N-isobutyloxycarbonylation for improved detection of 3'-hydroxystanozolol and its 17-epimer in doping control

An improved screening method was developed for 3'-hydroxystanozolol and its 17-epimer in human urine involving gas chromatography-mass spectrometry (GC-MS) with N-isobutyloxycarbonyl (isoBOC) and O-trimethylsilyl (TMS) derivatization. A procedure was reported previously for the pentane extraction of many steroids from urine in doping control, but it was not suitable for the detection of stanozolol metabolites. Compared with the n-pentane extraction method, which gave a poor recovery (< 10%), isoBOC extraction resulted in a good recovery (> 80%). The sensitivity and specificity of mixed N-isoBOC-O-TMS derivatization were adequate for the detection of 3'-hydroxystanozolol and its 17-epimer when 3 ml of urine was used with spiking at a level of 2 ng ml-1. When applied to a stanozolol-positive urine sample, the proposed method allowed rapid and sensitive screening for the detection of 3'-hydroxystanozolol and its 17-epimer.     

catena‐Poly[[copper(II)‐μ‐2‐[bis­(2‐pyridylmeth­yl)amino]butyrato‐κ4N,N′,N′′,O:κO′] perchlorate]

The copper(II) ion in the syn–anti carboxyl­ate‐bridged one‐dimensional zigzag chain title complex, {[Cu(C₁₆H₁₈N₃O₂)]ClO₄}_n, exhibits a distorted trigonal–bipyramidal environment. Two N atoms and one carboxyl­ate O atom of the ligand form the basal plane, while the axial positions are filled by an N atom of the ligand and one O atom belonging to the carboxyl­ate group of an adjacent mol­ecule. The crystal packing is enhanced by C—H⋯O(perchlorate) hydrogen bonds.     

Determination of impurities in semiconductor grade silicon by instrumental neutron activation analysis

Instrumental neutron activation analysis has been applied to semiconductor grade silicon to study the concentration levels of impurity elements, the contamination during the single crystal growing process, and the vertical and radial distributions of impurities, along with the decontamination effect in the analysis. Twenty elements of Au, Br, As, W, Cr, Co, Na, Eu, La, Se, Zn, U, Th, Hf, Fe, Sb, Ag, Ce, Tb and Ta have been analyzed in p- and n-type wafers, single crystals and a polycrystal by a single comparator method using two comparators of gold and cobalt. Considerable surface contamination has been found and could be removed by etching the surface with nitric and hydrofluoric acid before and after irradiation. The impurity concentration has been found to be generally increased in the process of single crystal growth. The vertical and radial distributions of impurities have revealed that some impurity elements were more concentrated in the top region of a single crystal rod than in the middle region, and that Br, Cr, La, Eu and Sb were enriched in the central region and As, U and Fe in the outer region.     

Preparation of (R)-11-hydroxyaporphine directly from (R)-10,11-dihydroxyaporphine ((R)-apomorphine)

A Regioselective synthesis of (R)-11-hydroxyaporphine 2 directly from (R)-10,11-dihydroxyaporphine ((R)-apomorphine, 1 ) is described for the first time. The isopropylidene ketal ring of 10,11-(isopropyl-idenyldioxy)aporphine 5 obtained by the isopropylidenation of apomorphine was regioselectively opened by ten equivalents of trimethylaluminum to give (R)-10-hydroxy-11-tert-butyloxyaporphine 6 . The free 10-hydioxyl position of 6 was triflated with N-pbenyltrifluoromethanesulfonimide and potassium carbonate under reflux to give (R)-10-[(trifluoromethyl)sulfonyloxy]-11-tert-butyloxyaporphine 7 . The reduced product, 11-tert-butyloxyaporphine 8 was prepared from 7 by a palladium-catalyzed hydrogenolysis. The ether cleavage of (R)-11-tert-butyloxyaporphine with 48% hydrobromic acid afforded the desired (R)-11-hydroxyaporphine 2 in good yield.     

Thermal properties of bio flour-filled polypropylene bio-composites with different pozzolan contents

In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric curve (DTG_max) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T _g), melting temperature (T _m) and percentage of crystallinity (X _c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X _c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was an effective method for enhancing the thermal stability and thermal expansion.     

