硝酸甲酯与不同亲核试剂的SN2反应的理论研究

用从头计算和半经验分子轨道ＡＭ１方法分别对系列亲核试剂和硝酸甲酯的电子结构以及它们之间的气相ＳＮ２反应进行了理论研究，揭示了反应过程中体系的结构，能量和电荷的递变规律，由反应活化能得了这些亲核试剂的亲核性次序为：ＯＨ＾－〉Ｆ＾－〉Ｉ＾－〉ＮＯ＾－３〉ＣＮ＾－〉Ｂｒ＾－〉Ｃｌ＾－〉Ｎ＾－３。     

Morphology Control over the Organic Nanoparticles of 1,3-Diphenyl-5-（9-anthryl）-2-pyrazoline

The organic nanoparticles of a blue-light-emitting molecule, 1,3-diphenyl-5-(9-anthryl)-2-pyrazuline, were prepared by reprecipitation method using acetonitrile as the solvent for the molecular precursor. Three morphologies, spherical, doughnut-shaped and cubic, could be observed on the silicon substrate forthe nanoparfides by the volume-controlled addition of acetonitrile. The evolution of particle morphology as a function of acetonitrile addition was attributed to the variation of the growth habits of the particles in the different environment. The nanoparticles exhibit the novel photoluminescence spectra as compared to those of monomer and the bulk crystals.     

荧光法猝灭测定木槿叶中混合氨基酸的总量

在乙酸-乙酸钠缓冲介质中,氨基酸能猝灭壳聚糖-茚三酮体系荧光,基于此,对木槿叶中混合氨基酸进行测定,并对该方法的测定条件进行了讨论.线性范围为0.5～3.0 mmol/L,检出限为0.1 mmol/L.木槿叶干粉中游离氨基酸的质量分数为10.18%,相对标准偏差为1.3%,回收率为102.5%～94.3%.     

间苯二胺、间氨基酚与间苯二酚混合液的萃取分离

在不同的酸碱条件下,分别以正丁醇(BuOH)、醋酸正丁酯(BuAc)及甲基异丁基甲酮(MIBK)作为萃取剂,对间苯二胺、间氨基酚及间苯二酚的水溶液混合体系进行萃取分离研究.HPLC分析实验结果表明:随着混合水溶液中H+浓度的增加,分离出间苯二酚的效果增强;而随着混合水溶液中OH-浓度的增加,分离间苯二胺的效果将大大增强;作为萃取剂,醋酸正丁酯和甲基异丁基甲酮优于正丁醇,能对水溶液混合体系中的三组分进行完全有效的分离,其中以甲基异丁基甲酮萃取效果最好.实验得到的最佳分离条件是:萃取剂为甲基异丁基甲酮,混合溶液中n(H+)/n(-NH2)≥1.32∶1时,萃取相中仅有间苯二酚;混合溶液中n(OH-)/n(-OH)≥1.11∶1时,萃取相中仅有间苯二胺.     

硅氢加成反应高选择性合成甲基苯乙基二氯硅烷

研究了硅胶负载聚乙二醇铂催化苯乙烯与甲基二氯氢硅的硅氢加成反应,β-加成产物甲基苯乙基二氯硅烷的选择性为100%,10℃下反应8h苯乙烯转化率为96.0%.反应存在一个诱导期,温度等反应参数对诱导期有重要影响,40℃下反应的诱导期不到1h,并探讨催化剂的催化机理和目标产物高选择性的原因.     

苯甲醛缩三乙烯四胺Schiff碱Co(Ⅱ)配合物固相合成及氧合性能研究

Three new cobalt complexes were synthesized by solid-state reaction at room temperature. It was found that one mole of complex reacted with two moles of oxygen at room temperature. And the oxygenated complexes [Co·(L₁)₂·2O₂](NO₃)₂·2H₂O (L₁=N,N′-bis(4-hydroxyl-3-methoxy-benzyl)-triethylenetetramine), [Co·(L₂)₂·2O₂](NO₃)₂ ·2H₂O (L₂=N,N′-bis(4-hydroxyl-benzyl)-triethylenetetramine) and [Co·L₃·2O₂](NO₃)₂·2H₂O (L₃=N,N′-bis(2-hydroxyl-benzyl)-triethylenetetramine) were obtained and characterized by elemental analysis, IR spectra, ¹H NMR, TG/DTA, UV-Vis and molar conductance. The coordinated oxygen contents in the oxygenated complex were also determined by weight method. It was found that one O₂ molecule coordinated to the Co ion and formed superoxo type oxygenated complex.     

TATB固体与表面吸附水的相互作用研究

TATB（1，3，5-三氨基-2，4，6-三硝基苯）是最著名的耐热钝感炸药；水在 TATB表面的吸附作用研究具有理论和实用双重意义。在B3LYP/6-31G~（**）水平上 ，在对TATB晶体（001）表面作周期性计算的基础上经基组叠加误差（BSSE）校正 ，求得TATB的表面能为-19.90 kJ·mol~(-1)，与实验值良好相符；首次求得水在 TATB（001）面的吸附能为-10.25kJ·mol~(-1)；重点讨论了吸附前后能带和电子 结构的变化。     

用于测量农药残留的小麦酯酶的选择

为研制探测农药残留的生物传感器，研究了农药乐果[O,O-二甲基S－（N－甲基胺基甲酰甲戎）二硫代磷酸酯]对各种小麦植物酯酶的抑制，从小麦中提取植物酶，以农药乐果为抑制剂，采用分光光度法研究了乐果对各种小麦酯酶活性的影响；研究显示，不同品种小麦酯酶对农药乐果的敏感度不同，在所研究的品种中，豫麦39和小麦周9对乐果较敏感，研究结果说明了选择小麦酶源的必要性。     

Nitration Reaction Catalyzed by Horseradish Peroxidase in the Presence of H2O2 and NaNO2

The enzymatic nitration of phenol and m-cresol catalyzed by horseradish peroxidase was studied in the presence of H2O2 and NaNO2. The results showed that the nitration products of phenol were 2-nitro and 4-nitrophenols. There was also a small amount of by-products of hydroquinone and catechol. The influences of various reaction parameters, including pH, organic solvent type, and concentrations of NaNO2 and H2O2, on the nitration products were investigated. The yields of 4-nitrophenol and 2-nitrophenol were 14% and 12%, respectively. The nitration products of m-cresol were 4-nitro-m-cresol and 6-nitro-m-cresol, and the yields of 4-nitro-m-cresol and 6-nitro-m-cresol were 19% and 30%, respectively.     

Theoretical Studies on Intermolecular Interactions of 4-Amino-5-nitro-1,2,3-triazole Dimers

1 INTRODUCTION Triazole, a five-membered heterocyclic compound with three nitrogen atoms, is an important interme- diate product of medicine and chemical industry as well as insecticide [1]. Due to its small volume and high nitrogenous density, triazole holds more and more attraction for the material researchers, espe- cially the researchers of high-energy insensitive explosive. It is reported that its nitro and amino deri- vatives are a sort of important high-energy mate- rials[2]. Previ…