Solution structure, oxidative DNA damage, biological activity and molecular docking of ternary copper(II) L-argininato complexes.

Continuing our search for metal drugs with markedly higher toxicity to cancer cells than to normal cells, we evaluated the effect of 2,2'-bipyridine (bpy) as a co-ligand in the compounds [Cu(μ-O,O'-NO)(L-Arg)(bpy)]NO} (1) and [CuCl(L-Arg)(bpy)]Cl·3HO (2) (L-Arg = L-arginine), on DNA interaction, cytotoxic and antiproliferative activity, compared to the effects induced by other co-ligands i.e. 1,10-phenanthroline (phen) and SCN ions, in similar Cu(II) compounds we have studied previously.

Unique Use of Dibromo-L-Tyrosine Ligand in Building of Cu(II) Coordination Polymer-Experimental and Theoretical Investigations.

Although the crystals of coordination polymer {[CuCl(O,O'-L-BrTyr)]}n (1) (L-BrTyr = 3,5-dibromo-L-tyrosine) were formed under basic conditions, crystallographic studies revealed that the OH group of the ligand remained protonated. Two adjacent [CuCl(L-BrTyr)] monomers, bridged by the carboxylate group of the ligand in the bidentate bridging mode, are differently oriented to form a polymeric chain; this specific bridging was detected also by FT-IR and EPR spectroscopy. Each Cu(II) ion in polymeric compound 1 is coordinated in the xy plane by the amino nitrogen and carboxyl oxygen of the parent ligand and the oxygen of the carboxyl group from the symmetry related ligand of the adjacent [Cu(L-BrTyr)Cl] monomer, as well as an independent chlorine ion.

Hybrid Cu-Containing Compounds Based on Lacunary Strandberg Anions: Synthesis under Mild Conditions, Crystal Structure, and Magnetic Properties.

A one-pot reaction of a copper source (metallic powder Cu or Cu salts) and bpy (bpy = 2,2'-bipyridine) in the presence of (NH)HPO and (NH)MoO·4HO yields heterometallic hybrid compounds of the general type {[Cu(bpy)(HO)][PMoO]}. The structures exhibit a number of phosphomolybdate POMs including not only a common Strandberg anion [PMoO] but also its unprecedented bi- and trilacunary derivatives [PMoO] and [PMoO]. The structural determinants including the metal source (copper powder copper salts), counterion of the salts, and stoichiometry of the reagents were examined.

Isothiocyanate l-argininato copper(II) complexes - Solution structure, DNA interaction, anticancer and antimicrobial activity.

l-argininato copper(II) complexes have been intensively investigated in a variety of diseases due to their therapeutic potential. Here we report the results of comprehensive structural studies (ESI-MS, NIR-VIS-UV, EPR) on the complexes arising in aqueous solutions of two ternary copper(II) complexes with molecular formulas from crystal structures, [Cu(l-Arg)(NCS)](NCS)·HO (1) and [Cu(l-Arg)(NCS)] (2) (l-Arg = l-arginine). Reference systems, the ternary Cu(II)/l-Arg/NCS as well as binary Cu(II)/NCS and Cu(II)/l-Arg, were studied in parallel in aqueous solutions by pH-potentiometric titration, EPR and VIS spectroscopy to characterize stability, structures and speciation of the formed species over the broad pH range.

Investigation of vanadium(III) and vanadium(IV) compounds supported by the linear diaminebis(phenolate) ligands: correlation between structures and magnetic properties.

A family of oxidovanadium(iv) compounds containing linear diaminebis(phenolate (salans) L1-5 ligands (L1 = [MeNCH2CH2NMe(CH2-4-CMe2CH2CMe3-C6H3O)2]2-; L2 = [MeNCH2CH2NMe(CH2-4-CH3-C6H3O)2]2-; L3 = [MeNCH2CH2NMe(CH2-4-Cl-C6H3O)2]2-; L4 = {MeNCH2CH2NMe[CH2-4,6-(CH3)2-C6H2O]2}2-; and L5 = {MeNCH2CH2NMe[CH2-4,6-(Br)2-C6H2O]2}2-) and non-oxidovanadium(iii) with L2,4 and acac ligands has been prepared and characterized by chemical and physical techniques. Reactions of [VO(acac)2] with ligand precursors H2L2,4 in toluene or hexane afforded vanadium(iii) compounds [V(L-κ4ONNO)(acac)] (1, L2; 2, L4), while the use of acetonitrile or ethanol led to the formation of dimeric oxidovanadium(iv) [(VO)2(μ-L-κ4ONNO)2] (3, L1; 4, L2; 5, L3) and monomeric [VO(L-κ4ONNO)] (6, L4, 7, L5) compounds. As shown by X-ray crystallography, compounds 1 and 2 are monomeric, in which the chelating ligands afford octahedral cis-α geometry at the vanadium center.

