Review:

Langmuir model and Vroman effect

= kc/(1+kc),
where = fraction of surface occupied by solute,
k = equilibrium constant for adsorption reaction,
and c = concentration of solute
• Langmuir model: reversible adsorption from
solution
• Vroman effect: displacement of proteins by other
proteins that have higher affinity for surface
 Preparation for Exam 1
(discussion in lectures before Exam; preparation for Exam 1)
• State clearly and succinctly motivation of each article
(shared drive: Folder (Exam 1 homework)
• Be able to describe succinctly the fundamental basis of all
of the experimental methods and biological processes
• Look up Langmuir-Freundlich equation:
– What is equation? What are assumptions? How well does it
match experimental results?
• Comment on the interpretation of the results
• What experiment(s) would you do next?
• Similar approach for DLVO papers
*Note:
1) May require researching related/cited reference list
2) Serves also to prepare you for the ‘mini grant’
 Lecture Outline
• Motivation for studying intermolecular and
surface forces
• Introduce (review) intermolecular and
surface forces involved in protein adsorption
• Use context of protein adsorption to discuss
origin of electrostatic and vdW interactions
and relevance in protein adsorption
• Describe DLVO theory
 Motivation for studying DLVO theory

How can we describe electrostatic, van der Waals,

hydrophobic interactions between surfaces, particles, and
particles and surfaces?
Why should we be interested in studying
intermolecular forces?

We would like to answer questions such as...

• Will a molecule (protein) be adsorbed or repelled from a surface?

• Under what conditions will it desorb from the surface? (pH, [salt], T)
• Under what conditions can I release it from the surface?
• How weakly/strongly is something adsorbed to the surface?
• Under what conditions will my particles aggregate or remain
dispersed?

Under what conditions would I want aggregated nano/microparticles?

Under what conditions would I want dispersed nano/microparticles?
 Example: Stability against aggregation
Theoretical prediction: Interaction between two MBs
Free energy of two interacting microbubbles (MBs) with a polymeric shell

• WPEGW5KPEGMB W
much WElectextended than PEG 2K MB.
VdW more

• PEG 5K MBs: 1
AH R marginally stable against
s æ k BT ö
aggregation æ e 0 ö
WVdW = . WElect = RZe , Z = 64 0ç ÷ tanh ç ÷ ,
æ ps ö 2 è e ø è 4kBT ø
• 12s çè
PEG 2K MBs: 1+ ÷ø
unstable at physiological conditions.
WPEG from a molecular theory

Polymer volume fraction Free energy

Park et al. (2012 epub) Langmuir
 Surface Forces Apparatus

D. Leckband (UIUC)
Conventions for force-distance curves:
DLVO example
1. Interactions b/w Macroscopic Bodies
•Interaction free energy
Electrostatic repulsion

W(D) WE (D) WA (D)

W(D)
D(nm)

2o
van der Waals
1o attraction

* Need to understand van der Waals and electrostatic interactions

to develop curves based on DLVO theory
 Classes of Intermolecular Forces
• electrostatic: Coulomb force between charges, permanent
dipoles (ion-ion, ion-dipole, dipole-dipole)
• polarization forces: arise from dipole moments induced by
E of nearby charges and permanent dipoles (all interactions
in a solvent medium involve polarization effects)
• quantum mechanical: covalent or chemical bonding or
charge transfer; and repulsive steric or overlap interactions
(occurs when the electron clouds of two closed-shell
molecules overlap – Pauli exclusion principle) that balance
attractive forces at very short distances
• dispersion or fluctuation interactions: induced dipole
induces a dipole in another molecule to form another
induced dipole
 Range of Forces
• short-range (rarely extending more than one
or two atomic distances)
• long-range (determines whether two surfaces
or particles are able to get close enough in
the first place before they can interact via
short-range interactions)
 Covalent or Chemical Bonding

• shared electrons between two or more

atoms so that the discrete nature of the
atoms is lost
• valency (e.g. carbon: 4; oxygen: 2)
• directionality of bond (well-defined angles)
• short range interactions (0.1-0.2 nm)
• strength ~ 100-300 kT per bond
 Difference between physical and
chemical bonds
• covalent bonds: electron charge distribution
changes completely and merge during binding
• physical ‘binding’: electron charge distribution is
only perturbed and atoms remain distinct
entities
• physical ‘binding’ forces can be as strong as
covalent bonds; weakest force is strong to hold
most atoms and molecules together in solids
and liquids at room temperature (eg:
streptavidin-biotin (35kT) )
 van der Waals forces
• exhibit common power law dependence ~ 1/r6
• Lennard-Jones potential
W(r) = A/r12 – B/r6
• three components: Keesom, Debye and London
– Keesom: dipole-dipole
– Debye: dipole-induced dipole
– London: dispersion
 What about macroscopic bodies?
W(D) vs. D
Sum up all interactions

W(D) UA n
D
D = separation distance
U = dimensional constant
A = Hamaker constant, p2Cr1r2
C = atomic or molecular parameters (Jm6)
 Hamaker Constant (A)
p2Cr1r2 (See table of geometries)

• Hamaker constant is closely related to range and the

strength of the vdW contribution.
• Hamaker constant depends on the dielectric
properties of the interacting materials and the
intervening medium.
Example of experimental measurement:
spectroscopic ellipsometry
• Hamaker constant of proteins in water ~ 3 – 10 kBT
 Lifshitz approach

A AL AKD
3hv e (n12 n32 )(n22 n32 )
AL 2 2 1/ 2 2 2 1/ 2 2 2 1/ 2 2 2 1/ 2
8 2(n 1 n3 ) (n2 n3 ) [(n1 n3 ) (n2 n ) ]
3

1 3 2 3
AKD kT
1 3 2 3

Israelachvili, Intermolecular and surface forces

Review from Last Lecture

DLVO is sum of vdW and e-statics

1. Interactions b/w Macroscopic Bodies
•Interaction free energy
Electrostatic repulsion

W(D) WE (D) WA (D)

W(D)
D(nm)

2o
van der Waals
1o attraction

* Need to understand van der Waals and electrostatic interactions

to develop curves based on DLVO theory
Review from Last Lecture
 Lecture Outline
• Electrical double layer
– Surface charge
– Surface potential
• Poisson-Boltzmann equation
– Debye-Huckel approximation
– Debye-Huckel parameter; Debye length

• Describe DLVO theory

 Diffuse Electrical Double Layer

(How do surfaces
acquire charge?)

We have a framework to describe vdW interaction. How do we describe the electrical

potential as a function of distance from a surface??
 Poisson equation
• gives relationship between electrical potential
and charge density in a vacuum
• Assumptions:
• ion-ion interactions dominate
• Average over solvent degree of freedom
• Eliminate ion-dipole and dipole-dipole interactions
 Boltzmann Equation
• Need to know potential as a function of x
• Boltzmann equation gives charge density per unit volume r
at any location in the solution

Need fx= f(x)

Use Poisson-Boltzman equation
Solved gives r(x), f(x), and
d f
2 E= df/dx at any point
2 zer / between surfaces
dx o
 Poisson-Boltzmann (P-B) Equation
Electrostatic interactions require solving the
P-B equation

2 1
n z e exp( z i e / kT )
o
i i
o i

• 2nd order nonlinear differential equation

• gives
• r(x),
• f(x), and
• E = df/dx at any point between surfaces
K-1= Debye length (L)