Synthesis and DNA binding behavior of a dipyridocatecholate bridged dicopper(II) complex

1,10-Phenanthroline-5,6-diol (dpcatH₂) was prepared conveniently from 1,10-phenanthroline-5,6-dione using hydrazine sulfate as reductant, and a new bimetallic Cu(II) complex, [(phen)Cu(dpcat)Cu(phen)](ClO₄)₂, where phen denotes 1,10-phenanthroline was synthesized by a “one-pot” method. Presence of calf thymus DNA would result in an evident change in the electronic absorption, quenching effect on the fluorescence, protection from fluorescence quencher ferrocyanide and disappearance of redox process of the complex, and the viscosity of DNA would be enhanced by addition of the complex. All these facts suggest that the dicopper(II) complex binds to double helix DNA by classical intercalation.     

NMR Investigation of the Copper(II)-Ciprofloxacin System

A proton NMR study was performed on the copper(ll)-ciprofloxacin system. The proton relaxation times (T(1)) were determined from the titration data in acidic and basic media. In acidic medium the H5 signal is dramatically affected and it is assumed that copper is bonded to the quinolone through carbonyl and one of the carboxyl oxygens. Such bonding is in agreement with the X-ray literature data for the complex [Cu(cf)(1)]Cl(2).6H(2)O isolated from the slightly acidic solution. There are additional significant changes in (1)T(1) of H3' and H5' atoms which suggest that the terminal nitrogen atom of the piperazine ring system-N4' also interacts with copper in the basic conditions. Thus it is plausible that more than one species are present in the solution at high pH values.     

新型含α-Keggin结构超分子化合物（C6H10N2）2[SiW12O40]的合成、结构表征及性质研究

利用水热合成法合成了目标化合物（C6H10N2）2[SiW12O40]通过X射线单晶衍射仪确定了晶体结构,晶体属单斜晶系,空间群C2／m。通过红外、热重分析和循环伏安曲线对晶体进行了结构表征、晶体的热稳定性和氧化还原性研究。晶体中的α-Keggin阴离子、有机配体通过氢键相互作用,形成超分子化合物。     

DNA-promoted electrochemical assembly of [Ru(bpy)2dpp] on the ITO electrode by introducing copper(II) ion

The electrochemical assembly of [Ru(bpy)₂dpp]^3+/2+ (where bpy = 2,2′-bipyridine, dpp = 2,3-bis (2-pyridyl) pyrazine) promoted by calf thymus DNA on an ITO electrode based on the introduction of copper(II) ion has been investigated. There exists a diffusion-controlled wave and two prewaves for the complex in the differential pulse voltammetric sweeping process. The formal potential of the high prewave shift ca. 0.530 V negatively compared with that of the diffusion-controlled wave. Dpp ligand with two vacant chelating N sites in the complex can bite Cu²⁺ and the resultant heterometallic complex shows a weakened assembly in contrast to that of [Ru(bpy)₂dpp]^3+/2+ alone. Furthermore, double stranded DNA is able to accelerate the assembly of the ruthenium complex and heterometallic complex generated by chelating with Cu²⁺ by using the ITO surface, the prompted strength of the latter is far stronger than the former. Their assembled mechanism enhanced by DNA is proposed.     

Extent of the Acidification by N7-Coordinated cis-Diammine-Platinum(II) on the Acidic Sites of Guanine Derivatives

Coordination of two monoprotonated 2'-deoxyguanosine 5'-monophosphate species, H(dGMP)(-), via N7 to cis-(NH(2))(2)Pt(2+) gives the complex cis-(NH(2))(2)Pt(H.dGMP)(2) which is a four-protonic acid. The corresponding acidity constants were measured by potentiometric pH titrations (25; I = 0.1 M, NaNO(3)). The first two protons are released from the two -P(O)(2)(OH)(-) groups (PK(a/1)= 5.57; PK(a/2) = 6.29) and the next two protons are from the H(N1) sites of the guanine residues (PK(a/3) = 8.73; PK(a/4) = 9.48). The micro acidity constants of the various sites are also evaluated. Comparison of these data with those determined for the three-protonic H(2)(dGMP)(+/-) (PK(a/1) = 2.69 for the H(+)(N7) site; PK(a/2) = 6.29 for -P(O)(2)(OH)(-) ;PK(a/3) = 9.56 for H(N1)) shows that on average the N-7-coordinated Pt(2+) acidifies the phosphate protons by Delta pK(a) = 0.36 and the H(N1) sites by Delta pK(a) = 0.46. These results are further compared with those obtained previously for cis-(NH(2))(2)Pt(L)(2), where L = 9-ethylguanine or monoprotonated 2'-deoxycytidine 5'-monophosphate. Conclusions regarding platinated DNA are also presented.     

