基于二氟荧光素内酰胺的一氧化氮分子荧光探针的合成及应用

合成了基于二氟荧光素内酰胺开环反应的一氧化氮分子荧光探针并对其结构进行了表征。二氟荧光素内酰胺本身无荧光,当与NO反应后开环水解生成二氟荧光素,在λex=484nm光激发下产生荧光且最大发射波长λem=514nm。在PH〉4．8的体系中二氟荧光素内酰胺与NO反应后荧光强度达最大且稳定。在H2O2、·OH、O2-、NO2-、ONOO-存在下,荧光探针对NO表现出很高的选择性。以NOC13为NO释放剂,荧光强度随NOC13浓度的增加而增大,可实现对NO的直接检测。     

用于检测铝离子的比色荧光探针及细胞成像研究

文章通过5-硝基水杨醛与二溴荧光素酰肼缩合反应,合成了一种新型的用于检测铝离子的荧光探针5-硝基水杨醛二溴荧光素腙(NDH),通过红外、核磁共振和质谱对化合物进行了表征。在THF:H_2O(9∶1,V/V)中,NDH与铝离子形成1∶1络合物,可以裸眼识别出颜色由黄色到无色的转变。荧光法检测Al~(3+)的线性范围为0.2～5.0μmol/L,检测限为0.01μmol/L。另外,细胞毒性试验结果表明Al~(3+)荧光探针可用于细胞成像的研究。     

N1-（3-苯氧基丙基）-6-甲基尿嘧啶类化合物的合成研究

以取代的苯酚为起始原料,与1,3-二溴丙烷反应合成3-芳氧基-1-溴丙烷(2),通过加布里埃尔反应,使化合物(2)和邻苯二甲酰亚胺钾进行N-烷基化反应合成了2-(3-苯氧基-丙基)二氢异吲哚-1,3-二酮(3),再经肼解得到了3-苯氧基-1-丙胺(4)。将化合物(4)和过量的尿素反应生成单取代的脲(5),再加入活性中间体双乙烯酮,最终得到目标产物N1-(3-苯氧基丙基)-6-甲基尿嘧啶(6)。合成出了5个N1-取代-6-甲基尿嘧啶类化合物,并用1H NMR,IR和元素分析表征了目标产物的结构。该方法路线简捷、原料易得、反应条件较温和,选择性较高。     

荧光素催化的SBA-15-g-PDEAEMA-co-Eu配合物杂化材料的制备及性能研究

首先利用介孔材料SBA-15表面的羟基,将3-氨基丙基三乙氧基硅烷偶联剂(KH550)负载到SBA-15表面,得到氨基化的SBA-15(SBA-15-NH₂),再通过SBA-15表面的氨基和2-溴异丁酰溴(BIBB)中的酰溴基团的反应,将2-溴异丁酰溴负载到SBA-15表面,得到溴代的SBA-15(SBA-15-Br)。然后以SBA-15-Br为引发剂,荧光素为催化剂,具有pH敏感性的甲基丙烯酸二乙氨基乙酯(DEAEMA)和具有荧光特征的铕配合物为单体,通过无金属原子转移自由基聚合(metal-free ATRP)方法制备具有pH敏感和荧光功能的SBA-15-g-PDEAEMA-co-Eu配合物杂化材料。通过傅里叶红外光谱、凝胶渗透色谱、X射线衍射、热失重分析、荧光光谱等测试方法对产物进行了表征和分析。结果表明,成功制备了SBA-15-g-PDEAEMA-co-Eu配合物杂化材料,杂化材料具有pH敏感性和荧光特性;杂化材料的药物释放试验结果表明,槲皮素在酸性条件下的释放速率和释放量远大于在碱性条件下的释放,显示出了明显的pH敏感性。     

2-芳基-3-羟基-4,9-二氢芳庚并吡喃-4,9-二酮类化合物的合成研究

以3-乙酰基酚酮(1)为原料,与自制的苯基三甲基三溴化胺在四氢呋喃中反应2h后,加水稀释得到甲基上单溴化产物3-(2-溴代乙酰基)酚酮(2)。化合物(2)与取代苯甲醛类化合物(3a-i)在以甲醇为溶剂的条件下,于冰水浴中滴加氢氧化钠溶液,反应3h闭环,酸化后即得类黄酮型缩杂环酮的一系列化合物(4a—i),其中4b—4f是未见报道的新化合物。所有化合物的结构通过红外光谱、液相色谱分析及物理常数的测定得以证实。     

