R. Cush et al., ROTATIONAL AND TRANSLATIONAL DIFFUSION OF A RODLIKE VIRUS IN RANDOM COIL POLYMER-SOLUTIONS, Macromolecules, 30(17), 1997, pp. 4920-4926
Depolarized dynamic light scattering was used to measure the translati
onal and rotational diffusion of tobacco mosaic virus, TMV, in aqueous
solutions of dextran (M similar to 505 000). TMV is an electrically c
harged, nucleoprotein assembly with the shape of a stiff, rigid rod. D
extran is an uncharged, flexible carbohydrate polymer. The TMV was hel
d at a fixed, dilute concentration (0.5 mg/mL), while the concentratio
n of dextran spanned both dilute and semidilute regimes (0-14.5% by we
ight). There was no evidence of phase separation or strong aggregation
of the TMV particles in the presence of the dextran. The TMV particle
s dominated the depolarized scattering at all dextran concentrations.
The angular variation of the decay rates of the autocorrelation functi
ons always followed the form expected for symmetric top molecules in t
he absence of translational-rotational coupling. Nevertheless, transla
tional and rotational motions are almost surely coupled in most dextra
n-containing solutions. The apparent translational and rotational diff
usion rates decreased with added dextran, but not exactly according to
the rise in macroscopic solution viscosity. A transition occurred at
about 6.5% dextran. Beyond this concentration, pronounced failures of
the continuum (Stokes-Einstein) relation between diffusion and viscosi
ty were found. Translational diffusion continued more rapidly than exp
ected on the basis of the macroscopic viscosity, while rotational diff
usion fell sharply below expectation. The quotient D-r/D-t of rotation
al and translational diffusion, which presumably cancels effects due t
o viscosity, also dropped suddenly above the transition point. These f
indings are consistent with a sudden onset of topological constraints
to rotational motion of the TMV, without onset of severe constraints t
o translational motion. Temperature dependent studies showed that eith
er the solution or the solvent viscosity can describe translation and
rotation fairly well, at least at concentrations below the transition.
Energies of activation for translational and rotational diffusion of
TMV were similar and not strongly dependent on dextran concentration i
n this regime.