Synthesis,characterization and biomolecular interactions of Cu(II) and Ni(II) complexes of acyclic Schiff base ligand

Mononuclear copper(II) (1) and nickel(II) complexes (2) of acyclic Schiff base ligand, N,N′-bis(2-hydroxy-1-naphthyl)-1,4-bis(3-iminopropyl) piperazine (L) were synthesized and characterized. The molecular structure of the ligand was confirmed using single crystal X-ray diffraction analysis. The complexes displayed good binding abilities to bovine serum albumin protein (BSA). The binding interactions of complexes 1 and 2 with calf thymus DNA (CT-DNA) was investigated by absorption, fluorescence, circular dichroism spectral analysis and molecular docking studies. Complex 1 showed greater interaction with DNA than nickel(II) complex 2. The cleavage studies with pBR322 DNA showed efficient oxidative cleavage in the presence of 3-mercaptopropionicacid (MPA) and for hydrogen peroxide for complexes 1 and 2 respectively.     

Electrocatalysis for the reduction of O2 and H2O2 based on complex of copper(II) with the tris(3-aminopropyl)amine and imidazole ligands

The Cu(II) complex of [tris(3-aminopropyl)][imidazole]Cu(II)perchlorate was synthesized. This complex can adsorb on a pyrolytic graphite electrode surface where it functions as an electrocatalyst for the reduction of O2 and H2O2. The electrocatalytic kinetics of both substrate reductions were studied by cyclic voltammetric and rotating disc electrode methods. The catalyst accomplishes the four-electron reduction of O2 to H2O at a significantly greater rate than it catalyses the two-electron reduction of H2O2, so that the latter cannot be an intermediate in the reduction of O2.     

组成对铜离子扩散着色玻璃光谱性能的影响研究

红色玻璃以其鲜艳的色彩备受消费者的青睐。本文以氯化亚铜为主要原料,添加一定量的黏结剂和填充剂,在空气气氛中制备了铜离子扩散红色玻璃。研究发现组成中氯化亚铜、硫酸亚铁、氧化亚锡等对铜离子扩散着色有很大的影响。通过控制氯化亚铜、硫酸亚铁、氧化亚锡等的用量可以制备出应用广泛的红色玻璃。     

新型salamo衍生物苦味酸铜(Ⅱ)配合物的合成与表征

以丙酮为溶剂,1,3-二胺氧丙烷双缩邻香草醛(H2L)与苦味酸铜反应,制备了一种新型salamo衍生物苦味酸铜(Ⅱ)配合物,其结构经元素分析,1HNMR,IR,TG-DTA及UV表征。结果表明,新型salamo衍生物是一种四齿配体,配合物的可能结构式为[Cu4L2(pic)4(H2O)2].2CH3COCH3.2H2O。     

Synthesis, Characterisation and Anti-Fungal Activities of Some New Copper(II) Complexes of Octamethyl Tetraaza-Cyclotetradecadiene

The ligand Me(8)[14]diene, L, in its free state as well as in the dihydroperchlorate form, L.2HClO(4), coordinates copper(ll) in different salts to yield a series of [CuLX(x)] X(y)(H(2)O)(z) complexes where X = NO(3), ClO(4), NCS, Cl and Br; x and y may have values of 0 or 2 and z = 0, 1 or 2. The complex, [CuL(ClO(4))(2)].2H(2)O is found to undergo axial ligand substitution reactions with SCN(-), NO(3) and Cl(-) to give a variety of substitution derivatives: [CuL(ClO(4))(m) X(n)] where X = NCS, NO(3) and Cl; m = 0 or 1, and n = 1 or 2. The complexes .have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. The anti-fungal activities of the ligand and its complexes have been investigated against a range of phytopathogenic fungi.     

