Synthese und Struktur von [(Ph3PAu)3NPPh3][PF6]2, einem Gold(I)‐phosphoraniminato‐Komplex

Synthesis and Crystal Structure of [(Ph₃PAu)₃NPPh₃][PF₆]₂, a Gold(I) Phosphoraneiminato Complex The photolytic reaction of Ph₃PAuN₃ with Cr(CO)₆ in THF yields the phosphoraneiminato complex [(Ph₃PAu)₃NPPh₃]²⁺ in low yield as well as the cluster cation [(Ph₃PAu)₈]²⁺ as the main product. The phosphoraneiminato complex crystallizes from CH₂Cl₂ with [PF₆]^? ions as [(Ph₃PAu)₃NPPh₃][PF₆]₂·CH₂Cl₂ in the triclinic space group with a = 1200.8(1), b = 1495.6(2), 2053.5(5), α = 86.97(2)°, β = 82.79(1)°, γ = 81.87(2)°, and Z = 2. The phosphoraneiminato ligand bridges through its N atom three Au atoms, which itself are connected to each other by weak aurophilic interactions.     

An in situ STM study on the long-range surface restructuring of Au(1 1 1) in a non-chloroaluminumated ionic liquid

We report an in situ STM study of a potential-dependent long-range surface restructuring of Au(1 1 1) electrode in neat 1-butyl-3-methylimidazolium tetrafluoroborates (BMIBF₄) ionic liquid. Au(1 1 1) undergoes a significant long-range surface restructuring upon cathodic excursion to −1.0 V vs. Pt quasi-reference. The restructuring involves the formation of tiny pits, which then develops into a stable worm-like network with an average width of the network grids 2 nm. Electrochemical annealing occurs at the cathodic limit with the presence of a reduction product of cation BMI⁺. A smooth surface is recovered with the appearance of the typical (√3 × 22) reconstruction of Au(1 1 1). The surface restructuring is reestablished upon anodic excursion to −1.3 V after the adsorbed reduction product is oxidized. The long-range surface restructuring phenomenon is tentatively explained as a result of partial charge transfer to the weakly adsorbed BMI⁺, which reduces the metal–metal cohesive energy. In addition, the synergetic effect of the counter anion BF₄⁻ may also be involved. The results provide a knowledge of Au(1 1 1) electrode behavior in the neat ionic liquid and are beneficial to understanding in situ STM results involving surface morphological changes in such a media.     

表面活性剂对纤维素接枝共聚物溶液粘度性质的影响

研究了阴离子十二烷基硫酸钠(SDS)、阳离子十六烷基三甲基溴化铵(CTAB)和非离子聚乙二醇辛基苯基醚(OP)等三种不同类型的表面活性剂对疏水化水溶性两性纤维素接枝共聚物(CGAO)溶液粘度性质的影响.结果表明,在SDS和OP的临界胶束浓度(cmc)附近，CGAO溶液粘度最大，SDS引起CGAO粘度的变化大于OP；即使在CTAB的cmc附近，随着CTAB浓度的增加，CGAO的粘度一直呈下降趋势；非疏水改性的纤维素接枝共聚物的溶液粘度随SDS或CTAB浓度的增加而下降，但几乎不随OP浓度的增大而变化.此外，通过凝胶渗透色谱法测得的保留时间证实了SDS、CTAB和OP与CGAO之间的疏水缔合作用.     

Novel Cyanine Dyes: Synthesis,Characterization and Photosensitization‐Structure Correlation

Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and ¹H NMR spectroscopy.     

Study of a molecular imprinting polymer coated BAW bio-mimic sensor and its application to the determination of caffeine in human serum and urine

A bio-mimic bulk acoustic wave (BAW) sensor was fabricated by coating the caffeine (CAF) template molecular imprinting polymer (MIP). This sensor exhibited high selectivity and a sensitive mass response to CAF. The response range of the sensor was between 5.0 x 10(-9) and 1.0 x 10(-4) M with a detection limit of 5.0 x 10(-9) M at pH 8.0. Recoveries were 96.1-105.6%. Influencing factors were investigated in detail and optimized. When employed to detect real samples, the proposed method proved to be a convenient method with the advantages of high sensitivity, good selectivity and ease of handling.     

Liquid chromatography particle beam-mass spectrometry with massive cluster impact

A new liquid chromatography-mass spectrometry technique is described that utilizes a particle beam interface to transport and deposit desolvated analyte molecules onto a target surface that is bombarded by a primary beam of massive multiply charged glycerol cluster ions to generate secondary ions for mass analysis. The massive cluster ion beam is generated by electrohydrodynamic emission from a solution of 1. 5-M ammonium acetate in glycerol. In the present instrumental configuration the massive cluster ion gun is placed above the target probe and the particle beam interface is connected through a side port of the mass spectrometer. The massive cluster ion beam and particle beam are intercepted by a target surface substituted for a conventional ion volume. The target surface is positioned such that it is ～ 45 ° to the primary cluster ion beam, the particle beam, and the mass analyzer axis. This geometric orientation represents a compromise among the performances of these three elements. The feasibility of this liquid chromatography-particle beam on-line with massive cluster impact is demonstrated by flow injections of acetylcholine chloride and gramicidin S. Spectra generated from this preliminary study indicate promise for routine liquid chromatography-mass spectrometry of polar compounds by using a robust inlet and an effective generation of secondary ions without an added matrix.     

Fast electron transfer repair of oxidizing OH adduct of dGMP by chlorogenic acid

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Synthesis of Insect Sex Pheromones and Their Homologues I. (Z,E)-9, 11-Alkadienyl Acetates

(Z, E)-9, 11-Tetradecadienyl-l-acetate (1), a major component of the sex pheromone of Spodoptera litura (F.), and (Z, E}-9, 11-pentadecadienyl-1-acetate (2) were synthesized by the Wittig reaction between (E)-2-alkenal (3) and the ylid derived from 9-hydroxynonyltriphenylphosphonium bromide (4).     

Photolysis of Isoniazid

The UV light irradiation of isoniazid (I) in methanol four products, isonicotinic acid (II), isonicotinamide (III), N, N′-bis(isonicotinic acid)hydrazide (IV) and isonicotinaldehyde isonicotinyl hydrazone (V), in ethanol three products, (III), (IV) and acetaldehyde isonicotinyl hydrazone (VI) were isolated and identified. Also, the photoreaction mechanism of isoniazid in methanol and ethanol were discussed.     

Tribromoisocyanuric Acid (TBCA) and Oxone®‐MX Systems as Oxidizing Agents: Oxidative Coupling of Thiols to Their Corresponding Disulfides under Mild and Heterogeneous Conditions

Tribromoisocyanuric acid (TBCA) and Oxone^®‐MX systems were used as effective oxidizing agents for the oxidation of thiols to their corresponding disulfides under mild conditions at room temperature with good to excellent yields.