Theoretical study on tetrazole and its derivatives (Ⅰ)──Ab initio study on chlorotetrazole

Molecular geomitries and electronic structures of four chlorotetrazoles are calculated with ab initio method at MP2/6-311G ** level. The results show that all the titled compounds are planar and aromatic. The skeletal bond lengths of the ring tend to be uniformized. Compared with 1- and 2-substituted chlorotetrazoles, 5-substituted chlorotetrazoles are more acidic and lower in total energy. 5-chloro-2H-tetrazole has the lowest energy and is the most stable.     

含哌嗪基团的芳氧乙酸酯类化合物的合成及其促学习记忆作用的研究

目的合成一系列2-[1-(2-吡啶)乙氧基]乙酸2-[4-取代哌嗪]乙酯类化合物,对其促小鼠学习记忆作用进行研究。方法将2-乙基吡啶进行NBS溴代反应,得到α-溴代2-乙基吡啶(2),化合物2与α-羟基乙酸乙酯反应得到芳氧乙酸乙酯(3),化合物3与1-取代-4-羟乙基哌嗪(5a-5g)进行酯交换得到目标化合物2-[1-(2-吡啶)乙氧基]乙酸2-[4-取代哌嗪]乙酯(6a-6g)。挑选两个化合物6a和6d,对其进行小鼠水迷宫实验,评价其促小鼠学习记忆活性。结果合成了一系列含哌嗪基团的芳氧乙酸酯类化合物,通过1H-NMR和红外光谱确证了其结构。结论小鼠水迷宫实验结果表明化合物6a和6d对乙醇所致小鼠学习记忆再现困难具有明显改善作用(P0.05)。     

二氟锗烯与乙烯环加成反应的机理

用二阶微扰和密度泛函理论研究单重态F2C＝Ge:与C2H4环加成反应机理,采用MP2/6-31G·和B3LYP/6-31G·方法计算势能面上驻点的构型参数、振动频率和零点能;利用CCSD(T)//MP2/6-31G·和CCSD(T)//B3LYP/6-31G·计算各构型的能量;利用CCSD(T)//MP2得到单线态F2...     

锂离子动力蓄电池充放电基本性能的研究

为了考察锂离子动力蓄电池应用于电动汽车的可行性 ,本文以MCMB和LiCoO2 为正负极材料 ,自行设计组装了 5A·h、2 5A·h和 50A·h的方形层叠式锂离子动力蓄电池 ,用恒电流限电压充放电方法研究了其在不同电流下的放电行为和荷电保持能力 .研究结果表明 :以0 .2C倍率、10 0 %DOD放电时 50A·h电池的质量比能量和能量密度可分别达到 10 7.4W·h/kg和 185.1W·h/L ,已经超过了美国电池先进联合体 (USABC)规定的动力蓄电池的中期开发目标。 5Ah电池的 1C倍率放电容量可保持 0 .1C倍率放电容量的 79.35% .电池的荷电保持性能良好 ,日平均自放电率小于 0 .32 4 % /d ,开路电压月下降只有 0 .1V左右     

一类包含σ紧空间和可分空间的拓扑空间

定义*σ紧空间的概念，讨论*σ紧空间的一些性质以及*σ紧性与*Lindelo(e)性。c，c，c与可分性之间的关系。结合点可数基讨论了一些空间的某些性质。     

A matrix version of the Wielandt inequality and its application to statistics

Suppose that A is an n × n positive definite Hemitain matrix. Let X and Y be n × p and n × q matrices (p+ q≤n), such that X* Y = 0. The following inequality is proved X*AY( Y* AY)-Y Y*AX≤( (λ1-λn)/(λ1+λn))2 X*AX, where λ1 and λn are respectively the largest and smallest eigenvalues of A, and M- stands for a generalized inverse of M. This inequality is an extension of the well-known Wielandt inequality in which both X and Y are vectors. The inequality is utilized to obtain some interesting inequalities about covari-ance matrix and various correlation coefficients including the canonical correlation, multiple and simple correlation.     