Synthesis,crystal structure and DNA-binding studies of a Ru(II) complex containing two main ligands

A new Ru(II)-polypyridyl complex, [Ru(L)(dppz)₂](PF₆)₄ (L = 5,5′-di(1-(trimethylammonio)methyl)-2,2′-dipyridyl cation; dppz = dipyrido[3,2-a:2′,3′-c]phenazine]), has been synthesized and structurally characterized. The binding of this complex with calf thymus DNA (CT-DNA) has been investigated by spectroscopic and viscosity measurement. Results indicate that the complex binds to CT-DNA via an intercalative mode. Moreover, the complex reveals a highly efficient DNA cleavage activity upon irradiation at 365 nm, during which supercoiled pBR322 DNA was converted to nicked DNA.     

Copper(I)-Dioxygen Adducts and Copper Enzyme Mechanisms

Primary copper(I)-dioxygen (O₂) adducts, cupric-superoxide complexes, have been proposed intermediates in copper-containing dioxygen-activating monooxygenase and oxidase enzymes. Here, mechanisms of C−H activation by reactive copper-(di)oxygen intermediates are discussed, with an emphasis on cupric-superoxide species. Over the past 25 years, many synthetically derived cupric-superoxide model complexes have been reported. Due to the thermal instability of these intermediates, early studies focused on increasing their stability and obtaining physical characterization. More recently, in an effort to gain insight into the possible substrate oxidation step in some copper monooxygenases, several cupric-superoxide complexes have been used as surrogates to probe substrate scope and reaction mechanisms. These cupric superoxides are capable of oxidizing substrates containing weak O−H and C−H bonds. Mechanistic studies for some enzymes and model systems have supported an initial hydrogen-atom abstraction via the cupric-superoxide complex as the first step of substrate oxidation.     

Synthesis and characterization of a macrocyclic nitritotetraamine nickel(II) complex

The complex [Ni(L)(O₂N)]Cl·H₂O (1) (L=3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized and structurally characterized. The coordination geometry around the nickel(II) ion is a six-coordinated bicapped square-pyramidal with four nitrogen atoms of the macrocycle and two oxygen atoms of the bidentate nitrito group. Electronic spectra and redox potentials of the complex also reveal a high-spin six-coordinated geometry, which is reflected by the nature of the nitrito group.     

Synthesis, Characterisation and Antifungal Activities of Some New Copper(II) Complexes of Isomeric 3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-Tetraazacyclotetradecanes

Three isomeric Me(8)[14]anes, L(A), L(B) and L(C), undergo complexation with copper(II) salts to form a series of [CuLX(n)(H(2)O)(x)]X(y).(H(2)O)(z) complexes where L = L(A), L(B) and L(C); X = Cl, Br, NO(3); n, x, y and z may have values of 0, 1 or 2. The complexes have been characterised on the basis of analytical, spectroscopic, magnetic and conductance data. Further, the X-ray crystal structure of one complex, [CuL(B)(OH(2))(2)](NO(3))(2), has been determined. The antifungal activity of all three isomeric ligands and their complexes has been investigated against a range of phytopathogenic fungi.     

Tetranuclear Thioureacopper(II) Complexes

By replacement of methanol in the Cu₄OX₆(MeOH)₄ (X  Cl, Br) complexes with thiourea (tu), N,N′-diphenylthiourea (diftu), N,N′-dimethlthiourea (dimtu), tetramethylthiourea (tmtu) and acetylthiourea (actu), the complexes Cu₄OCl₆L₄ where L  tu, tu(0.3 Et₂O), diftu, dimtu, tmtu, actu (0.5Et₂O) and the complexes Cu₄OBr₆L₄, where L  tu, diftu, dimtu, tmtu have been prepared. Their infrared and electronic spectra indicate the presence of Cu₄O grouping and the trigonal bipyramidal coordination of copper(II). These complexes exhibit e.p.r. signals in the temperature range 100–260 K, in contrast to other known complexes of this structural type, which showed the e.p.r. signals at significantly lower temperatures. Thiourea and its derivatives are not able to reduce copper(II) in reaction with the tetranuclear Cu₄OX₆(MeOH)₄ complexes in methanol-ether solution due to the redox stabilizing effect of the tetranuclear structure.     

