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Structural and mechanical properties of biopolymer gels

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Biopolymers

Part of the book series: Advances in Polymer Science ((POLYMER,volume 83))

Abstract

The structural and mechanical properties of gels formed from biopolymers are discussed both in terms of the techniques used to characterise these systems, and in terms of the systems themselves. The techniques included are spectroscopic, chiroptical and scattering methods, optical and electron microscopy, thermodynamic and kinetic methods and rheological characterisation. The systems considered are presented in order of increasing complexity of secondary, tertiary and quaternary structure, starting with gels which arise from essentially ‘disordered’ biopolymers via formation of ‘quasicrystalline’ junction zones (e.g. gelatin, carrageenans, agarose, alginates etc.), and extending to networks derived from globular and rod-like species (fibrin, globular proteins, caseins, myosin) by a variety of crosslinking mechanisms. Throughout the text, efforts are made to pursue the link (both from experiment and from theory) between the structural methods and mechanical measurements. As far as we are aware this is the first major Review of this area since that of J. D. Ferry in 1948 — The interest shown by polymer physicists in more complex biochemical systems, and the multi-disciplinary approaches now being applied in this area, make the format adopted here, in our opinion, the most logical and appropriate.

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Abbreviations

BST:

Blatz, Sharda and Tschoegl (equation)

CD:

circular dichroism

CSK:

Coniglio, Stanley and Klein (theory)

DCF:

density correlation function

DLVO:

Deryjaguin-Landau-Verwey-Overbeck (theory)

d.s.c.:

differential scanning calorimetry

FRS:

forced Rayleigh scattering

FS:

Flory-Stockmayer (theory)

M/G:

mannuronic/galacturonic acid ratio (alginates)

NMR:

nuclear magnetic resonance

ORD:

optical rotatory dispersion

i.r.:

infrared spectroscopy

QELS:

quasi-elastic light scattering

UV:

ultraviolet spectroscopy

a:

generalised front factor

C:

concentration

C0 :

critical gelling concentration

C*:

chain overlap concentration

C0 :

initial concentration

C1, C2 :

Mooney-Rivlin coefficients

D:

Hausdorff dimension

D:

Z-average translational diffusion coefficient

Dapp :

apparent D measured at finite q

Dm :

mutual diffusion coefficient

Dself :

self diffusion coefficient

DZ :

effective diffusion coefficient

DPn :

number average degree of polymerisation

E:

Young's modulus

f:

friction coefficient

f:

functionality

fw :

weight-average functionality

f1 :

fraction of residues in ordered conformation

g:

rubber elasticity front factor

G:

shear modulus

G′:

real part of oscillatory shear modulus

G″:

imaginary part of oscillatory shear modulus

G*:

complex oscillatory shear modulus

Ge :

equilibrium shear modulus

h:

fraction of residues in helical conformation

hg :

value of h at the gel point

ΔHu :

enthalpy of gel melting (Takahishi theory)

ΔH0 :

van't Hoff enthalpy

J(t):

creep compliance at time t

Je :

equilibrium creep compliance

k:

Boltzmann's constant

ks :

Smoluchowski rate constant

M:

molecular weight between crosslinks

Me :

entanglement molecular weight

Mj :

molecular weight of junction zone

Mos :

osmotic modulus

Mr :

relative molecular mass (molecular weight)

Mw :

weight average molecular weight

M0 :

initial molecular weight (coagulation kinetics)

n:

parameter in BST equation

n:

molecularity of junction zones

Ne :

number of elastically active junction zones

p:

axial (length/diameter) ratio for rods

pB :

bond probability (CSK theory)

q:

scattering vector =(4ν/λ) sin (ϑ/2)

r:

molecular weight ratio (Eq. 36)

R:

gas constant

s:

order parameter in helix-coil transition theory

〈S2〉Z :

Z-average mean square radius of gyration

t:

time

tg :

gel time

T:

absolute temperature

Tm :

helix-coil midpoint temperature

Tmk :

gel melting temperature (°K)

T2 :

transverse relaxation time (NMR)

Tτ :

effective lifetime of temporary crosslinks

v:

extinction probability

Vmax :

maximum rate of enzyme cleavage

Vmol :

volume per mole of primary chains

\(\bar V_2\) :

polymer partial specific volume

Wg :

gel fraction

x:

number of junction zones per primary chain

α:

proportion of reacted functionalities

αc :

critical value of α at the gel point

[α]:

specific optical rotation

[α]t :

value of [α] at time t

γ:

shear strain

γmax :

maximum shear strain

\(\dot \gamma\) :

shear strain rate

δ:

loss angle (tan δ = G″/G′)

δ:

exponent in concentration dependence of modulus

ε:

tensile strain

εB :

tensile strain at failure

ζ:

correlation length

η:

viscosity

[η]:

intrinsic viscosity

ϑ:

scattering angle

λ:

wavelength

λ:

extension ratio

μ′:

constraint release parameter

ξ:

statistical weight (CSK theory)

π:

osmotic pressure

ϱ(r):

density of particles in volume element r from 0

σ:

shear stress

σ:

helix interruption constant

σt :

shear stress at time t

σT :

tensile stress

σB :

tensile stress at failure

τ:

relaxation time

τ:

scaled time in coagulation equation

φ:

proportionality constant in theory of elasticity

φ:

volume fraction

φg :

critical volume fraction for gelation

φp :

volume fraction of rods in Flory theory

φ *p :

critical value of φp

φs :

volume fraction of solvent

ω:

oscillatory frequency

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    Allan H. Clark & Simon B. Ross-Murphy

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Clark, A.H., Ross-Murphy, S.B. (1987). Structural and mechanical properties of biopolymer gels. In: Biopolymers. Advances in Polymer Science, vol 83. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0023332

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  • DOI: https://doi.org/10.1007/BFb0023332

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