大连水云科藻类的研究

大连地区水云科藻类有9属19种,其中前人报道过的2种,本地区新记录17种。在这17种中,有11种是我国首次记录。本文对新记录种的形态、生态与分布作简要描述。     

CH3I分子的光吸收谱的多参考组态计算

采用完全活化空间多组态自洽场方法优化了CH3I分子基态的几何结构,根据二阶自旋-轨道多参考组态相互作用理论计算了CH3I分子的势能曲线,并计算了该分子较低几个激发态的垂直激发能、CH3I分子的吸收谱.讨论了温度对吸收谱的影响,并估计了激发态碘原子I#(2P1/2)的量子产额,结果表明实验测量值与理论计算值吻合得很好.     

Cis-trans isomerization at a proline opens the pore of a neurotransmitter-gated ion channel

5-hydroxytryptamine type 3 (5-HT3) receptors are members of the Cys-loop receptor superfamily. Neurotransmitter binding in these proteins triggers the opening (gating) of an ion channel by means of an as-yet-uncharacterized conformational change. Here we show that a specific proline (Pro 8*), located at the apex of the loop between the second and third transmembrane helices (M2-M3), can link binding to gating through a cis-trans isomerization of the protein backbone. Using unnatural amino acid mutagenesis, a series of proline analogues with varying preference for the cis conformer was incorporated at the 8* position. Proline analogues that strongly favour the trans conformer produced non-functional channels. Among the functional mutants there was a strong correlation between the intrinsic cis-trans energy gap of the proline analogue and the activation of the channel, suggesting that cis-trans isomerization of this single proline provides the switch that interconverts the open and closed states of the channel. Consistent with this proposal, nuclear magnetic resonance studies on an M2-M3 loop peptide reveal two distinct, structured forms. Our results thus confirm the structure of the M2-M3 loop and the critical role of Pro 8* in the 5-HT3 receptor. In addition, they suggest that a molecular rearrangement at Pro 8* is the structural mechanism that opens the receptor pore.     

银杏叶黄酮类化合物水提工艺的响应面优化

研究水浸提银杏叶中总黄酮类物质的最佳工艺条件.以银杏粉碎叶为试验材料,以水为提取溶剂,采用响应面设计方法,对影响黄酮提取效果的提取温度、提取时间和料液比等3个因素先后进行了部分因子试验和中心组合设计试验,并建立数学模型,研究这些因素对黄酮提取率的影响.部分因子试验结果表明:提取时间和料液比是影响仙人掌黄酮提取效果的主要因子;中心组合设计试验建立的黄酮提取率(Y1)与提取温度(X1)、提取时间(X2)、料液比(X3)间的数学模型为Y1=6.423 667+0.161*X1+0.684 25*X2-0.523 75*X3-0.660 083*X1*X1+0.174 5*X1*X2-0.657 5*X1*X3-0.534 583*X2*X2-0.013 5*X2*X3-1.527 583*X3*X3;最佳的提取工艺条件为料液比1∶13.76,提取时间3.70 h,提取温度93.37℃,该条件下模型预测的最大提取率为6.75%.结果表明应用响应面方法对黄酮类物质的提取条件进行优化是非常有效的.     

基于参数微扰法精确计算铍离子Be2+和硼离子B3+的基态能量

建立含有屏蔽参数σ的铍离子Be~(2+)(z=4)和硼离子B~(3+)(z=5)的哈密顿方程.以有效核电荷数为z*=z-σ的类氢原子基态1s和激发态ns(n=2,3,…)组合的双电子波函数,作为铍离子Be~(2+)和硼离子B~(3+)的基态近似波函数.应用参数微扰法确定铍离子Be~(2+)的屏蔽参数σ=0.56350197和硼离子B~(3+)的屏蔽参数σ=0.525070444,应用参数微扰法计算铍离子Be~(2+)三级近似基态能量和硼离子B~(3+)四级近似基态能量的理论值与实验值的误差为ΔE≈10~(-4)~10~(-5)a.u..     

