N,N'-双(2-氨基乙基)-2,6-吡啶二甲酰胺铜配合物催化DNA裂解

本文通过凝胶电泳分析研究了N,N'-双(2-氨基乙基)-2,6-吡啶二甲酰胺铜配合物(BAP)和DNA的相互作用。结果表明BAP-Cu^2＋配合物能够有效催化裂解超螺旋质粒DNA, 它是DNA自然裂解的3.2×10⁶倍,成功地用简单化合物模拟了核酸酶水解DNA的功能。同時本文也初步提出铜离子和氨基协同催化水解DNA磷酸二酯键的裂解机理。     

Efficient DNA Cleavage by Copper（Ⅱ） Complex Derived from 1,1＇-Dimethyl-2,2＇-biimidazole Ligand

The cleavage of DNA （pBR322） by [Cu（Dime-biim）2（H2O）]（ClO4）2 （Dime-biim=1, 1＇- dimethyl-2, 2＇-biimidazole） was investigated. The results showed that the complex could cleave DNA efficiently at pH=8.0 and 37℃.     

Cleavage of DNA by a New Mixed-ligand Cu（ Ⅱ ） Complex

Cleavage of DNA pUC19 by [Cu(saldien)(NH3)]C12 (here, saldien=bis(salicylicdene)-diethylenetriamine) was investigated at different pHs, times, concentrations, and 37℃. It wasfound that the copper( Ⅱ ) complex could cleave DNA without added coreactants.     

A Tetranuclear Complex Assembled from N,N＇-Bis（4-（3＇-formyl-5＇-methylsalicyclidene）-iminoethyl）-4-methyl-2,6-bimethyliminophenol

The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.     

Structure, Antibacterial Activities and DNA Cleavage of a Copper（Ⅱ） Complex with 2-（2＇-Pyridyl）benzimidazole and L-Alaninate

设计合成了新的（2-（2＇-吡啶）苯并咪唑）（L-丙氨酸根）铜（II）配合物：[Cu（HPB）（L-Ala）（ClO4）（H2O）]2 H2O[HPB=2-（2＇-吡啶）苯并咪唑,L-Ala=L-丙氨酸根].应用元素分析、红外光谱、紫外可见光谱、摩尔电导率、电喷雾质谱及X射线单晶衍射等方法对配合物的组成及结构进行了表征.该配合物晶体属单斜晶系,P21空间群,晶胞参数：a=1.1900（2）nm,b=0.80500（16）nm,c=1.9700（4）nm,β=94.78（3）°,Z=2,Dc=1.672 g cm-3,F（000）=968,残差因子R1=0.0427,wR2=0.1106[I〉2σ（I）],S=0.999.在配合物分子中,2-（2＇-吡啶）苯并咪唑和L-丙氨酸根以双齿配位方式在分子平面上与中心铜（II）离子配位,而水分子及高氯酸根单齿弱配位于分子轴向上,构成了一拉长的八面体结构.利用二倍试管稀释法测定了配合物的抗菌活性,并且研究了配合物对pBR 322 DNA的断裂作用.结果表明,该配合物对枯草杆菌（B.subtilis,G＋）,金黄色葡萄球菌（S.aureus,G＋）,大肠杆菌（E.coil,G-）和沙门氏杆菌（Salmonella,G-）具有良好的抑制活性,最小抑菌浓度为50～80μg mL-1,在维生素C存在下能够通过羟基自由基OH氧化断裂pBR 322 DNA双螺旋结构.     

A New Diiminopyridyl Cobalt Complex [CoCl_2L]（L=2,6-Bis（N,N＇-bis（2,6-diisopropyl-4-（2,3-dimethyoxylbenzoylamide）phenylimino））pyridine）

The reaction of CoCl2·6H2O with 2,6-bis(N,N'-bis(2,6-diisopropyl-4-(2,3-dimethy-oxyl-benzoylamide)phenylimino))pyridine(L) afforded the complex [CoCl2L],which was fully characterized by elemental analysis,UV-vis,IR spectroscopy,fluorescence,and X-ray diffraction analysis.The compound is of triclinic system,space group P1 with a = 13.058(3),b = 13.798(3),c = 16.695(3) ,α = 98.191(3),β = 102.792(3),γ = 101.820(3)°,V = 2815.0(9) 3,Z = 2,F(000) = 1122,μ = 0.45 mm-1,R = 0.061 and wR = 0.1349 for 9842 observed reflections(Ⅰ 2σ(Ⅰ)).The Co(Ⅱ) center adopts a distorted square-pyramidal coordination geometry.The extended structure shows a one-dimensional zigzag double chain linked by hydrogen bonds and π-π stacking interactions.     

