Crystal structure of the complex of trichosanthin with NADPH at 0.172 nm resolution

The orthorhombic crystal structure of the complex of trichosanthin with nicotinamide adenine dinucleotide phosphate has been determined by molecular replacement method using one of the molecules of the monoclinic crystal structure of trichosanthin at 0.27 nm resolution as the search model. The crystallographic refinement at 0.172 nm resolution led to a final R-factor of 17.4% with root-mean-square deviations of 0.0013 nm and 3.8 from the ideal bond lengths and bond angles, respectively. The quality of the structure, the polypeptide chain fold and the comparison of it with that of the monoclinic trichosanthin structure, the location of nicotinamide adenine dinucleotide phosphate, the active site structure as well as the solvent structure are described.     

水合偏硼酸钾的热化学研究

Hydrated potassium monoborate(KBO₂·4/3H₂O) was obtained from an aqueous solution in a mole ratio of K₂O∶B₂O₃=2∶1 and characterized by powder X-ray diffraction(XRD)， infrared spectroscopy(FT-IR) and Raman spectroscopy. The enthalpy of solution of hydrated potassium monoborate， KBO₂·4/3H₂O， in approximately 1mol·dm^-3 aqueous hydrochloric acid was determined. Together with the previously determined enthalpies of so-lution of H₃BO₃ in approximately 1mol·dm^-3 HCl(aq) ，and of KCl in aqueous(hydrochloric acid+boric acid)， the standard molar enthalpy of formation of -(1411.11±0.84)kJ·mol^-1 for KBO₂·4/3H₂O was obtained from the standard molar enthalpies of formation of KCl(s)， H₃BO₃(s)， and H₂O(l). The standard molar entropy of formation of -422.94J·K^-1·mol^-1 and standard molar entropy of 163.47J·K^-1·mol^-1 for KBO₂·4/3H₂O were calculated from the thermodynamic relations. A group contribution method is applicable to KBO₂·4/3H₂O.     

Nb+离子活化甲烷脱氢反应机理密度泛函(DFT)研究

通过DFT-UB3LYP方法, 计算了五重、三重和单重自旋态下的气相Nb+离子活化甲烷脱氢反应的能量变化, 并对其直接式和插入式反应机理进行了比较, 考察了自旋翻转对反应的影响. 结果表明, 插入式脱氢较直接式有利, CH4上的H转移到Nb+上形成的中间体HNbCH+3中, 多重度由五重降为三重, 反应活化能垒显著降低; HNbCH+3可经四中心过渡态转化为(H2)NbCH+2, 最后生成三重态的NbCH+2+H2. 速控步骤为(H2)NbCH+2的脱氢. 此外, 通过对V+, Nb+, Ta+活化甲烷的比较研究了三者活化甲烷的反应活性.     

用非等温DSC估算3,4-双(4’-硝基呋咱-3’-基)-2-氧化呋咱(BNFOF)放热自催化分解反应的热爆炸临界温升速率和动力学参数

A method of estimating the kinetic parameters and the critical rate of temperature rise in the thermal explosion for the autocatalytic decomposition of 3,4-bis（4＇-nitrofurazan-3＇-yl）-2-oxofurazan （BNFOF） with non-isothermal differential scanning calorimetry （DSC） was presented. The rate equation for the decomposition of BNFOF was cstablished, and information was obtained on the rate of temperature increase in BNFOF when the empiric-order autocatalytic decomposition was converted into thermal explosion.     

