A simplified experimental method to study conductivity percolation.

A simplified experimental setup and a measurement method adapted to the simplified data analysis proposed in previous works are described in detail. The setup is intended for investigation of the conductivity percolation in the water network formed on granular materials and studied in the course of dehydration. The results show that the new, easily accessible experimental setup enables determination of the principal percolation parameters with the same accuracy as the more sophisticated equipment employing an impedance analyzer. Mean critical exponents obtained from data collected for the samples of moisturized sand grains sized 0.6-0.8 mm by means of both experimental methods give the same results within the limit of measurement uncertainty.

Electric conductivity percolation in naturally dehydrating, lightly wetted, hydrophilic fumed silica powder.

In studying the dehydration of surface-moistened fumed silica Aerosil powders, we found a conductivity percolation transition at low hydration levels. Both the percolation exponent and the threshold are typical for correlated site-bond transitions in complex two-dimensional (2D) systems. The exponent values, 0.94-1.10, are indicative of severe heterogeneity in the conducting medium. The surface moisture at the percolation threshold takes on a universal value of 0.65 mg([H2O])/m(2)([silica]), independent of the silica grain size, and equivalent to twice the first hydration monolayer. This level is just sufficient to sustain a quasi-2D, hydrogen-bonded water network spanning the silica surface.

Multifrequency electron spin resonance study of the dynamics of spin labeled T4 lysozyme.

An extensive set of electron spin resonance spectra was obtained over a wide range of frequencies (9, 95, 170, and 240 GHz) and temperatures (2 to 32 degrees C) to explore the dynamic modes of nitroxide-labeled T4 lysozyme in solution. A commonly used nitroxide side chain (R1), or a methylated analogue with hindered internal motion (R2), was substituted for the native side chain at solvent-exposed helical sites, 72 or 131. The spectra at all four frequencies were simultaneously fit with the slowly relaxing local structure (SRLS) model. Good fits were achieved at all the temperatures. Two principle dynamic modes are included in the SRLS model, the global tumbling of the protein and the internal motion consisting of backbone fluctuations and side chain isomerizations. Three distinct spectral components were required for R1 and two for R2 to account for the spectra at all temperatures. One is a highly ordered and slow motional component, which is observed in the spectra of both R1 and R2; it may correspond to conformers stabilized by interaction with the protein surface. The fraction of this component decreases with increasing temperature and is more populated in the R2 spectra, possibly arising from stronger interaction of the nitroxide ring with the protein surface due to the additional methyl group. The other two components of R1 and the second component of R2 are characterized by fast anisotropic diffusion and relatively low ordering, most likely corresponding to conformers having little or no interactions with nearby residues. Ficoll of different concentrations was added to increase the solution viscosity, thereby slowing down the global tumbling of the protein. A significant effect of Ficoll on the internal motion of an immobilized component was apparent in R2 but not in R1. The ability of such multifrequency studies to separate the effects of faster internal modes of motion from slower overall motions is clearly demonstrated, and its utility in future studies is considered.

High-frequency ESR at ACERT.

High-field ESR offers many advantages in exploring fundamental questions of structure and dynamics in chemical, biological and physical samples. We provide a review of recent work performed at ACERT demonstrating the utility and flexibility of our methods for extracting both qualitative and quantitative information from a variety of systems. In particular, we emphasize the utility of multi-frequency ESR techniques for unraveling the details of the complex dynamical modes of proteins in solution and in heterogeneous systems such as lipid bilayers. We also include indications of directions for future work where appropriate.

Phase equilibria in solutions of platelike particles: systems with steric and dispersive interactions between the platelets.

Our statistical thermodynamics model of solution of stiff, platelike, biaxial particles interacting solely via repulsion on contact (athermal limit) [Phys. Rev. E 62, 5011 (2000)] is extended to incorporate dispersion interactions between the particles. Dispersion forces between anisotropic particles are accounted for using the Imura-Okano approach. Numerical calculations specialized to solutions of either rods or disks show that besides the isotropic-nematic biphasic coexistence range, inclusion of attractive forces resulted in the appearance of nematic-nematic coexistence in both, disks and rods, solutions. The critical divergence of the difference between the order parameters and concentrations of the two nematics is observed while approaching the critical temperature. The minimum aspect ratio of rods or disks for the formation of the nematic phase is also discussed.

Water-network percolation transitions in hydrated yeast.

We discovered two percolation processes in succession in dc conductivity of bulk baker's yeast in the course of dehydration. Critical exponents characteristic for the three-dimensional network for heavily hydrated system, and two dimensions in the light hydration limit, evidenced a dramatic change of the water network dimensionality in the dehydration process.