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Chapter 7 Lecture
Biological PhysicsNelson
Updated 1st Edition
Slide 1-1
Entropic Forces at Work
Slide 1-2
Last time
• We need Chapter 6 on ENTROPY, visit here:
• Main points:
• And the partition function Z
• -kBT ln(Z) minimizes the free energy!
• Entropic forces f = - dFa/dx
Slide 1-3
A great Sci-fi quote
• “The struggle between life elements is the
struggle for the free energy of a system.”
• DUNE, Frank Herbert, 1967
Slide 1-4
Outline
• 7.1 Microscopic view of entropic forces
– Fixed volume and pressure approaches
• 7.2 Osmotic pressure
– From ideal gas law and depletion forces
• 7.3 Beyond Equilibrium: Osmotic flow
– Rectification of Brownian motion
• 7.4 A repulsive interlude
– Electrostatics, Gauss’ Law and more
• 7.5 Properties of water (extra reading)
– Water generates an entropic attraction
between nonpolar objects
Slide 1-5
Comment & Focus questions
• F = E – TS, macroscopic systems tend to lower
their free energy even if:-
– The change actually increases the energy
(but increases TS more)
– The change actually decreases entropy (but
decreases E/T more)
• What keeps cells full of fluid?
• How can a membrane push fluid against a
pressure gradient?
• Osmotic pressure is a simple example of an
entropic force
Slide 1-6
• Constant volume case leads to (pressure case,
extra-reading). Derive p = kBNT/V from partition
function where in this case Z is
• And Fa=-kBTln(Z(L)) where many of the terms
above are just constants →
• So Z is a constant × L3N →
F(L) = A - kBTNlnL3
• Using entropic force then recovers the ideal gas
law:
7.1 Microscopic view of entropic forces
Slide 1-7
Osmosis and entropic forces?
Slide 1-8
7.2.1 Equilibrium osmotic pressure from
ideal gas law
• Consider Fig. 1.3 (previous slide). For a dilute
concentration we apply same methods as for an
ideal gas to find the free energy
• This time V is RHS of chamber in Fig. 1.3 and
derivative of ln Z is again N/V and (c = N/V)
• How about when there is air (or atmospheric
pressure)? In this case we get Δp=zf ρm g
• See figure 7.1 and the thistle-tube experiment
– How does this work? Try Your Turn 7B
Slide 1-9
Osmotic pressure experiment
thistle-tube experiment
Slide 1-10
7.2.1 Cell safety: Laplace’s formula
• Estimates
– Homework/whiteboard for now …
– Result is
• Surface tension, Σ, estimated ~1.5×10-3 N m-1
– Enough to rupture a eukaryotic cell
membrane
• Summary
– Osmotic pressure is significant for cells …
Slide 1-11©1993. Used by permission of Springer-Verlag.
7.2.2 Depletion force for large molecules
Slide 1-12
7.2.2 Osmotic pressure creates a depletion
force between large molecules
• The hierarchy in Fig. 7.2 leads to surprising
“entropic effects”
– Depletion interaction or molecular crowding
• Consider two LARGE “sheep” in a bath
containing smaller “sheepdogs” with number
density c. The sheepdogs herd the larger sheep
together. How (see Fig. 7.3)
• In order to decrease Fa depletion zone is short
range of order 2a (a size of sheepdog)
• Pressure is change of free energy per change of
volume →
Slide 1-13
The depletion zone (interactions)
Slide 1-14©1998, American Chemical Society. Used by permission.
Experimental data (depletion is real!)
Slide 1-15
7.3.1 Beyond Equilibrium: Osmotic Flow
• Where does osmotic pressure come force from?
• Ultimately, from membrane itself (see Fig.7.5)
• Using & hydrostatic eq:
• Leads to Eq. 7.13: where 𝑓 = −𝑑𝑈
𝑑𝑍
• How do we solve this. We need a result for c(z)?
• Using c=c0 and steps on p. 258 gives
• This is just Δp=c0kBT or more generally:
Slide 1-16
Osmotic flow: Fluid forces
Slide 1-17
7.3.1 Osmotic flow
The equilibrium pressure difference across a
semipermeable membrane equals kBT times the
difference in concentration between the two force-free
regions on either side of the membrane.
• Read 7.3.2 for homework (see section 5.3.4 as
well)
•Generally we have
where 𝐿𝑝 is the filtration constant of the membrane
• Reverse osmosis occurs when Δp≥ΔckBT (see
Fig 7.6d)
Slide 1-18Figure 7.6 (Schematic, sketch graphs.) Caption: See text.
