Electrical double layer

Electrical double layer

Jasna Urbanija
Supervisor: dr. Veronika Kralj-Igli
Outline
Outline

Colloids
Colloids

Forces in colloid systems
Forces in colloid systems

A bit of history
A bit of history

Double layer free energy for counterions
Double layer free energy for counterions

Double layer free energy for rod
Double layer free energy for rod
-
-
like
like
counterions
counterions

Giant phospholipid vesicles
Giant phospholipid vesicles

Experiments
Experiments
Colloids
Colloids

one or more of the components has at least one
one or more of the components has at least one
dimension within the
dimension within the
nanometre
nanometre
(10
(10
- -9 9
m) to
m) to
micrometre
micrometre
(10
(10
- -6 6
m) range, i.e. systems containing large molecules
m) range, i.e. systems containing large molecules
and/or small particles
and/or small particles
Examples of systems
Examples of systems
which are colloidal (at least in
which are colloidal (at least in
some respects):
some respects):
Plastics
Plastics
Foams
Foams
Emulsions
Emulsions
Pharmaceuticals
Pharmaceuticals
Dyestuffs
Dyestuffs
Blood
Blood
Soil
Soil
Paper
Paper
Cosmetics
Cosmetics
Paint
Paint
Cement
Cement
Ink
Ink
Agrochemicals
Agrochemicals
Foodstuffs
Foodstuffs
Aerosols
Aerosols
Examples of processes which rely heavily on the
application of colloid/surface phenomena
Emulsion
Emulsion
polymerization
polymerization
Water clarification
Water clarification
Adhesion
Adhesion
Road surfacing
Road surfacing
Ion exchange
Ion exchange
Soil conditioning
Soil conditioning
Wetting
Wetting
Food processing
Food processing
Precipitation
Precipitation
T
T
he factors which contribute most to the overall
he factors which contribute most to the overall
nature of a colloidal system
nature of a colloidal system
:
:
Particle
Particle

particle
particle
interactions
interactions
Particle size
Particle size
Particle
Particle

solvent
solvent
interactions
interactions
Surface
Surface
(
(
electrical)
electrical)
properties
properties
Particle shape and
Particle shape and
flexibility
flexibility
The importance of the interface
The importance of the interface
At the interfaces between the dispersed phase and the dispersion At the interfaces between the dispersed phase and the dispersion
medium medium characteristic surface properties characteristic surface properties, such as adsorption , such as adsorption
and and electric double layer effects electric double layer effects, are evident and play a very , are evident and play a very
important part in determining the physical properties of the important part in determining the physical properties of the
system as a whole. system as a whole.
S Substantial ubstantial modification of modification of the overall the overall bulk properties bulk properties of a of a
colloidal dispersion can often be effected by small quantities o colloidal dispersion can often be effected by small quantities of f
suitable additives suitable additives (ions) (ions)
Surface science Surface science is, therefore, closely linked with is, therefore, closely linked with colloid colloid
science science
The surface or interfacial phenomena associated with colloidal The surface or interfacial phenomena associated with colloidal
systems are often studied by means of systems are often studied by means of experiments on experiments on
artificially prepared flat surfaces artificially prepared flat surfaces rather than on the colloidal rather than on the colloidal
systems themselves systems themselves
Caution!
Caution!

Many body effects screening
Many body effects screening

Medium dielectric constant
Medium dielectric constant
Fritz London, 1928 Fritz London, 1928
Forces in colloid systems
Forces in colloid systems

Electrostatic
Electrostatic
(Coulomb ion
(Coulomb ion
-
-
ion
ion
~
~
r
r
- -
1 1
, ion
, ion
-
-
dipole
dipole
~
~
r
r
- -
2 2
, dipole
, dipole
-
-
dipole
dipole
~
~
r
r
- -
3 3
, ion
, ion
-
-
induced dipole
induced dipole
~
~
r
r
- -
4 4
,
,
dipole
dipole
-
-
induced dipole or Debye
induced dipole or Debye
~
~
r
r
- -
6 6
, thermally
, thermally
averaged dipole
averaged dipole
-
-
dipole or Keesom
dipole or Keesom
~
~
r
r
- -
6 6
)
)

Van der Waals
Van der Waals
(Debye, Keesom, London
(Debye, Keesom, London
dispersion)
dispersion)
C
h
a
r
l
e
s

A
u
g
u
s
t
i
n

d
e

C
o
u
l
o
m
b
C
h
a
r
l
e
s

A
u
g
u
s
t
i
n

d
e

C
o
u
l
o
m
b

Solvation
Solvation
forces
forces
oscillatory: originating from molecular ordering oscillatory: originating from molecular ordering
monotonic: surface monotonic: surface- -solvent interactions induce positional or orientational solvent interactions induce positional or orientational
order in the adjacent liquid order in the adjacent liquid

Hydrophobic/hydrophilic forces
Hydrophobic/hydrophilic forces
strong attraction/repulsion between hydrophobic/hydrophilic mole strong attraction/repulsion between hydrophobic/hydrophilic molecules in cules in
water: entropic origin, rearrangement of H water: entropic origin, rearrangement of H- -bond configurations bond configurations

Thermal fluctuation or protrusion forces
Thermal fluctuation or protrusion forces
repulsive: repulsive: surfaces with thermally mobile surface groups (cell membrane) surfaces with thermally mobile surface groups (cell membrane)

