The Oxidation of Thiols by Flavoprotein Oxidases: a Biocatalytic Route to Reactive Thiocarbonyls

Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C? O, C? N, or C? C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C? S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioethers. Herein, we report that various flavoprotein oxidases, previously thought to solely act on alcohols, also catalyze the oxidation of thiols to thiocarbonyls. These results highlight the versatility of enzymatic catalysis and provide a potential biocatalytic route to reactive thiocarbonyl compounds, which have a variety of applications in synthetic organic chemistry.     

Micellar capillary electrophoresis – Electrochemical detection of neurochemicals from Drosophila

The fruit fly is one of the most heavily studied model organisms for genetics research and has significantly contributed to the molecular, cellular, and evolutionary understandings of human behavior. Recent research in the analytical chemistry of the fruit fly has focused on developing methods to obtain highly sensitive chemical quantification information of Drosophila melanogaster, especially looking at the nervous system. We provide a brief overview of work in the area of CE of the fly head and brain.     

Improving resolution for channel-format chip-based electrophoresis with electrochemical array detection

Resolution in channel electrophoresis has been improved by means of the addition of a surfactant to the running buffer and minimization of the channel internal height and sampling capillary internal diameter. Micellar electrokinetic channel chromatography with electrochemical detection has been applied to the separation of several cationic catecholamines and has been used to continuously monitor a dynamic system of dopamine, norepinephrine, and epinephrine. Resolution was also enhanced by coupling small internal-diameter (5 microm) sampling capillaries with sub-micrometer internal-height separation channels. The improvements in resolution offered by these methods will extend the applicability of channel electrophoresis with electrochemical detection to more complex samples while permitting sample volumes in the nL range to be probed.     

Arrays of silicon microdischarge devices with multicomponent dielectrics

Arrays as large as 15x15 of microdischarge devices having inverted pyramidal silicon cathodes (50mumx50mum) and SiO(2)- Si(3)N(4)- polymer composite dielectrics have been fabricated and characterized with Ne gas. The lifetimes, reliability, and ignition characteristics of the arrays are superior to those of earlier designs having a single polymer dielectric. Operating voltages as low as 150 V for a 10x10 pixel array and 1000 Torr of Ne have been measured. Single (50mumx50mum) pyramidal cathode devices operate at voltages as low as 113 V when the Ne pressure is 900 Torr.     

Growth and surface characterization of sputter-deposited molybdenum oxide thin films

Molybdenum oxide thin films were produced by magnetron sputtering using a molybdenum (Mo) target. The sputtering was performed in a reactive atmosphere of an argon-oxygen gas mixture under varying conditions of substrate temperature (T_s) and oxygen partial pressure (pO₂). The effect of T_s and pO₂ on the growth and microstructure of molybdenum oxide films was examined in detail using reflection high-energy electron diffraction (RHEED), Rutherford backscattering spectrometry (RBS), energy-dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurements. The analyses indicate that the effect of T_s and pO₂ on the microstructure and phase of the grown molybdenum oxide thin films is remarkable. RHEED and RBS results indicate that the films grown at 445 °C under 62.3% O₂ pressure were stoichiometric and polycrystalline MoO₃. Films grown at lower pO₂ were non-stoichiometric MoO_x films with the presence of secondary phase. The microstructure of the grown Mo oxide films is discussed and conditions were optimized to produce phase pure, stoichiometric, and highly textured polycrystalline MoO₃ films.     

The effects of sample preparation methods on the variability of the electrospray ionization response for model drug compounds

A post-column infusion system was developed in order to analyze suppression of electrospray ionization (ESI) tandem mass spectrometry response in the presence of endogenous plasma interferences. By enabling direct detection of these interfering components, this experimental system was used to analyze the ability of several common extraction procedures to remove endogenous plasma components that cause changes in the ESI response of model drug substances. Methyl-t-butyl ether (MTBE) liquid-liquid, Oasis and Empore solid-phase, and acetonitrile (ACN) protein precipitation sample preparation methods were tested using the post-column infusion system. In all cases, ACN protein precipitation samples showed the greatest amount of ESI response suppression while liquid-liquid extracts demonstrated the least. In addition, the three test compounds, phenacetin, caffeine, and a representative Merck compound, demonstrated that ESI response suppression is compound dependent. Suppression was greatest with caffeine, the most polar analyte, and the smallest for the Merck compound, the least polar analyte. Copyright 1999 John Wiley & Sons, Ltd.     

Gamma-ray spectroscopy with relativistic exotic heavy-ions

Feasibility of gamma-ray spectroscopy at relativistic energies with exotic heavy-ions and new generation of germanium detectors (segmented Clover) is discussed. An experiment with such detector array and radioactive is discussed.