杂多酸在活性炭上的固载化Ⅲ．活性炭在酸性介质中对钨硅杂多酸（SiW_（12））的吸附

在氢离子浓度均为３ｍｏｌ／Ｌ的硫酸，盐酸，磷酸，醋酸水溶液中和冰醋酸中研究了具有Ｋｅｇｇｉｎ结构的硅钨杂多酸（ＳｉＷ＿（１２））在不同来源活性炭上的吸附作用。各活性炭对ＳｉＷ＿（１２）吸附等温线的形式是不相同的，吸附剂载体的微孔结构以及杂多酸的溶剂化起着重要的作用。并且在无机酸介质中，杂多酸的吸附量比在水溶液中成规律性地增加，且与酸强度成正比关系。在有机酸介质中，吸附作用比较复杂。根据所得结果，提出了在酸性介质中杂多酸在活性炭表面的吸附模型。     

Mechanism of UV photoreactivity of alkylsiloxane self-assembled monolayers

A molecular level understanding of the photoreactivity of self-assembled monolayers (SAMs) becomes increasingly important as the spatial resolution starts to be limited by the size of the resist and the spatial extent of the photochemical reactions in photoresist micropatterning. To this end, a number of surface characterization techniques were combined to understand the reactive agents, reactive sites, kinetics, and reaction pathways in the UV photoreactivity of octadecylsiloxane (ODS) SAMs. Quantitative analysis of our results provides evidence that ground state atomic oxygen is the primary reactive agent for the UV degradation of ODS SAMs. UV degradation, which follows zero-order kinetics, results in the scission of alkyl chains instead of the siloxane headgroups. Our results suggest that the top of the ODS SAMs is the preferential reactive site. Using a novel, highly surface sensitive technique, fluorescence labeling of surface species, we identified the presence of submonolayer quantities chemical functional groups formed by the UV degradation. These groups are intermediates in a proposed mechanism based on hydrogen abstraction.     

原子发射光谱法间接测定黄连素片剂中盐酸小檗碱的研究

本文提出了离子对-原子发射光谱间接测定黄连素片剂中盐酸小檗碱的新方法。发现用1,2-二氯乙烷作萃取剂效果最佳。用此怯测定实际样品的结果与药典法一致,相对误差为0.61％,单一测定的相对标准偏差为0.67％。本法还可在盐酸普鲁卡因共存下单独测定盐酸小檗碱。方法可靠、适用,选择性较好。     

Electrochemical control of CO/NO ligand exchange in a triruthenium cluster monolayer assembled on a gold electrode surface

A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.     

面向化妆品产业升级的江南大学应用化学专业建设思考与实践

Based on the development prospect of cosmetics industry, the advantage of light industry characteristic and the foundation of applied chemistry in Jiangnan University, a systematic upgrading of applied chemistry was carried out through "emerging engineering education (3E)" project "upgrade and practice of chemistry-related majors of local and/or trade university responding to the social developments" supported by the Ministry of Education. On the basis of investigation and analysis, the orientation and training goal of applied chemistry were updated first, and then the curriculum system was determined and the curriculum construction is strengthened, so as to achieve more distinctive characteristics, more solid foundation and more comprehensive quality. In view of the new requirements of the 3E for talent training, some practices have been formed in the aspects of multi-disciplinary integration, multi-angle coordination and close integration to industry. Contributing the development of cosmetics industry and seizing the commanding point of science and technology from the perspective of talent training, will play a unique role in human social progress.     

Studies on fluorescent species of spiro-indolinonaphthooxazines and their fluorescence spectra

Photophysical behavior of spiro[1,3,3-trimethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP1) and spiro[1,3,3,2′-tetramethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP2) were studied. The fluorescent species and their spectra of SP1 and SP2 in polar solvents (acetonitrile and methanol) and non-polar solvent (cyclohexane) were investigated. The fluorescence decay in polar solvents was studied by picosecond time-correlated single photon counting. In most cases, fluorescence decay obeyed triexponential decay kinetics. The major fluorescent species is an excited intermediate which has similar conformation as its precursor (¹ SP ^*) formed after the bond cleavage between spirocarbon and oxygen in oxazine ring. The effects of molecular structure and solvent polarity on fluorescence spectra and fluorescence decay lifetime were studied.     

