Synthesis and Crystal Structure of a Copper（Ⅱ） Compound Constructed by N-（4,6- Dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea

A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.     

光谱法研究N-丁基-N ＇-(对氨基苯磺酸钠)硫脲与人血清白蛋白的相互作用及其分析应用

利用荧光光谱法和紫外光谱法研究了模拟生理条件下N-丁基-N＇-(对氨基苯磺酸钠)硫脲(BPT)与人血清白蛋白(HSA)的相互作用.研究结果表明,BPT对HSA内源荧光的猝灭是静态猝灭.由热力学参数确定了BPT与HSA间存在疏水作用,根据Firster能量转移理论计算出结合距离为2.97 nm.通过三维荧光光谱研究了BP...     

Crystal Structure and Biological Activities of N-（5-（4-Chloro-2-（trifluoromethyl）phenyl）furan-2-carbonyl）-N＇-（4,6,dimethylpyrimidin-2-yl）thiourea

The new title compound N-（5-（4-chloro-2-（trifluoromethyl）phenyl）furan-2-carbon-yl）- N＇-（4,6-dimethylpyrimidin-2-yl）thiourea （C19H14C1F3N4O2S） has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932（5）, b = 33.46（2）, c = 7.556（5） A, β = 98.058（9）°, V = 1986（2） A^3 Mr = 454.85, Z = 4, Dc = 1.521 g/cm^3, μ = 0.349 mm^-1 and F（000） = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR= 0.1429 for 3494 observed reflections （I 〉 2σ（I））. Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidalactivity for the title compound.     

Synthesis and Crystal Structure of a Ni（Ⅱ） Complex of 2＇-[4-N,N＇-（Dimethylaminobenzyl- idene）]-3,5-dihydroxybenzoylhydrazide and Its Spectral Properties

A new nickel（II） complex [NiL2]（DMF）4 （HL = 2＇-[4-N,N＇-（dimethylamino- benzylidene）]-3,5-dihydroxybenzoylhydrazide） has been synthesized and its structure was characterized by IR,UV-Vis,1H NMR and elemental analysis. The fluorescence emission mechanism of the complex was discussed by fluorimetric spectra. The single-crystal structure was determined by X-ray diffraction analysis. The crystal belongs to the triclinic system,space group P1 with a = 0.9918（4）,b = 1.1297（4）,c = 1.1331（4） nm,α = 76.860（7）,β = 75.105（6）,γ = 89.022（7）°,V = 1.1936（8） nm^3,Z = 1,μ = 0.472 mm^-1,Dc = 1.319 g/cm^3,F（000） = 502 and Rint = 0.0913. In the title compound,the nickel（II） atom is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The complex is centrosymmetric with nickel located at the center.     

Synthesis, Crystal Structure, Antibacterial Activity and Interaction with BSA of Copper( Ⅱ ) Complex with Ligand N, N' -Bis ( 4-chlorobenzyl ) propane-1, 2-diamine

合成了N,N'-双(4-氯苄基)-1,2-丙二胺铜(Ⅱ)配合物[ CuCl( C17 H20C12N2)2]·(NH4)·Cl2,通过元素分析和IR光谱对其进行了表征,并通过X射线单晶衍射确定了其晶体结构.晶体结构分析表明,该晶体属于三斜晶系,P1空间群,晶胞参数a=1.35222(16) nm,b=1.37899(17) nm,c=1.39806(19) nm;α=60.954(1)°,β=87.502(2)°,γ=65.970(1)°,V=2.0424(4) nm3,Dc=1.357 g/cm3,Z=2,F(000)=862,R1=0.0925,wR2=0.2668[ Ⅰ＞2σ(Ⅰ)],S=1.001.配合物的金属中心与来自2个配体的4个氮原子和1个末端氯原子配位,形成了轻微扭曲的四方锥几何构型,扭曲指数τ=0.04(1).抗菌实验结果显示,配合物对大肠杆菌、枯草杆菌和金色葡萄球菌均表现出良好的抑菌作用.采用荧光光谱研究了不同温度下配合物与牛血清白蛋白( BSA)的相瓦作用,结果表明,配合物对BSA的荧光猝灭属于静态猝灭.计算了不同温度下配合物与BSA间的结合常数(Ka)、结合位点(n≈1)及相关热力学参数(△H＞0,△S＞0,△G＜0),结果表明,二者主要靠疏水作用力结合.依据F(o)ster的非辐射能量转移理论,求得给体(BSA)与受体(配合物)间的距离r=2.56 nm,说明配合物与BSA之间可能发生了非辐射能量转移.     