Tris(2,2′-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor based on carbon nantube dispersed in sol-gel-derived titania-Nafion composite films

A highly sensitive and stable tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy)₃²⁺ immobilized in the ECL sensor by adsorption of Ru(bpy)₃²⁺ onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-titania-Nafion showed improved ECL sensitivity for tripropylamine (TPA) compared to the ECL sensors based on both titania-Nafion composite films without CNT and pure Nafion films. The present Ru(bpy)₃²⁺ ECL sensor based on the MWCNT-titania--Nafion composite gave a linear response (R² = 0.999) for TPA concentration from 50 nM to 1.0 mM with a remarkable detection limit (S/N = 3) of 10 nM while the ECL sensors based on titania-Nafion composite without MWCNT, pure Nafion films, and MWCNT-Nafion composite gave a detection limit of 0.1 μM, 1 μM, and 50 nM, respectively. The present ECL sensor showed outstanding long-term stability (no signal loss for 4 months).     

Effect of Fiber-Polymer Interactions on Fracture Toughness Behavior of Carbon Fiber-Reinforced Epoxy Matrix Composites

The effect of anodic oxidation on high-strength polyacrylonitrile-based carbon fibers has been studied in terms of fiber surface energetics and fracture toughness of the composites. According to contact angle measurements based on the wicking rate of a test liquid, anodic oxidation leads to an increase in surface free energy, mainly due to the increase of its specific (or polar) component. For the carbon-fiber-reinforced epoxy resin matrix system, a direct linear relationship is shown between the specific component and the critical stress intensity factor measured by the single edge notched beam fracture toughness test. From a surface-energetic point of view, the anodic treatment may be suitable for carbon fibers incorporated in a polar organic matrix, resulting in an increased specific component of the surface free energy. Good wetting plays an important role in improving the degree of adhesion at interfaces between fibers and matrices of the resulting composites. Copyright 2000 Academic Press.     

Inhibitory effects of 1,3-selenazol-4-one derivatives on mushroom tyrosinase

This study reports depigmenting potency of 1,3-selenazol-4-one derivatives, which would be based upon the finding of direct inhibition to mushroom tyrosinase. 1,3-Selenazol-4-one derivatives exhibited inhibitory effect on dopa oxidase activity of mushroom tyrosinase. In this study, inhibitory effects of six kinds of 1,3-selenazol-4-one derivatives (A, B, C, D, E and F) on mushroom tyrosinase were investigated. Compounds at a concentration of 500 microM exhibited 33.4-62.1% of inhibition on dopa oxidase activity of mushroom tyrosinase. Their inhibitory effects were higher than that of kojic acid (31.7%), a well known tyrosinase inhibitor. 2-(4-Methylphenyl)-1,3-selenazol-4-one (A) exhibited the strongest inhibitory effect among them dose-dependently and in competitive inhibition manner.     

A novel way to study the initial stages of soap-free emulsion polymerizations: The intercalation of polystyrene oligomers into hydrotalcite

The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg₄Al₂(OH)₁₂]²⁺[A]^2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers. The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 Å on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 Å (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.     

Alcohol sensing membrane based on immobilized ruthenium(II) complex in carboxylated PVC and surface covalently bonded alcohol oxidase

Alcohol sensing membranes coated on overhead transparency films for the continuous monitoring of ethanol, propanol and butanol are presented. Alcohol oxidation catalyzed by alcohol oxidase in conjunction with the fluorescence quenching reaction of oxygen-sensitive dye ion-pair, tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) didodecylsulphate was chosen for the determination. Alcohol oxidase was immobilized covalently on a plasticized carboxylated poly(vinyl chloride) membrane and the oxygen-sensitive dye ion-pair was entrapped in the same membrane. The sensing membrane relates oxygen consumption, as a result of enzymatic oxidation, to alcohol concentration. Measurements have been performed in air-saturated alcohol standard solutions of pH 7.0. Storage stability, reproducibility and the effect of pH on sensing membrane performance have been studied in detail. The alcohol sensing membrane proposed here is simple to prepare and has a fairly rapid response time of <1 min. It has been successfully applied to the determination of the ethanol contents in various spirits.