N-苯基溴代马来酰亚胺和胺的亲核取代反应

针对氨基马来酰亚胺骨架的重要性,以芳香胺和N-苯基溴代马来酰亚胺为原料,通过亲核取代反应制备了氨基马来酰亚胺产物。考察了碱的类型、溶剂和反应温度等条件对亲核取代反应产率的影响。进行了氨基马来酰亚胺取代产物的Pd/C还原反应和水解反应,探索了非天然N-芳基天冬氨酸的制备条件。实验结果表明:在75℃条件下,以碳酸氢钠为碱,乙醇作为溶剂时,氨基马来酰亚胺的产率可达97%。亲核取代反应产物在碱性条件下水解可以获得酰亚胺单水解产物。     

N-苯基溴代马来酰亚胺和胺的亲核取代反应

针对氨基马来酰亚胺骨架的重要性,以芳香胺和N-苯基溴代马来酰亚胺为原料,通过亲核取代反应制备了氨基马来酰亚胺产物。考察了碱的类型、溶剂和反应温度等条件对亲核取代反应产率的影响。进行了氨基马来酰亚胺取代产物的Pd/C还原反应和水解反应,探索了非天然N-芳基天冬氨酸的制备条件。实验结果表明:在75℃条件下,以碳酸氢钠为碱,乙醇作为溶剂时,氨基马来酰亚胺的产率可达97%。亲核取代反应产物在碱性条件下水解可以获得酰亚胺单水解产物。     

5H-茚并[1,2-b]吡啶的某些5-取代衍生物的合成

报告了文题化合物的合成方法。实验结果表明,5-溴-5H-茚并[1,2-b]吡啶(Ⅱ)的溴原子比较活泼,可被多种亲核试剂所取代。溴代物与含活泼亚甲基的丙二酸二乙酯反应,溴被(二乙氧羰基-)甲基取代,经水解,生成5-(二羧基-甲基)-5H-茚并[1,2-b]吡啶(Ⅳ),再经脱羧,即转化成5-羧甲基-5H-茚并(1,2-b)吡啶(Ⅴ)。溴代物与饱和环状仲胺哌啶反应,溴被哌啶子基取代,生成5-哌啶子基-5H茚并(1,2-b)吡啶(Ⅶ)。溴代物与芳胺类化合物邻-氨基苯甲酸酯反应,溴被N-芳胺基取代,生成5-(邻-烷氧羰基苯胺基)-5H-茚并[1,2-b]吡啶(Ⅷ)和5-(邻-烷氧羰基苯亚胺基)-5H-茚并[1,2-b]吡啶(IX)。所得各种反应产物,均经波谱分析得以证实。     

新型水溶性希夫碱化合物的合成

从绿色化学的角度出发,实现水相中过渡金属催化的偶联反应已经成为人们研究的热点。希夫碱作为配位催化反应的重要配体,对其水溶性结构的设计合成研究具有重要的意义。本文通过五步反应:首先利用邻苯二甲酰亚胺钾盐与长链二溴烷烃发生单取代反应,得到N-溴烷基取代邻苯二甲酰亚胺产品,然后与三乙胺的乙醇溶液作用生成N-烷基季铵盐取代邻苯二甲酰亚胺化合物,进一步水解得到季铵盐取代的长链氨基溴化氢产物,最后与水杨醛缩合脱水得到两种新型水溶性希夫碱化合物,总收率分别为40%和33%。通过核磁氢谱对产品进行表征,确定其结构。该合成方法具有反应条件温和,产率较高,操作简单等优点;该配体在过渡金属催化的C-C、C-N偶联反应具有潜在的应用价值。     

镧系荧光探针DATTA-Eu~(3+)光诱导电子转移机理的理论计算

含有镧系金属铕的DATTA-Eu~(3+)络合物是基于光诱导电子转移(PET)的荧光探针分子,能够高灵敏、高选择性地监控一氧化氮.应用含时密度泛函理论计算方法研究该探针分子的荧光开-关效应和PET机理.结果表明:联三吡啶分子作为配体和荧光母体,受光激发后发生HOMO到LUMO的电子跃迁,由于与其共价相连的邻二氨基苯氧基团的HOMO轨道能级高于联三吡啶HOMO轨道能级,能够将电子转移到单电子占据的联三吡啶HOMO轨道,使激发态电子无法正常回落,阻断了能量向中心Eu~(3+)离子的转移,无法产生铕的特征荧光.当邻二氨基苯氧基团与NO反应生成苯并三唑后,其HOMO轨道能级降低,PET过程被阻断,联三吡啶返回基态时将能量转移到Eu~(3+)离子而产生铕的特征荧光.     

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