Formation of a,a＇-Bis（substituted benzylidene）cycloalkanones from Masked Aldehydes Promoted by Samarium（III） Triiodide

1,1-Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(Ⅲ) iodide (SmI3) to afford a,a‘-bis(substituted benzylidene)cycloalkanones in good yields.     

Synthesis,DNA-binding,and Photocleavage of 2,3-Di-2-pyridylquinoxaline-silver（I） Complex

A new dinuclear complex, [Ag（L）（CH3CN）]2（ClO4）2·2H2O（L=2,3-di-2-pyridylquinoxaline）, was prepared and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. The interaction of the complex with calf thymus DNA（CT-DNA） was investigated by absorption, fluorescence spectroscopies, and viscosity measurement. The results suggested that the complex was bound to DNA via an intercalative mode. The intrinsic binding constant value Kb was found to be approximately 1.48×10^3 L·mol^-1. Moreover, the Ag（I） complex could cleave the plasmid pUC19 DNA from the supercoiled Form Ⅰto the nicked FormⅡ under irradiation at 365 nm.     

Synthesis and Crystal Structure of a Novel Copper （Ⅱ） Complex with Acetylenedicarboxylate and 2, 2＇-Bipyridine

The title compound [Cu （ADC） （2, 2＇-bipy）]n （ADC = C2 （COO）2^2.） was prepared and characterized by elemental analysis, IR spectroscopy, X-ray analysis, respectively. The analysis of the crystal structure reveals that the copper atom is five-coordinated with two nitrogen atoms of 2, 2＇-bipy and three oxygen atoms of different acetylenedicarboxylate dianions. ADC as bridging ligands link the Cu （Ⅱ） ions, forming coordination polymer structure.     

Synthesis and Crystal Structure of N,N＇-Dimethyldithio-arbamato-Copper（Ⅰ） Polymer {[Cu（Me2dtc）]2}n

Reactions of CuSCN with tetramethylthiuram disulfide in CH₃CN in the presence of styrene and N,N,N′,N″,N″‐pentamethyldiethylenetriamine gave rise to a new copper(I) complex ofN,N′‐dimethyldithiocabamate ([CU(S₂CNMe₂)]₂)_n. The title compound crystallized in the triclinic P‐1 space group with lattice parameters a=0.7610(4) nm, b=0.8911(4) nm, c=0.9268(5) nm, α=68.66(1)°, β=83.88(2)°, γ=79.31(2)°, V=0.5748(5) nm³, Z=2. The compound has a unique 1D chain structure composed of CuSCSCuSCS eight‐membered rings and a pair of CU? S bonds, the structure of which has been determined by singlecrystal X‐ray crystallography. The isolation of this compound may provide some helpful information for the cause of the induction periods of the reverse atom transfer radical polymerization.     

Synthesis and Crystal Structure of a One-dimensional Ladder-like Complex [Cu2（L）（dca）2]n （dca = [N（CN）2]^-, L = 1,4-Bis（3-furanyl）-2,3-diaza-1,3-butadiene）

A new Cu（I）-dicyanamide with formula [Cu2（L）（dca）2]n （dca = dicyanamide anion, L = 1,4-bis（3-furanyl）-2,3-diaza-1,3-butadiene） has been synthesized and structurally characterized. The complex crystallizes in the monoclinic system, space group P21/n with a = 9.271（2）, b = 7.7355（16）, c = 11.967（3）A,β = 102.693（3）°, V= 837.3（3）A^3, Z = 4, Mr = 223.68, Dc = 1.775 g/cm^3,μ（MoKa） = 2.567 mm^-1, F（000） = 444, R = 0.0782 and wR = 0.2582 for 951 observed reflections （I 〉 2σ（I））. Single-crystal X-ray analysis reveals that the copper atom is three-coordinated by two nitrogen atoms from two dicyanamide anions and another one from the ligand, and each copper atom is connected by two [N（CN）2] anions to form an infinite double-stranded bridge fashion leading to 1D ladder-like motifs.     