Dinuclear Copper(II) Complexes with Schiff Bases Derived from 2-Hydroxy-5-Methylisophthalaldehyde and Histamine or 2-(2-Aminoethyl)pyridine and Their Application as Magnetic and Fluorescent Materials in Thin Film Deposition.

Two Cu(II) complexes, and , with tridentate Schiff bases derived from 2-hydroxy-5-methylisophthalaldehyde and histamine or 2-(2-aminoethyl)pyridine , respectively, were obtained and characterized by X-ray crystallography, spectroscopic (UV-vis, fluorescence, IR, and EPR), magnetic, and thermal methods. Despite the fact that the chelate formed by the NNO ligand donors (C26-C25H-C24H-N23=C23H-C22-C19Ph(O1)-C2(Ph)-C3H=N3-C4H-C5H-C6 fragment) are identical, as well as the synthesis of Cu(II) complexes (Cu:L = 2:1 molar ratio) was performed in the same manner, the structures of the complexes differ significantly. The complex , {[Cu(L1)Cl][CuCl]}·2MeCN·2HO, consists of [Cu(L1)Cl] units in which Cu(II) ions are bridged by the ligand oxygen and each of these Cu(II) ions is connected with Cu(II) ions of the next dimeric unit via two bridging Cl ions to form a chain structure.

How accurate is density functional theory in predicting spin density? An insight from the prediction of hyperfine coupling constants.

Electron paramagnetic resonance (EPR) spectroscopy has been proven to be an important technique for studying paramagnetic systems. Probably, the most accessible EPR parameter and the one that provides a significant amount of information about molecular structure and spin density is the hyperfine coupling constant (HFCC). Hence, accurate quantum-chemical modeling of HFCCs is frequently essential to the adequate interpretation of EPR spectra.

Role of architecture of N-oxide surfactants in the design of nanoemulsions for Candida skin infection.

In this work we present comprehensive research on the formation, stability and structural properties of oil-in-water (o/w) nanoemulsions with the ability for topical administration, penetration of the skin and acting as antifungal agents against C. albicans. The studied nanoemulsions were composed of different ratios of double-head - single-tail surfactants {1-bis{[3-(N,N-dimethylamino)ethyl]amido}alkane-di-N-oxides (C-MEDA), N,N-bis[3,3'-(dimethyl-amino)propyl]alkyl-amide di-N-oxides (C(DAPANO)} and single-head - single-tail surfactants {2-(alkanoylamino)-ethyldimethyl-amine-N-oxides (C-EDA), and 3-(alkanoylamino) propyldimethylamine-N-oxides, (C-PDA)} added to the oil {isooctane IO, isopropyl myristate IPM or glyceryl monocaprylate GM as (O)} and to the water phase (W).

A Cu/Zn heterometallic complex with solvent-binding cavity, catalytic activity for the oxidation of 1-phenylethanol and unusual magnetic properties.

Mononuclear and polymeric complexes of zinc(ii) and copper(ii) have been synthesized using two isomers of the hemi-salen ligand with a different mutual orientation of donor atoms. The heterometallic Cu/Zn metallocycle features a catalytic niche filled with the molecule of water and molecules of methanol. This unusual compound exhibits both pronounced catalytic activity in the reaction of oxidation of a secondary alcohol to ketone and field induced slow magnetic relaxation, which is a very rare phenomenon among Cu(ii) complexes.

Synthesis, structure and biological evaluation of ruthenium(III) complexes of triazolopyrimidines with anticancer properties.

