水溶液中异喹啉与羟基的作用机理

利用脉冲辐解技术对异喹啉水溶液与羟基的作用机理进行了详细研究,对其瞬态吸收峰进行了归属,初步考察了这些瞬态粒子的生成和衰减行为.研究表明,.OH与异喹啉在中性和碱性条件下反应生成羟基加合物,生成速率常数分别为3.4×109和6.6×109mol-1.dm3.s-1.在酸性条件下异喹啉先被质子化,再与羟基发生加成反应,反应速率常数为3.9×109mol-1.dm3.s-1,这为异喹啉的氧化降解提供了理论基础.     

O（^3p）原子与乙醚和异丙醚化学反应速率常数的测定

用流动放电-化学发光技术测定了O(~3p)原子与乙醚和异丙醚总包二级反应速率常数。反应速率常数与温度关系可表达为k_1=(1.91±0.70)×10~(-11)exp[-(2.14±0.16)kcal·mol~(-1)/RT]·cm~3·molec.~(-1)·s~(-1) [O(~3p) 乙醚] k_2=(3.25±0.80)×10~(-11)exp[-(2.57±0.20)kcal·mol~(-1)/RT]·cm~3·molec.~(-1)·s~(-1) [O(~3p) 异丙醚] 还讨论了醚分子中氧原子对α-位C—H键能及其反应活化能的影响。结果表明,氧原子使α位C—H键能减弱而降低了反应活化能。     

稀土钐离子与牛血清白蛋白相互作用研究

利用荧光光谱法研究了稀土钐离子(Sm~(3+))与牛血清白蛋白(BSA)的相互作用,探讨了不同pH值的缓冲溶液和不同钐离子浓度对BSA荧光强度的影响.通过改变钐离子标准溶液浓度范围,扫描Sm~(3+)与牛血清白蛋白相互作用的荧光发射光谱,证实了稀土钐离子(Sm~(3+))对BSA的荧光猝灭属于静态猝灭.利用荧光猝灭的Stern-Volmer方程和静态猝灭公式线性拟合,求得反应的荧光猝灭过程速率常数K_q=4.12×10~(12) L·mol~(-1)·s~(-1),结合常数K_a=9.652×10~5 L·mol~(-1),结合数n=1.22.     

O(~3P)原子与环戊酮的二级反应速率常数测定

我们用流动微波放电—化学发光方法首次测定了O(~3p)原子与环戊酮分子在303—503K温度范围内的反应速率常数,反应速率常数与温度关系为k=3.79±1.41×10~(-11)exp(-18.6±1.5kJ·mol~(-1)/RT)cm~3·molecule~(-1)·s~(-1)O(~3p)原子由流动微波放电产生,利用检测其与NO反应生成NO_2~*的化学发光强度的方法来检测O(~3p)浓度。此外,还就这类反应速率常数与环形分子结构关系进行了讨论。     

Mo(Ⅵ)-8-羟基喹啉-5-磺酸-氯酸钠体系络合吸附催化波

提出了 Mo(VI)-HQSA(8-羟基喹啉-5-磺酸)-ClO_3~-的络合吸附催化体系,灵敏度较高,Mo(VI)的测定下限为2×10~(-10)mol/L,并应用于水中痕量 Mo(VI)的测定.用多种电化学测试手段研究体系的性质和反应机理.实验表明为络合吸附催化波.恒电解法证明,电极反应电子数为1,是络合物中 Mo(VI)还原为 Mo(V).在经典极谱仪上,测得催化反应的速率常数 k_(25℃)为7.9×10~2mol~(-1)·L·s~(-1).     

HO_2与Cl反应机理及动力学性质的理论研究

揭示Cl对HO_2的消耗机制对改善大气环境质量具有指导作用,文中采用CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G(2d,2p)计算方法研究了HO_2+Cl抽氢和抽氧反应机理.研究发现,该反应共有R1(~3O_2+HCl,路径1)、R2(~1O_2+HCl,路径2)和R3(ClO+OH,路径3和路径4)三条反应通道,其中路径1和路径3分别为抽氢和抽氧通道的优势路径.利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了抽氢和抽氧通道主路径1与路径3在213～320 K温度范围的内k~(CVT/SCT)值.结果表明,在213～320 K温度范围内路径1的速率常数为4.69×10~(-11)～3.98×10~(-10) cm~3·molecule~(-1)·s~(-1),比路径3的速率常数高出了13～19个数量级,即路径1是HO_2+Cl反应进行的主通道,298 K时路径1的速率常数(6.27×10~(-11) cm~3·molecule~(-1)·s~(-1))与实验值(6.80×10~(-11) cm~3·molecule~(-1)·s~(-1))相吻合.此外,在213～320 K温度范围内,变分效应对路径1的速率常数影响较小,而隧道效应在低温段对路径1的速率常数有显著影响.     

