The molecular structure of tetrathiofulvalene-13C (TTF) from proton magnetic resonance studies using nematic solvents

The molecular structure of TTF dissolved in nematic liquid crystalline solvents has been determined from the proton magnetic resonance including couplings due to ¹³C in natural abundance. The molecule is puckered in a boat conformation with the SCHCHS planes making a dihedral angle of 13 ± 2° with the S₂C  CS₂ plane. The other structural parameters obtained are r_CH = 1.085 ± 0.014 Å and the angel CCH = 123.7 ± 1.5°.     

Simultaneous Determination of Oxytetra- cycline, Doxycycline, Tetracycline and Chlortetracycline in Tetracycline Antibiotics by High-Performance Liquid Chromatog- raphy with Fluorescence Detection

A simple, rapid and sensitive high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of oxytetracycline, doxycycline, tetracycline and chlortetracycline was developed, and successfully applied to the analysis of commercial tetracycline antibiotics. The separation was performed on a reverse-phase C₁₈ column with a gradient elution composed of methanol and sodium acetate buffer (containing disodium ethylenediaminetetraacetate and calcium chloride, pH 8.10) as the mobile phase, and fluorescence detection at 532 nm (excitation at 380 nm). The detection limits for oxytetracycline, doxycycline, tetracycline and chlortetracycline were 0.1, 0.5, 0.3 and 0.4 g L^–1, respectively. Data with respect to precision and accuracy were reported and discussed.     

Optimization of zinc phosphate coating on 7075-T6 aluminum alloy

A zinc phosphate coating process on 7075-T6 aluminum alloy has been significantly improved through a combined approach of titanium colloid pretreatment, pH level adjustment, fluoride additive and ZnO/H₃PO₄ ratio adjustment. In particular, optimum phosphate coatings were formed in coating baths with a ZnO/H₃PO₄ ratio of 0.205 and 0.256. Coating morphology studied by SEM reveals that the adjustment in the coating procedure produces an improved crystalline coating layer with high coverage and small grain size. For coatings formed in a bath with a ratio of 0.205, the coverage of the crystalline patches on top of the amorphous coating base is almost complete. The chemical composition of the coating layers has been characterized by XPS and SIMS. The crystalline and amorphous coating phases formed in the bath with a ratio of 0.205 were found to have compositions given schematically as Zn_x(PO₄) and Zn_xAl_y(PO₄), respectively. In contrast, neither coating phase formed in the bath with a ratio of 0.256 shows the presence of Al.     

The ring-closing metathesis of vinyl ethers with Grubbs'' catalyst for the synthesis of dihydropyrans

A series of acyclic vinyl ethers have been prepared and treated with Grubbs' ruthenium catalyst ((Cy₃P)₂RuCl₂=CHPh). Contrary to previous findings, it has been shown that certain vinyl ethers are excellent substrates for the ring closing metathesis with ruthenium based catalysts.     

A mesoporous Pt/TiO2 nanoarchitecture with catalytic and photocatalytic functions

A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film.     

Nickel speciation via voltammetric quantification of nickel metal,oxides and salts

A practical speciation method for a solid mixture of nickel species applicable to atmospheric monitoring of Ni⁰, Ni²⁺ and NiO_x is reported. This involves magnetic extraction of Ni⁰ to separate it from the water-soluble nickel salts and the insoluble oxides, followed by adsorptive stripping voltammetry to quantify the nickel in each fraction. The separation scheme was validated by using calibration standards and by simulating air-filter samples prepared with authentic nickel products. The recoveries of nickel were Ni⁰ 94–105% and total nickel 95–102%.     

Reversed-phase liquid chromatographic method for the analysis of aminoglycoside antibiotics using pre-column derivatization with phenylisocyanate

A pre-column derivatization liquid chromatographic method has been developed for the analysis of aminoglycoside antibiotics using phenylisocyanate as a derivatization reagent. Derivatives including kanamycin, neomycin and gentamicin were formed by reaction of the analytes with phenylisocyanate in the presence of triethylamine. Phenylisocyanato groups were attached to corresponding amino groups of aminoglycoside and their molecular mass was confirmed by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). The experimental conditions for derivatization and separation of aminoglycoside derivatives were optimized and validated. A simple liquid chromatographic method for the determination of aminoglycoside antibiotics was demonstrated.     

Chemistry of constrained dioxocyclam ligands with Co(III): unusual examples of C-H and C-N bond cleavage

The reactions between H(2)dc3 and Co(acac)(3) have been studied in the presence and absence of base. In the presence of base, a complex with an intramolecular Co-C bond, Co(dc3-C-(8))(H(2)O), 1, is formed, presumably through heterolytic C-H bond activation. An X-ray crystallographic study demonstrates the presence of a Co-C bond and shows that the diazacyclooctane (daco) subunit adopts the chair-boat conformation with respect to the metal. The cobalt-carbon bond induces strain in the macrocycle as demonstrated by bond angles significantly deviating from tetrahedral. The (13)C NMR resonance of the carbon atom bound to cobalt (-10.5 ppm) suggests significant ionic character in the cobalt-carbon bond. However, we were unable to cleave this bond in the presence of strong acid. In the absence of base, the reaction of Co(acac)(3) with H(2)dc3 resulted in C-N cleavage of the ligand and the formation of a complex of dioxocyclam, Co(dc)(acac), 2. This complex has subsequently been prepared in high yield by the reaction of Co(acac)(3) with dioxocyclam. An X-ray crystallographic study demonstrates that dioxocyclam adopts the heretofore unreported cis configuration, having folded along a N-Co-N axis that is perpendicular to the Co-acac plane.     

The efficacy and progress in using radiation as a quarantine treatment of tropical fruits—a case study in Hawaii

Most tropical fruits for export must be treated with an approved quarantine treatment. Three and a half decades of research have demonstrated the efficacy of irradiation as a quarantine treatment in terms of efficiency, effectiveness, and product quality retention. The USFDA and the USDA-APHIS approved irradiation to disinfest fresh foods/fresh papayas in 1986 and 1989, respectively. In early 1995, the Hawaii Department of Agriculture was granted a special permit from USDA-APHIS allowing untreated Hawaiian fruits to be irradiated on the US mainland. The objectives were to gain experience in commercial irradiation as a quarantine treatment and to gather data on shipping and handling procedures, and on product quality. In April 1995, the first shipment of Hawaiian fruit was irradiated at a minimum quarantine dose of 0.25 kGy in an Isomedix plant near Chicago, and then distributed to supermarkets in Illinois and Ohio. Continuous shipments, irradiation, and marketing of various tropical fruits in the US have shown commercial efficacy, quality retention, and excellent consumer acceptance. A commercial e-beam/converted X-ray facility was installed by Titan Corp. on the Island of Hawaii and was operational by late July 2000. Hawaii has become the first place in the world to use irradiation as a quarantine treatment of fruits.