Cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia for chiral separation in high performance liquid chromatography.

Porous zirconia particles are very robust material and have received considerable attention as a stationary phase support for HPLC. We prepared cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia (CDMPCCZ) as a chiral stationary phase (CSP) for separation of enantiomers of a set of 14 racemic compounds in normal phase (NP) and reversed-phase (RP) liquid chromatography. Retention and enantioselectivity on CDMPCCZ were compared to those on CDMPC-coated zirconia (CDMPCZ) to see how the change in immobilization method of the chiral selector affects the retention and chiral selectivity. In NPLC, retention was longer and the number of resolved racemates was smaller on CDMPCCZ than on CDMPCZ. However, chiral selectivity factors for some resolved racemates were better on CDMPCCZ than on CDMPCZ. The longer retention on CDMPCCZ is likely due to strong, non-chiral discriminating interactions with the carbon layer on CDMPCZ. In RPLC only two racemates were resolved on CDMPCCZ, but retention times were shorter than, and resolutions were comparable to, those in NPLC, indicating a potential for improving chromatographic performance of the CDMPCCZ column in RPLC with optimized column preparation and separation conditions.     

Emission and sputtering characteristics of Ne-Ar mixed gas glow discharge plasmas.

The emission characteristics of several Cu lines emitted from a Ne-Ar mixed gas glow discharge plasma were investigated. The addition of small amounts of Ar to a Ne plasma increases the sputtering rate of a Cu sample because Ar ions, which work as the impinging ions for cathode sputtering, are predominantly produced through Penning ionization collisions between Ne metastables and Ar atoms. Ar addition also elevates the number density of electrons in the plasma. These changes occurring in the Ne-Ar mixed gas plasma result in enhanced emission intensities of the Cu lines. The Cu II 270.10-nm and the Cu II 224.70-nm lines yield different intensity dependence on the Ar partial pressure added. This phenomenon is because these Cu II lines are excited principally through different charge transfer processes: collisions with Ne ions for the Cu II 270.10-nm line and collisions with Ar ions for the Cu II 224.70-nm line. The shape of sputtered craters in the Ne-Ar glow discharge plasma was measured. The depth resolution was improved when Ar was added to a Ne plasma because the crater bottoms were flatter with larger Ar partial pressures.     

Preparation of antimicrobial poly(vinyl alcohol) nanofibers containing silver nanoparticles

Polyvinyl alcohol (PVA) nanofibers containing Ag nanoparticles were prepared by electrospinning PVA/silver nitrate (AgNO₃) aqueous solutions, followed by short heat treatment, and their antimicrobial activity was investigated for wound dressing applications. Since PVA is a water soluble and biocompatible polymer, it is one of the best materials for the preparation of wound dressing nanofibers. After heat treatment at 155 °C for 3 min, the PVA/AgNO₃ nanofibers became insoluble, while the Ag⁺ ions therein were reduced so as to produce a large number of Ag nanoparticles situated preferentially on their surface. The residual Ag⁺ ions were reduced by subsequent UV irradiation for 3 h. The average diameter of the Ag nanoparticles after the heat treatment was 5.9 nm and this value increased slightly to 6.3 nm after UV irradiation. It was found that most of the Ag⁺ ions were reduced by the simple heat treatment. The PVA nanofibers containing Ag nanoparticles showed very strong antimicrobial activity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2468–2474, 2006     

Pit your wits against young minds!

This column is a place for those bits of contagious mathematics that travel from person to person in the community, because they are so elegant, suprising, or appealing that one has an urge to pass them on. Contributions are most welcome.     

Kinetics of phenyl radical reactions with propane,n‐butane,n‐hexane,and n‐octane: Reactivity of C6H5 toward the secondary C?H bond of alkanes

The kinetics of C₆H₅ reactions with n‐C_nH_2n+2 (n = 3, 4, 6, 8) have been studied by the pulsed laser photolysis/mass spectrometric method using C₆H₅COCH₃ as the phenyl precursor at temperatures between 494 and 1051 K. The rate constants were determined by kinetic modeling of the absolute yields of C₆H₆ at each temperature. Another major product C₆H₅CH₃ formed by the recombination of C₆H₅ and CH₃ could also be quantitatively modeled using the known rate constant for the reaction. A weighted least‐squares analysis of the four sets of data gave k (C₃H₈) = (1.96 ± 0.15) × 10¹¹ exp[?(1938 ± 56)/T], and k (n‐C₄H₁₀) = (2.65 ± 0.23) × 10¹¹ exp[?(1950 ± 55)/T] k (n‐C₆H₁₄) = (4.56 ± 0.21) × 10¹¹ exp[?(1735 ± 55)/T], and k (n?C₈H₁₈) = (4.31 ± 0.39) × 10¹¹ exp[?(1415 ± 65)T] cm³ mol^?1 s^?1 for the temperature range studied. For the butane and hexane reactions, we have also applied the CRDS technique to extend our temperature range down to 297 K; the results obtained by the decay of C₆H₅ with CRDS agree fully with those determined by absolute product yield measurements with PLP/MS. Weighted least‐squares analyses of these two sets of data gave rise to k (n?C₄H₁₀) = (2.70 ± 0.15) × 10¹¹ exp[?(1880 ± 127)/T] and k (n?C₆H₁₄) = (4.81 ± 0.30) × 10¹¹ exp[?(1780 ± 133)/T] cm³ mol^?1 s^?1 for the temperature range 297‐‐1046 K. From the absolute rate constants for the two larger molecular reactions (C₆H₅ + n‐C₆H₁₄ and n‐C₈H₁₈), we derived the rate constant for H‐abstraction from a secondary C? H bond, k_s?CH = (4.19 ± 0.24) × 10¹⁰ exp[?(1770 ± 48)/T] cm³ mol^?1 s^?1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 49–56, 2004     

Atomistic phenomena in dense fluid shock waves

The shock structure problem is one of the classical problems of fluid mechanics and at least for non-reacting dilute gases it has been considered essentially solved. Here we present a few recent findings, to show that this is not the case. There are still new physical effects to be discovered provided that the numerical technique is general enough to not rule them out a priori. While the results have been obtained for dense fluids, some of the effects might also be observable for shocks in dilute gases.     

Approximation of transient temperatures in complex geometries using fractional derivatives

It is shown that time-dependent temperatures in a transient, conductive system can be approximately modeled by a fractional-order differential equation, the order of which depends on the Biot number. This approximation is particularly suitable for complex shapes for which a first-principles approach is too difficult or computationally time-consuming. Analytical solutions of these equations can be written in terms of the Mittag-Leffler function. The approximation is especially useful if a suitable fractional-order controller is to be designed for the system.