Mn(II)与HSA或BSA的结合平衡研究

作者[1] 曾在紫外区观察 LMCT谱带 ,研究了 1∶ 1Mn( ) - HSA和 Mn( ) - BSA在生理 p H(7.43)下金属中心的结构 ,认为 Mn( )在人血清白蛋白 (Human Serum Albumin,简称 HSA)和牛血清白蛋白 (Bovine Serum Albumin,简称 BSA)中的优先结合部位最可能位于 HSA或 BSA的N-端三肽段上 ,涉及 4个含氮基团 ,第 5个配位原子是 ASP1上的羧基氧。用平衡透析法进一步研究了生理 p H条件下 Mn( )在 HSA和 BSA中的结合部位的类型、数目及结合能力 ,并探讨了优先结合部位的可能位置和 (或 )配体。实验同文献 [2 ]。1　Mn( )在 HSA或 B…     

重镧系离子在发光材料中的应用

讨论了Gd^3 ,Pb^3 ,Dy^3 ,Ho^3 ,Er^3 ,Tm^3 ,Yb^3 ,Yb^2 ,Lu^3 等重镧系离子的光谱性质及其在发光材料中的应用，尤其是在近期内的应用前景。     

Crystal Structure, Thermal Decomposition Behavior and the Standard Molar Enthalpy of Formation of a Novel 3D Hydrogen- Bonded Supramolecular [Co（HnicO）2·（H2O）2]

Hydrothermal synthesis and X-ray characterized 3D supramolecular networks were constructed by [Co（HnicO）2·（H2O）2] （HnicOH=2-hydroxynicofinic acid） （1） as building block via abundant dimeric homomeric （N--H…O） and unusually cyclic tetrameric heteromeric （O-H…O） hydrogen-bonds. It is noted that there exist unusually linear metal-water chains comprised of tetrameric units linked by vertexes sharing cobalt centers through hydrogen-bonding. TG-DTG curves illustrated that thermal decomposition was completed by two steps, one is the loss of two terminal water molecules in the range of 156--234℃, and the other is the pyrolysis of HnicO ligand in the range of 234--730 ℃. The standard molar enthalpy of formation of the complex was determined to be （-1845.43± 2.77） kJ·mol^-1 by a rotary-bomb combustion calorimeter.     

金属—血清白蛋白的结构研究——Ⅵ.等离子点附近HSA和BSA中Cu(Ⅱ)和Ni(Ⅱ)金属中心的结构

本文用紫外光谱研究了等离子点附近HSA或BSA (?)Cu(Ⅱ)或Ni(Ⅱ)金属中心的结构。结果表明:在pH4.0～5.3时,Cu(Ⅱ)—HSA配合物在低浓度时独具五配位的四方锥构型,高浓度时(>10~(-4)mol·1~(-1))为四配位的四方平面构型,Cu(Ⅱ)—BSA、Ni(Ⅱ)—BSA在上述pH范围内均只存在四方平面构型。Cu(Ⅱ)、Ni(Ⅱ)结合位置与生理pH下的相同,均在白蛋白的N端三肽段上,与Asp~1的α-NH_2、His~3的咪唑基N及两个去质子肽氮配位,Cu(Ⅱ)在HSA中的第五结合基团为Asp~1的羧基。本文还对上述pH效应进行了讨论。     

[ZnL2Cl2]·2H2O (L = N’-苯甲酰基异烟酰肼)的合成、晶体结构及其表征

标题化合物中，锌（Ⅱ）为四配位畸变的四面体构型。通过相邻分子之间的氢键把配合物连接成三维网络结构，而且，配合物中吡啶环与苯环之间存在着面-面的π–π相互作用。配体与配合物均可发出蓝色荧光，其固态时的最大发射峰为480 nm。     

Scchiff碱N-氧化吡啶-2-甲醛缩氨基脲及其铜配合物的合成、晶体结构及谱学性质的研究

合成了Schiff碱N-氧化吡啶-2-甲醛缩氨基脲(PNOS)及其配合物[Cu(PNOS)(NO3)2],并用单晶X射线衍射法测定了配体和配合物结构.PNOS晶体中通过传统氢键形成双层二维网状结构,再由非传统氢键自组装成三维网状结构.配合物[Cu(PNOS)(NO3)2]中的铜为六配位,畸变八面体结构,Schiff碱(PNOS)通过N-氧化吡啶N-O的O原子,亚胺基C=N的N原子,及羰基C=O的O原子与铜配位;一个硝基以单齿配体形式与铜配位,另一个则以双齿配体形式配位.配合物分子通过经典氢键相互作用,形成单层二维网状结构,再通过非经典氢键作用,自组装成双层二维网状结构.     

