Novel nucleophilic substitution of alkyl bromo-2(1H)-pyridones

Nucleophilic substitution of certain alkyl bromo-2(1H)-pyridones gave some unexpected products where the alkyl group is substituted and the ring bromine is replaced by hydrogen. The expected ring substituted product is also formed, but only as the minor product in most cases. Many reactions are cited with various nucleophiles, and a plausible mechanism is also presented.     

基于壳聚糖膜固定双酶的胆碱传感器的研究

提出了一种基于壳聚糖膜固定辣根过氧化物酶 胆碱氧化酶的胆碱传感器的制备方法。该传感器以电聚合于玻碳电极的硫堇作为电子传递介体,在pH6. 8,外加电压-0. 2V(vs.SCE)条件下,其峰电流与浓度范围 5. 0×10-5 ~3. 0×10-3 mol/L的胆碱呈良好的线性响应;检出限为 1. 0×10-5 mol/L。传感器有良好的选择性和稳定性,使用一月后,仍能保持其初始活性的 80%。     

密封罐微波消化法序列ICP-AES测定环境试样中多元素

本文采用密闭罐微波消化方法快速分解生物、土壤、沉积物等环境样品。按样品性质,分别采用HNO3/H_2O_2或HNO_3/H_2O_2/HF在聚四氟乙稀密闭罐中于500W微波功率分解0.1～0.2g样品2～3min,溶液(或在其中加入10ml硼酸饱和溶液)稀释至2.5～5.0ml后,直接用序列ICP-AES法测定。方法准确度经分析6个生物、土壤、沉积物标准参考物质验证,10个元素的均值均与定值吻合。     

核-壳型聚丙烯酸酯复合乳液

简述了核-壳型聚丙烯酸酯复合乳液的合成方法、形态及其影响因素与判断方法、结构与性能等方面的研究进展;认为核-壳型复合乳液膜机械性能优良的原因是:核、壳两相间存在的过渡区适当地抑制了二者的相分离。     

Calculation of binding energy differences for receptor–ligand systems using the Poisson-Boltzmann method

An approach using the finite difference solution of the Poisson-Boltzmann equation to estimate binding free energy changes for two receptor–ligand systems, arabinose binding protein and sulfate binding protein, is presented. The eight calculated binding free energy changes agree with experiment, showing a correlation coefficient of 0.92 and energy deviations of 1 kcal/mol or less. More importantly, the decomposition of solvation and assembly energies in this approach provides an understanding of binding mechanisms and therefore could suggest directions to alter binding affinities. The method is demonstrated to be useful in analyzing experimental binding structures and predicting binding effects of mutants or modified ligands for macromolecular systems, in which the electrostatic forces dominate the overall interaction and the structural perturbations upon modifications are small. © 1995 by John Wiley & Sons, Inc.     

A comparative study on photo-induced electron transfer from fluorescein to anthraquinone and injection into colloidal TiO2

A dyad-anthraquinone-methyl ester of fluorescein-and its model compound-butyl ester-were synthesized. The effects of photo-induced electron transfer from fluorescein to an organic anthraquinone acceptor and injection into inorganic colloidal TiO(2) were studied respectively. It is found that the photo-induced electron transferring to an organic acceptor is much faster than injecting into inorganic colloidal particles when fluorescein was excited by visible light. While inorganic colloidal TiO(2) was excited by UV, the electron of fluorescein will inject into TiO(2).     

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.     

茂基稀土胺化物与异氰酸正己酯的反应-{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2的合成及表征

茂基稀土胺化物(MeCp)2YbNPh2(THF)与异氰酸正己酯(n-HexylNCO)按11摩尔比反应, 分离出产物{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2. 产物经元素分析和核磁共振表征, 并测定了其晶体结构. 配合物属三斜晶系, R-3空间群, 晶胞参数为a=2.9533(11) nm, b=2.9533(11) nm, c=1.5873(6) nm, V=11.9896(80) nm3, Z=9, Dc=1.562 mg·m-3, μ=3.536 mm-1 (Mo Kα), F(000)=5670, R=0.034, Rw=0.064. 该化合物具有二个对称氧桥的双分子结构, 并存在着由氮原子向中心金属镱分子内配位而形成的三环骨架, 中心金属镱的配位数是九, 整个分子呈中心对称.     

咪喹莫特的波谱学数据与结构表征

对咪喹莫特的红外(IR)、紫外(UV)、质谱(MS)、氢-氢相关谱(^1H--^1H COSY)、碳氢相关谱(HMQC)、碳氢远程相关谱(HMBC)予以解析并进行了报道。对所有的^1H NMR、^13C NMR谱的信号进行了归属；讨论了质谱的主要碎片离子的可能的裂解方式和红外特征吸收峰所对应的官能团的振动形式。     

Sensitive HPLC-fluorometric and HPLC-MS determination of diarrhetic shellfish poisoning (SP)-toxins as 4-bromomethyl-7-methoxycoumarin esters

 Extracts containing the diarrhetic shellfish poisoning (DSP) toxins okadaic acid (OA), dinophysistoxin-2 (DTX₂), and dinophysistoxin-1 (DTX₁) were purified on a silica gel cartridge and derivatized with 4-bromomethyl-7 methoxycoumarin (BrMmc). After pre-column derivatization the BrMmc derivatives of the DSP toxins were directly injected into an HPLC system, isocratically eluted, and quantified by fluorescence detection. The signals of the esters showed good linearity in the fluorescence detector within the examined contamination range of 0.03 mg DSP/kg to 2.5 mg DSP/kg. The detection limits for the DSP toxins as 7-Mmc esters were 0.04 ng (corresponding to 0.05 mg DSP/kg). The chromatographic conditions allow to couple the HPLC device with mass spectrometry. The method was tested with various mussel tissue samples. Received: 14 December 1995/Revised: 26 January 1996/Accepted: 30 January 1996