N-(2-吡啶甲基)-L-丝氨酸铜配合物的合成、晶体结构及抑制蛋白酪氨酸磷酸酶活性

在甲醇溶液中, 还原希夫碱HL[N-(2-吡啶甲基)-L-丝氨酸]与CuCl₂·2H₂O以摩尔比1∶1反应, 得到1个新的中性单核铜配合物[CuLCl(H₂O)](Ⅰ). 通过X射线单晶衍射、 元素分析、 红外光谱、 电喷雾质谱和粉末X射线衍射分析等对其进行了表征. 晶体结构分析表明, 在该配合物中还原希夫碱以三齿双螯合环配位到中心铜离子, 同时氯离子和溶剂水分子也参与配位, 形成1个具有四方锥构型的五配位铜(Ⅱ)配合物, 该配合物通过分子间弱相互作用连接成二维超分子结构. 生物活性测试结果表明, 配合物Ⅰ能有效抑制蛋白酪氨酸磷酸酶1B(PTP1B)和T细胞蛋白酪氨酸磷酸酶(TCPTP), IC₅₀值分别为0.32和0.45 μmol/L.     

Synthesis and Structure of a Ladder-like Co-crystal Cu~ICl with 3,5-Dipropyl-4-amino-1,2,4-triazole

Redox reaction of a mixture of CuCl2·2H2O, H3PO3 and dpatrz(3,5-dipropyl-4-amino-1,2,4-triazole) at room temperature yields one new compound, [Cu(Ⅰ)(μ2-dpatrz)2Cu(Ⅰ)Cl2], with two independent cis- and trans-propyl side chain molecules. Compound 1 crystallizes in monoclinic, space group P21/c with a = 7.474(1), b = 17.807(1), c = 18.851(1) , β = 108.32(1)o, V = 2381.7(2) 3, Z = 4, C16H32Cl2Cu2N8, Mr = 534.48, Dc = 1.491 g·cm-3, μ = 2.03 mm-1, F(000) = 1104, GOOF = 1.050, the final R = 0.0445 and w R = 0.1162 for 3162 observed reflections(Ⅰ 2δ(Ⅰ)). Compound 1 shows discrete dimeric structures(A and B) containing inversion centers and the Cu(Ⅰ) ions are coordinated in triangle geometries. The isomers are connected by N–H···Cl hydrogen bonds, chains with graph-set C(7) and rings R22(14) and C–H···π interactions into stair-step chains(Tapes A and B) running parallel to the [01–1] direction. The N–H···Cl hydrogen bonds result in chain and cyclic structures with graph-sets C22(17) and R34(18) linking tapes A and B to form two-dimensional networks along the [031] direction. Packing of crystal 1 is stabilized by rings R34(18) and weak C–H···Cl hydrogen bonds parallel to the [01–2] direction. Bond valence sum(BVS) and UV-Vis absorption spectra support the existence of Cu(Ⅰ) ions. Compound 1 exhibits extensive green blue phosphorescence in the solid state at room temperature.     

Construction and Photoluminescence Properties of Zn(Ⅱ)/Cd(Ⅱ) Complexes with 4-Amino-3,5-propyl-1,2,4-triazole Ligand

Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole(dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4](I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4](Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a = 11.865(2), b = 14.464(3), c = 15.985(3) , V = 2743.4(9) 3, Z = 4, C16H32N8Cl4Zn2, Mr = 609.4, Dc = 1.475 g·cm3, μ = 2.16 mm-1, F(000) = 1248, GOOF = 1.091, the final R = 0.0295 and wR = 0.0665 for 1999 observed reflections(I 2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a = 11.408(2), b = 15.211(3), c = 18.152(6) , β = 123.75(2)o, V = 2619.1(1) 3, Z = 2, C32H64N22Cl4Cd3, Mr = 1236.05, Dc = 1.567 g·cm3, μ = 1.46 mm-1, F(000) = 1244, GOOF = 1.042, the final R = 0.0444 and wR = 0.0913 for 3466 observed reflections(I 2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids(τ = 0.34). The hydrogen bonds of C–H···Cl and N–H···Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.     

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

近年来,人们从结构上逐步认识到与核酸有关的多种天然酶的活性部位含有两个或三个协同作用的金属离子,如Zn(Ⅱ)、Mg(Ⅱ)、Mn(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)等[1,2],因此从结构和功能上模拟酶的活性部位,合成一些小分子模型物是很有意义的.     

配合物[Ni(EDTB)]·2Cl·CH3OH·C2H5OH的合成、晶体结构及 SOD模拟活性的研究

报道六齿配体N,N,N',N'四(2-苯并咪唑亚甲基)-1,2-乙二胺(EDTB)及单核镍(Ⅱ)配合物[Ni(EDTB)]·2Cl·CH3OH·C2H5OH的合成、晶体结构和SOD模拟活性.该配合物为三斜晶系,P1-空间群,a=1.0931(2)nm,b=1.1693(2)nm,c=1.6756(4)nm,a=76.042(3)°,β=88.787(3)°,γ=72.044(3)°,V=1.9740(7)nm3,Dc=1.321 g/cm3,Z=2,F(000)=824,μ=0.670mm-1.最终因子R[I＞2σ(I)]R1=0.0011,wR2=0.1497;R(全部数据)R1=0.0870,wR2=0.1604.结构分析表明,镍(Ⅱ)分别与配体中的四个苯并咪唑氮和两个亚胺基氮配位形成扭曲的八面体构型.改良的邻苯三酚自氧化活性测定表明,该配合物具有较高的SOD模拟活性.     

