键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成及催化烯烃环氧化反应性能研究

本文研究了键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成，以及在ＣＨ_２Ｃｌ_２／Ｈ_２Ｏ两相体系中催化苯乙烯环氧化反应的性能．探索了催化反应体系中溶液ｐＨ值、ＮａＯＣｌ浓度、轴向配体及相转移催化剂对催化反应的影响．结果说明键联聚乙二醇高分子担载锰（Ⅲ）卟啉是烯烃环氧化反应的一种有效催化剂，其中聚乙二醇链可以络合Ｎａ，使ＯＣｌ富集于金属卟啉周围，起到较好的相转移催化作用．在催化反应的各影响因素中，水相ｐＨ值对反应的影响最大．     

键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成及催化烯烃环氧化反应性…

本文研究了键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成，以及在ＣＨ２Ｃｌ２／Ｈ２Ｏ两相体系中催化苯乙烯环氧化反应的性能，探索了催化反应体系中溶液ｐＨ值、ＮａＯＣｌ浓度、轴向配体及相转移催化剂对催化反应的影响。结果说明键联聚乙二醇高分子担载锰（Ⅲ）卟啉是烯烃环氧化反应的一种有效催化剂，其中聚乙二醇链可以络合Ｎａ，使ＯＣｌ富集于金属卟啉周围，起到较好的相转移催化作用。在催化反应的各影响因素中，水相ｐＨ值对     

杯芳烃-金属卟啉仿酸酶模型化合物的合成及其电子光谱研究

本文首次报导杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中, 杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

杯芳烃-金属卟啉仿酶模型化合物的合成及其电子光谱研究(英文)

本文首次报道杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物的光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中,杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

高分子键联金属卟啉的合成及催化性能

高分子键联金属卟啉的合成及催化性能;高分子担载金属卟啉; 环己烯; 催化氧化     

聚乙二醇相转移催化剂在Perkin反应中的催化作用

本文以聚乙二醇(PEG)为相转移催化剂,对Perkin反应进行了研究。实验结果表明:聚乙二醇在Perkin反应中有明显的催化作用,平均分子量为600的聚乙二醇催化效果较好;PEG-600可使Perkin反应产率提高10％以上;反应时间显著缩短;PEG-600用量1％mol左右为宜。     

CO2与环氧化合物聚合反应的金属卟啉催化体系研究

作为金属卟啉催化作用的新研究领域,金属卟啉作为催化剂催化CO2与环氧化合物合成具有生物降解性能的聚碳酸酯,具有良好的应用前景,在碳资源利用、环境保护和高分子合成化学方面具有重大意义.自从1978年Inoue首次采用金属卟啉催化剂由CO2与环氧化物合成聚碳酸酯以来,化学家们在金属卟啉催化剂体系的设计与合成方面进行了大量研究.在此基础上,本文对金属卟啉作为催化剂应用于CO2与各种环氧化合物的聚合反应、偶联反应及其反应机理研究加以综述;并展望了其应用前景.     

长链烷基冠醚在烯烃环氧化反应中的相转移催化作用

为了实现温和条件下烯烃的环氧化,近年来模拟细胞色素P-450单加氧酶催化烃类氧化的研究十分活跃,其中以金属卟啉/NaOCl(CH_2Cl_2/H_2O)模拟体系研究最多.从近年文献看,在Meunier等建立的该两相催化反应体系中,通过改变催化剂的结构、各种助剂及氧源浓度等可达到较好的催化效果,其相转移剂一般选用季铵盐类化合物.有文献报导以聚乙二醇取代季铵盐,结果证明聚乙二醇的相转移作用也很明显.本文将一类新型的非离子型表     