Synthesis and Crystal Structure of N-Benzyl-N＇-（2-pyridyl）urea and Its Mononuclear Cu（Ⅱ） Complex

A new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu（Ⅱ） ions. The coordinated units are connected through intermolecular N-H...Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings     

Synthesis and Crystal Structure of a New Hexadentate Ligand N,N＇-Bis（di（2-pyridyl）methyl）ethylenediamine

The reaction of di(2-pyridyl)ketone with ethylenediamine produced hexadentate Schiff base 1 which can be reduced to form a new ligand N,N-bis(di(2-pyridyl)-methyl)ethylene- diamine (BDPM) in ethanol solution. The two compounds were characterized by elemental analyses and spectroscopic methods. Their structures were determined by X-ray diffraction study. Crystal data for 1: C24H20N6, Mr = 392.5, monoclinic, P21/c, a = 13.871(3), b = 13.510(2), c = 12.153(2) ? b = 112.97(2)? Z = 4, V = 2094.1(6) ?, Dc = 1.245 g/cm3, m(MoKa) = 0.078 mm-1, F(000) = 824, the final R = 0.0545 and wR = 0.0557 for 2048 observed reflections (I > 2s(I)); for BDPM: C24H24N6, Mr = 396.49, monoclinic, C2/c, a = 21.411(3), b = 8.053(1), c = 11.868(1) ? b = 92.63(1)? Z = 4, V = 2044.2(4) 3, Dc = 1.288 g/cm3, m(MoKa) = 0.080 mm-1, F(000) = 840, the final R = 0.0401 and wR = 0.0939 for 1673 observed reflections (I > 2s(I)).     

新试剂N—壬基—N′—（氨基对苯磺酸钠）硫脲（NPT）与Cu^2＋ …

通过对新合成的显色剂Ｎ－壬基－Ｎ′－（氨基对苯磺酸钠）硫脲与Ｃｕ＾２＋显色反应的研究,确定了光度测定铜,在ｐＨ６．２￣７．０的ＫＨ２ＰＯ４＾－Ｎａ２Ｂ４Ｏ７缓冲溶液中,Ｃｕ＾２＋和ＮＰＴ形成１：３的水溶性配合物,最大吸收波长为３４３．２ｎｍ,表观摩尔吸光系数ε３４３．２＝４．８７×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。Ｃｕ＾２＋含量在２￣５５·ｇ／２５ｍｌ范围内符合比耳定律,相关系数０．９９９９。     

Syntheses, Structures, and Blue Luminescent Properties of 2,6-Bis（benzimidazolyl） Pyridine and Its Mercury Complex

IntroductionLuminescent metal complexes have attracted in-creasing attention because of their potential applicationin the areas of chemistry, medicine, and material sci-ences[1—4]. Several luminescent complexes of the maingroups and the transition metals…     

Synthesis,Crystal Structure,and Catalytic Performance of 2,6-Bis[1-（2,4,6-trimethylphenylimino）ethyl]pyridine Nickel（II） Complex

A novel nickel（II）-complex Ni[L]Cl2-CH3CN（1） containing the tridentate ligand 2,6-bis[1-（2,4,6- trimethylphenylimino）ethyl]pyridine（L） has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane（MAO）.     

Synthesis, Crystal Structure and Antimicrobial Study of N, N,N＇-Tris（3- aminopropyl）ethylenediamine Copper（Ⅱ） Diperchlorate

1 INTRODUCTION The researches on organic polyamines are currently of great interest because of their potential applications as useful organic ligands, in which the amine nitrogen atoms have strong coordination ability to the transition metal ions. Their transition metal complexes play an excellent role in catalysis and the mimic studies on superoxide dismutase and chlorophyll[1～6]. N,N,N?,N?-Tetrakis(3-ami- nopropyl) ethylenediamine has been extensively stu- died[7～9], but few new ineq…