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.     

琥珀酰化壳聚糖-铜(Ⅱ)-苯并咪唑衍生物配合物的合成、表征及抗菌活性

文章利用琥珀酸酐对壳聚糖进行改性,并合成了两个新的配合物:sucts-Cu(Ⅱ)-hpb(1)和sucts-Cu(Ⅱ)-tbz(2)[sucts=琥珀酰化壳聚糖,hpb=2-(2’-吡啶)-苯并咪唑,tbz=2-(4′-噻唑基)苯并咪唑]。应用红外光谱,紫外-可见光谱,原子吸收光谱对配合物进行了表征,采用试管倍比稀释法研究了这些配合物对苏云金杆菌、枯草芽孢杆菌、大肠杆菌和金黄色葡萄球菌的抑制作用。结果表明,两种配合物对四种细菌均有较强的抑菌活性,配合物1、2,最小抑菌浓度(MIC)分别为62.5～125μg.mL-1和125～250μg.mL-1,抗菌效果明显强于自由配体。     

Development of Novel DNA Cleavage Systems Based on Copper Complexes. Synthesis and Characterisation of Cu(II) Complexes of Hydroxyflavones

Copper(II) complexes of several hydroxyflavones were prepared and characterised through their physico-chemical properties. The nuclease activity of three synthesised complexes is reported. These copper(II) complexes present more nuclease activity than the ligands and the copper(II) ion.     

Synthesis,Characterization and Catalytic Activities of Palladium(II) Nitroaryl Complexes

Two palladium(II) nitroaryl complexes trans-[bromo(p-nitrophenyl)bis(triphenylphosphine)palladium(II)] 1 and trans-[bromo(2,4-dinitrophenyl)bis(triphenylphosphine)palladium(II)] 2 have been synthesized. The complexes were characterized by FTIR and NMR (¹H, ¹³C and ³¹P) spectroscopy and elemental analysis. The molecular structure of complex 2, as confirmed by X-ray crystallography, reveals that the Pd atom and its neighboring groups (two PPh₃, Br and phenylene group) lie in a slightly distorted square plane. In the UV–Vis spectra of the complexes 1 and 2, the palladium to aryl charge transfer bands were observed. The emission peaks from the singlet excited states (S₁ → S₀) were observed in the photoluminescence spectra of the complexes. The thermal stability of the complexes has been studied by thermal gravimetric analysis (TGA). TGA data showed that both complexes are thermally stable up to 200 °C, and complex 1 is more stable than 2. The catalytic efficiency of the new palladium(II) complexes was studied as demonstrated using the Sonogashira coupling reactions with good yields. The experimental results suggest that the Sonogashira coupling reactions can be performed at moderate temperature (50 °C) using these new palladium(II) complexes as catalysts.     

Synthesis of New Five Coordinated Copper(II) and Nickel(II) Complexes of L-Valine and Kinetic Study of Copper(II) with Calf Thymus DNA

Five coordinated novel complexes of CuII and NiII have been synthesized from benzil and 1,3- diaminopropane-CuII/NiII complex and characterized by elemental analysis, i.r., n.m.r., e.p.r, molar conductance and u.v-vis, spectroscopy. The complexes are ionic in nature and exhibit pentaeoordinated geometry around the metal ion. The reaction kinetics of C25H36N5O2CuCl with calf thymus DNA was studied by u.v-vis, spectroscopy in aqueous medium. The complex after interaction with calf thymus DNA shows shift in the absorption spectrum and hypochromicity indicating an intercalative binding mode. The Kobs values have been calculated under pseudo-first order conditions. The redox behaviour of complex C25H36N5O2CuCl in the presence and in the absence of calf thymus DNA in the aqueous solution has been investigated by cyclic voltammetry. The cyclic voitammogram exhibits one quasi-reversible redox wave corresponding to CuII/CuI redox couple with E1/2 values of -0.377 and -0.237 V respectively at a scan rate of 0.1Vs-1 .On interaction with calf thymus DNA, the complex C25H36N5O2CuCl exhibits shifts in both Ep as well as in E1/2 values, indicating strong binding of the complex to the calf thymus DNA.     