高效疏水作用色谱分离蛋白质的聚乙二醇键合相的研究

〕聚乙二醇键合相已用于高效疏水作用色谱分离活性蛋白质。本文中,我们进一步研究了聚乙二醇的分子量和硅胶孔径对键合相覆盖率和蛋白质分离效能的影响。实验结果表明,较大孔径的键合相具有高的覆盖率和好的分离效能。分子量小的聚乙二醇键合相适合于分离疏水性强的蛋白质;反之,分子量大的键合相则对亲水性蛋白质有好的分离效果。其中PEG-1500键合相（50nm）具最佳分离效能。蛋白质在此柱上可得90％以上的活性回收率。2mg以上的蛋白质样品可一次注入100×5mmＩ.D.分析柱上而不影响分辨率和保留时间。     

金属卟啉存在下芳醛氧化反应的研究

本文研究了在金属四苯基卟啉[Co(II)TPP,Fe(III)TPPCl,Mn(III)TPPCl,Zn(II)TPP,Cu(II)TP.TPP=四苯基卟啉]存在下,用氧气氧化芳醛的过程.测定了反应体系的吸氧动力学曲线;观察了氧化过程中金属卟啉的可见光谱的变化;研究了底物,金属卟啉在反应体系中的浓度以及溶剂等因素对反应的影响.结果发现,除能可逆键合分子氧的Co(II)TPP外,不具此种功能的Fe(III)TPPCl和Mn(III)TPPCl也能加速芳醛的氧化反应.然而,它们的催化作用是在金属四苯基卟啉与反应过程中积累起来的过酸作用,卟啉环遭到破坏后观察到的,此时可能形成了某种新的催化活性中心.金属卟啉本身对反应起抑制作用,它只是表观上的催化剂,其催化作用看来不应归结为对分子氧的活化.     

m-4-m型Gemini表面活性剂对铂电极上亚甲蓝吸附溶出伏安行为的影响

在0.050 mol·L-1磷酸盐缓冲溶液(PBS)中(pH=6.4), 亚甲蓝(MB)在铂电极上于-0.2 V产生一对不明显的伏安峰. 当向溶液中加入阳离子型Gemini表面活性剂Br-C16H33N+(CH3)2-C4H8-N+(CH3)2C16H33Br-, Br-C12H25N+(CH3)2-C4H8-N+(CH3)2C12H25Br-或Br-C8H17N+(CH3)2-C4H8-N+(CH3)2C8H17Br-后, 亚甲蓝的氧化峰显著增高, 还原峰降低, 氧化还原峰峰电位均正移, 这和表面活性剂与MB在电极表面的协同吸附有关. 联接基团相同的Gemini表面活性剂, 其影响程度随烷基链的增长而逐渐增强. 增大表面活性剂的浓度, MB的氧化峰先升高后缓慢降低. 如当Br-C16H33N+(CH3)2-C4H8-N+(CH3)2C16H33Br-的浓度为15 μmol·L-1 时, 5 μmol·L-1 MB的氧化峰峰电流达到最大值. 此外,溶液pH值和富集电位等对MB及表面活性剂的吸附亦有影响.     

A novel ordered cubic mesoporous silica templated with tri-head group quaternary ammonium surfactant

An ordered mesoporous silica with novel cubic structure (space group Fd3m) has been synthesized by using tri-head group quaternary ammonium surfactants [CmH2m + 1N+(CH3)2CH2CH2N+(CH3)2CH2CH2CH2N+(-)(CH3)(3).3Br-] (Cm-2-3-1, m = 14, 16, 18) as the structure-directing agents under basic conditions at low temperature.     

二苯酮在功能胶束中的光还原反应的研究

本文研究了一种具有分子自聚集作用的二苯酮(BP)衍生物p-C6H5COC6H4CH2^+N(CH3)2C12H25.Br^-(PKT)的光还原反应及其光物理性质。连接在PKT上BP的光还原反应活性在胶束形成前后有很大差别。 反应速率随着浓度增大在形成的胶束中比均相水溶液中快1.5倍。值得指出, 在PKT功能胶束中的BP还原速率与普通胶束相比, 增加10倍以上。动力学数据测定表明, PKT胶束大大加速了BP-三乙胺(TEA)光还反应中的电子转移, 在TEA高浓度时有利于质子转移, k~d/k~r值减少,k~n/k~e值增加, 对不同TEA浓度的光还原机理亦作了讨论。     

