Assembling of copper(II) dipicolinate complexes

The role of ancillary ligands, namely imidazole (im), pyridine (py), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) in the assembly of copper(II) dipicolinate complexes are presented. Mononuclear complexes are observed in the case of monodentate ligands. The mononuclear complex [Cu(im)₃L]·4H₂O (1) (L = dipicolinate anion) has a distorted octahedral structure with Z′ = 2, whereas [CuL(py)(H₂O)]·2H₂O (2) adopts distorted square pyramidal geometry. The bidentate ligands bpy and phen favor the formation of dinuclear complexes. The dinuclear complex [CuL(bpy)(μ-L)Cu(bpy)(H₂O)]·9H₂O (3) has one carbonyl oxygen atom of a carboxylate group of dipicolinate acting as a bridging ligand to the copper site that is devoid of a coordinated water molecule. The complex has an angle of 83.55° between the plane of L and bpy attached to one copper site, whereas it has an angle of 78.13° between the plane L and bpy attached to the other copper site. A 1,10-phenanthroline containing dinuclear copper(II) dipicolinate complex, [Cu(phen)(H₂O)(μ-L)Cu(phen)₂][CuL₂]·12H₂O (4), has been structurally characterized. It has an unusual carboxylate bridge.     

Complexation of diazaperylene and bisisoquinoline with transition metal ions in the gas phase studied by electrospray ionization mass spectrometry

The complex formation of the ligands 1,12-diazaperylene (dap), 1,1'-bisisoquinoline (bis), 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) with transition metal ions (M = Fe, Co, Ni, Cu, Zn, Ru, Os, Re, Pd, Pt, Ag and Cd) in the gas phase has been studied by electrospray ionization mass spectrometry. With the exception of Ru, Os, Fe, Ni and Cu, singly charged complexes [MLn](+) (n = 1,2) were observed. The complexes of dap and bis with Ru, Os, Fe and Ni ions, and the mixed ligand complexes with bpy and phen, are preferably of the doubly charged type [ML3]2+. In addition, collision-induced dissociation (CID) measurements were employed to evaluate the relative stabilities of these complexes. The CID experiments of mixed-ligand complexes which contain both dap and phen or dap and bpy exhibit preferential elimination of bpy, indicating that bpy is a weaker ligand than phen and dap.     

DNA-accelerated atom transfer radical polymerization on a gold surface

A significantly increased polymer growth rate was observed during a surface-initiated ATRP reaction in the presence of DNA molecules. To investigate this phenomenon, thiolated single-stranded DNA molecules (ssDNAs) with ATRP initiators coupled at the distal point were used as the model molecule in the study. In comparison, a small molecule, HS-(CH(2))(11)NHCOC(CH(3))(2)Br, was used to provide a less-polar surface coating for polymer grafting. 2-Hydroxyethyl methacrylate (HEMA) and monomethoxy-capped oligo(ethylene glycol) methacrylate (OEGMA) were used as the ATRP monomers. The polymer growth rates were monitored by measuring the thickness of the polymer films formed at different times. Our results show that the presence of DNA molecules, although at a less-than-1% surface coverage, significantly accelerated the growth rates of both poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(oligoethylene glycol methacrylate) (POEGMA) at the beginning of the ATRP reactions. This accelerating effect was suspected to be a combined result of the highly charged sugar-phosphate backbones of DNA molecules and the formation of Cu complexes with DNA bases. After the initial polymer growth, a smaller yet constant polymer growth rate was observed, suggesting the reduced influence of DNA molecules as the ATRP reaction centers moved farther away from the surface. Similar to conventional ATRP reactions, the polymer growth from surface-anchored DNA molecules was found to be strongly dependent on the composition and the concentration of the catalysts used. Specifically, a catalyst mixture of CuCl/30% CuBr(2)/bpy with 23 mM CuCl was found to provide the optimal reaction condition to yield the fastest polymer film growth among the conditions tested.     

