Syntheses, Spectroscopic and Structural Characterization of a new Polymeric Dinuclear Copper(II) Nitrilotriacetate

摘要本实验体系主要研究了配合物Ba[M(nta)Cl]×3H2O（M＝Cu2+,Co2+,Ni2+）和配位聚合物[M(H2O)6]n[Cu2(nta)2]n·2nH2O（M＝Co2+,Ni2+）的合成方法，结果表明：在水溶液体系中，配合物Ba[M(nta)Cl]×3H2O（M＝Cu2+,Co2+,Ni2+）和硫酸铜可以发生过渡金属离子之间的交换或取代反应，从而合成出一种新型的一维双核配位聚合物。同时，本论文也对这些配合物的合成方法及结构特征分别进行了讨论。Abstract The syntheses of complexes Ba[M(nta)Cl]×3H2O（M＝Cu2+, Co2+, Ni2+）and [M(H2O)6]n[Cu2(nta)2]n·2nH2O（M＝Co2+, Ni2+）were investigated in the system, the results show that: the substitution of two different transition-metal ions between the complexes of Ba[M(nta)Cl]×3H2O（M＝Cu2+, Co2+, Ni2+）and copper sulfate pentahydrate had reacted in the solution, and a new polymeric dinuclear copper(II) nitri...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：X20042501

Syntheses of a Series of Lactato Cobalt Complexes and Their Interaction with Bovine Serum Albumin

合成和表征了系列乳酸钴配合物,测定二水二乳酸钴配合物的结构,配合物中乳酸的羟基和羧基配位键平均键长分别为0.206 0(2)nM和0.206 8(2)nM。当[CO(HlACT)2(H2O)2](2)或[CO(HlACT)2(PHEn)].2H2O(4)配合物与牛血清白蛋白(bSA=bOVInE SEruMAlbuMIn)相互作用后,红外光谱显示乳酸或邻菲咯啉的特征吸收消失,钴离子与bSA出现新的配位,初步推定乳酸或邻菲咯啉配体被bSA中的强配体所取代。A series of lactate cobalt complexes are synthesized and characterized by spectral and structural analyses,including [Co(Hlact)2(H2O)2]·H2O(1),[Co(Hlact)2(H2O)2](2),[Co(Hlact)(phen)(H2O)2]Cl(3) and [Co(Hlact)2(phen)]·2H2O(4)(Lactic acid=H2lact;1,10-phenanthroline=phen).Their interactions with Bovine Serum Albumin(BSA) are investigated with infra-red spectra.国家自然科学基金(No.20805041);国家重点基础研究发展计划(No.2010CB126504)资助项

Synthesis and Characterization of [Ni(Hlact)_2(phen)]·2H_2O and Its Interaction with BSA Studied by Fluorescence Spectroscopy

利用溶液法合成了配合物[nI(HlACT)2(PHEn)]·2H2O(1),并对该配合物进行了元素分析、红外光谱和X-射线单晶衍射表征。通过荧光光谱法研究了不同温度下配合物1与牛血清白蛋白相互作用时的荧光强度的变化,计算了在不同温度下,配合物1与牛血清白蛋白(bSA)的结合常数、结合位点数以及热力学函数,并进一步讨论了配合物1与bSA相互作用时的作用力类型和两者之间的距离。结果表明,配合物1对牛血清白蛋白的荧光猝灭为静态猝灭过程,它与牛血清白蛋白的相互作用有一个位点,结合常数的平均值5.06x105l·MOl-1,作用距离为2.35 nM,相互作用力表现为氢键和范德华力。The compound [Ni(Hlact)2(phen)]·2H2O is synthesized in the solution and fully characterized by elemental analysis,IR and X-ray structural analyses.The interaction of Bovine Serum Albumin(BSA) and [Ni(Hlact)2(phen)]·2H2O at different temperatures are investigated with fluorescence spectra.The binding constant,binding sites and thermodynamic functions are calculated at different temperatures.The binding force and distance are discussed for BSA with complex 1.In the result,the model of fluorescence quenching is considered as static quenching process based on Stern-Volmer equation.The binding constant and binding sites are calculated for BSA and [Ni(Hlact)2(phen)]·2H2O as 5.06 ×105L·mol-1 and 2.35nm respectively.Parameters of thermodynamic functions are calculated and the interaction is determined as hydrogen bonding and van der Waal interactions between BSA and complex.国家自然科学基金(No.21073150)资助项