Synthesis, Spectral and Antibacterial Studies of Copper(II) Tetraaza Macrocyclic Complexes

A novel family of tetraaza macrocyclic Cu(II) complexes [CuLX(2)] (where L = N(4) donor macrocyclic ligands) and (X = Cl(-), NO(3) (-)) have been synthesized and characterized by elemental analysis, magnetic moments, IR, EPR, mass, electronic spectra and thermal studies. The magnetic moments and electronic spectral studies suggest square planar geometry for [Cu(DBACDT)]Cl(2) and [Cu(DBACDT)](NO(3))(2) complexes and distorted octahedral geometry to the rest of the ten complexes. The biological activity of all these complexes against gram-positive and gram-negative bacteria was compared with the activity of existing commercial antibacterial compounds like Linezolid and Cefaclor. Six complexes out of twelve were found to be most potent against both gram-positive as well as gram-negative bacteria due to the presence of thio group in the coordinated ligands.     

配合物{[Co（HFlu）2Cl2】·2C2H5OH}n的合成、结构及体外抗真菌活性

新合成了1种钴-氟康唑配合物{[Co（HFlu）2Cl2】·2C2H5OH}n,利用X-射线单晶衍射仪等对配合物进行了结构分析,并研究了该配合物的体外抗真菌活性,标题化合物对丝状真菌的抗菌效果明显优于氟康唑,对酵母菌的体外抗真菌活性与氟康唑相当,     

Copper(II) Complexes of Pyridazine-Based Azo-azomethine Ligands: Synthesis, Characterization Thermal and Absorption Properties

New copper(II) complexes with blue–violet light wavelength absorption were synthesized using direct reaction of acyclic azo-azomethine pyridazine-based ligands with copper ion. The prepared complexes were characterized using elemental analysis, spectroscopic methods and thermal analyses. The absorption properties of the prepared complexes in the region 200–800 nm and also the influence on the difference of absorption maximum of complexes were investigated. The thermogravimetric results show that the framework of all complexes is stable up to 270–320 °C.     

New Cyclams and Their Copper(II) and Iron(III) Complexes: Synthesis and Potential Application as Anticancer Agents

New cyclam derivatives (HOCH₂CH₂CH₂)₂(PhCH₂)₂Cyclam and (HOCH₂CH₂CH₂)₂( PhCH₂)₂Cyclam, as well as their Cu^II and Fe^III complexes, were synthesized and characterized and their stability in cellular media was assessed. The cytotoxic effect of all compounds was examined on human cervical cancer (HeLa) cells, revealing strong anticancer activity. After 24 h, only complexes with the (HOCH₂CH₂CH₂)₂( PhCH₂)₂Cyclam ligand are cytotoxic, whereas after incubation for 72 h all compounds show significant antiproliferative effects. Notably, compounds containing PhCH₂ pendant arms on the cyclam ring revealed the most activity, with cytotoxicity values up to 12 times higher than those of cisplatin. All metal complexes seem to induce cell death through the formation of reactive oxygen species.     

不对称水杨醛亚胺Schiff碱及其铜（Ⅱ）配合物的合成和抑菌活性研究

合成了一种新5-溴水杨醛亚胺席夫碱配体及其与铜(Ⅱ)的配合物，并由元素分析和红外光谱所表征。采用琼脂稀释法测定了配合物的抑菌活性，测得了它们抑制细菌生长的最小浓度。结果表明，Schiff碱对几种受试菌均有较强的抑制作用。配合物比配体有更高的抑菌活性。     

Structure-Activity Relationships for Some Diamine, Triamine and Schiff Base Derivatives and Their Copper(II) Complexes