The synthesis and structure of heteroleptic tris(diimine)ruthenium(II) complexes

The reactions of bidentate diimine ligands (L2) with cationic bis(diimine)[Ru(L)(L1)(CO)Cl]+ complexes (L, L1, L2 are dissimilar diimine ligands), in the presence of trimethylamine-N-oxide (Me3NO) as a decarbonylation reagent, lead to the formation of heteroleptic tris(diimine) ruthenium(II) complexes, [Ru(L)(L1)(L2)]2+. Typically isolated as hexafluorophosphate or perchlorate salts, these complexes were characterised by UV-visible, infrared and mass spectroscopy, cyclic voltammetry, microanalyses and NMR spectroscopy. Single crystal X-ray studies have elucidated the structures of K[Ru(bpy)(phen)(4,4'-Me(2)bpy)](PF(6))(3).1/2H(2)O, [Ru(bpy)(5,6-Me(2)phen)(Hdpa)](ClO(4))(2), [Ru(bpy)(phen)(5,6-Me(2)phen)](ClO(4))(2), [Ru(bpy)(5,6'-Me(2)phen)(4,4'-Me(2)bpy)](PF(6))(2).EtOH, [Ru(4,4'-Me(2)bpy)(phen)(Hdpa)](PF(6))(2).MeOH and [Ru(bpy)(4,4'-Me(2)bpy)(Hdpa)](ClO(4))(2).1/2Hdpa (where Hdpa is di(2-pyridyl)amine). A novel feature of the first complex is the presence of a dinuclear anionic adduct, [K(2)(PF(6))(6)](4-), in which the two potassium centres are bridged by two fluorides from different hexafluorophosphate ions forming a K(2)F(2) bridging unit and by two KFPFK bridging moieties.     

Photoactive cryptands. Synthesis of the sodium cryptates of macrobicyclic ligands containing bipyridine and phenoanthroline groups

The NaBr cryptates of five macrobicyclic ligands containing bipyridine (bpy) and phenanthroline (phen) groups, i.e, of [bpy.bpy.bpy] 1 [bpy.bpy.phen] 2 [phen.phen.-phen] 3 [2.1.phen] 4 and [2.2.phen] 5 , have been prepared. 1, 2, 4 and 5 have been obtained in high yield by condensation of bis(bromomethyl)bipyridine 6 or -phenanthroline 9 with the corresponding macrocyclic diamines in presence of Na₂CO₃. Direct access to the NaBr complexes of th symmetrical cryptands 1 and 3 was achieved by a one-step macrobicyclisation procedure. The metal-ion complexes of ligands 1-5 have the attractive feature of combining the cation inclusion, nature of cryptates with the photoactivity of bipyridine and phenanthroline groups; they may thus be expected to posses a variety of interesting physical and chemical properties.     

铜络合物与生物小分子次黄嘌呤相互作用的光谱电化学和荧光光谱

以光谱电化学和荧光光谱法证明了络合物Ｃｕ（ｐｈｅｎ）２２＋和Ｃｕ（ｂｐｙ）２２＋与次黄嘌呤能发生络合作用并求出它们的络合比为 １．络合常数分别为 １． ２１× １０４ Ｌ／ｍｏｌ和 ２． ３２ × １０４Ｌ／ｍｏｌ；相互作用的产物的光谱电化学性质发生了明显的变化，结合了次黄嘌呤后的 Ｃｕ（Ｐｈｅｎ）２＋－ＨＸ和Ｃｕ（ｂｐｙ）２＋－ＨＸ在空气中氧化的动力学常数明显减小．这些相互作用的定量数据为铜络合物与ＤＮＡ作用部位提供了重要信息．     

Syntheses,crystal structures,and physical properties of dinuclear copper(I) and tetranuclear mixed-valence copper(I,II) complexes with hydroxylated bipyridyl-like ligands

Four copper complexes with hydroxylated bipyridyl-like ligands, namely [Cu(2)(ophen)(2)] (1), [Cu(4)(ophen)(4)(tp)] (2), [Cu(4)(obpy)(4)(tp)] (3), and [Cu(4)(obpy)(4)(dpdc)].2H(2)O (4), (Hophen=2-hydroxy-1,10-phenanthroline, Hobpy=6-hydroxy-2,2'-bipyridine, tp=terephthalate, dpdc=diphenyl-4,4'-dicarboxylate) have been synthesized hydrothermally. X-ray single-crystal structural analyses of these complexes reveal that 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy) ligands are hydroxylated into ophen or obpy during the reaction, which provides structural evidence for the long-time argued Gillard mechanism. The dinuclear copper(I) complex 1 has three supramolecular isomers in the solid state, in which short copper-copper distances (2.66-2.68 A) indicate weak metal-metal bonding interactions. Each of the mixed-valence copper(i,ii) complexes 2-4 consists of a pair of [Cu(2)(ophen)(2)](+) or [Cu(2)(obpy)(2)](+) fragments bridged by a dicarboxylate ligand into a neutral tetranuclear dumbbell structure. Dinuclear 1 is an intermediate in the formation of 2 and can be converted into 2 in the presence of additional copper(II) salt and tp ligands under hydrothermal conditions. In addition to the ophen-centered pi-->pi* excited-state emission, 1 shows strong emissions at ambient temperature, which may be tentatively assigned as an admixture of copper-centered d-->s,p and MLCT excited states.     

