新型大位阻取代茂钛,锆化合物的合成及其谱学性质

通过１－环庚烯基锂与６，６－二烷基富烯发生环外双键的加成反应形成的大取代茂锂试剂与ＭＣｌ４（Ｍ＝Ｔｉ，Ｚｒ）反应，合成了１２个含或不含手性碳的大位阻取代茂金属有机化合物，并研究了它们的１ＨＮＭＲ，ＥＩＭＳ和ＩＲ．     

Synthesis of new vitamin D3 analogues with a decalin-type CD-ring

Vitamin D analogues, characterized by a decalin CD-ring fragment are described.     

钠硼解石碳化机理的研究

采用Ｃａ（２＋）选择电极，ｐＨ电极和电导电极对钠硼解石水溶液碳化过程进行跟踪测定。实验结果表明：反应分二步进行，反应最终结果是钠硼解石完全分解，硼全部进入溶液并大部分以Ｈ３ＢＯ３的形式存在，同时考察了温度，气流量对钠硼解石水溶液碳化结果的影响。根据碳化机理，提出了较佳的碳化条件。     

Mechanism of TiO2-assisted photocatalytic degradation of dyes under visible irradiation: photoelectrocatalytic study by TiO2-film electrodes

Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO(2) nanoparticles electrode has been investigated to reveal the mechanism for TiO(2)-assisted photocatalytic degradation of dyes. The degradation of both cationic and anionic dyes at different biases, including the change in the degradation rate of the dyes and the photocurrent change with the bias potential, the degraded intermediates, the voltage-induced adsorption of dyes, the accumulation of electrons in the TiO(2) electrode, the effect of various additives such as benzoquinone (BQ) and N,N-dimethyl aniline (DMA), and the formation of active oxygen species such as O(2)(*-) and H(2)O(2) were examined by UV-visible spectroscopy, HPLC, TOC, and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with the TiO(2) surface by external bias changes and charging of dyes. The cationic dyes such as RhB and MG underwent efficient mineralization at negative bias, but the N-dealkylation process predominated at positive bias under visible light irradiation. The discolorations of the anionic dyes SRB and AR could not be accelerated significantly at either negative or positive bias. At a negative bias of -0.6 V vs SCE, O(2)(*-) and dye(*+) were formed simultaneously at the electrode/electrolyte interface during degradation of cationic RhB. In the case of anionic dyes, however, it is impossible for the O(2)(*-) and dye cationic radical to coexist at the electrode/electrolyte surface. Experimental results imply both the superoxide anionic radical and the dye cationic radical are essential to the mineralization of the dyes under visible light-induced photocatalytic conditions.     

Immunoaffinity Column Clean-Up and Liquid Chromatography with Post-Column Derivatization for Analysis of Aflatoxins in Traditional Chinese Medicine

A rapid tandem mass spectrometric (MS-MS) method for the quantification of gabapentin (GBP) in human plasma using 4-phenyl-4-aminobutanoic acid as an internal standard (IS) has been developed and validated. The drug and the internal standard were analyzed, by flow injection analysis without chromatographic separation, using a mobile phase of acetonitrile-water-formic acid (50:50:0.025, v/v/v) at a flow rate of 0.1 mL min^?1. The run-cycle time was <3 min injection-to injection. Quantitation was achieved using multiple reaction monitoring (MRM) scan at MRM transitions m/z 172 > 154 and m/z 180 > 117 for GBP and the IS, respectively. Ion suppression study indicated practically no suppressive effect of plasma constituents on the mass ions detection of GBP and IS, when measured in MRM scanning mode. Calibration curves were linear over the concentration range of 0.1–10 μg mL^?1 (r > 0.999) with a limit of quantification of 0.1 μg mL^?1 (RSD%; 7.6 and % DEVs; ?3.0 to +17.0%). Validation data showed that the RSD% values were in the range of 1.85 to 13.06%, whereas, the % DEVs values ranged from ?1.4 to +10.0% indicating good precision and accuracy. Analytical recoveries of GBP from spiked human plasma were in the range of 98.9 to 101.3%. On the other hand, recoveries of GBP from stored human plasma samples were in the range of 100.0 to 107.5% indicating that GBP was stable in plasma, with no appreciable degradation, when stored at ?20 °C. The developed method was applied for GBP monitoring in plasma samples of patients treated with GBP.     

