Effect of templated quenched disorder on fluid phase equilibrium.

Templating offers a means to direct the structure of quenched disorder. We show here that changes in phase equilibrium due to the presence of quenched disorder can themselves be altered by templating. We calculate the phase diagram of a fluid in a collection of template-directed, quenched particles by solving a set of replica Ornstein-Zernike equations within the mean spherical approximation and show templating to enhance phase behavior, that is, shift the phase envelope upward from its location for a nontemplated system of identical available volume. This enhancement is due to an augmented number of fluid-fluid interactions.

History dependence of protein adsorption kinetics.

The behavior of proteins at biological and synthetic interfaces is often characterized by a strong history dependence caused by long relaxation times or irreversible transitions. In this work, we introduce the rate of adsorption as a means to systematically quantify the extent, and identify the underlying causes, of history dependence. We use multistep kinetic experiments in which the i'th step is an exposure of a Si(Ti)O(2) surface to a flowing fibronectin or cytochrome c solution of concentration c(i) for a time t(i) (c(i) = 0 corresponds to a rinse) and measure the protein adsorption by optical waveguide light mode spectroscopy. The rate of adsorption is sensitive to the structure of the adsorbed layer, and we observe it to greatly increase, for a given adsorbed density, when going from a first to a subsequent adsorption step. This increase is most pronounced when the duration of the initial adsorption step is long. We attribute these observations to the gradual and irreversible formation of protein clusters or locally ordered structures and use them to explain previous underestimates of kinetic data by mesoscopic model descriptions. A thorough understanding of these complex postadsorption events, and their impact on history dependence, is essential for many physiological and biotechnological processes. Optical waveguide lightmode spectroscopy is a promising technique for their macroscopic quantification.

Theoretical model of adsorption in a templated porous material.

We introduce a theoretical description of adsorption in a templated porous material modeled as a quenched binary mixture configuration with one component removed. Using tools from equilibrium statistical mechanics, we analyze the diagrammatic structure of and derive an approximate formula for this nonequilibrium material's porosity and Henry regime selectivity. We find that templating significantly increases the porosity as well as the selectivity for the larger component of a mixture.

Zeolite adsorption site location and shape shown by simulated isodensity surfaces.

The graphics software package Ribbons is used to display isodensity surfaces of Xe atoms adsorbed in the alpha cage of zeolite NaA. The location, size, and shape of the adsorption sites are highly dependent on the loading and the crystal cation content. When the zeolite has a high number of cations, ellipsoidal sites arrange in a cuboctahedron. When the zeolite has fewer cations, cone-shaped sites arrange in an octahedron at low loading, but at high loading the sites become ellipsoidal and new sites form at cuboctahedral positions. The effect of the nature of the adsorption site on the development of a universal adsorption model is discussed.