Partial molar volumes and partial molar adiabatic compressibilities of bipyridine and phenanthroline complexes with Fe(II), Co(II), Ni(II), and Cu(II) and chlorides of these metals

Densities and ultrasonic velocities were measured at 25°C for aqueous solutions of bipyridine and phenanthroline complexes [M(bpy)₃]Cl₂ and [M(phen)₃]Cl₂ (M=Fe, Co, Ni, and Cu, bpy=2,2-bipyridine, and phen=1,10-phenanthroline), and chlorides of these metals. The partial molar volumes V ₂ ^o and partial molar adiabatic compressibilities K _s ^o were calculated. For the complex ions, [M(bpy)₃]²⁺ and [M(phen)₃]²⁺, electrostatic interactions with the solvent are not nearly as important as effects due to the hydrophobic ligands bpy and phen. The relationship between V ₂ ^o and K _s ^o of the complex ions and common metal ions are examined.     

Synthesis of heteroleptic bis(diimine)carbonylchlororuthenium(II) complexes from photodecarbonylated precursors

The reactions of bidentate diimine ligands (L2) with binuclear [Ru(L1)(CO)Cl2]2 complexes [L1 not equal to L2 = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), di(2-pyridyl)ketone (dpk), di(2-pyridyl)amine (dpa)] result in cleavage of the dichloride bridge and the formation of cationic [Ru(L1)(L2)(CO)Cl]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(phen)(CO)Cl]+, [Ru(4,4'-Me2bpy)(5,6-Me2phen)(CO)Cl]+ (as two polymorphs), [Ru(4,4'-Me2bpy)(4,7-Me2phen)(CO)Cl]+, [Ru(bpy)(dpa)(CO)Cl]+, [Ru(5,5'-Me2bpy)(dpa)(CO)Cl]+, [Ru(bpy)(dpk)(CO)Cl]+, and [Ru(4,4'-Me2bpy)(dpk)(CO)Cl]+ cations were confirmed by single crystal X-ray diffraction studies. In each case, the structurally characterized complex had the carbonyl ligand trans to a nitrogen from the incoming diimine ligand, these complexes corresponding to the main isomers isolated from the reaction mixtures. The synthesis of [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)(NO3)]+ from [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)Cl]+ and AgNO3 demonstrates that exchange of the chloro ligand can be achieved.     

Structures and DNA-binding and cleavage properties of ternary copper(II) complexes of glycine with phenanthroline, bipyridine, and bipyridylamine

The crystal structures of the series of three complexes, [Cu(Gly)(bpy)Cl].2H2O (1) (Gly=glycine; bpy=2,2'-bipyridine), [Cu(Gly)(phen)Cl]2.7H2O (2) (phen=1,10-phenanthroline), and [Cu(Gly)(bpa)(H2O)Cl] (3) (bpa=2,2'-bipyridylamine) were determined, and the coordination modes of Cu(II) ternary complexes were compared. The central Cu(II) atoms of complexes 1 and 3 have a similar distorted octahedral coordination geometry, while the Cu(II) atom of complex 2 has a distorted square pyramidal coordination. In all complexes, the aromatic heterocyclic compounds bpy, phen, and bpa, behave as a bidentate N,N' ligand, and Gly behaves as a bidentate N,O ligand. DNA-binding properties of the complexes to calf thymus (CT) DNA were studied by using the fluorescence method. Each of the complexes showed binding propensity to CT DNA with the relative order 2>3> or =1. DNA cleavage studies indicate that each of the complexes, especially 2, can cleave plasmid supercoiled pBR322 DNA in the presence of H2O2 and ascorbic acid with cleavage efficiency in the order 2>3 approximately 1. The degradation of the conformation of CT DNA by the complexes was also reflected in the decrease in the intensities of the characteristic CD bands with the relative order 2>3 approximately 1.     