氯仿至全氯代稠环芳烃的液相电弧合成

以石墨电极在惰性气氛中放电,已成功地合成了C_（60）等碳原子簇。Grosser等人将此反应在氰气与氯气氛中进行,获得了一系列“棒状分子”与全氯代芳烃。我们又将这样的放电反应进一步扩展至溶液体系,将产生原子团簇的物理方法与传统的化学合成方法结合起来。最近,我们分析和研究了在液态的氯仿中放电的产物,在其中先后分离出六氯代苯（Ⅰ）、全

戊型肝炎病毒衣壳蛋白中和表位间的构象诱导

重组蛋白NE2包含了戊型肝炎病毒(HEV)衣壳蛋白(pORF2)的aa394～606片段。在NE2上已鉴定出了2个HEV中和表位,并获得了3个识别中和表位的单克隆抗体(MAb)8C11、13D8和8H3。这3个MAb间的交叉阻断ELISA实验发现,8C11和13D8可以彼此完全阻断,8H3对8C11和13D8均不能阻断,而8C11非但不能阻断8H3,反而显著增强了8H3与抗原的结合。用生物传感器进行的抗体与抗原结合的动力学分析也证实了这一现象。这些结果提示,在NE2上8H3表位区域受到抗原上某些结构的掩盖,而8C11与NE2的结合引起了抗原空间结构的改变,导致了掩盖8H3表位的结构的去除和8H3表位的充分暴露。免疫捕获RT PCR发现,8C11同样可以显著增强8H3对天然HEV病毒的捕获能力,提示这种结合诱导的衣壳蛋白空间构象改变在天然HEV病毒颗粒上同样存在

庚型肝炎病毒基因在大肠杆菌中表达的初步研究

利用原核表达载体 pRSET或 (和 )pGEX在大肠杆菌内表达了覆盖庚型肝炎病毒 (HGV)C NS3和NS5区的多段基因。CE1、E2、NS3、NS5及NS3 NS5嵌合基因等的 8段基因均有高效表达 ,各重组蛋白产量与菌体总蛋白之比在 10 %～ 35 %之间。对以上重组蛋白进行免疫学筛选 ,证实其中 7个重组蛋白均具免疫学活性 ,在一定程度上确定了重组HGV抗原表位的分布 ,为HGV的血清学和免疫学诊断试剂的研究奠定了坚实基

传染性非典型肺炎病毒核蛋白的表达与活性检测

用PCR方法,人工合成传染性非典型肺炎病毒(SARS-CoV)核蛋白(N)全编码基因,并构建原核表达载体,在大肠杆菌中进行表达。结果重组N蛋白表达产量占菌体总蛋白的40％以上,主要以可溶形式存在。用SARS患者急性期血清进行蛋白印迹检测,表明可溶形式和包含体形式均有明显活性。包含体形式的重组蛋白经纯化后纯度可达90％以上,活性与纯化前相当,可作为SARS抗体诊断试剂盒的抗原原料

Desorption Electrospray Ionization Mass Spectrometry for Monitoring the Kinetics of Baeyer-Villiger Solid-State Organic Reactions

Desorption electrospray ionization mass spectrometry (DESI-MS) has been used for monitoring solid-state organic reaction in ambient air, specifically the Baeyer-Villiger (BV) type reaction involving the oxidation of ketones (benzophenone or deoxybenzoin) by m-chloroperbenzoic acid (m-CPBA) in solid-state. The DESI mass spectra obtained at regular intervals during the BV reaction processes are featured, with the amount of ester products increasing as those of ketone reactants decrease. Quantitative analyses of relative intensities of the product, made to quantify the reaction degree of typical solid-state organic reaction (SSOR), show a precision with RSDs of around 5% to 12%, though the RSDs for direct analysis of intensities of the reactant or the product in the solid-state are obviously larger. The kinetics of the Baeyer-Villiger type reactions in solid-state are shown to be dramatically different, in reaction rate, kinetic curve, as well as concentration dependence, from those of the same reactions taking place in solution.NSFC,20525103,20721001 National Basic Research Program of China (973 Program)2007CB81530