Agonist–PPARγ interactions: Molecular modeling study with docking approach

Docking simulation of 18 agonists with the ligand binding pocket (LBP) of PPARγ has been performed. The binding conformations and binding affinities of these agonists were obtained by use of the flexible docking protocol FlexX. Test compound calculations indicated that FlexX can reproduce the binding conformation of the crystal structure (root mean square deviation = 1.43 Å); moreover, the predicted binding affinities correlate well with the activities of these agonists. The interaction model and pharmacophore of PPARγ agonists were derived and the difference in biologic activities of these agonists can be well explained. The PPARγ agonists must have both polar head and the hydrophobic tail, which form hydrogen bonds and hydrophobic contacts with hydrophilic and hydrophobic regions of the LBP of PPARγ, respectively. In addition, a suitable linker is also necessary. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 405–410, 2003     

大型液相色谱分离过程FAD－SMT数学模型及其数值解

提出大型液相色谱分离过程ＦＡＤ－ＳＭＴ数学模型，把色谱分离连续性方程转变为对流扩散方程和常微分方程组，并提出模型的数值方法，分析了数值解的稳定条件和收敛条件以及空间和时间步长的选取。实验结果表明，ＦＡＤ－ＳＭＴ数学模型计算的液相色谱分离葡萄糖、果糖和分离甘露醇、山梨醇理论与实验流出曲线相吻合。灵敏度分析结果表明：相平衡常数比轴向扩散系数和总传质系数对色谱分离有较大的影响。     

利用差异衍生同步分析醛糖和酮糖

建立了一种可同时对醛、酮糖进行精确定性和定量分析的方法。以肌醇作为内标，用80％乙醇超声提取，利用醋酸酐和HMDS＋TMCS（1：3）进行差异衍生，在EI源下用SIM模式进行GC／MS分析。结果表明：11种标准单糖在1—4mg／L范围内线性良好；仪器检出限：醛糖在8．15—22．4μg／L之间；酮糖为2．32μg／L和3．47μg/L；高、中、低3个量的平均回收率在73．0％-95．7％，相对标准偏差在3．1％-10．0％。对枸杞游离单糖进行测定，各单糖含量分别在0．26—368．6mg／g。该方法弥补了以前单糖分析中的缺陷，对既含有醛糖又含有酮糖的样品可同时进行精确的定性定量分析。     

Solution-phase synthesis and electrochemical hydrogen storage of ultra-long single-crystal selenium submicrotubes

Ultra-long single-crystalline trigonal selenium submicrotubes were synthesized using a facile one-step solution-phase approach with the assistance of nonionic surfactant Polyoxyethylene(20)sorbitan monolaurate (Tween-20), which turned out to be significant for the formation of ultra-long Se submicrotubes. XRD, Raman, SEM, and TEM were adopted to characterize the morphology, structure and phase composition of the as-prepared Se products. It was found that the length of the obtained Se submicrotubes was over 100 microm. By variation of the experimental parameters, the t-Se spheres, nanowires, and broken microtubes can be prepared. The possible growth mechanism of the ultra-long selenium submicrotubes was explained. In addition, we have also demonstrated that the synthesized ultra-long t-Se submicrotubes using the Tween-20-assisted approach can electrochemically charge and discharge with the high capacity of 265 mAh/g (corresponding to 0.97 wt % hydrogen in SWNTs) under normal atmosphere at room temperature. Cyclic voltammetry was adopted to investigate the adsorption-oxidation behavior of ultra-long selenium submicrotubes. It was observed that the morphology of the synthesized selenium products had a remarkable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of tubes as well as the microcosmic morphology of different Se samples. The as-obtained ultra-long Se submicrotubes are expected to find wide applications in hydrogen storage, high-energy batteries, and optoelectronic, biologic, and catalytic fields as well as in the studies of structure-property relationships. This simple Tween-assisted approach might be extended to the preparations of one-dimensional nanostructures of tellurium and other anisotropic materials.