Ethylenediamine (en), putrescine (pu), diethylenetriamine (dien), dipropylenetriamine (dpta), spermidine (spmd) and their Cu(II) compounds as well as the Schiff bases with 2-furaldehyde (dienOO), 2- thiophenecarboxaldehyde (dienSS) and pyrrole-2-carboxaldehyde (dienNN) of dien and that of dpta with 2- thiophenecarboxaldehyde (dptaSS), were prepared and characterised. They were tested against Bacillus substilis, Bacillus cereus, Staphylococcus aureus, Escherichia coli, Proteus vulgaris and Xanthomonas campestris as antibacterial reagents, the highest activity being exhibited by Cu(dptaSS)(NO(3))(2) complex, which acts as antibiotic. In the antiproliferative tests (vs. T(47)D,L(929) and BHK(21/c13) cell lines) the best results were obtained with Cu(dptaSS)(2+) and Cu(dienSS)(2+). Electronic structure calculations gave for dptaSS and dienSS the higher negative charges on the N atoms. The counter-ions (Br(-), NO(3) (-) and SO(4) (2-)) play an important role by modulating the reagent's selectivity versus the bacteria [Gram(+) or Gram(-)], but they have no effect on the antiproliferative activity.     

Studies on Some Biologically Cobalt(II), Copper(II) and Zinc(II) Complexes With ONO, NNO and SNO Donor Pyrazinoylhydrazine-Derived Ligands

Biologically active complexes of Co(II), Ni(II), Cu(II) and Zn(II) with novel ONO, NNO and SNO donor pyrazinoylhydrazine-derived compounds have been prepared and characterized on the basis of analytical data and various physicochemical studies. Distorted octahedral structures for all the complexes have been proposed. The synthesized ligands and their complexes have been screened for their antibacterial activity against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Klebsiella pneumonae. The activity data show the metal complexes to be more active than the parent free ligands against one or more bacterial species.     

Synthesis, Spectroscopy and Electrochemistry of Fe(II) and Fe(III) Quinonemonooxime Complexes and Their DNA Cleaving Activities

Iron(II) and iron(III) complexes of 3,5-di-tert-butyl-o-benzoquinonemonooxime were synthesized and characterized by spectroscopic and electrochemical studies. Their ability to cleave DNA has been investigated under aerobic conditions at room temperature and in the presence and absence of H(2) O(2). The plasmid DNA pBR322 was effectively cleaved by these complexes in a concentration dependant manner.     

Synthesis, Characterization and Antifertility Activity of New Unsymmetrical Macrocyclic Complexes of Tin(II)

A new series of unsymmetrical macrocyclic complexes of tin(ll) has been prepared by the template process using bis(3-oxo-2-butylidene)propane-1,3-diamine as precursor. This affords a method to synthesize these complexes with various ring sizes. The tetradentate macrocyclic precursor [N(4)mL] reacts with SnCl(2) and different diamines in a 1:1:1 molar ratio in refluxing methanol to give complexes of the type [Sn(N(4)mL)Cl(2)]. The ring expansion has been achieved by varying the diamine between the two diacetyl amino nitrogen atoms. The macrocyclic precursor and its metal complexes have been characterized on the basis of elemental analysis, molar conductance, molecular weight determinations, IR, (1)H NMR,(13)C NMR, (119)Sn NMR and electronic spectral studies. An octahedral geometry around the metal ion is suggested for these complexes. On the basis of molecular weights and conductivity measurements, their monomeric and non-electrolytic nature has been confirmed. The precursor and complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential. The testicular sperm density and testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemicals parameters of reproductive organs have been examined and discussed.     

Sonochemical Synthesis of Two New Nano-structured Cadmium(II) Supramolecular Complexes

Nano-particles of two new Cd(II) supramolecular complexes, [Cd(4,4-di-tert-bubipy)Cl₂(DMSO)] (1) and [CdI₂(4,4′-dmbpy)(DMSO)] (2) have been synthesized by sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The structure of compound 1 has been characterized by single crystal X-ray diffraction. The prepared nano-structure was characterized by scanning electron microscopy and X-ray powder diffraction. The nano-structures of supramolecular complexes have been synthesized with calcination of complexes at oleic acid as a surfactant at 190 ºC too. The size of the samples prepared by sonochemical method and calcination are about 30–40 and 40–50 nm respectively.     

