Synthesis and characterization of an intermediary of new heat-resistant energetic materials

<正>Nitration of 4,4'-biphenyldicarboxylic acid(BPDC) was studied and an aromatic carboxylic acid containing two nitro groups was synthesized and characterized through elemental analysis and IR spectra.Crystal structure of DNBPDC(DNBPDC=2,2'- dinitro-4,4'-biphenyldicarboxylic acid) was determined by X-ray single crystal diffraction and the thermal decomposition was carried out through DSC and TG-DTG analyses.     

正电子发射断层显像剂[18F]FET前体N-叔丁氧羰基-O-(2-三氟甲磺酰氧乙基)-L-酪氨酸甲酯/叔丁酯的合成

本文合成了正电子发射断层显像剂[¹⁸F]FET的两个新型前体：N-叔丁氧羰基-O-(2-三氟甲磺酰氧乙基)-L-酪氨酸甲酯9a和N-叔丁氧羰基-O-(2-三氟甲磺酰氧乙基)-L-酪氨酸叔丁酯9b. 化合物9a或9b以L-酪氨酸为原料, 先与甲醇发生酯化反应或与乙酸叔丁酯进行酯交换, 再用叔丁氧羰基保护氨基, 接着在苯环的酚羟基上引入羟乙基, 最后与三氟甲磺酸酐反应形成目标化合物, 这四步反应总收率分别是30%或15%.     

稀醋酸/水溶液中单个醋酸与水分子的氢键结构

在醋酸/水体系的工业分离中,溶液中的氢键对分离效率有很大影响.本文采用两种第一性原理方法,即从头算分子动力学模拟(AIMD)和量子化学计算(QCC),对由单个醋酸和不同水分子所组成聚合体的氢键相互作用进行了研究,采用极化统一模型和自洽反应场模型计算得到了聚合体在水溶液中的热力学数据.从QCC计算的气相和水溶液中的聚合自由能表明六元环在两种状态下都为最优结构,热力学数据反映出的各种结构的相对稳定性与AIMD模拟的环分布符合得相当一致.研究表明,由于存在醋酸和水分子间的氢键作用,稀醋酸/水溶液中的醋酸分离要比在浓醋酸溶液中困难得多.     

糖类相关基因芯片的设计与制备

随着糖组学的发展,研究表明某些疾病如肿瘤等的发生伴随着体内糖蛋白表面糖链结构的变化,而糖链结构的形成与修饰经过糖基转移酶、糖苷酶和磺基转移酶的参与.本研究从Genebank等数据库中选取人类糖基转移酶基因127条、糖苷酶基因34条和磺基转移酶34条以及管家基因10条.通过对每个基因的mRNA序列进行探针设计,制备出一款糖类相关基因芯片,用于研究糖类相关基因的表达谱,旨在揭示疾病发生与糖类相关基因表达变化的关联性.制备的芯片应用于人肝癌细胞系SMMC-7721与正常肝细胞系Chang’s liver的研究,筛选出差异表达的基因34个,其中上调基因19个、下调基因15个.通过对2个上调基因和2个下调基因进行Realtime-PCR验证,得到了一致的实验结果.     

Two new eudesmane derivatives from Verbesina virginica

<正>Two new eudesmane derivatives were isolated from the leaves and flowers of Verbesina virginica,along with the known 6-O-β-E -p-coumaroyl-4α-hydroxyeudesmane(1).Their structures were determined as 6-O-β-Z-p-coumaroyl-4α-hydroxyeudesmane(2) and 6-O-α-E-p-coumaroyl-1β-4α-dihydroxyeudesmane(3) by spectroscopic methods.     

Electrochemical biosensing for dsDNA damage induced by PbSe quantum dots under UV irradiation

<正>An electrochemical sensor for the detection of the natural double-stranded DNA(dsDNA) damage induced by PbSe quantum dots(QDs) under UV irradiation was developed.The biosensing membranes were prepared by successively assembling 3- mercaptopropionic acid,polycationic poly(diallyldimethyl ammonium) and dsDNA on the surface of the gold electrode.Damage of dsDNA was fulfilled by immersing the sensing membrane electrode in PbSe QDs suspension and illuminating it with an UV lamp. Cyclic voltammetry was utilized to detect dsDNA damage with Co(phen)_3~(3+) as the electroactive probe.The UV irradiation,Pb~(2+) ions liberated from the PbSe QDs under the UV irradiation and the reactive oxygen species(ROS) generated in the presence of the PbSe QDs also under the UV irradiation were the three factors of inducing the dsDNA damage.The synergistic effect of the three factors might dramatically enhance the damage of dsDNA.This electrochemical sensor provided a simple method for detecting DNA damage,and may be used for investigating the DNA damage induced by other QDs.     