2-[1-(2-吡啶)乙氧基]乙酸-2-取代胺基乙酯的合成及其对小鼠学习记忆能力的影响

为探讨2-[1-(2-吡啶)乙氧基]乙酸2-取代胺基乙酯衍生物对小鼠学习记忆能力的影响,使用2-乙基吡啶为起始原料,经Whol-ziegler反应得到2-(1-溴乙基)吡啶(2),再与羟基乙酸乙酯的醇钠盐缩合得到2-[1-(2-吡啶)乙氧基]乙酸乙酯(3),化合物3与2-取代胺基乙醇在二丁基氧化锡催化下反应,得到目标产物2-[1-(2-吡啶)乙氧基]乙酸-2-取代胺基乙酯(4~12)。采用通道式水迷宫法测定了化合物(5,6,10)对小鼠学习记忆能力的影响。结果显示化合物6和10对400 mL/L乙醇所致小鼠学习记忆再现困难具有明显改善作用(P0.05)。     

甲酰胺热分解反应机理的理论探讨

对甲酰胺的热分解反应进行了精确理论研究,在CAS（6,6）／6－21G优化构型的基础上,用CASPT2法做了单点能量校准,推测反应有2种途径：反应I经三元环过渡态形成NH3和CO产物,反应II经四元环过渡态形成H2和HNCO产物,这2个反应为一对竞争反应,并且有B3LYP,MP2和HF方法进行了对比分析。     

Si+/As+双离子注入SI-GaAs对注入层电激活均匀性改善的研究

研究了单 (Si )双 (Si / As )离子注入半绝缘砷化镓 (SI-Ga As)电激活的均匀性 .结果表明 ,L ECSi-Ga As衬底中深电子陷阱能级 (EL 2 )均匀性分布好坏 ,对注入层电激活性有一定影响 .当 SI-Ga As中碳含量小于 5× 1 0 15cm- 3时 ,对注入层电激活影响不大 .采用多重能量 Si 注入 ,可改善栽流子纵向分布的均匀性 ,采用 Si / As 双离子注入可改善 L EC SI-Ga As衬底中 EL 2横向不均匀分布对电激活均匀性的影响 ,可获得注入层横向的电激活 .     

MONTE-CARLO CALCULATIONS OF NUCLEON EMISSION AND ENERGY DEPOSITION OF SPALLATION NEUTRON SOURCES INDUCED BY INTERMEDIATE ENERGY PROTONS

ＭＯＮＴＥ┐ＣＡＲＬＯＣＡＬＣＵＬＡＴＩＯＮＳＯＦＮＵＣＬＥＯＮＥＭＩＳＳＩＯＮＡＮＤＥＮＥＲＧＹＤＥＰＯＳＩＴＩＯＮＯＦＳＰＡＬＬＡＴＩＯＮＮＥＵＴＲＯＮＳＯＵＲＣＥＳＩＮＤＵＣＥＤＢＹＩＮＴＥＲＭＥＤＩＡＴＥＥＮＥＲＧＹＰＲＯＴＯＮＳＳｈｅｎＱｉ...     

2,5—二取代噁唑的荧光量子产率和激光转换效率的研究

测试了2—联苯基—5—苯基噁唑和13种5—对位取代苯基衍生物的荧光量子产率和激光转换效率,发现其中的十一种化合物作为近紫外区的激光染料使用,比2,5—二苯基噁唑(PPO)要好,并就取代基效应和光谱性质之间的关系进行了初步探讨。     