Synthesis, Crystal Structure and Magnetic Properties of a Cobalt（II） Coordination Polymer with 4,4＇-（Propane-2,2-diyl）dibenzoate and 4,4 ＇-Bis（1-imidazolyl）biphenyl

A novel coordination polymer, {[Co（CBA）（BIMB）0.5]＇H20}n （1, H2CBA = 4,4＇- （propane-2,2-diyl）dibenzoic acid, and BIMB = 4,4＇-bis（1-imidazolyl）biphenyl）, has been hydro- thermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P2/c with a = 14.909（3）, b = 7.1963（15）, c = 24.592（5） A, β = 104.312（2）, V = 2556.5（9） A3, C26H23N2OsCo, Mr = 502.39, Dc = 1.305 g/cm3, F（000） = 1040,μ = 0.708 mm-1 and Z = 4. The final R= 0.0580 and wR = 0.1605 for 3228 observed reflections （1 〉 2a（I））. Single-crystal structure analysis shows that complex 1 exhibits a three-dimensional 2-fold interpenetrating pillared helical-layer open framework of a-Po topology based upon binuclear paddlewheel units. Moreover, its magnetic properties have also been investigated.     

6-O-（Hydroxypropyltrimethylammonia）-β-cyclodextrin with Low Degree of Substitution： Convenient Preparation and its Application as a Chiral Selector in Capillary Electrophoresis

Cyclodextrins (CDs) have been widely used as host compounds in molecular recognition, chiral separation and enzyme models1,2. For constructing additional potential host models, research has focused on the regioselective functionalization of nature CDs, wh…     

Theoretical Study of Synthesis Mechanism and Electronic Structure for 3-Octylthien-2,5-ylenediethynylenecobenzo[c]- 1 ＇ 2＇ 5＇ -thiadiazo-3,6-ylenedi（2,5-thienylene）

采用密度泛函理论中的广义梯度近似（DFT／GGA）方法,在PW91／DNP水平上研究了4,7-（2-噻吩基）苯并噻二唑-3-辛基噻吩二炔在PdCl2（PPh3）2催化下的合成机理．优化了反应过程中的反应物、中间体、过渡态和产物,通过能量分析结果证实了中间体和过渡态的真实．在同样的方法和精度研究了4,7．二（2．噻吩基）苯并噻二唑．3．辛基噻吩二炔在没有催化剂下的合成机理．通过计算结果得到此反应在有PdCl2（PPh3）2催化情况下的活化能小于没有催化剂情况下的活化能,从而证明了PdCl2（PPh3）2催化剂的催化活性．采用密度泛函理论与周期性平板模型相结合的方法,研究了产物P在Ti02（100）表面的吸附,通过Mulliken charge和前线轨道分析表明：当P吸附在Ti02（100）表面时,P向Ti02（100）表面转移0．692e电荷,前线轨道能隙变窄．理论预测的结果与实验值吻合．     

The electrochemical behavior of N-n-undecyl-N'-(sodium-p- amino-benzenesulfonate) thiourea and its interaction with bovine serum albumin

In pH 5.5 phosphate buffer solution,N-n-undecyl-N'-(sodium-p-amino-benzenesulfonate)thiourea(UPT)produced a pair of redox peaks on the bare glassy carbon electrode.At the multi-walled carbon nanotube(MWNT)modified electrode,the electrochemical behavior of UPT enhanced greatly.In the presence of bovine serum albumin (BSA),the peak currents of UPT decreased linearly due to the formation of a super-molecular complex.This method was successfully applied to the determination of BSA in a bovine serum sample.     

Electrochemical oxidation and determination of ceftriaxone on a glassy carbon and carbon-nanotube-modified glassy carbon electrodes

The electrochemical behavior of ceftriaxone was investigated on a carbon-nanotube-modified glassy carbon (GC-CNT) electrode in a phosphate buffer solution, pH = 7.40, and the results were compared with those obtained using the unmodified one [glassy carbon (GC) electrode]. During oxidation of ceftriaxone, an irreversible anodic peak appeared, using both modified and unmodified electrodes. Cyclic voltammetric studies indicated that the oxidation process is irreversible and diffusion-controlled. The number of electrons exchanged in the electrooxidation process was obtained, and the data indicated that ceftriaxone is oxidized via a one-electron step. The results revealed that carbon nanotube promotes the rate of oxidation by increasing the peak current. In addition, ceftriaxone was oxidized at lower potentials, which thermodynamically is more favorable. These results were confirmed by impedance measurements. The electron-transfer coefficients and heterogeneous electron-transfer rate constants for ceftriaxone were reported using both the GC and GC-CNT electrodes. Furthermore, the diffusion coefficient of ceftriaxone was found to be 2.74 × 10⁻⁶ cm² s⁻¹. Binding of ceftriaxone to human serum albumin forms a kind of electroreactive species. The percentage of interaction of ceftriaxone with protein was also addressed. A sensitive, simple, and time-saving differential-pulse voltammetric procedure was developed for the analysis of ceftriaxone, using the GC-CNT electrode. Ceftriaxone can be determined with a detection limit of 4.03 × 10⁻⁶ M with the proposed method.     

