Ionic liquid-regulated sulfamic acid: chemoselective catalyst for the transesterification of β-ketoesters

1-Propyl-3-methylimidazolium chloride ([C₃MIm]Cl) ionic liquid and sulfamic acid (NH₂SO₃H), as a synergetic catalytic medium, were used for the transesterification of acetoacetate with alcohols of different structures. It shows the good ability for the chemoselective transesterificatin of β-ketoesters and maintains its catalytic activity in the reuse.     

Simultaneous determination of trace cadmium and mercury in Chinese herbal medicine by non-dispersive atomic fluorescence spectrometry using intermittent flow vapor generator.

A method was proposed for the simultaneous determination of trace cadmium and mercury by vapor generation non-dispersive atomic fluorescence spectrometry using an intermittent flow system. The effects of the parameters on the performance were studied systematically. The parameters such as acid concentration of the reaction medium, flow rate of the carrier gas and shield gas, the observation height and the atomizer temperature, etc. which affected the sensitivity, were optimized. Ascorbic acid, cobalt ion and thiourea were used as enhancement reagents or masking agents to enhance the generation efficiency of the volatile species of Cd and Hg. The mechanisms of their effects on vapor generation were investigated. In the presence of thiourea and ascorbic acid, the influences of some coexisting elements on the determination of cadmium and mercury were investigated. The detection limits (3sigma) were 0.010 microg l(-1) for Cd and 0.019 microg l(-1) for Hg, respectively. The relative standard deviations for Cd and Hg at 1.00 microg l(-1) were 2.6% and 0.97% (n = 11), respectively. The proposed method has been satisfactorily applied to the determination of trace cadmium and mercury in Chinese herbal medicine.     

A theory of coupled diffusion and large deformation in polymeric gels

A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter.     

负载型双金属簇催化剂的多相一氧化碳加氢反应性能

负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶，李晔（内蒙古工业大学化学工程系，呼和浩特０１００６２）殷元骐，金道森（中国科学院兰州化学物理研究所，兰州７３００００）关键词一氧化碳加氢，多相催化，双金属簇催化剂，钾效应。１．引言异核金属羰基簇作...     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

桥联双β-环糊精对N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸的手性识别及机理研究

利用紫外-可见吸收和荧光发射光谱, 结合非线性最小二乘法拟合曲线以及分子力学(MM2)模拟系统地研究了手性分子N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸(PDP和PLP, 总称PPs)与β-环糊精(β-CD)、 2-位硒桥联双β-CD(2-SeCD)和2-位碲桥联双β-CD(2-TeCD)的包结能力大小及这3个环糊精对PPs手性识别能力的差异和识别机理. 研究结果表明, PPs不能与单疏水空腔的β-CD形成很好的包结复合物, 与具有较长桥联链的2-TeCD结合能力最强. 2-TeCD与PDP和PLP的结合常数分别为2.33×104和6.07×103 L/mol, 对PPs的手性识别比达到KD/KL=3.84, 高于2-SeCD(KD/KL=2.61). 用MM2模拟得出了PPs与这两个双环糊精形成复合物的三维结构: PPs的绝大部分位于双环糊精两个空腔之间, 但是在这两个复合物中, 苯环与芘环所成的二面角不同. 此外, PPs与这两个双环糊精作用时均存在明显的氢键相互作用, 且2-TeCD强于2-SeCD.     

Pre-Column Derivatization of Amines with 1,2-Benzo-3,4-Dihydrocarbazole-9-Isopropyl Chloroformate Followed by LC-Fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCI-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH]⁺ under APCI in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH₂-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0–10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of I_BCIC/I_CEOC and I_BCIC/I_FMOC are, respectively, 1.23–3.14 and 1.25–3.08 for fluorescent (FL) responses (here, I is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C₈ column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6–37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV<7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997. Revised: 12 December 2005 and 13 Febrauary 2006     

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。     

藏药香芸火绒草Leontopodium Haplophylloides化学成分的研究

从藏药香芸火绒草Leontopodium Haplophylloides Hand Mazz的甲醇提取物中分得四个B环未取代的黄酮, 分别为乔松素(1), 高良姜素(2), 3, 7-二羟基-5-甲氧基黄(3), 3, 5-二羟基-7-甲氧基黄酮(4), 化合物(2)对人皮肤痤疮菌具有一定的疗效。     

Fe_3(CO)_9(μ_3-S)_2的P(SR)Cl_2和P(SR′)_3取代物的合成和结构研究

用P(SR)Cl_2和P(SR′)_3作n-酸配体,分别与Fe_3(CO)_9(μ_3-S)_2进行取代反应,得到6种新的一取代产物Fe_3(CO)_8(μ_3-S)_2L和3种新的二取代产物Fe_3(CO)_7(μ_3-S)_2L_2,并对它们进行了IR、~1H NMR和MS表征,测定了其中一种取代物Fe_3(CO)_8(μ_3-S)_2[P(SC_6H_5)Cl_2]的分子和晶体结构。