Slide 1-19
Figure 7.6 Caption
Figure 7.6: (a) A literal model of a semipermeable membrane, consisting of a
perforated wall with channels too small for suspended particles to pass. (b)
The force along z exerted by the membrane on approaching particles is
−dU/dz, where U is the potential energy of one particle. (c) In equilibrium, the
pressure p is constant inside the channel (between dashed lines), but p falls in
the zone where the particle concentration is decreasing. (d) Solid curve: If the
pressure on both sides is maintained at the same value, osmotic flow through
the channel proceeds at a rate such that the pressure drop across the channel
(from viscous drag) cancels the osmotic pressure jump. Dashed curve: In
reverse osmosis, an external force maintains a pressure gradient even greater
than the equilibrium value. The fluid flows oppositely to the case of ordinary
osmotic flow, as seen from the reversed slope of the pressure profile inside the
channel.
Slide 1-20
4.6.1 Recall Membrane Diffusion*
• Imagine a long thin membrane/tube of Length L,
with one end in ink C(0)=c0 and in water C(L)=0
• This leads to a quasi-steady state so we set
dc/dt =0 and hence d2c/dx2=0
• This means that c is constant and js=-DΔc/L
where Δc0=cL-c0 and subscript s means the flux
of solute not water
• Now define js=-PsΔc where Ps is the permeability
of the membrane.
Slide 1-21
• In simple cases Ps roughly relates to the width of
the pore and thickness of the membrane (length
of pore)
• Using dN/dt=-Ajs leads to
Slide 1-23
Last week’s homework: Your Turn 4C
Generalizing Fig. 7.6 to concentrations 𝑐1 & 𝑐2• a) Δ𝑝 = 𝑝1 − 𝑝2 < 𝑐1 − 𝑐2 𝑘𝐵𝑇
• b) Δ𝑝 = 𝑝1 − 𝑝2 > 𝑐1 − 𝑐2 𝑘𝐵𝑇 (reverse osmosis)
Slide 1-24
A REPULSIVE INTERLUDE
Section 7.4
Slide 1-25
7.4.1 Bulk electroneutrality?
• Example: For a raindrop with R=1 mm, how
much work is needed to remove 1 electron from
1% of the water molecules in the drip?
• If we take away charge then we form a shell with
electrostatic potential energy
Eelectrostatic =1
2𝑞𝑉 𝑅 =
𝑞2
8𝜋𝜀0𝑅where
𝑒2
4𝜋𝜀0= 2.3 ⋅ 10−28 Jm.
• This implies
𝑞1%
𝑒
2=
103𝑘𝑔
𝑚3
6⋅1023
0.0018 𝑘𝑔×
4𝜋
310−3𝑚 3 × 0.01
2
×
2.3⋅10−28
2𝑅= 2 ⋅ 1011 𝐽 ≫ 𝑘𝐵𝑇𝑟 = 4.1 ⋅ 10−21𝐽 .
• So electrically neutral!
Slide 1-26
7.4.1 Electrostatic interactions are critical
for cell functioning
• From Your Turn 7D, if R=1 nm we see that
separation energy ≈ 0.7𝑘𝐵𝑇𝑟.
• Hence on nanoscales DNA is a macroion which
is nearly fully dissociated (cf. Chapter 8)
• Even though the electrostatic interaction is of
long range in vacuum, in solution the screening
effect of counterions reduces its effective range,
typically to a nanometer or so.
• Macroions will not feel each other until they’re
nearby. Once nearby, detailed surface pattern of
+ve and –ve residues on a protein can be felt by
its neighbor, not just the overall charge.
Slide 1-27
Continued ...
• While each individual electrostatic interaction
between matching charges is rather weak
(compared to kBTr), still the combined effect of
many such interactions can lead to strong
binding of two molecules—if their shapes and
orientations match precisely.
• Molecular recognition implies we understand the
counterion cloud around a charged surface
• This implies Gauss’s Law
• This is not enough as we also need to worry
about orientation (stereospecificity)
Slide 1-28
7.4.2 The Gauss Law (for later use)
• You should have already studied the Gauss law:
which for a flat charged surface gives
• Considering Fig. 7 (next slide) we find that a
solid element satisfies
implying
Slide 1-29
7.4.2 The Gauss Law
Slide 1-30
7.4.3 Counterions on charged surfaces
• Example: You might want to coax DNA into a
cell for gene therapy, but both are negatively
charged
– We want to know by how much?
• Consider the slightly simpler problem depicted
in Figure 7.8a
– Assume monovalent counterions e.g. Na+
• Problem is that we are not given the charge
distribution?