锌与烟酰胺苦味酸根配合物的合成与晶体结构

烟酰胺（NA）与苦味酸锌（Zn（Pic）2）在乙醇水混合液中反应,制得氢键连接的超分子配合物[Zn（NA）2·4H2O]·（Pic）2。该配合物的晶体属三斜晶系,空间群为P1,晶胞参数为a=0.7050（1）,b=0.8839（3）,c= 1.4035（3）nm,α=81.16（2）,β=81.92（2）,γ=66.55（2）°,V=0.7898（3）nm3,Z=1,Dc=1.762g/cm3,F（000）=428;μ=0.886mm-1,最终偏离因子R=0.0419,wR=0.1094。结构单元中Zn原子与两个NA和四个水分子配位,配位水又通过氢键与Pic-和相邻单元的NA结合,同时NA上的氨基又与本单元和相邻结构单元中的Pic-上硝基氧形成氢键,形成了三维网状氢键的超分子化合物。     

Synthesis, Crystal Structure, Fluorescence Property and Antibacterial Activity of Two Unprecedented One-dimensional Chain Metal organic Coordination Polymers： Zn（H-SSA）（Phen）（H20）2 and Cu（H-SSA） （Phen） （H20）2

The reaction of 5-sulfosalicylic acid(H3-SSA) with o-phenanthroline(Phen),NaOH,and Mcl2(M=Zn,Cu) affords Zn(H-SSA)(Phen)(H2O)2(1) and Cu(H-SSA)(Phen)(H2O)2 (2),respectively ,compounds 1 and 2 are characterized by elemental analysis,IR,fluorescence spectra and single crystal Xray diffraction analysis.The X-ray diffraction analyses reveal that compounds 1 and 2 are isostructure.The 5-sulfosalicylic acid ligand loses two protons at the sulfo-group and carboxylic group during the reaction.The Zn(II) and Cu(II)ions are sixcoordinated and adopt distorted octahedral geometry,which are surrounded by two N atoms from Phen,two O atoms from two water molecules,one O atom from-SO3 group and one oxygen from carboxylic group of the other H-SSA.Compounds 1 and 2 have unprecedented one-dimensional linear chain formed by a repeating mononuclear structureal unit.which is bridged by H-SSA.The fluorescence intensity of 1 and 2 is stronger than that of Phen and H3-SSA at 400nm.The lowest excited single states of these complexes are assigned as mainly Phen localized 1(π π),The antibacterial activity test shows that compounds 1 and 2 strongly inhibit the growth of Streptococcus haemolyticus,Straphylococcus aureus and Escherichia coli.     

Binding equilibrium study of phosphotungstic acid and HSA or BSA with UV spectrum, fluorescence spectrum and equilibrium dialysis

The binding equilibrium between phosphotungstic acid (H7[P(W2O7)6] · XH2O;PTA) and human serum albumin (HSA) or bovine serum albumin (BSA) has been studied by UV-Vis, fluorescence spectroscopies and equilibrium dialysis. It has been observed that UV absorption enhanced and the fluorescence quenched as the PTA binding to HSA or BSA at physiological pH 7.43(?.02). The Scatchard analysis indicated that there exists a strong binding site of PTA in both HSA and BSA, and the successive stability constants of these two systems are obtained by nonlinear least-squares methods fitting Bjerrum formula.     

Schiff碱水杨醛缩异烟肼和水杨醛缩4-氨基安替吡啉的合成和晶体结构

通过水杨醛和异烟肼,4-氨基安替吡啉的缩合反应分别合成了Schiff 碱水杨醛缩异烟肼1,水杨醛缩4-氨基安替吡啉2,并获得其单晶结构。用元素分析,UV-Vis和IR谱进行表征。晶体结构通过X-射线衍射法测定,晶体结构均用直接法解出, 经全矩阵最小二乘法对原子参数进行修正。化合物1:化学计量式为:C13H11N3O2,Mr = 241.25,晶体属于单斜晶系,空间群P21/n, 晶胞参数:a = 8.153(1),b = 15.574(4) , c = 9.554(2) ? b =105.48(1)? V =1169.1(4) ? , Z = 4, Dc =1.371 g/cm3 , m =0.096 mm-1, F(000) = 504,结构偏离因子R = 0.0832, wR = 0.1158,共收集到2384个独立衍射点,其中其I >2(I)的可观测点为2059个。化合物2:化学计量分子式为:C18H17N3O2,Mr = 307.35,晶体属于单斜晶系,空间群P21/n, 晶胞参数: a = 7.597(1),b = 7.500(1) , c = 27.266(5) , b = 95.31(1), V = 1546.7(4) ? , Z = 4, Dc = 1.320 g/cm3 , m = 0.088 mm-1, F(000) = 648,结构偏离因子R = 0.0413, wR = 0.0952,共收集到3282个独立衍射点,其中其I >2(I)的可观测点为2711个。X-射线分析显示化合物1和2的晶体结构均由分子间氢键和-弱相互作用堆积而成的二维层状结构。