对硝基甲苯邻磺酸氧化缩合反应工艺研究

本文对三组工艺条件下对硝基甲苯邻磺酸(NTS)的氧化缩合反应进行研究.实验发现,NTS氧化缩合反应分两阶段进行,在生成中间产物4,4'-二硝基二苯乙烷-2,2'-二磺酸(DND)的阶段,NTS浓度和碱浓度对反应的影响较为显著,在中间产物DND生成4,4'-二硝基二苯乙烯-2,2'-二磺酸(DNS)的阶段,温度对反应的影响较为显著;主要副产物4-硝基苯甲醛-2磺酸(NBS)和4-硝基苯甲酸-2磺酸(NSB)可由NTS直接氧化生成,又可由DNS深度氧化发生断键生成;红料现象是在高物料浓度和较高温条件下,大量NTS、DND的快速积聚,物料粘稠度的迅速增大,使体系空气分散不均、局部供氧量不足,造成NTS因局部缺氧而引发聚合反应,导致红料现象发生的主要原因.红料现象发生后,物料粘度进一步增大,使空气分散更加不均匀,导致红料现象加剧和副产物NSB急剧增加.     

含氢空位氢化金刚石2维原子晶体体系与硫酸吲哚酚和水分子相互作用的第一性原理计算

基于立方金刚石晶体结构构建了2种2维原子晶体:氢化立方金刚石(hydrogenated cubic diamond, HCD)和含氢空位氢化立方金刚石(hydrogen vacancy-HCD, Hv-HCD);将含氢空位氢化立方金刚石与单层六方氮化硼(h-BN)和石墨烯(graphene, G)组装构建了2种2维原子晶体范德华异质结构:h-BN/Hv-HCD和G/Hv-HCD.根据第一性原理,对含氢空位氢化立方金刚石2维原子晶体体系、硫酸吲哚酚和水分子的Fukui函数进行了计算.研究结果显示,含氢空位氢化立方金刚石2维原子晶体体系的氢空位碳原子具有较大的f+(r)和f-(r)值,表明氢空位碳原子的亲电和亲核反应趋势较为显著.有关能量效应的计算结果表明:水分子与含氢空位氢化立方金刚石2维原子晶体体系的氢空位碳原子形成氢键;硫酸吲哚酚分子在氢空位碳原子位点发生化学分解,生成3-吲哚酮和二氧化硫,原磺酸基羟基与氢空位碳原子结合形成醇羟基.该体系可以作为基于2维原子晶体研发生物活性分子、人体血液毒素分子吸附清除以及检测分析核心材料的参考依据.     

2-(双苯并咔唑)-乙基咪唑酸酯探针分子用于药厂废水中脂肪胺的测定

利用2-(7H-二苯[a,f]咔唑)-乙醇与N,N’-羰基双咪唑(CDI)缩合,生成2-(双苯并咔唑)-乙基咪唑酸酯(DBCEIC)中间体,以乙腈作共溶剂,4-二甲氨基吡啶(DMAP)作催化剂,80℃条件下DBCEIC可与脂肪胺发生亲核取代反应,生成稳定的衍生物.在激发波长和发射波长分别为300 nm和390 nm下,通过梯度洗脱对12种脂肪胺衍生物进行了分离和在线质谱定性,实现了药厂废水中脂肪胺的定性及其含量的测定.脂肪胺的线性相关系数除了C10胺以外均大于0.9990,检测限在15.00-85.13 fmol之间.     

二氟二氯甲烷与乙腈的碳化反应

介绍了在KOH固体及相转移催化剂参与下,二氟二氯甲烷(F12)与乙腈发生一种新颖的碳化反应,生成棕色的富碳材料.这种碳材料在700℃下加热分解提纯后得到直径在30～80nm的多孔碳粒子.其结构中同时含有sp、sp2与sp3杂化的碳原子.     

2-硅萘与乙烯和四氰基乙烯杂iDels-Alder反应的理论研究

采用密度泛函理论(DFT)方法在B3LYP/6-311G(d,p)水平上研究2-硅萘与乙烯和四氰基乙烯的杂D iels-A lder反应的微观机理和势能剖面,考察反应的取代基效应和溶剂效应.计算结果表明,所研究反应均以协同非同步的方式进行.乙烯分子中碳原子上的吸电子基团对反应活化能垒的影响取决于2-硅萘中硅上所连接基团的类型.2-硅萘分子中硅原子上的C(CH3)3取代基对反应势能剖面的影响比较小,而其上的CC l3和NH2取代基对反应势能剖面的影响则与亲二烯体分子中碳原子上的取代基的类型有关.苯溶剂对所研究反应的势能剖面影响不大.2-硅萘作为杂二烯烃参与杂D iels-A lder反应的反应性远低于硅苯.     

闪电产生一氧化氮（NO）过程的理论研究

依据闪电产生氮氧化物(LNOx)的基本理论,利用有关化学反应速率的半经验公式,计算了在闪电消散阶段对产生一氧化氮(NO)有主要贡献的化学反应的速率. 结果分析表明:闪电冲击波之后,通道温度从10 000 K衰减到2 000 K的过程中,等离子体复合生成氮氧化物(NOx).随着温度的降低,生成N原子和O原子的化学反应速率逐渐减小,而由N原子和O原子复合生成NO及O2、N2的反应速率逐渐增大,当温度衰减到2 000 K左右时,复合生成NO的主要反应的速率最大.由此推断:对于给定的反应物浓度,此时生成NO达到最多.     

2,6-二巯基嘌呤和2,6-二氯嘌呤的工业化合成

2-巯基-6-羟基-4,5-二氨基嘧啶和甲酰胺环化缩合,巯基化后得到2,6-二巯基嘌呤,再经氯化得到2,6-二氯嘌呤。对以上巯基化和氯化两个反应过程,在反应条件上分别采用盐酸代替醋酸和直接在浓盐酸体系中氯化进行改进,并用于工业生产。     

几种β-二酮化合物的合成及表征

在三苯基膦二氯化钯/碘化亚铜的催化下,对溴苯甲酸甲酯与苯乙炔发生偶合反应,生成化合物l,化合物l分别与苯乙酮、2-乙酰呋喃、2-乙酰噻吩发生克莱森缩合反应,合成了三种新型β-二酮化合物3(a-c),并利用1HNMR, IR, MS,元素分析对其结构进行了表征.     

二硫基二苯并噻唑的绿色合成

以2-巯基苯并噻唑(M)为原料,于水相(含少量丙酮)体系中,在过氧化氢的氧化下发生反应,高产率获得二硫基二苯并噻唑(DM)。     

雌甾化合物反应活性的量子化学研究

从理论上论证了雌甾化合物的反应活性确系A环,A环中的2号位碳原子和4号位碳原子是活性位置,此处易发生亲电取代反应,生成2位和4位的混合物,可得到2位的单一产物,但无4位单一产物,更无1位产物.     

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     

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     

Journal of Donghua University ( English Edition) Contents of Volume 31

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Brief Introduction to “Journal of Jilin University( Science Edition) ”

<正>"Journal of Jilin University(Science Edition)"is a comprehensive academic journal in the fields of science sponsored by Jilin University and administrated by the Ministry of Education of the Peoples Republic of China.The journal started publication in 1955.The original name at starting publication was"Journal of Natural Science of Northeast People University",which was changed into"Acta Scientiarum Naturalium Universitatis Jilinensis"in 1958 owing to the name change of the university.The present journal name has