Analysis of inorganic anions by electrostatic ion chromatography using zwitterionic/cationic mixed micelles as the stationary phase

The inability to separate fluoride, phosphate and sulfate by electrostatic ion chromatography (EIC) was overcome by using an ODS silica column coated with mixed zwitterionic-cationic surfactants as the stationary phase. The best results were obtained using the zwitterionic surfactant, 3-(N,N-dimethylmyristylammonium)-propanesulfonate (C19H41NO3S), and the cationic surfactant, myristyltrimethylammonium, CH3(CH2)13N+(CH3)3, in a 10:1 molar ratio in the column coating solution. With a dilute solution of sodium tetraborate as the eluent the model analyte anions were completely separated in the following elution order: F, HPO42-, SO42-, Cl-, NO2-, Br-, NO3-. The very early elution of phosphate and sulfate is most unusual and is unique to this system. Detection limits better than 1.1 x 10(-4) mM and linear calibration plots up to 7.0 mM were obtained with a suppressed conductivity system.     

PMO[KIT-5]-n: synthesis of highly ordered three-dimensional periodic mesoporous organosilicas with Fm3m symmetry

Divalent surfactant [CH3(CH2)15N(CH3)2(CH2)3N(CH3)3]2+ - 2Br- (C16-3-1) was used as a structure directing agent (SDA) for the synthesis of highly ordered periodic mesoporous organosilicas (PMOs) with cubic Fm3m symmetry from 1,2-bis(triethoxylsilyl)ethane (BTEE) under basic conditions.     

Study of the Pm3n space group of cubic mesoporous silica.

By using a Gemini surfactant, [C14H25N+(CH3)2-(CH2)2-N+(CH3)2C14H25]2 Br-(C(14-2-14)), with a short spacer group (s = 2) as structure-directing agent and sodium silicate as precursor, high-quality, ordered cubic mesoporous silica with space group Pm3n was prepared by the S+I-route (S = surfactants, I = precursor). The samples were characterized by small-angle X-ray diffraction, transmission electron microscopy, and N2 adsorption-desorption. The results showed that the pore structure of the resulting mesoporous silica belonged to the cubic system (space group Pm3n). The unit-cell parameter of the cubic system was in the range of 8.81-9.14 nm. The high-quality cubic mesoporous structure was formed at molar ratios of C(14-2-14) to sodium silicate of 0.33:1 to 0.16:1 and a molar ratio of ethyl acetate to sodium silicate of 2:1. N2 adsorption-desorption curves revealed type IV isotherms and H1 hysteresis loops. The primary pore volume, and the most probable pore size according to the Barrett-Joyner-Halenda (BJH) model, increased with increasing molar ratio of C(14-2-14) to sodium silicate.     

酯基Gemini型季铵盐表面活性剂与SDS的相互作用

研究了酯基Gemini型季铵盐表面活性剂[Cm-1H2m-1COOCH2CH2(CH3)2N+(CH2)n+N(CH3)2CH2CH2OOCCm-1H2m-1]•2Br-(简称II-m-n, m=10, 12; n=3, 4, 6)与十二烷基硫酸钠(SDS)的复配体系的相互作用以及无机盐(NaBr)对复配体系表面活性的影响. 结果发现, 其复配体系具有显著的胶团化协同增效作用和降低表面张力的增效作用, 并且II-10-n与SDS的复配体系的增效作用具有等链长效应. II-m-n/SDS复配体系的胶团化协同增效作用随n增大而增强. 混合胶团中II-m-n与SDS的摩尔比均近似为1:1, 显示各复配体系的混合胶团均带电性, 因此NaBr的加入能增强复配体系的表面活性和促进混合胶团的形成.     