Hydrophilic Treatment of the Dyed Nylon-6 Fabric using High-density and Extensible Antenna-coupling Microwave Plasma System

High density and well surface-distributed oxygen microwave plasma with an extensible antenna-coupling design was utilized to modify a densely weaved and large-surface-area Nylon-6 fabric within a short treatment time. Plasma pretreatment and subsequent acrylic acid (AAc) or 2-hydroxyethyl methacrylate (HEMA) grafting process were studied and optimized at the stage after dyed and finished procedure. The monomer-grafted dyed Nylon-6 fabrics evolved lasting hydrophilic properties and thereafter created or improved surface properties such as water diffusion, drainage, moisture regain and water absorbency, in different degrees. The pHEMA-grafted sample exhibited minor effect in color perception, which was also much hydrophilic than the pAAc-grafted one. Based upon surface analyses and wetting assessment, the penetration of HEMA monomer into the plasma-treated fabric matrix contributed to the facilitation of wetting properties. This work accordingly ensures such plasma-induced system to incorporate with the pattern of hydrophilic properties on the analogous textiles without interrupting their finishing process.     

利用电荷迁移反应测定头孢羟氨苄

提出一种基于电荷迁移反应简便可靠地测定头孢羟氨苄的分光光度法。在甲醇－乙醇介质中，头孢羟氨苄与氯冉酸于５０℃反应１５ｍｉｎ能够形成稳定的１：１络合物，其λｍａｘ＝５２８ｎｍ，线性范围为２０￣４００ｍｇ／Ｌ。用拟定的方法测定原粉和胶囊，结果与药典法一致。对浓度１００ｍｇ／Ｌ的药物１０次测定相对标准偏差为１．４％，样品的标准加入回收率为９９．０％￣１００．８％。     

ZrO2纳米粉末复合羊毛纤维研究

ＺｒＯ_２纳米粉末复合羊毛纤维研究陈代荣，樊悦朋（山东大学化学系济南２５０１００）关键词ＺｒＯ_２纳米粉末，羊毛纤维，复合纤维由陶瓷粉末和天然纤维形成的复合纤维的强度、织品的保暖性、抗起球性及防缩性能等均有所提高，报道较多的是微米级陶瓷粉末（粒径０．５...     

A constant-denominator perturbation theory using circulant orbitals

Molecular-orbital calculations, using the INDO procedures, were carried out on the tautomers of 1, 2, 4-triazole and its benzo-derivative as well as on 1, 2, 5-oxadiazole and its benzo-derivative. Calculations of the transition energy as well as the dipole moment helped to predict the predominant tautomer in an equilibrium mixture. The correspondence between the calculated and observed data is satisfactory. The results of calculations indicated some differences in the electronic structures of the tautomers of a compound.     

Pt/TiO_2催化剂上的氢—氧作用 Ⅰ.氢、氧的吸咐—脱附行为以及相互促进作用

本文采用程序升温脱附(TPD)技术研究了光沉积方法制备的Pt/TiO_2催化剂经过氧化、还原后氧、氢的脱附行为.光沉积过程中,Pt/TiO_2表面上可以生成大量的吸咐氢,在TPD中脱附;同时Pt/TiO_2表面上化学吸附的水在TPD过程中也可以分解释氢.氧化处理的Pt/TiO_2在TPD过程中于550～750K温区出现氧脱附峰,随着氧化温度升高,脱附峰位向高温移动,经实验证明,这种可脱附活泼氧物种的生成是由样品前身中留存氢引起的.还原处理的Pt/TiO_2在TPD过程中分别在300～600和大于600K出现两个氢脱附峰,认为是由于表面羟基和钛—氢(Ti~(4+)—H~-)物种的分解释氢引起的Pt/TiO_2上活泼氧物种的存在,增加了样品在室温条件下的吸氢量;在中温(473～573K)这种活泼氧物种则和氢发生反应,减少了TPD过程中的脱氢量;Pt/TiO_2在大于673K温度还原,可以消除活泼氧物种的影响.