水相中对羟基苯甲酸分子印迹聚合物的制备及异构体识别

以对羟基苯甲酸为模板分子,2-乙烯基吡啶为功能单体,在甲醇-水体系中制备了以对羟基苯甲酸为模板的分子印迹聚合物。通过高效液相色谱评价,该固定相对对羟基苯甲酸及其异构体分离效果良好。     

单体3,5-二(4-叠氮丁氧基)苯甲酸甲酯的合成与表征

目的：单体分子3,5-二（4-叠氮基丁基）苯甲酸甲酯的合成与表征。方法：采用3,5-二羟基苯甲酸甲酯与叠氮化钠发生亲核取代反应及与卤代烷发生“Williamson”醚化反应,从而形成合成单体分子,该分子叫做3,5-二（4-叠氮基丁基）苯甲酸甲酯。通过1H NMR和FTIR对合成单体进行结构表征。结果：在大量的1,4-二溴丁烷中添加3,5-二羟基苯甲酸甲酯的DMF溶液,反应48个小时后,得到产物3,5-二(4-叠氮丁氧基)苯甲酸甲酯和3,5-二(4-溴丁氧基)苯甲酸甲酯。结论：3,5-二羟基苯甲酸甲酯与叠氮化钠发生亲核取代反应及与卤代烷发生“Williamson”醚化反应,能够形成3,5-二（4-叠氮基丁基）苯甲酸甲酯。     

配合物Na2（4—apyH）2[CoCl2（H2O）4·（tp）2]的合成及晶体结构

为了研究过渡金属借助氢键引导的自组装,合成了线性刚性配体对二苯甲酸与钴(Ⅱ)、4-氨基吡啶和水的配合物Na     

海洋真菌K26号代谢产物的研究

从南海真菌K26号中共分离得到8个化合物,其中硫酸酯胆碱和3,4,5-三羟基苯甲酸首次从中国南海海洋真菌中分离得到．它们的结构通过IR,FABMS,NMR及2DNMR得到确定．     

一种合成3,5-二(吡啶-4-甲氧基)苯甲酸的新方法

以3,5-二羟基苯甲酸乙酯为原料,在一定的条件下与4-氯甲基吡啶盐酸盐反应,合成3,5-二(吡啶-4-甲氧基)苯甲酸.研究发现,当使用N,N-二甲基甲酰胺(DMF)作为反应溶剂时,目标产物的产率可达到65%.同时,通过傅立叶变换红外光谱(FT-IR)、核磁共振氢谱(1H NMR)等技术手段对目标产物3,5-二(吡啶-4-甲氧基)苯甲酸的结构进行表征.     

偶氮基团修饰的苝酰亚胺染料的合成及其光响应行为

以3,5二羟基苯甲醇为原料,经醚化、溴代反应得到3,5二（十二烷氧基）苄基溴,然后与4羟基4′硝基偶氮苯反应,再还原得到含氨基的偶氮化合物6,最后与3,4;9,10苝四甲酸二酐缩合得到新型偶氮-苝酰亚胺二元染料7。考察了紫外光光照时间及浓度等因素对偶氮-苝酰亚胺二元染料光学性能的影响,结果表明浓度越大,偶氮生色团由反式结构向顺式结构的转变速度越慢;对相转移法组装形成的聚集体形貌结构的研究表明,当甲醇与三氯甲烷体积比为7∶1或5∶1时,更易形成较规整的短棒;比较研究紫外光光照和未光照下快速溶剂扩散法组装形成的聚集体形貌结构发现,光照下制备的聚集体结构的规整性不及未光照下制备的;吸收光谱表明在光照下组装的聚集体分子间π*π堆积作用更弱,这是由于偶氮基团由反式结构向顺式结构的转变导致分子空间几何构型的变化,破坏了分子堆积的有序性,不利于低维功能材料的形成。     