The multi-concentration and two-dimensional capillary electrophoresis method for the analysis of drugs in urine samples

A novel method has been developed by integration of multi-concentration and two-dimensional(2D) capillary electrophoresis(CE) for simultaneous enhancement of detection sensitivity and separation power in complex samples.Capillary zone electrophoresis(CZE) was used as the first dimension separation according to mobilities,from which the effluent fractions were further analyzed by micellar electrokinetic capillary chromatography(MEKC) acting as the second dimension.Cation-selective exhaustive injection(CSEI) ...     

单电子卤键复合体系H_3C…Br—Y(Y=H,CN,NC,CCH,C_2H_3)的作用机制

对单电子溴键复合物H3C…Br—Y(Y=H,CCH,CN,NC,C2H3)的结构与性质进行了理论研究.在B3LYP/6-311++G**水平上计算了稳定构型并做了频率分析.BSSE矫正的相互作用能(EBSSE)和NBO及AIM分析输入的波函数在MP2/6-311++G**水平下完成.复合物H3C…Br—Y中,CH3(供电子体)自由基均提供一未成对电子与Br—Y中Br(受电子体)形成了单电子溴键,此单电子溴键也具有三电子键的特征.单电子溴键的形成导致甲基H的背向Y弯曲和Br—Y键的拉长及红移单电子溴键复合物的产生.考察了电子受体中不同取代基,C(spn)-Br杂化及溶剂的存在对复合物作用的影响,将单电子氢键,单电子卤键和单电子锂键的作用强度做了对比,进一步对Popelier提出的氢键体系中的前三个重要拓扑指标在单电子溴键体系中的重现性进行了探讨.     

超细红色荧光粉LaMgAl_(11)O_(19):Eu~(3+)的制备与发光性能

采用凝胶-燃烧法制备了稀土Eu3+掺杂的LaMgAl11O19红色荧光粉的前驱粉末,在低于700℃退火处理时,得到非晶态样品,而高于850℃退火处理后为单一六方相结构LaMgAl11O19:Eu3+样品.SEM结果表明,该法制备的样品为颗粒分布均匀,粒径在200～400nm之间的超细粉末.通过激发光谱和发射光谱研究了Eu3+在LaMgAl11O19基质中的发光性能,结果显示,非晶态和晶态La1-xMgAl11O19:xEu3+样品都可发光,在613nm波长光的监测下所得荧光粉的激发光谱为一宽带和系列锐峰,其最强激发峰出现在蓝光465nm处,次强峰为394nm,表明该荧光粉与广泛使用的紫外和蓝光LED芯片的输出波长相匹配.在465nm波长光的激发下观察到超细LaMgAl11O19粉末中Eu3+的613nm(5D0→7F2)强的特征发射,且随着粉末逐渐成相5D0→7F2跃迁明显增强,说明LaMgAl11O19:Eu3+超细粉末可作为白光LED的红色补偿荧光粉.     

Et_3NHCl-AlCl_3催化苯与1-十二烯烃烷基化反应机理的研究

本文利用同位素取代法考察了离子液体催化苯与烯烃烷基化反应机理.首先进行了Et3NHCl-AlCl3催化氘代苯与1-十二烯烃的反应,通过GC-MS及NMR分析产物结构,根据分析结果,在反应过程中一个D原子从苯环转移到侧链的1-碳.由此推断离子液体催化苯与长链烯烃的烷基化反应机理为:反应由Lewis酸AlCl3引发;AlCl3吸引1-十二烯烃的π电子向1-碳转移,形成碳正离子;碳正离子进一步与苯反应形成不稳定的σ络合物,σ络合物苯环上的sp3杂化碳相连的D+转移到侧链的负电1-C上取代AlCl3,生成产物2-十二烷基苯.