– We need to find it, but an electrostatic force is
long range so we need to know positions of all
the other charges
Slide 1-31
7.4.3 Counterions near surfaces
Slide 1-32
7.4.3 Charged surfaces are surrounded by
neutralizing ion clouds
• We need to evaluate the effect of many ions all
moving around and repelling each other?
• This is too complicated so we make a very
common assumption in physics:
• The Mean Field Approximation (MFA)
– For a large no. of ions we assume that all the
other ions contribute to an average charge
density <ρ> and can ignore individual
charges ρi between ions
– We’ll use this to solve the Poisson-Boltzmann
equation but first we need to derive it ...
Slide 1-33
7.4.3 Poisson-Boltzmann Equation
• The Boltzmann part comes from the MFA
assuming c+(x→∞)→0 with
c+(x)=c0exp[-eV(x)/kBT]
and V(0)=0 fixes c0=c+(x=0) is the no. of counter-
ions at the surface
• The Poisson relation comes from bulk Gauss
law: dE/dx = ρq /ε with Ε=-dV/dx gives
d2V/dx2=-ρq /ε
Slide 1-34
7.4.3 Poisson-Boltzmann Equation*
• Equating the charge now leads to
d2V/dx2=-ec+(x)/ε=-ec0/ε exp[-eV(x)/kBT]
• Defining
and dimensionless variables
gives
• Problem: How to solve this equation?
Slide 1-35
Mean Field Approximation
Slide 1-36
7.4.3 Boundary conditions
• Like any differential equation we need to find
boundary or initial conditions: d2z/dt2=-g does
NOT tell you how high a rock will rise into the air
– Need to know how hard you threw it or it’s
initial speed and height.
• Solution for Poisson-Boltzmann case?
• Use boundary Gauss Law -dV/dx|surface = - σq /ε
or in terms of new variables
NB. Remember σq is a positive number
Slide 1-37
Solutions of the PB equation: Case 7.8a
• We have the BC at surface (previous slide) plus
another solution at infinity: dṼ/dx= 0 and Ṽ (0)=0
• PB eqn is non-linear and generally very difficult
to solve; however the exponent implies Ṽ(x)=ln x
might be a solution, but this blows up at x=0:
• Therefore try
• We need to find B and x0? (class exercise) →
• This is the “Gouy-Chapman” layer with length x0
Slide 1-38
PB solution continued: Case 7.8a
• A diffuse layer forms with thickness x0: The
counterions are willing to pay some electrostatic
energy to gain entropy
• Note, turning off thermal motion (T→0) implies
an infinite Bjerrum lenth and hence x0→0.
• How much energy? Think of two sheets of
charge with capacitive energy E=qtot2/(2C) where
C = εA/x0 . Combining the preceding formulae
we find (Case 7.8c?):𝐸
𝑎𝑟𝑒𝑎≈ 𝑘𝐵𝑇
𝜎𝑞
𝑒
for no added salt
Slide 1-39
7.4.4 Repulsion of like charged surfaces
• Solution of the PB equation for two negatively
charged surfaces, Case 7.8b
• We now have a symmetric solution with 𝑉 0 =
0: ⇒ 𝑉 = 2 ln 𝛽𝑥, where 𝛽 = 2𝜋ℓ𝐵𝑐0 and
𝑐+ 𝑥 = 𝑐0 cos 𝛽𝑥 −2
• Finally, applying surface charge b.c. leads to
4𝜋𝑙𝐵𝜎𝑞
𝑒= 2𝛽tan 𝐷𝛽
• This is a great example of solving a problem
graphically (used a lot in quantum mechanics)
• The important point is that this has been
observed experimentally (see next next slide)
Slide 1-40
Graphical solution to Poisson-Boltzmann
• Two oppositely charged surfaces (Fig. 7.8b)
Slide 1-41
Comparison with experiment: it works!
Slide 1-42
The Big Picture: Conclusion
• What is the big picture from Chapter 7?
• Entropic forces ubiquitous in the cellular world
– Depletion Forces
– Osmosis
– Reverse osmosis
• Neutral objects can be charged on nanoscales
Slide 1-43
Homework I
• Read Section 7.5
– Special properties of water
• Figure out Figure 7.6 and try
– “Your Turn 7A, 7B and 7C and Poisson
Relation”
– Think about electric neutrality and whether or
not this is true for either macroscopic or
nanoscopic systems?
– Try 7.4.3:- Track 2 on page 284 (book); pg.
250 of ebook. Including a salt solution
Slide 1-44
NEXT TIME …
Chapter 8: Chemical Forces & Self Assembly