Probing Hydrogen Bond Energies by Mass Spectrometry

E-mail Addresses: [email protected]; [email protected] spectrometry with desorption electrospray ionization (DESI) is demonstrated to be useful for probing the strength of hydrogen bonding, exemplified by various complexes of benzothiazoles and carboxylic acids in the solid state. Efficiencies for fragmentation of the complexes, quantified by collision-induced dissociation (CID) technology, correspond well with energies of the hydrogen bonds of O-H center dot center dot center dot N and N-H center dot center dot center dot O bridging each pair of benzothiazole and carboxylic acid. Linear correlations (with correlation factors of 0.8953 and 0.9928) have been established for the calibration curves of normalized collision energy at 100% fragmentation rate vs the length between donor and acceptor (in the hydrogen bond of O-H center dot center dot center dot N) as well as the slope of the fragmentation efficiency curve vs the average length difference between O-H center dot center dot center dot N and N-H center dot center dot center dot O in the complex. The mechanism responsible for determination of the hydrogen bonds is proposed on the basis of the experiments starting from the mixtures of the complexes as well as labeling with deuterium. As a complement of previously available methods (e.g., X-ray diffraction analysis), expectably, the proposed mass spectrometric method seems to be versatile for probing hydrogen bond energies.NNSF of China 21031004 21021061 U120511

Study of Interaction Between Bovine Serum Albumin and Cobalt Complexes of Phenanthroline and Nitrilotriacetate by Fluorescence Spectrometry

利用溶液法合成了邻菲啰啉(PHEn)和氨三乙酸(H3nTA)钴配合物CO(PHEn)2Cl2(1),nA[CO(nTA)].H2O(2),[CO(PHEn)2(H2O)2][CO(nTA)(PHEn)]2.12H2O(3),对配合物3进行了X射线单晶衍射表征,结果表明:该配合物属三斜晶系,P1空间群,A=1.2448(2)nM,b=1.5898(3)nM,C=1.7412(3)nM,α=91.746(3)°,β=97.807(3)°,γ=103.745(3)°,V=3.309(1)nM3.利用荧光光谱法研究了室温下这3种配合物与牛血清白蛋白(bSA)的相互作用,并测定了不同温度下这3种配合物与bSA相互作用的荧光强度变化,确定配合物1和3对bSA的荧光猝灭方式均为静态猝灭;分析了配合物1和3与bSA相互作用时的结合常数、结合位点数以及热力学函数与温度之间的关系,进一步讨论了这2种配合物分别与bSA相互作用时的作用位点、作用力的类型以及两者之间的距离.Cobalt complexes [Co(phen)2Cl2(1),Na[Co(nta)]·H2O(2),[Co(phen)2(H2O)2]·[Co(nta)(phen)]2·12H2O(3)](phen: phenanthroline,nta: nitrilotriacetate) were synthesized in solution,and the structure of complex 3 was characterized by single-crystal X-ray diffraction analysis(XRD).It crystallized in the triclinic system,space group P1 with a=1.2448(2) nm,b=1.5898(3) nm,c=1.7412(3) nm,α=91.746(3)°,β=97.807(3)°,γ=103.745(3)°,V=3.309(1) nm3.The interaction between bovine serum albumin(BSA) and complexes 1—3 was investigated with fluorescence spectra at room temperature.Fluorescence quenchings were shown as static quenching for complexes 1 and 3 based on the fluorescence spectrum at different temperatures.The binding constant,binding sites and thermodynamic functions were calculated.The interaction sites,binding force and distance for BSA with complexes 1 and 3 were discussed respectively.国家自然科学基金(批准号:21073150)资