The Effect of Solute Concentration on Equilibrium Partitioning in Polymeric Gels

The effect of solute concentration on the equilibrium partitioning of sphere-like, colloidal solutes in stiff polymer hydrogels is examined theoretically and experimentally. The theoretical development is a statistical mechanics approach, and allows quantitative calculations to be performed to determine the concentration-dependent partition coefficient correct to first order in solute concentration at specific surface charge densities. The theory predicts that repulsive steric and/or electrostatic solute-fiber interactions exclude solute from the gel phase, but that repulsive solute-solute interactions cause partitioning into the gel to increase with increasing solute concentration. These trends are enhanced for larger solutes, increased fiber volume fractions, or stronger electrostatic repulsion. Partition coefficients have also been measured for two proteins, bovine serum albumin (BSA) and alpha-lactalbumin (ALA), in a system consisting of a salt solution and cubes of agarose hydrogel. To investigate the effect of electrostatic interactions, the experiments were performed at 0.15 M KCl and 0.01 M KCl. The theory underpredicts the strong electrostatic repulsion between BSA macromolecules at the lower ionic strength. The experimental results for ALA show the influence of an attractive interaction between the protein macromolecules, in addition to hard-sphere repulsive and electrostatic interactions. Copyright 2001 Academic Press.     

Solvothermal syntheses of Cu3P via reactions of amorphous red phosphorus with a variety of copper sources

Polycrystalline Cu₃P was successfully prepared under a wide variety of solvothermal conditions. The reaction of red phosphorus with several copper sources (copper metal, copper (I) iodide, copper (I) chloride and copper (II) chloride) at 150-200 °C for 1-2 days in water produced Cu₃P. Products were examined with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Thermal analyses and optical spectroscopy were also performed. A detailed list of reaction conditions, products and impurity phases (where applicable) are reported.     

Synthesis, characterization and electrochemistry of diruthenium complexes linked by aryl acetylide bridges

The reactions between Ru₂(ap)₄Cl and the appropriate lithiated aryl acetylene resulted in the complexes Ru₂(ap)₄(CC4-C₆H₄CCX) with X as SiMe₃ (1), H (2) and Ru₂(ap)₄ (3), 1,3-[Ru₂(ap)₄(CC)]₂(C₆H₄) (4), 1,3-[{Ru₂(ap)₄(CC)}₂]C₆H₃5-CCH (5) and 1-[Ru₂(ap)₄(CC)]C₆H₃3,5-(CCH)₂ (6), where ap is 2-anilinopyridinate. The spectroscopic and electrochemical properties of the new complexes have been assessed. Complexes 3, 4 and 6 display two-electron oxidation and reductions, implying the absence of any significant electronic interaction between the two Ru₂(ap)₄ units in these complexes.     

Enumeration of total yeasts and molds in foods by the SimPlate Yeast and Mold-Color Indicator method and conventional culture methods: collaborative study

The relative effectiveness of the SimPlate Yeast and Mold-Color Indicator method (Y&M-CI) was compared to the U.S. Food and Drug Administration's (FDA) Bacteriological Analytical Manual (BAM) method and the proposed International Organization for Standardization (ISO) method, ISO/CD 21527, for enumerating yeasts and molds in foods. Test portions were prepared and incubated according to the conditions stated in both the BAM and ISO methods. Six food types were analyzed: frozen corn dogs, nut meats, frozen fruits, cake mix, cereal, and fresh cheese. Nut meats, frozen fruits, and fresh cheese were naturally contaminated. All other foods were artificially contaminated with either a yeast or mold. Seventeen laboratories throughout North America and Europe participated in the study. Three method comparisons were conducted. In general, there was <0.3 mean log count difference in recovery between the SimPlate method and the 2 corresponding reference methods. Moreover, mean log counts between the 2 reference methods were also very similar. The repeatability (Sr) and reproducibility (SR) standard deviations were comparable between the 3 method comparisons. These results indicate that the BAM method and the SimPlate method are equivalent for enumerating yeast and mold populations in foods. Similarly, the SimPlate method is comparable to the proposed ISO method when test portions are prepared and incubated as defined in the proposed ISO method.     

