decreases with increasing
alkyl chain length
(2) CMC of neutral surfactants lower than ionic
(3) CMC of ionic surfactants decreases with increasing salt
concentration.
(4) For the same head group and alkyl chain length, CMC
increases with increase in number of ethylene oxide (EO)
groups.
(5) For mixed anionic-cationic surfactants, CMC much lower
compared to those of pure components.
 Surfactants at the Solid-Liquid Interface

• Adsorption of surfactants at the solid/liquid interface is of

prime importance in industry and agriculture, e.g. to control
stability, floatability and rheology of particulates.

• Many different forces come into play during surfactant

adsorption. Dominant forces will depend upon not only
nature of surfactant (head group, chain length, charge, etc.)
but also nature of surface.

• Behavior of surfactants is different on hydrophobic surfaces

(e.g. teflon) compared to hydrophilic surfaces (e.g. metal
oxides).
 SURFACTANTS AT INTERFACES
Low Concentration - Surfactant Adsorption

Moderate Concentration - Hemimicelle Formation

High Concentration - Self-Assembled Surface Aggregates

 INTRODUCTION
-- Ionic surfactants and conformation --
or

70 100 10 -4
0.25  m sol-gel silica
90 CMC
Advancing Contact Angle

60 pH 4.0

Adsorption Density (mol/m2)

80 0.1 M NaCl 10-5
Zeta Potential (mV)

50 70 HMC
60
40 10 -6
50
30 40
10 -7
30
20 20
10 10 -8
10
0
0 -10 10 -9
0 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1
Concentration C 12 TAB (M)
 ISOELECTRIC POINT SHIFT

• Adsorbed amount, conformation, dissociation of surfactant,

surface charge influence the IEP
Solomon, Saeki, Wan, Scales, Boger, Usui, Langmuir, 15, 20 (1999)
 RHEOLOGICAL BEHAVIOR

Yield stress controlled by IEP

Solomon, Saeki, Wan, Scales, Boger, Usui, Langmuir, 15, 20 (1999)
IONIC SURFACTANT -- Hydrophilic Surface --
• Total free energy of adsorption, Go, can be split into
two components;
Go = Gelec + Gspec
ads
Gelec accounts for electrical interactions, while Gspec is
 a specific adsorption encompassing all other “specific” or
 non-electrical contributions.

• Further expansion of Gspec yields the fundamental

adsorption equation which is commonly expressed as;
Gads
o
= Gelec + Gh-s+ Gc-c
Gc-c is due to hydrophobic surfactant lateral chain-chain
 interactions; Gh-s arises from headgroup-surface
 chemical interactions.
 ELECTROSTATIC INTERACTIONS
• For ionic surfactants, Gelec is generally attributed as
being entirely due to coulombic interactions such that;
Gelec = Gcoul = zei
z is surfactant charge, e is the charge on electron
iis potential of the molecule in the double layer

• If net surface charge density, (i) is same sign as

the surfactant ions, i.e. zei > 0
 electrostatic repulsion opposes adsorption.

• For higher surface coverages, sufficient ionic surfactant

can adsorb until |i|||, , i.e. to point where i.e.p. is
traversed and i reverses in sign, thus opposing
adsorption.
 ELECTROSTATIC INTERACTIONS
Adsorption favored when surfactant ions and surface
are oppositely charged, i.e. z and i areof opposite sign
(zei < 0).

e.g. adsorption of SDS onto alumina with increasing pH

decreases as surface becomes less positively charged.
However, under i.e.p. conditions, Gelec = 0 and adsorption
 governed by the Gspec term.
Al2O3 Gelec
dominates i.e.p.
+ ~9
Al2O3 + SDS
o pH
_ Gspec
dominates
 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --
• As surface concentration of ionic surfactant increases, if
attractive hydrophobic interactions between alkyl chains
can compensate for ionic head group repulsion,
hemimicelles can form.

• At low coverages, patches can form on the surface.

_ _
_ _ _ _ _ _
+ + + + + +
 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --

•Hemi-micellization occurs at lower concentrations with

increasing alkyl chain length
 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --
Stern-Grahame equation (originally developed for ion
adsorption at low concentration) used by Fuerstenau
and Somasundaran (1964) to describe ionic surfactant
adsorption;
⎛ ΔG o ⎞
à = 2rC o exp⎜
⎜- ads
⎟
⎟
⎝ kT ⎠
r is the radius of the adsorbed ion (m)
Co is the initial concentration of surfactant (mol/m3)
k is Boltzmann constant and T is temperature (K)
 is adsorption density (mol/m2)
• Adsorption free energy then expressed as;
o
ÄGads = zeØ i + è h -s + nφc -c
Gelec Gh-s Gc-c
 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --

•  is a measure of adsorption energy due to lateral

interactions between n CH2 groups (and CH3 at the end)
of the surfactant alkyl chain.
• Substituting into the Stern-Grahame equation and
rearranging;
⎛ è h -s zeΨi ⎞ nφc -c
lnCo = ⎜lnà - ln2r + + ⎟+
⎝ kT kT ⎠ kT
At the i.e.p., there are no electrical interactions between
surfactant and surface, i.e. zei = 0.
• Assuming h-s is constant  bracketed term becomes
constant.
 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --
By determining surfactant concentration where i.e.p. is
zero as function of chain length, value of c-c can be extracted
from plot of lnCo versus n, where gradient is equal to c-c/kT.

(Hunter, Zeta Potential in Colloid Science, Fig. 8.7, p. 318, 1981)

 SPECIFIC INTERACTIONS
-- Chain-Chain Interactions --

Magnitude of c-cfor adsorption of ionic surfactants onto

oxides ~ -0.7 to -1kT per CH2 group. Values similar to those
for micellization in bulk solution, ie. the energy required to
completely remove a CH2 group from water.
(Hunter, Zeta Potential in Colloid Science, Fig. 8.6, p. 316, 1981)
Will be continued.