Biomedical subjects

William L Bourcier

Publications and source records attributed to William L Bourcier.

5 recordsLinked to original sources

PubMed2006

Pore conductivity control at the hundred-nanometer scale: an experimental and theoretical study.

We report on the observation of an unexpected mechanism that controls conductivity at the 100-nm scale on track-etched polycarbonate membranes. Transport measurements of positively charged methyl viologen performed by absorption spectroscopy under various pH conditions demonstrate that for 100-nm-diameter pores at pH 2 conductivity is blocked, while at pH 5 the ions move through the membrane according to diffusion laws. An oppositely charged molecular ion, naphthalene disulfonate, in the same membrane, shows the opposite trend: diffusion of the negative ion at pH 2 and very low conductivity at pH 5. The influence of parameters such as ionic strength and membrane surface coating are also investigated. A theoretical study of the system shows that at the 100-nm scale the magnitude of the electric field in the vicinity of the pores is too small to account for the experimental observations; rather, it is the surface trapping of the mobile ion (Cl- or Na+) that gives rise to the observed control of the conductivity. This surprising effect has potential applications for high-throughput separation of large molecules and bio-organisms.

Chlorides↗

PubMed2005

The influence of ionic strength on the interaction of viruses with charged surfaces under environmental conditions.

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q beta, and Norwalk. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. A second model of the virus involving surface charges only is included for comparison. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements as a function of pH. The environmental surface is modeled as a homogeneous plane held at constant potential with and without a finite region (patch) of opposite potential. The results indicate that the electrostatic interaction between the virus and the oppositely charged patch is significantly influenced by the conditions of ionic strength, pH and size of the patch. Specifically, at pH 7, the Norwalk virus interacts more strongly with the patch than MS2 (approximately 51 vs approximately 9kT) but at pH 5, the Norwalk-surface interaction is negligible while that of MS2 is approximately 5.9kT. The resulting ramifications for the use of MS2 as a surrogate for Norwalk are discussed.

Adsorption↗

PubMed2004

Dielectrophoretic forces on the nanoscale.

We have developed a method of calculation of the dielectrophoretic force on a nanoparticle in a fluid environment where variations in the electric field and electric field gradients are on the same nanoscale as the particle. The Boundary Element Dielectrophoretic Force (BEDF) method involves constructing a solvent-accessible or molecular surface surrounding the particle, calculating the normal component of the electric field at the surface boundary elements, and then solving a system of linear equations for the induced surface polarization charge on each element. Different surface elements of the molecule may experience quite different polarizing electric fields, unlike the situation in the point dipole approximation. A single 100-A-radius ring test configuration is employed to facilitate comparison with the well-known point dipole approximation (PDA). We find remarkable agreement between the forces calculated by the BEDF and PDA methods for a 1 A polarizable sphere. However, for larger particles, the differences between the methods become qualitative as well as quantitative; the character of the force changes from attractive at the origin of the ring for a 50-A sphere, to repulsive for a 75-A sphere. Equally dramatic differences are found in a more complex electrical environment involving two sets of 10 rings.

Journal Article↗

PubMed2004

Electrostatic potentials and fields in the vicinity of engineered nanostructures.

We have developed a method for calculating the electrostatic potentials and fields in the vicinity of geometrically complex engineered nanostructures composed of varying materials in electrolytes of arbitrary pH and ionic strength. The method involves direct summation of charged Debye-Hückel spheres composing the nanostructural surfaces and, by including charge redistribution on the surface of conducting materials held at constant potential, is applicable to mixed boundary conditions. The method is validated by comparison to analytical solutions for an infinite plane (Gouy-Chapman), an infinite cylinder (Bessel functions), and an infinite plane which contains a hole and which is held at constant potential. Excellent agreement between the potentials obtained by our numerical method and the closed form solutions is found for these conditions. The method is applied to the calculation of the electric field enhancement in the vicinity of a nanomembrane whose pore wall is held at constant charge and whose membrane surfaces are held at constant potential. The electric field is found to be enhanced by the charge buildup in the rim of the hole of the nanomembrane; the buildup results from the potential being held constant in the conducting region. Ion concentrations are also calculated. Positive ion rejection is found to be enhanced by this charge buildup in the region of the rim when a constant positive potential is applied.

Journal Article↗

PubMed2004

Investigation of pyrochlore-based U-bearing ceramic nuclear waste: uranium leaching test and TEM observation.

A durable titanate ceramic waste form (Synroc) with pyrochlore (Ca(U,Pu)Ti2O7) and zirconolite (CaZrTi2O7) as major crystalline phases has been considered to be a candidate for immobilizing various high-level wastes containing fissile elements (239Pu and 235U). Transmission electron microscopy study of a sintered ceramic with stoichiometry of Ca(U(0.5)Ce(0.25)Hf(0.25))Ti2O7 shows the material contains both pyrochlore and zirconolite phases and structural intergrowth of zirconolite lamellae within pyrochlore. The (001) plane of zirconolite is parallel to the (111) plane of pyrochlore because of their structural similarities. The pyrochlore is relatively rich in U, Ce, and Ca with respect to the coexisting zirconolite. Average compositions for the coexisting pyrochlore and zirconolite at 1350 degrees C are Ca(1.01)(Ce3+(0.13)Ce4+(0.19)U(0.52)Hf(0.18))(Ti(1.95)Hf(0.05))O7 (with U/(U + Hf) = 0.72) and (Ca(0.91)Ce(0.09))(Ce3+(0.08)U(0.26)Hf(0.66)Ti(0.01))Ti(2.00)O7 (with U/(U + Hf) = 0.28), respectively. A single pyrochlore (Ca(U,Hf)Ti2O7) phase may be synthesized at 1350 degrees C if the ratio of U/(U + Hf) is greater than 0.72, and a single zirconolite (Ca(Hf,U)Ti2O7) phase may be synthesized at 1350 degrees C if the ratio of U/(U + Hf) is less than 0.28. The synthesized products were used for dissolution tests. The single-pass flow-through dissolution tests show that the dissolution of the U-bearing pyrochlore is incongruent. All the elements are released at differing rates. The dissolution data also show a decrease in rate with run time. The results indicate that a diffusion-controlled process may play a key role during the release of U. TEM observation of the leached pyrochlore directly proves that an amorphous leached layer that is rich in Ti and Hf formed on the surface after the ceramic was leached in pH 4 buffered solution for 835 days. The thickness of the layer ranges from 6 to 10 nm. A nanocrystalline TiO2 phase also forms in the leached layer. The U leaching rate (g/(m2 day)) in acidic solutions can be expressed as log(NR) = -5.36-0.20 pH, where NR is the normalized rate. Conservative leaching rates of uranium [log(NR)] for the U-bearing ceramic at pH 2 and pH 4 solutions are -5.76 and -6.16 g/(m2 day), respectively. The results show that the U release rate of the ceramic waste is 10 times slower than that of defense high-level waste glass and about 1000 times slower than that of spent fuel. The pyrochlore-based ceramic is an ideal waste form for immobilizing long-lived radionuclides of 239Pu and 235U due to the Ti- and Hf-rich leached layer that forms on the ceramic surface. The leached layer functions as a protective layer and therefore reduces the leaching rate as thickness of the leached layer increases.

Ceramics↗