N-(3-氟苯甲酰基)-N′-芳基硫脲衍生物的合成及其生物活性

在超声波辐射下,以PEG-400为相转移催化剂,通过3-氟苯甲酰氯与硫氰酸铵反应制得3-氟苯甲酰基异硫氰酸酯(2);2与芳胺反应,高产率地合成了11种未见文献报道的3-氟苯甲酰基硫脲衍生物(1)。初步生物活性实验结果表明,1对油菜幼苗的胚根生长具有明显的促进作用。     

聚乙二醇在N-烃化反应中的相转移催化作用

N-烃基邻苯二甲酰亚胺类化合物是合成脂肪族伯胺和α-氨基酸的重要中间体。近年来,Landini,D.,Santaniallo,E.等先后报道过在鎓盐存在下进行邻苯二甲酰亚胺的相转移催化烃化反应。     

Reaction pathways and free energy barriers for alkaline hydrolysis of insecticide 2-trimethylammonioethyl methylphosphonofluoridate and related organophosphorus compounds: electrostatic and steric effects

Reaction pathways and free energy barriers for alkaline hydrolysis of the highly neurotoxic insecticide 2-trimethylammonioethyl methylphosphonofluoridate and related organophosphorus compounds were studied by performing first-principles electronic structure calculations on representative methylphosphonofluoridates, (RO)CH3P(O)F, in which R = CH2CH2N+(CH3)3, CH3, CH2CH2C(CH3)3, CH2CH2CH(CH3)2, CH(CH3)CH2N+(CH3)3, and CH(CH3)CH2N(CH3)2. The dominant reaction pathway was found to be associated with a transition state in which the attacking nucleophile OH- and the leaving group F- are positioned on opposite sides of the plane formed by the three remaining atoms attached to the phosphorus in order to minimize the electrostatic repulsion between these two groups. The free energy barriers calculated for the rate-determining step of the dominant pathway are 12.5 kcal/mol when R = CH2CH2N+(CH3)3, 15.5 kcal/mol when R = CH3, 17.9 kcal/mol when R = CH2CH2C(CH3)3, 16.5 kcal/mol when R = CH2CH2CH(CH3)2, 13.4 kcal/mol when R = CH(CH3)CH2N+(CH3)3, and 18.7 kcal/mol when R = CH(CH(3))CH(2)N(CH(3))(2). The calculated free energy barriers are in good agreement with available experimentally derived activation free energies, i.e. 14.7 kcal/mol when R = CH(3), 13.4 kcal/mol when R = CH2CH2N+(CH3)3, and 13.9 kcal/mol when R = CH(CH3)CH2N+(CH3)3. A detailed analysis of the calculated energetic results and available experimental data suggests that the net charge of the molecule (M) being hydrolyzed is a prominent factor affecting the free energy barrier (DeltaG) for the alkaline hydrolysis of phosphodiesters, phosphonofluoridates, and related organophosphorus compounds. The electrostatic interactions between the attacking nucleophile OH- and the molecule M being hydrolyzed favor such an order of the free energy barrier: DeltaG(M(+)+OH-) < DeltaG(M0+OH-) < DeltaG(M(-)+OH-), where M+, M0, and M- represent the cationic, neutral, and anionic molecules, respectively. The change of the substituent R in (RO)CH(3)P(O)F from CH3 to CH2CH2N+(CH3)3 is associated with both the electrostatic and steric effects on the free energy barrier, but the electrostatic effect dominates the substituent shift of the free energy barrier. This helps to better understand why the alkaline hydrolysis of (RO)CH3P(O)F with R = CH2CH2N+(CH3)3 and CH(CH3)CH2N+(CH3)3 is significantly faster than that with R = CH3. The effect of electrostatic interaction also helps to understand why the rate constants for the alkaline hydrolysis of phosphodiesters, such as intramolecular second messenger adenosine 3',5'-phosphate (cAMP), are generally smaller than those for the alkaline hydrolysis of the phosphonofluoridates and related phosphotriesters.