Synthesis,structure and spectral studies on mixed ligand copper(II) complexes of diimines and acetylacetonate

Two new mixed ligand complexes of copper(II) with acetylacetonate (acac), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) belonging to the class of cytotoxic and antineoplastic compounds known as CASIOPEINAS^® were synthesized and structurally characterized. Crystals of both complexes [Cu(acac)(bpy)(H₂O)]NO₃ · H₂O (1), [Cu(acac)(phen)Br] (2) contain square pyramidal Cu(II) complex species. In frozen solution both compounds give well resolved EPR spectra with very similar parameters.     

Synergic extraction of lanthanoids by mixtures of LIX 54 (high molecular weight beta-diketone) and bidentate neutral amines.

The synergic extraction of lanthanoids has been investigated using mixtures of high molecular weight beta-diketone, LIX 54 (HA; major component, 1-phenyl-3-isoheptyl-1,3-propanedion) and bidentate neutral ligands (S) in toluene. The distribution behavior of bidentate amines (2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp)) was investigated and their related equilibrium constants were evaluated. The synergic effect is produced by the formation of such adduct complexes as MA3 x S. The extraction constants with LIX 54 alone and those in the presence of bidentate ligands were determined for lanthanoid-series elements.     

水分散体系中甲基丙烯酸甲酯和丙烯酸八氟戊酯嵌段共聚物的合成与表征

在聚合物链上引入氟元素可以赋予聚合物很多优异的性能 ,如良好的热稳定性、化学稳定性、生物相容性和憎水憎油性等 .含氟单体与一般单体共聚是合成含氟共聚物的重要途径 .通过原子转移自由基聚合 (ATRP)不仅可以实现多种单体的控制 (共 )聚合 ,而且可以合成出具有预定分子量、窄分子量分布以及结构明晰聚合物[1] ,我们曾报道了溶液体系中用ATRP方法合成含氟嵌段共聚物[2～ 4] .众所周知 ,大多数含氟聚合物都是通过乳液或悬浮聚合反应合成的 .然而 ,普通的乳液或悬浮聚合难以合成结构和组成可控的聚合物 ,如嵌段共聚物 ,所以近年来 ,水…     

Dinuclear copper(II) complexes with {Cu2(mu-hydroxo)bis(mu-carboxylato)}+ cores and their reactions with sugar phosphate esters: A substrate binding model of fructose-1,6-bisphosphatase

Reactions of CuX2.nH2O with the biscarboxylate ligand XDK (H2XDK = m-xylenediamine bis(Kemp's triacid imide)) in the presence of N-donor auxiliary ligands yielded a series of dicopper(II) complexes, [Cu2(mu-OH)(XDK)(L)2]X (L = N,N,N',N'-tetramethylethylenediamine (tetmen), X = NO3 (1a), Cl (1b); L = N,N,N'-trimethylethylenediamine (tmen), X = NO3 (2a), Cl (2b); L =2,2'-bipyridine (bpy), X = NO3 (3); L = 1,10-phenanthroline (phen), X = NO3 (4); L = 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), X = NO3 (5); L = 4-methyl-1,10-phenanthroline (Mephen), X = NO3 (6)). Complexes 1-6 were characterized by X-ray crystallography (Cu...Cu = 3.1624(6)-3.2910(4) A), and the electrochemical and magnetic properties were also examined. Complexes 3 and 4 readily reacted with diphenyl phosphoric acid (HDPP) or bis(4-nitrophenyl) phosphoric acid (HBNPP) to give [Cu2(mu-phosphate)(XDK)(L)2]NO3 (L = bpy, phosphate = DPP (11); L = phen, phosphate = DPP (12), BNPP (13)), where the phsophate diester bridges the two copper ions in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.268(3)-4.315(1) A). Complexes 4 and 6 with phen and Mephen have proven to be good precursors to accommodate a series of sugar monophosphate esters (Sugar-P) onto the biscarboxylate-bridged dicopper centers, yielding [Cu2(mu-Sugar-P)(XDK)(L)2] (Sugar-P = alpha-D-Glc-1-P (23a and b), D-Glc-6-P (24a and b), D-Man-6-P (25a), D-Fru-6-P (26a and b); L = phen (a), Mephen (b)) and [Cu2(mu-Gly-n-P)(XDK)(Mephen)2] (Gly-n-P = glycerol n-phosphate; n = 2 (21), 3 (22)), where Glc, Man, and Fru are glucose, mannose, and fructose, respectively. The structure of [Cu2(mu-MNPP)(XDK)(phen)2(CH3OH)] (20) was characterized as a reference compound (H2MNPP = 4-nitrophenyl phosphoric acid). Complexes 4 and 6 also reacted with d-fructose 1,6-bisphosphate (D-Fru-1,6-P2) to afford the tetranuclear copper(II) complexes formulated as [Cu4(mu-D-Fru-1,6-P2)(XDK)2(L)4] (L = phen (27a), Mephen (27b)). The detailed structure of 27a was determined by X-ray crystallography to involve two different tetranuclear complexes with alpha- and beta-anomers of D-Fru-1,6-P2, [Cu4(mu-alpha-D-Fru-1,6-P2)(XDK)2(phen)4] and [Cu4(mu-beta-D-Fru-1,6-P2)(XDK)2(phen)4], in which the D-Fru-1,6-P2 tetravalent anion bridges the two [Cu2(XDK)(phen)2]2+ units through the C1 and C6 phosphate groups in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.042(2)-4.100(2) A). Notably, the structure with alpha-D-Fru-1,6-P2 demonstrated the presence of a strong hydrogen bond between the C2 hydroxyl group and the C1 phosphate oxygen atom, which may support the previously proposed catalytic mechanism in the active site of fructose-1,6-bisphosphatase.     

