铜(II)-5-取代邻菲啰啉-二氧四胺大环三元体系的稳定性研究

The stability of copper (Ⅱ)-13-(2'-Hydroxy-3',5'-substituted benzyl)-1,4,8,11-tetraazacyclotetradecane-12, 14-dione(RTADO-14) binary complex compounds and of copper (Ⅱ)-5-substituted-1,10-phenanthrolines(R'TADO)-RTADO-14 ternary complex compounds was studied by means of pH titration method at 25.0±0.1 ℃ and I=0.1mol?dm-3KNO3. The formation constants of binary and ternary complexes were obtained. The structures of the binary and ternary complxes and the effects fo substituents on macrocyclic ligands and on R'Phen were also discussed.     

邻、间、对-氯苯甲酸钠的NMR(1H,13C)和振动光谱

研究了邻、间、对 -氯苯甲酸钠并记录了这些化合物的 NMR和振动光谱。用能量合适的分子做了单点计算 ,确立了氯和钠对分子中电荷分布的影响 ,并对邻、间、对氯苯甲酸钠分别与苯甲酸钠以及邻、间、对氯苯甲酸做了比较。从各种不同的方法中得出的结论是相同的 ,且表明氯和钠影响了苯甲酸的芳香体系 ,氯和钠的影响特征取决于氯在环上的位置 ,并在碳原子上计算的形式电荷和它的化学位移之间提出相关性。     

凝胶-燃烧法合成YAG∶Eu3+纳米荧光材料的结构和发光性能

Y₃Al₅O₁₂∶Eu nanophosphors were synthesized by a gel combustion method. The structure of phosphors was characterized by XRD and FTIR. YAG phase came to occur when YAG∶Eu precursors were sintered at 800 ℃, although the phase was mainly amorphous. The organic groups pyrolyzed completely and pure YAG phase was obtained in the samples sintered at 900 ℃. In the formation of YAG phase, no intermediate phases such as YAP and YAM were detected. Both ⁵D₀ → ⁷F₁ orange and ⁵D₀ → ⁷F₂ red emission could be observed for all the sintered samples. However, the emission of amorphous samples was greatly different from that of crystalline ones. The former was mainly ⁵D₀→ ⁷F₂ red emission, but the latter was ⁵D₀ → ⁷F₁ orange emission. As sintering temperature rises, the ratio of orange to red for phosphors increases. Eu could be doped up to 8% in YAG host lattice, and fluorescence quenching was absent. It indicated that the gel combustion synthesis method can increase emission intensity and quenching concentration due to a good distribution of Eu³⁺ activators in Y₃Al₅O₁₂ matrix.     

16-脱氢孕烯醇酮醋酸酯的环境友好合成法

Instead of environmentally toxic chromium oxidant, singlet oxygen generated photcchemically was used as environmentally friendly and benign oxidizing agent to accomplish the transformation of pseudodiosgenin diacetate to diosone efficiently in a low toxic and less expensive solvent acetone. Accordingly 16-dehydropregnenolone acetate(16-DPA), an important intermediate for preparation of steroidal drugs, was prepared in good yield (75%) when photoreaction was run in acetone/acetic anhydride/pyridine system. The mild reaction condition as well as simple and environmentally friendly process made the method commercially viable and important for production of 16-DPA in industrial scale.     

双氮桥联1,10-菲咯啉大环化合物分子构型的从头算研究

应用规范不变原子轨道法(GIAO)在RHF/6-31G**和B3LYP/6-31G**水平上计算了质子化双氮桥联1,10-菲咯啉大环化合物(H4HAPP2+)C2h和C2h构型的1HNMR,并用TDDFT法计算了H4HAPP2+电子光谱.结果表明,B3LYP/6-31G*优化的C2h构型为较优构型,经谐振频率验证无虚频,C2h构型是H4HAPP2+合理的对称性构型.     

化妆品及香精中27种香料的气相色谱-质谱检测方法

建立了气相色谱-质谱同时检测化妆品及香精中27种香料的方法。采用甲醇作为提取溶剂，经弱极性毛细管柱分离，用气相色谱-质谱检测，离子源为电子轰击离子（EI）源。该方法对麝香二甲苯、羟基香茅醛和羟异己基3-环己烯基甲醛的检出限分别为1.2、15和15 mg/kg，其余香料的检出限为3.0 mg/kg。27种香料在相应的线性范围内线性关系良好，相关系数均大于等于0.996。在3个加标浓度下，麝香二甲苯的回收率为73.3%~76.1%，其余为81.5%~118%，相对标准偏差小于10%。采用建立的方法对69份香精或标示含香料化妆品进行检测，全部样品都检测出含有一种或多种香料。该方法适用于化妆品及香精中27种香料的测定。     

水杨酸-2’-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2’-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱. 结果表明, EHS可增溶在胶束中, 2’-乙基己基碳链朝向胶束内核, 而水杨酸基朝向胶束-水界面; 胶束环境有利于EHS分子对紫外光的吸收和分子内氢键的形成, 从而使ESIPT 荧光显著增强, 激发态分子以发射可见光和非辐射去活化方式衰减; 并根据EHS和表面活性剂分子的结构和大小, 解释了EHS分子在胶束中的结合位点, 荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

C12-2-En-C12•2Br与SDS混合水溶液的胶团化研究

与[C12H25N＋(CH3)2CH2]2•2Br－(简记为C12-2-C12•2Br)/ C12H25SO4Na(SDS)混合水溶液相比,随着联接链上乙氧基团(E)数目增加,[C12H25N＋(CH3)2]2C2H4(OC2H4)n•2Br－(简记为C12-2-En-C12•2Br, n=2,3)与SDS混合水溶液澄清区域明显增大. C12-2-E3-C12•2Br/SDS混合胶团化过程中二组分产生了协同效应,理论预测在澄清区域所能达到的最小临界胶团总浓度(cmcT,min)= 0.0339 mmol•L－1,对应的SDS在溶液体相中的摩尔分数(x2*)=0.447.当水溶液体相中SDS摩尔分数(x2)=0.5时,混合胶团总聚集数(NT)=36,混合胶团中SDS的摩尔分数(x2M)=0.43.     

合成天然产物曲古抑菌素A的新方法

报道了一条组蛋白去乙酰化酶抑制剂曲古抑菌素A的有效合成路线. 通过L-脯氨酸催化对硝基苯甲醛与丙醛的羟醛缩合反应, 高立体选择性地构建了目标分子的手性中心, 羟醛缩合产物的ee值大于99%, anti∶syn＝16∶1. 随后的合成过程中无消旋化现象, 合成的曲古抑菌素A是单一R型异构体, ee值大于99%.     

噁二唑肟醚取代的均三唑水杨醛席夫碱衍生物的合成及抗菌活性

均-三唑;噁二唑;肟醚;席夫碱;合成;抗菌活性