O（^3p）原子与丙酮和3.3—2甲基—2—丁酮化学反应动力学研究

用流动微波放电—化学发光方法测定O(~3p)原子与CH_3COCH_3和CH_3COC(CH_3)_3的化学反应速率常数k=3.37±1.00×10~(-12)exp(-7.03±0.22kcal.mol~(-1)/RT) (丙酮 0(~3p),T=373-503K)和k=4.61±2.60×10~(-11)exp(-5.46±0.44kcal·mol~(-1)/RT) (3.3-2甲基-2-丁酮 O(~3p),T=303-503K)并就测定的O(~3p)原子与一系列酮分子反应速率常数进行了讨论,估算了O(~3p)原子与各类C—H键反应速率的Arrhenius参数。发现与羰基相邻的C—H键与O(~3p)反应的活化能要略大于非相邻的同类键反应的活化能。还根据Evans-Polanyi关系式,对这些键的键能进行了讨论。     

理论研究水和甲酸催化甲胺与羟基自由基的反应

本文采用量子化学计算方法和变分过渡态理论研究了水或甲酸的催化作用下羟基自由基提取甲胺中甲基氢和氨基氢的反应机理和动力学.在MC-QCISD//MP2/6-311++G(d,p)理论水平下计算的势能面表明,水或甲酸催化作用下的过渡态形成了很强的氢键,提取甲基氢反应过渡态的相对能量从裸反应的0.72 kcal·mol~(-1)分别降低到-4.59和-9.78 kcal·mol~(-1);提取氨基氢的反应过渡态相对能量则从裸反应的-0.40 kcal·mol~(-1)分别降低到-2.25和-9.12 kcal·mol~(-1).然而,提取甲基氢的速控步的能垒却从5.93 kcal·mol~(-1)变为5.68和7.30 kcal·mol~(-1);提取氨基氢的能垒则从4.81 kcal·mol~(-1)增加到8.04 kcal·mol~(-1)和7.96 kcal·mol~(-1).但是,动力学计算表明298 K下水或甲酸催化下的反应速率常数分别比裸反应小3或2个数量级,而且考虑水或甲酸催化该反应前驱络合物的浓度后,计算得到的有效速率常数则分别降低6或8个数量级,因此水或甲酸均不能加速大气中甲胺与羟基的提氢反应.     

O（^3p）原子和丙烯醇化学反应动力学研究

用流动放电—化学发光方法测定O(~3p)原子和丙烯醇分子化学反应速率常数.在293K—473K 范围内,反应速率常数的Arrhenius 形式为k=(6.41_(-0.61)~(+0.67))×10~(-11)exp[-(6.4±0.3)kJ·mol~(-1)/RT]cm~3·molecule~(-1)·s~(-1)并对该反应的反应机理进行了讨论.     

新显色剂5-(4-磺基-1-萘偶氮)-8-羟基喹啉与铜显色反应的研究与应用

本文研究了显色剂5-(4-磺基-1-萘偶氮)-8-羟基喹啉与铜显色反应的条件,结果表明:在pH=12.5的介质中,显色剂与铜生成了3:1黄色稳定配合物,利用褪色光度法,529nm=3.7×10~4L mol~(-1)cm~(-1),铜量在0—35μg/50mL范围内遵循比耳定律,方法选择性好,可用于铅合金中铜含量的测定。     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

Features of Women's language

Language is a means of verbal communication. People use language to communicate with each other. In the society, no two speakers are exactly alike in the way of speaking. Some differences are due to age, gender, statue and personality. Above all, gender is one of the obvious reasons. The writer of this paper tries to describe the features of women＇s language from these perspectives： pronunciation, intonation, diction, subjects, grammar and discourse. From the discussion of the features of women＇s language, more attention should be paid to language use in social context. What＇s more, the linguistic phenomena in a speaking community can be understood more thoroughly.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the     

An affordable accurate evaluation of the binding conformations predicted by molecular docking studies in bio-system

Franck-Condon factors bridge the gap between theoretical modeling and experimental observations for molecular electronic spectroscopy and electron transfer.Under the displaced harmonic oscillator approximation,multidimensional Franck-Condon factors are decomposed into a product of many one-dimensional(1D)Franck-Condon(FC)factors,and each 1D-FC factor is associated with one Huang-Rhys factor that determines the leading contribution of     

Call for Papers

<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with