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

A new complex with binuclear nickel(Ⅱ) complex [Ni₂(bbimp)(CH₃CH₂OH)₂Cl₂]Cl·4H₂O (bbimp=2，6-bis[bis(2-benzimidazolylmethyl)]aminomethyl-4-methylpheno)(o)had been synthesized and characterized by ele-mentary analysis， IR and UV. The molecular structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is monoclinic， space group P2₁/n with a=20.803(2)?， b=30.708(3)?， c=20.959(2)?， β=105.776(2)°， Z=8， V=12885(2)?³， D_x=1.132Mg·m^-3， μ=0.755mm^-1， F(000)=4592， R₁=0.1267， S=1.376. It was showed that the nickel(Ⅱ) cation is the central ion of a distorted octahedral coordination with two N belonging to benzimidazole， a bridging phenolate O， a N of tertiary amine， a Cl anion， and an O of an ethanol molecule. Two nickel(Ⅱ) cations in a molecular structure had the same coordinated environment. CCDC： 197601.     

Construction of a New(4,8)-Connected Coordination Polymer Based on the Zinc Cluster: Structure,Topology, and Luminescence

The title complex, [Zn_3(L)_2(H_2 O)_2]_n(1, H_3 L = 5-((3-formylphenoxy)methyl)isophthalic acid), has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Compound 1 exhibits a 3D binodal(4,8)-connected net based on trinuclear [Zn_3(COO)4] clusters with the topology symbol of(4~(16)·6~(12))(4~4·6~2)_2. It crystallizes in monoclinic system, space group P2_1/c, with a = 13.548(3), b = 13.291(3), c = 8.2750(1) ?, β = 97.08(3)°, V = 1478.7(6) ?~3, Z = 2, M_r = 858.6 g/mol, D_c = 1.928 mg/m~3, μ = 2.49 mm-1, F(000) = 864, GOOF = 1.12, the final R = 0.0457 and wR = 0.1329 for 4334 observed reflections with I 2σ(I). Additionally, the photoluminescent behaviours of 1 and H3 L have also been investigated in the solid state at room temperature.     

配合物[Ni(EDTB)]•2Cl•CH3OH•C2H5OH的合成、晶体结构及SOD模拟活性的研究

报道六齿配体N,N,N',N'-四(2-苯并咪唑亚甲基)-1,2-乙二胺(EDTB)及单核镍(II)配合物[Ni(EDTB)]•2Cl• CH₃OH•C₂H₅OH的合成、晶体结构和SOD模拟活性. 该配合物为三斜晶系, P1空间群, a＝1.0931(2) nm, b＝1.1693(2) nm, c＝1.6756(4) nm, α＝76.042(3)°, β＝88.787(3)°, γ＝72.044(3)°, V＝1.9740(7) nm³, D_c＝1.321 g/cm³, Z＝2, F(000)＝824, μ＝0.670 mm^－1. 最终因子R[I＞2σ(I)]: R₁＝0.0611, wR₂＝0.1497; R(全部数据): R₁＝0.0870, wR₂＝0.1604. 结构分析表明, 镍(II)分别与配体中的四个苯并咪唑氮和两个亚胺基氮配位形成扭曲的八面体构型. 改良的邻苯三酚自氧化活性测定表明, 该配合物具有较高的SOD模拟活性.     

Studies on the Interaction of Dinitratobis（phen） Cadmium Complex with DNA

DNA-binding properties of the dinitratobis（phen） cadmium complex [Cd（phen）2（NO3）2] （where phen = 1,10-phenanthroline） have been investigated with absorption titration, fluorescence spectroscopy, viscosity measurement, molecular modeling and density functional theory （DFT） calculations. The results indictate DNA-binding mode of the complex to be weak groove binding rather than partial intercalative interaction expected of the extended planar aromatic phen ring. In addition, the DNA cleavage study was carried out by gel electrophoresis experiment. The results showed that the complex both hardly cleaves pBR322 DNA in the absence and present ascorbate. So it is suggested that the formation of cadmium complex can decrease cadmium toxicity to some extents.     

含氮杂环氧钒配合物对PTP1B和ALP的抑制活性研究

蛋白酪氨酸磷酸酶1B (protein tyrosine phosphatase 1B, PTP1B)是当前开发治疗糖尿病药物的优秀靶标, 也是钒配合物抗糖尿病作用相关的重要靶蛋白. 研究了三种含氮平面杂环螯合配体2,2’-联咪唑(L1), 2,2’-联吡啶(L2), 1,10-邻菲咯啉(L3)的氧钒配合物对PTP1B以及碱性磷酸酶(alkaline phosphatase, ALP)的体外抑制作用. 结果表明, 1∶1和2∶1型配位的氧钒化合物均表现出对PTP1B较强的抑制活性, IC50值在120～260 nmol/L间, 抑制能力接近双麦芽酚氧钒配合物(BMOV). 抑制动力学实验表明这些氧钒配合物对PTP1B的抑制模式均为竞争性抑制, 抑制常数在20～160 nmol/L. 其对PTP1B抑制活性较ALP高103倍, 表明氧钒配合物对两种磷酸酶的抑制具有一定的选择性.