Steric
Steric
repulsive: finite size, entropic origin repulsive: finite size, entropic origin
Electric double layer
Electric double layer
-
-
a bit of history
a bit of history
First approximative theory:
Gouy (1910) and Chapmann (1913) Gouy (1910) and Chapmann (1913)
interaction between infinite charged wall interaction between infinite charged wall
(surface charge density (surface charge density ) and electrolyte ) and electrolyte
solution solution
point like charges point like charges
in water medium (permitivitty in water medium (permitivitty ) )
electric potential function and charge electric potential function and charge
distribution are computed distribution are computed
electroneutrality condition electroneutrality condition
Model: Model:
Poisson equation: Poisson equation:
Poisson Poisson Boltzmann equation Boltzmann equation for symmetrical ionic solution: for symmetrical ionic solution:
Boltzmann distribution: Boltzmann distribution:
DLVO theory
DLVO theory
Finite ion size Stern layer (1934) Finite ion size Stern layer (1934)
How to explain colloid stability? How to explain colloid stability?
Van der Waals forces Van der Waals forces
Interaction of two double layers Interaction of two double layers
Free energy of the system Free energy of the system
D Derjaguin and erjaguin and L Landau (1941), andau (1941), V Verwey and erwey and O Overbeek (1948) verbeek (1948)
Adapted from J.N. Israelachvili:
Intermolecular and surface forces
Otto Stern, Otto Stern,
Nobel prize 1943 Nobel prize 1943
Annie&Theo Overbeek,
Boris Derjaguin
Double layer free energy
Double layer free energy
-
-
lattice model
lattice model
Model: Model:
Single particle Single particle
canonical function: canonical function:
Stirling approximation: Stirling approximation:
M M number of lattice sites number of lattice sites
N N number of ions number of ions
Free energy: entropic and electrostatic contributions: Free energy: entropic and electrostatic contributions:
Electrostatic energy
Free energy
Entropic energy
= 0.1As/m = 0.1As/m
2 2
v0=5nm v0=5nm
3 3
Free energy for rod
Free energy for rod
-
-
like
like
counterions
counterions
Model: Model:
Conditional probability Conditional probability
Electrostatic term Electrostatic term
Entropic term Entropic term
Entropic term due to Entropic term due to
particles conformations particles conformations
Electroneutrality Electroneutrality condition condition
Probability condition Probability condition
L=2nm L=2nm
L=5nm L=5nm
Free energy in Free energy in dependance dependanceof the distance between the two plates: of the distance between the two plates:
POPC:CHOL:CAR=2:2:3
14min after addition of mAb 14min30s 15min
Phospholipid bilayer
Phospholipid bilayer
-
-
liposomes
liposomes
unilamellar
SUVs: 25-50nm
LUVs: > 100nm GUVs: 5-100 um
Liposome solutions are used to explore the physical aspects of membranes.
GUV
GUV

s preparation
s preparation

Dissolve lipids in chloroform:methanol=2:1 in
Dissolve lipids in chloroform:methanol=2:1 in
concentration 1mg/ml
concentration 1mg/ml

Put
Put
different
different
lipid solutions
lipid solutions
(POPC,Chol,cardiolipin)
(POPC,Chol,cardiolipin)
in desired proportions
in desired proportions
into a glass jar and shake it thoroughly
into a glass jar and shake it thoroughly

Apply 10
Apply 10
u
u
l of
l of
mixture on each of the two
mixture on each of the two
platinum electrodes
platinum electrodes

Leave the electrodes to evaporate in low vacuum
Leave the electrodes to evaporate in low vacuum
for 2 hours
for 2 hours
Chamber preparation
Chamber preparation
Vesicles formation
Vesicles formation
20um
Observation
Observation
I
n
v
e
r
t
e
d

m
i
c
r
o
s
c
o
p
e
Z
e
i
s
s

A
x
i
o
v
e
r
t

2
0
0
45ul of sample
grease Sony XC-77CE video camera
Temperature controller
Antiphospholipid syndrom
Antiphospholipid syndrom
Antiphospholipid syndrome (APS) is
an autoimmune disease characterized
by thromboticeventsand/or
pregnancy morbidity. The etiology
and underlying mechanisms of APS
are not yet understood, however,
activation of the coagulationsystem is
evident.
anticardiolipin /
anti 2GPI
antibodies
(present in sera
of patients with
APS)
GUVs containing
cardiolipin
(10-40%)
antigen beta2-
glycoprotein1
(2GPI)
?
We observed:
adhesion of vesicles to the ground and to each other,
suppression of vesicle contour fluctuations,
enhancement of the contrast of the vesicle contour,
permeabilisation of vesicle membrane to sugar resulting in dissapearance of the
contrast between the vesicle interior and exterior,
lateral sagregation of the membrane constituents
bursts of vesicles
POPC:CHOL:CAR=2:2:3
POPC:CHOL=4:1
POPC:CHOL:CAR=2:2:3
Addition of monoclonal
antibodies HCAL
Florescence labelling of cardiolipin
Florescence labelling of cardiolipin
10 nonyl acridine orange (NAO)
The
The
E
E
nd
nd
POPC:CHOL:CAR=2:2:3
14min after addition of mAb 14min30s 15min
Theoretical model
L
Electroneutrality condition Probability condition
Electrostatic term
Entropic term
Entropic term due to particles conformation
Partition function for the
lattice model
Minimum in free energy attractive force