RUTHENIUM-TPPTS CATALYZED REDUCTlON OF NITROBENZENE TO ANILINE——A HIGHLY SELECTIVE WATER-SOLUBLE CATALYST SYSTEM

The ruther ium catalvst complex formed from RuCl_3·3H_2O andthe water-soluble ligand tris-(sodium m-sulfophenyl)phosphine, TPPTS, hasbeen examined as a catalyst for the reduction of nitrobenzene to anilineunder water gas shift conditions. The reactions, which were conducted inaqueous methanol. were studied as a function of CO pressure and addedamine base The major product observed over the temperature range of100～150℃ was aniline (>90% yield abovc 130℃ ), with only minor amountsof the corresponding carbamate PhNHCO_2Me(<3%) and formanilide(<4%)being observed. Of the several amine bases examined in this reaction, Et_3Nhas been found to be superior in promoting the fastest rate of nitrobenzenereduction. Replacement of methanol by either THF or xylenes led to a drastic retardation in the amount of aniline produced.     

镍钛合金表面离子液体掺杂聚苯基吡咯纤维涂层的制备及其对多氯联苯的高效固相微萃取

采用水热法和电沉积法在镍钛(NiTi)合金表面构筑1-丁基-3-甲基咪唑六氟磷酸盐离子液体(IL)掺杂聚苯基吡咯(PPPy)纤维涂层,成功制备了新型IL@PPPy-TiO_2/NiOCNSs固相微萃取(SPME)纤维。将该新型纤维与高效液相色谱(HPLC)联用,以多氯联苯(PCBs)、邻苯二甲酸酯(PAEs)、多环芳烃(PAHs)和紫外线(UV)吸收剂为模型分析物评价其萃取性能。结果显示,该纤维对PCBs有较强的萃取选择性和较高的萃取效率。在优化条件下,5种PCBs在一定质量浓度范围内呈良好线性,相关系数r≥0.998 6,检出限(LOD)为0.015～0.11μg/L。采用单支纤维在同日和隔日对50μg/L PCBs混合标准溶液进行萃取测定,相对标准偏差(RSD)分别为4.7%～6.1%和5.4%～7.0%,相同方法制备的5支纤维测定的RSD为6.5%～7.7%。实际水样的加标回收率为83.0%～104%,RSD不大于8.6%。所建立的SPME/HPLC法适用于不同环境水样中痕量PCBs的快速萃取和高效测定。     

聚乙二醇为分散剂的沉淀法制备IF-MoS2

通过添加聚乙二醇（PEG）作为分散剂的沉淀法制备非晶态MoS₃前驱体，并在高温氩气气氛中用氢气脱硫制备了MoS₂颗粒。用扫描电镜（SEM）、X-射线衍射（XRD）和高分辨透射电镜（HRTEM）表征了MoS₂颗粒的结构和形貌。溶液中添加PEG后，脱硫温度对所制备的MoS₂颗粒粒径没有明显影响。MoS₃在900 ℃保温7 h脱硫获得了球形的嵌套层状封闭结构的IF-MoS₂纳米颗粒。分析讨论了IF-MoS₂形成机制以及聚乙二醇分散剂的作用机理。     

A Mild and Efficient Oxidation of Alcohols in Water

A mild and efficient oxidation of alcohols to the corresponding carbonyl compounds using the PhI(OAc)2 (1.1 eq.) with n-Bu4NBr (8 mol %) in water at room temperature is described.This new procedure is very simple and affords the desired carbonyl compounds in high yields.     

4-甲氧基-N-(2-N′, N′-二甲基氨基乙基)萘二甲酰亚胺烯丙基氯化铵的合成与光学性质

4-甲氧基-N-(2-N′; N′-二甲基氨基乙基)萘二甲酰亚胺烯丙基氯化铵的合成与光学性质;荧光单体;季铵盐;合成;萘酐     

甲基丙烯酸甲酯的基团转移聚合

<正> 基团转移聚合(Group Transfer Polymerization,GTP)作为一种新的加聚方式,由于具有室温下使极性单体快速聚合;得到预期分子量和窄分子量分布的聚合物;可进行活性聚合,制备嵌段共聚物,对合成丙烯酸酯类橡胶或热塑性弹性体极为有利;可合成带有功能性端基和遥爪的聚合物等优点,近几年来发展迅速。到目前为止,最有效和最常用的GTP引发剂是二甲基乙烯酮甲基三甲基硅基缩醛