Six novel ruthenium(III) complexes of general formula [RuCl(L)] (1,3,5) and [RuCl(HO)(L)] (2,4,6), where L stands for three different triazolopyrimidine-derived ligands, are reported. The compounds have been structurally characterized (IR, EPR, SCXRD), and their magnetic moments have been determined. The single-crystal X-ray diffraction study revealed a slightly distorted octahedral geometry of the Ru(III) complexes with mer configuration in 1 and 5, and fac configuration in 3.

X-ray structure and magnetic and fluorescence characteristics of new Cu(ii) complexes with Schiff bases derived from 2-(2-aminoethyl)pyridine and 2-hydroxy-1-naphthaldehyde; morphology and fluorescence of their thin films.

Cu(ii) complexes with tridentate Schiff bases derived from 2-(2-aminoethyl)pyridine and 2-hydroxy-1-naphthaldehyde and COO-, Cl- and NO3- as ligands were obtained and characterized by crystal and molecular, spectroscopic (UV-Vis, fluorescence, IR, and EPR), magnetic and thermal methods. The X-ray crystal structure analysis revealed a distorted square planar geometry for [Cu(ii)(PEMN)CH3COO]CHCl3, 1, and [Cu(ii)(PEMN)Cl], 2, and a distorted square-pyramidal geometry for [Cu(ii)(PEMN)NO3], 3, corresponding to the values of EPR g-matrix diagonal components. The copper(ii) complexes exhibited fluorescence in solution in the range of 370-410 nm.

Copper(II) Complexes with Bulky N-Substituted Diethanolamines: High-Field Electron Paramagnetic Resonance, Magnetic, and Catalytic Studies in Oxidative Cyclohexane Amidation.

The novel coordination compounds [Cu(H BuDea)(OAc)] (1) and [Cu(H BuDea)Cl]· nHO (2) have been prepared through the reaction of the respective copper(II) salts with N- tert-butyldiethanolamine (H BuDea, for 1) or N-butyldiethanolamine (H BuDea, for 2) in methanol solution. Crystallographic analysis reveals that, in spite of the common binuclear {Cu(μ-O)} core, the supramolecular structures of the complexes are drastically different. In 1 binuclear molecules are linked together by H-bonds into 1D chains, while in 2 the neighboring pairs of binuclear molecules are H-bonded, forming tetranuclear aggregates.

Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with OH, persistent DPPH and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested.

Strategies for overcoming tropical disease by ruthenium complexes with purine analog: Application against Leishmania spp. and Trypanosoma cruzi.

Tropical diseases currently constitute a major health problem and thus a challenge in the field of drug discovery. The current treatments show serious disadvantages due to cost, toxicity, long therapy duration and resistance, and the use of metal complexes as chemotherapeutic agents against these ailments appears to be a very attractive alternative. Herein, we describe three newly synthesized ruthenium complexes with a bioactive molecule, the purine analogue 5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine (tmtp): cis,fac-[RuCl(dmso)(tmtp)] (1), mer-[RuCl(dmso)(HO)(tmtp)]·2HO (2) and fac,cis-[RuCl(HO)(tmtp)] (3).

Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl, Br; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions.

A series of monochloride-bridged, dinuclear metallacycles of the general formula [M(μ-Cl)(μ-L)](ClO) have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (L), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (L*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO)·6HO, MCl, and the ligand, L or L*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M(μ-Cl)(μ-L)](BF), L = L, M = Cu(II), and L = L*, M = Co(II), Cu(II), were prepared from the reaction of [M(μ-F)(μ-L)](BF) and (CH)SiCl.

Oxidation of 1-Methyl-1-phenylhydrazine with Oxidovanadium(V)-Salan Complexes: Insight into the Pathway to the Formation of Hydrazine by Vanadium Nitrogenase.

A series of oxidovanadium(V) complexes [VO(L-κO,N,N,O)(OR)] (1a, R = Et, L = L; 1b, R = Me, L = L; 2, R = Me, L = L; 3, R = Me, L = L) were synthesized by the σ-bond metathesis reaction between [VO(OR)] and the linear diaminebis(phenol) derivatives HL (salans) containing different para-substituents on the phenoxo group [CMeCHCMe, L; Me, L; Cl, L]. As shown by X-ray crystallography complexes 1a, 1b, and 2 exhibit cis-α geometry, do have a stereogenic vanadium center, and exist as a racemic mixture of the Δ cis-α and Λ cis-α enantiomers. In solution, as demonstrated by H and V NMR investigations, the structures of complexes 1-3 are consistent with their solid state.