Investigations of ternary complexes of Co(II) and Ni(II) with oxydiacetate anion and 1,10-phenanthroline or 2,2′-bipyridine in solutions

Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H₂O)], [Co(ODA)(bpy)(H₂O)], [Ni(ODA)(phen)(H₂O)] and [Ni(ODA)(bpy)(H₂O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.      

Spectroscopic study of ternary copper(II) complexes on a silica surface

The formation of ternary surface complexes of copper(II) with one or two molecules of 2,2′-bipyridine (bpy) or α-picolinic acid (Hpic), which were obtained after adsorption on the silica surface in different ways, was studied by electronic and ESR spectroscopy. Coordination of the ligands, which were preliminarily adsorbed by copper ions, afforded only 1∶1 ternary surface complexes. In both cases, coordinatively more saturated ternary surface complexes were formed only when Cu(bpy)₂ ²⁺ and Cu(pic)₂ were adsorbed on the SiO₂ surface from solutions. The compositions and structures of the ternary surface complexes containing bipyridine ligands are temperature independent, whereas in the picolinate-containing ternary surface complexes, the coordination spheres of the adsorbed complexes are rearranged as the temperature changes. Presented at the First Moscow Workshop on Highly Organized Catalytic Systems (June 19, 1997). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1765–1771, October, 1997.     

Synthesis and spectroelectrochemistry of Ir(bpy)(phen)(phi)(3+), a tris(heteroleptic) metallointercalator

A tris(heteroleptic) phenanthrenequinone diimine (phi) complex of Ir(III), Ir(bpy)(phen)(phi)(3+), was synthesized through the stepwise introduction of three different bidentate ligands, and the Lambda- and Delta-enantiomers were resolved and characterized by CD spectroscopy. Like other phi complexes, this tris(heteroleptic) iridium complex binds avidly to DNA by intercalation. Electrochemical studies show that Ir(bpy)(phen)(phi)(3+) undergoes a reversible one-electron reduction at E(0) = -0.025 V in 0.1 M TBAH/DMF (versus Ag/AgCl), and spectroelectrochemical studies indicate that this reduction is centered on the phi ligand. The EPR spectrum of electrochemically generated Ir(bpy)(phen)(phi)(2+) is consistent with a phi-based radical. The electrochemistry of Ir(bpy)(phen)(phi)(3+) was also probed at a DNA-modified electrode, where a DNA binding affinity of K = 1.1 x 10(6) M(-1) was measured. In contrast to Ir(bpy)(phen)(phi)(3+) free in solution, the complex bound to DNA undergoes a concerted two-electron reduction, to form a diradical species. On the basis of UV-visible and EPR spectroscopies, it is found that disproportionation of electrochemically generated Ir(bpy)(phen)(phi)(2+) occurs upon DNA binding. These results underscore the rich redox chemistry associated with metallointercalators bound to DNA.     