Synthesis, Ligational and Biological Properties of Cobalt(II), Copper(II), Nickel(II) and Zinc(II) Complexes With Pyrazinedicarboxaimide Derived Furanyl, Thienyl and Pyrrolyl Compounds

Preparation, ligational and biological properties of some pyrazinedicarboxaimide derived furanyl, thienyl and pyrrolyl compounds with Co(ll), Cu(ll), Ni(ll) and Zn(ll) metals are described. Magnetic moments, electronic, infrared, nuclear magnetic resonance spectra and elemental analysis data indicate that co-ordination of the ligands with the metal ions take place through the pyrazine ring nitrogen, azomethine nitrogen and heteroatom of heterocyclic ring system. The compounds are all novel and are proposed to possess an octahedral geometry for Co(ll) and Ni(ll), and a distorted octahedral geometry for Cu(ll) and Zn(ll) complexes. The comparative biological properties of the title ligands and their metal chelates against different bacterial species are also described.     

Synthesis,Characterization, and Antimicrobial Activity of Silver(I) and Copper(II) Complexes of Phosphate Derivatives of Pyridine And Benzimidazole

Two silver(I) complexes—{[Ag(4‐pmOpe)]NO₃}_n and [Ag(2‐bimOpe)₂]NO₃—and three copper(II) complexes—[Cu₄Cl₆O(2‐bimOpe)₄], [CuCl₂(4‐pmOpe)₂], and [CuCl₂(2‐bis(pm)Ope]—were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin‐4‐ylmethyl)phosphate (4‐pmOpe), 1H‐benzimidazol‐2‐ylmethyl diethyl phosphate (2‐bimOpe), and ethyl bis(pyridin‐2‐ylmethyl)phosphate (2‐bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4‐pmOpe)]NO₃}_n and [Cu₄Cl₆O(2‐bimOpe)₄] were determined by single‐crystal X‐ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ～19 μM ). [Ag(2‐bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin‐resistant Staphylococcus epidermidis, with MIC values of ～5 and ～10 μM , respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL^?1.     

Synthesis and Catalytic Activities of Silica-Supported Multifunctional Azo-Containing Schiff Base Complexes with Cu(II), Co(II), Ni(II) and Mn(II)

A novel 4-((5-formyl-2,4-dihydroxyphenyl)diazenyl)benzylphosphonic acid (FPABP) ligand was synthesized and bound to silica-gel which was activated with 3-aminopropyltriethoxysilane (APTES). Cu(II), Co(II), Ni(II) and Mn(II) complexes of silica-supported ligand (FDPDABP) were synthesized. The ligand and its complexes were characterized by using NMR, FT-IR, elemental analysis, ICP-OES and scanning electron Microscope (SEM). Catalytic properties of the complexes were investigated for the selective oxidation of cyclohexane under microwave power. SiO₂-FDPDABP-Cu(II) complex showed good catalytic activitiy for the selective oxidation of cyclohexane to cyclohexanol with 35.61% yield and cyclohexanone with 7.74% yield.     

Polymer Complexes. XLIII. EPR, Spectra, and Stereochemical Versatility of Novel Copper(II)Polymer Complexes

Copper(II) polymer complexes of empirical formula [Cu(ligand)₂X₂] (where X = Cl, Br, I, NO₃, and SO₄) and [Cu(ligand)(CH₃COO)₂] have been prepared with poly(3-phenylacrylidine semicarbazone). All the polymer complexes prepared have been characterized by elemental analysis, magnetic moment, conductance, IR, electronic, ¹H-NMR, and electronic paramagnetic resonance spectral studies. The polymer complexes [Cu(ligand)₂X₂] and [Cu(ligand) (CH₃COO)₂] may have tetragonal symmetry while the [Cu(ligand)₂( SO₄)₂] may be five-coordinate trigonal bipyramidal in structure. All complexes exhibit normal magnetic moments corresponding to one unpaired electron except [Cu(ligand)(CH₃COO)₂] which shows a subnormal magnetic moment. EPR spectra of the polymer complexes have been studied with a view to assigning their stereochemistries. Various EPR parameters have been calculated. The g, A, G values for all the polymer complexes are consistent with a tetragonal 1–5 and trigonal bipyramidal 6 stereochemistry in the Cu(II) polymer complexes of homopolymer.