Effects of substituent position on the interactions between PBDEs/PCBs and DOM

Dissolved organic matters (DOM) have important influence on the environmental behavior and fate of organic pollutants, therefore rationalization of interaction mechanisms between pollutants and DOM has become a hot topic in the field of environmental studies. In this paper, polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), widely detected pollutants, were chosen as target compounds. The effects of substituent position on the interaction between PBDEs/PCBs and DOM were explored. Equilibrium dialysis technique combined with quantum chemistry and molecular docking calculations were employed to reveal the interaction mechanism from the view of charge distribution and molecular conformation. It is shown that non-ortho-substituted isomers have larger volumes and stronger hydrophobicity than those of ortho-substituted, therefore non-ortho-substituted isomers bind more favorably with DOM by hydrophobic partition. By calculating the atomic charge distribution of target chemicals and Leonardite humic acid (LHA) molecular model, π-πinteractions between the aromatic rings of target chemicals with LHA are proposed and further proved in molecular docking calculations. There were 10, 8, 6 docking conformations demonstrating π-πinteraction with LHA for CB-77, BDE-77 and BDE-47, respectively, but none was found for CB-47. By comparing the change of dihedral angle of the aromatic rings and energy barrier, non-ortho-substituted PBDEs/PCBs have larger dihedral angle adjustment space and flexibility, which results in stronger interaction and binding capability with DOM than ortho-substituted isomers. This paper shed some lights on the effect of substituent position on the environmental behaviors of PBDEs and PCBs.     

有效核电荷数的编程计算及应用

有效核电荷数（Z^＊）是元素最重要参数之一，由于它的人工计算比较复杂，作者利用Visual Basic语言编写的程序来完成该计算，从而使Z^＊的计算变得方便、快捷．并且将得到的Z^＊数据用Excel的作图功能绘制成曲线，讨论周期表中Z^＊的递变规律．最后，还讨论了与Z^＊相关的一些原子结构参数（如电子能量、电离势和电负性等）．     

Theoretical study on the mechanism of cycloaddition between dimethyl methylene carbene and acetone

The mechanism of the cycloaddition reaction of singlet dimethyl methylene carbene and acetone has been studied by using second-order Moller-Plesset perturbation and density functional theory. The geometrical parameters, harmonic vibrational frequencies and energy of stationary points on the potential energy surface are calculated by MP2/6-31G and B3LYP/6-31G methods. The results show that path b of the cycloaddition reaction （1） would be the major reactive channel of the cycloaddition reaction between singlet dimethyl methylene carbene and acetone, which proceeds in two steps： i） The two reactants form an energy-rich intermediate （INT1b）, which is an exothermic reaction of 23.3 kJ/mol with no energy barrier. ii） The intermediate INT1b isomerizes to a three.membered ring product （P1） via transition state TS1b with energy barrier of 22.2 kJ/mol. The reaction rate of this reaction and its competitive reactions do greatly differ, with excellent selectivity. In view of dynamics and thermodynamics, this reaction is suitable for occurring at 1 atm and temperature range of 300-800 K, in which the reaction will have not only the larger spontaneous tendency and equilibrium constant but also the faster reaction rate.     

Continuous wavelet transform and discrete multi-resolution analysis of surface fluxes and atmospheric stability

Variations of land surface fluxes of sensible heat (H), latent heat (LE), and CO₂ (F-CO₂) obtained from the eddy-covariance measurements above a winter wheat field from March 30 to April 24, 2001 have been studied at scales ranging from 10 minutes to days. Wavelet transform is used in the analysis of land surface fluxes and atmospheric stability (ζ) calculated from the measurements to reveal the changes in land surface fluxes in hours to days scales. The main results are: (1) Concise and compact information about the fluxes, net radiation (R_n), temperature (T) and ζ in the scale-time domain are extracted from the data by continuous wavelet analysis, and 1 day, 0.5 day and short-period (shorter than 0.5 day) components are revealed. Continuous wavelet coefficients can be used to characterize periodic components of changes in fluxes and ζ. (2) Discrete-time multi-resolution analysis can be used to concentrate total energy variance of time series of the measurements to a small number of coefficients, plotting the relative energy distribution to get several meaningful characteristics of the data. (3) Under neutral atmospheric conditions, the relative energy distributions of the Haar multi-resolution analysis of the three non-dimensional coefficients (T/T^*, q/q^* and c/c^*) display clear similarities.