The Kinetics of the Reaction Between Copper (II)-Ions and Tropaeolin O

The system Cu(II)-ions-tropaeolin O has been investigated at 25°C. Spectrophotometric measurements indicate that a 1:2 complex is formed in which one of the originally internally bonded hydrogens is retained. The kinetic results, obtained by the temperature-jump technique, essentially confirm this suggestion.     

Electrochemical characterisation of an Os (II) conjugated polymer in aqueous electrolytes

The electrochemical behaviour of an Os (II) complex of the structurally well-defined conjugated polymer alternating regioregularly alkylated thiophene and 2,2′-bipyridine units (P4Os) has been elucidated in aqueous solution. In typical aqueous electrolyte systems, the cyclic voltammogram of the resulting P4Os film exhibits a one-electron reversible process corresponding to the Os^3+/2+ redox system. However, the observance of this reversible couple did depend upon the concentration of the supporting electrolyte. It was found that the Os³⁺ form did form ion-pairs with an anion from the electrolyte solution. Preliminary investigations into the homogeneous charge transport dynamics associated with this redox couple have been undertaken. The technique of cyclic voltammetry, and hence the Randles-Sevick expression, in conjunction with platinum microelectrodes have been employed to determine the value.     

Isoxazole-Derived Aroylhydrazones and Their Dinuclear Copper(II) Complexes Show Antiproliferative Activity on Breast Cancer Cells with a Potentially Alternative Mechanism Of Action

This paper reports the design, synthesis and cytotoxicity studies of two new isoxazole-derived aroylhydrazone ligands and their dinuclear copper(II) complexes. Compounds were fully characterized by various spectroscopic and analytical techniques. The molecular structures of four derivatives were confirmed by X-ray crystallography. The stability of the ligands and the complexes in aqueous medium was monitored spectroscopically. Both the ligands and the complexes were shown to interact with calf thymus DNA (ct-DNA). Additionally, structures containing a phenol pendant arm were significantly more cytotoxic than those carrying a pendant pyridine substituent, reaching sub-micromolar IC₅₀ values on the triple-negative human breast cancer cell line MDA-MB-231. The metal chelation and transchelation ability of the compounds towards Fe^II, Fe^III and Zn^II ions was explored as a possible mechanism of action of these compounds.     

Studies on thermodynamic nature of steroselectivity for ruthenium(II) polypyridyl complex binding to DNA

A pair of ruthenium(II) complex isomers, Δ- and Λ-[Ru(bpy)₂(p-mpip)]²⁺ {bpy = 2,2′-bipyridine, p-mpip = 2-(4-methylphenyl)imidazo[4,5-f]1,10-phenanthroline} have been synthesized and characterized. Thermodyanmics of binding of the two isomers to calf thymus DNA (CT DNA) has been investigated by isothermal titration calorimetry (ITC). It is rare that the Λ isomer binds to DNA more strongly than the Δ isomer, which has been verified by viscosity measurements, and can be explained by their different thermodynamic driving forces of DNA binding for the first time. This suggests that the dominant factor governing the stereoselectivity of DNA binding of metal complex may be the different thermodynamic driving forces between interactions of its different isomer with DNA. This new finding may be very helpful to understand the nature of steroselective DNA binding of small chiral molecules, and be useful to the development of DNA molecular probes and new DNA targeting therapeutic drugs.     

DNA-enhanced assembly of [Ru(bpy)2ITATP] on an ITO electrode

A novel technique for controllable assembly of [Ru(bpy)₂ITATP]^3+/2+ (where bpy = 2,2′-bipyridine, ITATP = isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) on an ITO electrode in the absence and presence of calf thymus DNA is proposed. The [Ru(bpy)₂ITATP]^3+/2+ and double stranded DNA is assembled onto the ITO electrode using repetitive voltammetric sweeping. The assembly is confirmed by ex situ cyclic voltammetry and the fluorescence microscopy. A pair of diffusion-controlled waves and prewaves for [Ru(bpy)₂ITATP]^3+/2+ is observed in the voltammetric sweeping process. The formal potential of the prewaves is found to be much negative than that of the diffusion-controlled waves. The controllable assembly of [Ru(bpy)₂ITATP]^3+/2+ on the ITO surface is accelerated by DNA and affected by ionic strength. With this DNA-prompted electrochemical technique, a multifunctional biomolecular film containing surface-confined redox center of controllable thickness is fabricated.