Limiting behavior of asymptotically flat gravitational fields

Couch and Torrence suggest that the vacuum Einstein equations admit a larger class of asymptotically flat solutions than those exhibiting the peeling property. Starting with the assumption that , (d/dr) and (/x ^A ) , wherex ^A (A = 2, 3) are angular coordinates, they show that , where ₁ 2 and ₁<₀; , where ₂ 1 and ₁< ₁; and ₄ and ₃ peel as they would under the stronger peeling conditions. The Winicour-Tamburino energy-momentun and angular momentum integrals for these solutions, in general, diverge. In fact, since Couch and Torrence determine only the radial dependence of the solution, it is not clear that the solutions are well defined. We find that the stronger assumption , (d/dr) , and (/x ^A ) does result in well-defined solutions for which both the energy-momentum and angular momentum intergrals are not only finite but result in the same expressions as are obtained for peeling space-times. This assumption appears to be the minimal assumption that is necessary for investigating outgoing radiation at null infinity.In part based on a dissertation by Stephanie Novak and submitted to Syracuse University in partial fulfillment of the requirement for the Ph.D. degree.     

Testing the reliability of non-LTE spectroscopic models for complex ions

Collisional-radiative atomic models are widely used to help diagnose experimental plasma conditions through fitting and interpreting measured spectra. Here we present the results of a code comparison in which a variety of models determined plasma temperatures and densities by finding the best fit to an experimental L-shell Kr spectrum from a well characterized, but not benchmarked, laser plasma. While variations in diagnostic strategies and qualities of fit were significant, the results generally confirmed the typically quoted uncertainties for such diagnostics of ±20% in electron temperature and factors of about two in density. The comparison also highlighted some model features important for spectroscopic diagnostics: fine structure was required to match line positions and relative intensities within each charge state and for density diagnostics based on emission from metastable states; an extensive configuration set was required to fit the wings of satellite features and to reliably diagnose the temperature through the inferred charge state distribution; and the inclusion of self-consistent opacity effects was an important factor in the quality of the fit.     

Chiral analytical method development and application to pre‐clinical pharmacokinetics of pinocembrin

An analytical method enabling the detection and quantification of the individual enantiomers of racemic (±) pinocembrin is required to fully characterize its pharmacokinetic disposition. Direct resolution of the enantiomers of pinocembrin was achieved using a novel and simple reversed‐phase high‐performance liquid chromatography method with electrospray ionization and detection by mass spectrometry in rat serum. A Chiralcel® AD‐RH column was employed to perform baseline separation with electrospray positive‐mode ionization with selected ion monitoring detection. The standard curves were linear from 0.5 to 100 µg/mL for each enantiomer. The limit of quantification was 0.5 µg/mL. The assay was applied successfully to stereoselective serum disposition of pinocembrin enantiomers in rats. Pinocembrin enantiomers were detected in serum. Both enantiomers had a serum half‐life of ~15 min in rats. Similar values of volume of distribution between the enantiomers were also observed: 1.76 L/kg for S‐pinocembrin and 1.79 L/kg for R‐pinocembrin. Total clearance was 5.527 L//h/kg for S‐pinocembrin and 5.535 L/h/kg for R‐pinocembrin, and the area under the curve was 1.821 µg h/mL for S‐pinocembrin and 1.876 µg h/mL for R‐pinocembrin. The large volume of distribution coupled with the short serum half‐life suggests extensive distribution of pinocembrin into the tissues. Copyright © 2012 John Wiley & Sons, Ltd.     

Functionalization of cellulose nanocrystal powder by non-thermal atmospheric-pressure plasmas

Cellulose - Despite promising characteristics such as the biodegradability and the environmentally benign nature of cellulose nanocrystal (CNC) based composites, their poor dispersion and...     

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

In order to form suitable systems designed for resonance energy transfer, a series of monodisperse methacrylate‐based monomers containing rigid π‐conjugated oligo(phenylene ethynylenes) with different sizes of the conjugated systems ( M1 – M3 ), and therefore different optoelectronic properties, were synthesized and subsequently polymerized using the reversible addition–fragmentation chain transfer polymerization technique ( P1 – P3 ). In addition, these oligomers were also copolymerized with methyl methacrylate. The obtained polymers were characterized by ¹H NMR spectroscopy, size exclusion chromatography, and analytical ultracentrifugation. The photophysical properties of the polymers were studied by UV–vis absorption and emission spectroscopy in diluted solutions as well as in thin films and compared to the photophysics of the corresponding monomers. Thereby, changes going from monomeric to polymeric systems could be detected in fluorescence quantum yields and lifetimes pointing to energy trapping, e.g., energy transfer. Donor–acceptor copolymers containing different numbers of monomeric units within the side chain exhibit differences in the emission spectra, indicating that energy trapping in polymers is very sensitive to structural properties such as the chain length. UV–vis absorption spectroscopy as well as time‐resolved lifetime studies indicate intrapolymer and interpolymer energy transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012