柱芳烃单分子管人工通道构筑及其对手性氨基酸的选择性跨膜输送

该课题通过设计结构精确的分子单体,通过氢键、配位作用及疏溶剂作用和pi-pi堆积作用等为驱动力,构筑多层次的自组装体系,进而探索组装体的功能。2013年度,我们根据计划书要求开展工作,在以下几个方面取得重要进展:(1)设计了一类三角型平面分子,在其周围引入单N-苯基联二吡啶VB+,通过葫芦脲[8]对两个VB单元的强络合作用,在水相中实现了有序蜂窝型超分子有机框架(SOF)结构的自组装。(2)设计了两类刚性四面体分子,分别引入4个紫精和四硫富瓦烯片段,在把紫精还原或把四硫富瓦烯氧化为正离子自由基后,这两类正离子自由基在水相强烈堆积,从而诱导其形成三维网络超分子组装结构。(3)利用氢键控制芳香酰胺线性分子的构象,从而研究其结构-性质关系,并进而利用构象控制开展分子识别与自组装研究。1利用单分子力谱首次研究了驱动形成芳香酰胺螺旋孔状结构的氢键的强度及不同位置氢键强度的差异;2利用手性离子对识别,从并入氢键折叠片段的UPy四氢键组装单体构筑了一类交替堆积的手性超分子聚合物;3设计合成了两个大环分子,引入酰胺和1,2,3-三氮唑片段,通过对二酰胺和三碘客体分子的氢键和卤键结合,研究了分子间氢键和卤键的相对强度;4设计了新的双卟啉和三卟啉主体分子,通过分子内氢键诱导其形成刚性梳型构象,进而用于研究配位作用和堆积作用协同诱导的多组分超分子结构组装。(4)在配位自组装研究方面取得重要进展:1研究了含有氮杂环卡宾-金属键的金属有机大环分子的合成,发现氮杂环卡宾与11族金属(Cu,Ag,Au)可以形成较强的配位键,由此获得了中间桥连基团是不同长度、含有不同吡啶数目的系列金属有机大环分子;2对含有多配位位点的氮杂杯吡啶大环分子进行配位组装及金属簇可控合成的机理进行了深入研究。发现含有多个配位位点的氮杂杯吡啶大环分子可以结合多个金属离子,形成一个分立的组装结构,并且一种大环分子与某种特定金属形成的复合物结构具有很好的稳定性,金属与配体的比例较为固定。(5)利用柱芳烃为骨架,构筑了一类新的自组装单分子纳米管,通过引入由苯丙氨酸构成的肽链,延长了单管长度并引入手性,从而实现了对氨基酸跨膜输送的手性选择性。     

葡萄糖酸内酯羟基选择性重排反应引发脂肪族聚酯研究

通过对葡萄糖酸内酯进行伯羟基保护以及分子内开环重排,合成了一种基于糖类结构的五元环状三羟基引发剂.该引发剂具有3个仲羟基结构,在有机碱1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)的催化下,控制内酯单体如丙交酯、己内酯与羟基的投料比,采用控制聚合法获得一系列具有不同相对分子质量的三臂聚乳酸以及三臂聚己内酯,通过聚合后脱保护及偶联聚乙二醇的策略制备了一系列两亲性三臂聚酯并用于药物载体的研究.利用核磁、质谱、傅里叶红外变换等对生物质引发剂进行了结构表征,利用凝胶色谱、核磁等对三臂聚酯进行了结构表征,通过纳米粒度仪对其自组装后胶束的性质进行了探究.结果表明,该生物基三臂引发剂为稳定的五元环结构,并成功制备了相对分子质量可控且分布较窄的三臂两亲性聚酯,该聚合物可以自组装成粒径为100～200 nm的胶束,并实现疏水药物的包载.     

沙丁胺醇与不同功能单体分子的印迹作用

采用密度泛函理论(DFT)的LC-WPBE方法,以沙丁胺醇(SAL)为模板分子,甲基丙烯酸(MAA)、丙烯酰胺(AM)和4-乙烯基吡啶(4-VP)为单一功能单体,MAA和AM为混合功能单体,模拟SAL与单一功能单体和混合功能单体分子印迹聚合物(MIPs)自组装体系的构型,并讨论其稳定复合物的成键作用位点及数目、自然键轨道(NBO)电荷的转移、结合能及溶剂化能,以及SAL与功能单体间相互作用的原理.计算结果表明,SAL与功能单体间均通过氢键形成分子结构互补的有序排列复合物,单体中MAA与SAL模板分子间的相互作用更强,且在印迹比例为1∶4,以乙腈(ACN)为溶剂时,复合物能量最低,电荷的转移趋势最大.基于计算结果,采用沉淀聚合法制备不同印迹比例沙丁胺醇分子印迹聚合物(SAL-MIPs),结果表明,印迹比例1∶4时制备的聚合物吸附量最大,实验结果与计算结果相符.     

非布索坦的合成工艺改进

以4-羟基硫代苯甲酰胺为原料制备出高纯度的非布索坦.通过优化工艺条件得到最佳合成方案.方法以4-羟基硫代苯甲酰胺为原料,经环合、甲酰化、醚化、醛肟化后脱水得到腈类化合物,该化合物再经过酯水解、酸化反应得到目标产物,最后经过重结晶得到合格的产品.结果最终产品的结构经核磁共振分析得到确证.经重结晶后其纯度可达99.7%,产品总收率为48.8%.结论原料廉价易得、合成条件温和,适合工业化生产.     

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