金属离子对一种分子内电荷转移荧光探针与牛血清白蛋白相互作用的影响

采用荧光光谱法研究了Fe~(3+)、Cu~(2+)、Pb~(2+)三种离子对1-酮-2-(对二甲氨基苯亚甲基)-四氢萘与牛血清白蛋白相互作用的影响.三种金属离子分别存在时能增强1-酮-2-(对二甲氨基苯亚甲基)-四氢萘对牛血清白蛋白的猝灭作用及二者的结合作用,使体系的猝灭常数及结合常数增大,且影响顺序为Fe~(3+)>Cu~(2+)>Pb~(2+).实验表明金属离子对蛋白质在物质的贮存、运转、代谢等方面有重要意义.     

用葡萄糖制备纳米金及其与牛血清白蛋白偶联的研究

报道了一种纳米金合成的新方法。采用葡萄糖还原氯金酸,成功制备出平均粒径为15~35 nm,且高度分散的纳米金溶胶。分别讨论了制备过程中的主要影响因素,确定了用葡萄糖制备稳定的纳米金溶胶的最优条件为:pH=5.0,葡萄糖∶Au=35,反应温度100℃,pH值在加入葡萄糖后再予以调节。用这种方法制备的纳米金与牛血清白蛋白(BSA)进行偶联,确定偶联最小蛋白用量为5μg/mL,并在该最小用量的基础上成功制得了BSA-纳米金复合物。     

PAN-蛋白质络合物的极谱吸附波及其应用

在0.05 mol/L HAc溶液中,PAN-牛血清白蛋白/人血清白蛋白络合物在-0.58 V(vs.SCE)处产生一灵敏吸附还原峰,峰电位较之游离PAN还原峰负约0.28 V,峰电流与牛血清白蛋白、人血清白蛋白浓度在0.1～12 mg/L,0.1～11 mg/L范围内呈线性关系;检测限均为0.05 mg/L。运用该法测定了人血清样品蛋白质含量。     

Studies on Interactions of Antibiotics with Serum Albumin by Surface Plasmon Resonance Biosensor

Introduction Humanserumalbumin(HSA)isawell known transportproteinforavarietyofmoleculesandions[1].Thebindingofadrugtoserumalbuminhasimportant pharmacokineticconsequencesbecauseitinfluences distribution,excretionandpharmacologicaleffectsof thedruginthebody…     

钙试剂-蛋白质体系的共振光散射光谱研究

基于蛋白质对钙试剂共振光散射的增强作用,拟定了一种测定蛋白质的共振光散射法。在pH 4.00的水溶液中,钙试剂在595 nm处的共振光散射增强与蛋白质浓度呈线性关系。此方法对人血清白蛋白、牛血清白蛋白的检出限分别可达0.068和0.085μg/mL。同时得到钙试剂与人血清白蛋白和牛血清白蛋白的结合常数(K)以及结合位点数(n)分别为8.15×104mol/L,0.18和7.67×104mol/L,1.5。     

手性钌配合物的合成、抗肿瘤活性及其与血清蛋白的相互作用

合成了手性钌配合物Δ, Λ-[Ru(bpy)₂(pyip)]²⁺, 通过元素分析、核磁共振、质谱和CD光谱对配合物进行了表征. 采用MTT法评价了3种异构体对多种肿瘤细胞株的体外抗肿瘤活性以及对正常细胞的毒性. 结果表明, Δ-[Ru(bpy)₂(pyip)]²⁺的抗肿瘤活性明显优于其异构体, 对A375, SW480, MCF-7和A549的半数抑制浓度低于顺铂. 通过荧光光谱法研究了在生理pH条件下, 手性钌配合物与牛血清白蛋白(BSA)之间的结合作用以及荧光猝灭机制. 依据Scatchard方程测定了结合常数和结合位点数, 根据热力学方程讨论了两者间的主要作用力类型. 结果表明, 钌配合物对牛血清白蛋白的荧光猝灭机制为静态猝灭. Δ-1, 1和Λ-1与牛血清白蛋白的结合常数分别为1.16×10⁵, 5.12×10⁴和3.64×10⁴, 结合位点数均为1, 主要作用力类型是静电作用. 钌配合物在体内能够被血清蛋白存储转运且结合时对蛋白构象无影响.