Low-dimensional Compounds Containing Cyano Groups. XI. Preparation,Crystal Structure and Properties of Two Copper(II) Dicyanamide Complexes with PF<Stack><Subscript>6</Subscript><Superscript>−</Superscript></Stack> Anions

From the reaction mixtures containing Cu(NO₃)₂, Na[N(CN)₂], KPF₆ and 2,2′-bipyridine (bpy) or 1,10- phenanthroline (phen) in 1:1:1:2 molar ratios, [Cu(bpy)₂N(CN)₂][Cu(bpy)₂(H₂O)](PF₆)₃ (1b) and [Cu (phen)₂N(CN)₂]PF₆ (1p) complexes were isolated. Measured i.r. spectra confirm the presence of all functional groups in both complexes and, moreover, they indicate monodentate coordination of dicyanamide through the cyano nitrogen atom in (1p). The structure of (1b) contains two crystallographically independent complex cations. In both, Cu is coordinated by two chelating bpy molecules, and either dicyanamide anion or water molecule fills the fifth position, completing the basal plane. The Cu^II atoms in (1p) are coordinated by two chelating phen ligands and by one dicyanamide anion in the equatorial plane. Hexafluorophosphate anions in (1b) and (1p) remain uncoordinated. Besides the ionic forces in both structures, the structure of (1b) is stabilized by strong O—H···F and O—H···N hydrogen bonds and, moreover, both structures are stabilized by weak C—H···F hydrogen bonds and possible π-π interactions between pyridine rings of bpy or phen molecules.     

Biological evaluation of copper(II) complexes on N(4)−substituted thiosemicarbazide derivatives and diimine co-ligands using DNA interaction,antibacterial and in vitro cytotoxicity

Abstract

A number of alternatives were made to overcome numerous life-threatening infectious diseases by metal-based anticancer compounds. At present, thiosemicarbazones and their metal complexes have received significant consideration as a result of their metal DNA-interaction, structural diversity and availability of bonding modes. In this study, the coordination characteristics of nine diimine copper(II) complexes with sulfur containing ligands, [Cu(L)₂] (1–3), [Cu(L)(bpy)]Cl (4–6) and [Cu(L)(phen)]Cl (7–9) (L?=?H(L1)–H(L3), phen = 1,10-phenanthroline, bpy = 2,2′-bipyridyl, H(L1) = (Z)-2-((4-methoxynaphthalen-1-yl)methylene)-N-methylhydrazinecarbothioamide, H(L2) = (Z)-N-ethyl-2-((4-methoxynaphthalen-1-yl)methylene)hydrazinecarbothioamide and H(L3) = (Z)-2-((4-methoxynaphthalen-1-yl)methylene)-N-phenylhydrazinecarbothioamide] have been synthesized from 4-methoxy-1-naphthaldehyde along with N(4)-substituted thiosemicarbazide derivatives. The synthesized ligands and their Cu(II) complexes were characterized through different spectroscopic techniques and square-planar coordination was proposed. Biological evaluation such as DNA-cleavage, antibacterial and in vitro cytotoxicity of thiosemicarbazone ligands and their resultant Cu(II) complexes were analyzed. Interestingly, Cu(II) complex containing heteroaromatic moiety 9 had potential cytotoxic activity with strong DNA-interaction. In the future, these may be helpful to design more effective novel chemotherapeutic drugs.     

Red-light photosensitized cleavage of DNA by (l-lysine)(phenanthroline base)copper(II) complexes

Ternary copper(II) complexes [Cu(l-lys)B(ClO4)](ClO4)(1-4), where B is a heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 3) and dipyrido[3,2-a:2',3'-c]phenazene (dppz, 4), are prepared and their DNA binding and photo-induced DNA cleavage activity studied (l-lys =l-lysine). Complex 2, structurally characterized by X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor l-lysine and N,N-donor heterocyclic base bind at the basal plane and the perchlorate ligand is bonded at the elongated axial site. The crystal structure shows the presence of a pendant cationic amine moiety -(CH2)4NH3+ of l-lysine. The one-electron paramagnetic complexes display a d-d band in the range of 598-762 nm in DMF and exhibit cyclic voltammetric response due to Cu(II)/Cu(I) couple in the range of 0.07 to -0.20 V vs. SCE in DMF-Tris-HCl buffer. The complexes having phenanthroline bases display good binding propensity to the calf thymus DNA giving an order: 4 (dppz) > 3 (dpq) > 2 (phen)> 1 (bpy). Control cleavage experiments using pUC19 supercoiled DNA and distamycin suggest major groove binding for the dppz and minor groove binding for the other complexes. Complexes 2-4 show efficient DNA cleavage activity on UV (365 nm) or visible light (694 nm ruby laser) irradiation via a mechanistic pathway involving formation of singlet oxygen as the reactive species. The amino acid l-lysine bound to the metal shows photosensitizing effect at red light, while the heterocyclic bases are primarily DNA groove binders. The dpq and dppz ligands display red light-induced photosensitizing effects in copper-bound form.