Biomedical subjects

Reghan J Hill

Publications and source records attributed to Reghan J Hill.

5 recordsLinked to original sources

PubMed2006

Reverse-selective diffusion in nanocomposite membranes.

The permeability of certain polymer membranes with impenetrable nanoinclusions increases with the particle volume fraction [T. C. Merkel, Science 296, 519 (2002)10.1126/science.1069580]. The discovery contradicts qualitative expectations based on Maxwell's classical theory of conduction or diffusion in composites with homogeneous phases. This Letter presents a theory based on an hypothesis that polymer chains are repelled from the inclusions during membrane casting. The accompanying increase in free volume, and hence solute diffusivity, yields bulk transport properties that are in good agreement with experiments.

Journal Article↗

PubMed2006

Transport in polymer-gel composites: response to a bulk concentration gradient.

This paper examines the response of electrolyte-saturated polymer gels, embedded with charged spherical inclusions, to a weak gradient of electrolyte concentration. An electrokinetic model was presented in an earlier publication, and the response of homogeneous composites to a weak electric field was calculated. In this work, the influence of the inclusions on bulk ion fluxes and the strength of an electric field (or membrane diffusion potential) induced by the bulk electrolyte concentration gradient are computed. Effective ion diffusion coefficients are significantly altered by the inclusions, so-depending on the inclusion surface charge or zeta potential-asymmetric electrolytes can behave as symmetrical electrolytes and vice versa. The theory also quantifies the strength of flow driven by concentration-gradient-induced perturbations to the equilibrium diffuse double layers. Similarly to diffusiophoresis, the flow may be either up or down the applied concentration gradient.

Journal Article↗

PubMed2004

Hydrodynamics and electrokinetics of spherical liposomes with coatings of terminally anchored poly(ethylene glycol): numerically exact electrokinetics with self-consistent mean-field polymer.

A detailed theoretical model is presented to interpret electrokinetic experiments performed on colloids with uncharged polymer layers. The methodology removes many of the degrees of freedom that otherwise have to be accounted for by adopting multiple empirical fitting parameters. Furthermore, the level of detail provides a firm basis for future studies examining liposome surface chemistry and charge, surface-charge mobility, and the dynamics of adsorbed polymer on fluidlike membranes. The model predictions are compared with experimental measurements of the electrophoretic mobility of stealth liposomes with molecular weights of terminally anchored poly(ethylene glycol) (PEG) in the range 0.35-10 kg mol(-1) [J.A. Cohen and V.A. Khorosheva, Colloids Surf. A 195, 113 (2001)]. The experimental data are interpreted by drawing upon self-consistent mean-field calculations of the polymer segment density distributions and numerically exact solutions of the governing transport equations [R.J. Hill, D.A. Saville, and W.B. Russel, J. Colloid Interface Sci. 258, 56 (2003)]. The approach leads to excellent agreement between theory and experiment with one adjustable parameter--the hydrodynamic size (Stokes radius) a(s) approximately equal to 0.175 A of the statistical PEG segments with (Kuhn) length l=7.1 A . The remarkably small Stokes radius is demonstrated to be consistent with other applications of the well-known Debye-Brinkman model and, consequently, this work reveals important limitations of the mean-field hydrodynamic model. Despite such limitations, the "full" electrokinetic model is robust in its predictive capacity. The molecular weights of the terminally anchored PEG span the range where the coatings undergo a transition from mushroomlike to brushlike conformations, and the hydrodynamic size and electrophoretic mobility of the liposomes are demonstrated to be sensitive to the PEG chain length and the effects of double-layer polarization.

Coated Materials, Biocompatible↗

PubMed2003

Polarizability and complex conductivity of dilute suspensions of spherical colloidal particles with uncharged (neutral) polymer coatings.

The polarizability of polymer-coated colloidal particles, as measured via dielectric relaxation spectroscopy, reflects on the degree to which convection, diffusion, and electromigration deform the equilibrium double layer. With a polymer coating, convection and electro-osmosis are resisted by hydrodynamic drag on the polymer segments. The electro-osmotic flow near the underlying bare surface is therefore diminished. Characteristics of the particles and the adsorbed polymer can, in principle, be inferred by measuring the frequency-dependent polarizability. In this work, "exact" numerical solutions of the electrokinetic equations are used to examine how adsorbed polymer changes the particle polarizability and, hence, the conductivity and dielectric constant increments of dilute suspensions. For neutral polymer coatings, the conductivity and dielectric constant increments are found to be very similar to those of the underlying bare particles, so the response depends mostly on the underlying bare particles. These observations suggest that dielectric spectroscopy is best used to determine the underlying surface charge, with characteristics of the coating inferred from the electrophoretic or dynamic mobility, together with the hydrodynamic radius obtained from sedimentation or dynamic light scattering. Addressed briefly are the effects of added counterions and nonspecific adsorption. The electrokinetic model explored in this work can be used to guide experiments (frequency and ionic strength, for example) to either minimize or maximize the sensitivity of the complex conductivity to the coating thickness or permeability.

Journal Article↗

PubMed2003

Polarizability and complex conductivity of dilute suspensions of spherical colloidal particles with charged (polyelectrolyte) coatings.

The dielectric relaxation of polyelectrolyte-coated colloidal particles is examined via "exact" numerical solutions of the governing electrokinetic equations. The charged polymer coatings are characterized by a nominal charge density, thickness, and permeability. Brush-like segment density profiles are considered here, but more sophisticated segment and charge density profiles are accommodated by the model. The role of added counterions and nonspecific adsorption is considered briefly before examining how the experimentally measured conductivity and dielectric constant increments reflect the frequency of the applied electric field, the strength of the electrolyte, and characteristics of the polymer coatings, namely the charge, charge density, and permeability. Finally, a strategy is suggested by which dielectric spectroscopy and electrophoresis can be used to characterize polymer-coated particles. This approach complements experiments where electroviscous effects such as dynamic light scattering and sedimentation are weak.

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