Metal-Metal Interactions in Trinuclear Copper(II) Complexes [Cu3(RCOO)4(H2TEA)2] and Binuclear [Cu2(RCOO)2(H2TEA)2]. Syntheses and Combined Structural, Magnetic, High-Field Electron Paramagnetic Resonance, and Theoretical Studies.

The trinuclear [Cu3(RCOO)4(H2TEA)2] copper(II) complexes, where RCOO(-) = 2-furoate (1), 2-methoxybenzoate (2), and 3-methoxybenzoate (3, 4), as well as dimeric species [Cu2(H2TEA)2(RCOO)2]·2H2O, have been prepared by adding triethanolamine (H3TEA) at ambient conditions to hydrated Cu(RCOO)2 salts. The newly synthesized complexes have been characterized by elemental analyses, spectroscopic techniques (IR and UV-visible), magnetic susceptibility, single crystal X-ray structure determination and theoretical calculations, using a Difference Dedicated Configuration Interaction approach for the evaluation of magnetic coupling constants. In 1 and 2, the central copper atom lies on an inversion center, while in the polymorphs 3 and 4, the three metal centers are crystallographically independent.

Zinc(II) and copper(II) complexes with hydroxypyrone iron chelators.

High stability of the complexes formed at physiological pH is one of the basic requisites that a good iron chelator must possess. At the same time the chelating agent must be selective toward iron, i.e.

Toward an Understanding of the Ambiguous Electron Paramagnetic Resonance Spectra of the Iminoxy Radical from o-Fluorobenzaldehyde Oxime: Density Functional Theory and ab Initio Studies.

Iminoxy radicals (R1R2C═N—O•) possess an inherent ability to exist as E and Z isomers. Although isotropic hyperfine couplings for the species with R1 = H allow one to distinguish between E and Z, unequivocal assignment of the parameters observed in the EPR spectra of the radicals without the hydrogen atom at the azomethine carbon to the right isomer is not a simple task. The iminoxyl derived from o-fluoroacetophenone oxime (R1 = CH3 and R2 = o-FC6H5) appears to be a case in point.

pH-dependent formation of Hg(II)-semiquinone complexes from natural phenols.

The ability of various natural phenols to form Hg(II)-semiquinone complexes was tested in the pH range of 2.8-12. EPR experiments performed at 9.

Syntheses, structural, magnetic, and electron paramagnetic resonance studies of monobridged cyanide and azide dinuclear copper(II) complexes: antiferromagnetic superexchange interactions.

The reactions of Cu(ClO4)2 with NaCN and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) yield [Cu2(μ-CN)(μ-Lm)2](ClO4)3 (1) and [Cu2(μ-CN)(μ-Lm*)2](ClO4)3 (3). In both, the cyanide ligand is linearly bridged (μ-1,2) leading to a separation of the two copper(II) ions of ca. 5 Å.

Coordinative interaction of microcrystalline chitosan with oxovanadium (IV) ions in aqueous solution.

Background: Chitosan, a non-toxic, biodegradable and biocompatible polysaccharide has attained great interest in pharmaceutical applications, as versatile drug delivery agent. Chitosan has been already shown to serve as vehicle for sustained drug release by chitosan-vanadium(IV) complex from a chitosan gel matrix. Therefore, chitosan gel proved to retain vanadium and preserve its insulin-mimetic efficacy.

Structural studies of copper(II) complexes with 2-(2-aminoethyl)pyridine derived Schiff bases and application as precursors of thin organic-inorganic layers.

Cu(ii) complexes with Schiff bases derived from 2-pyridin-2-ylethanamine were obtained and characterized by UV-Vis, fluorescence, and IR spectra. The X-ray crystal structures determined for [Cu(ii)(epy(di-t-Buba))Cl] × 0.042H2O and [Cu(ii)(epy(di-t-Buba))O2CCH3] revealed tetrahedral distortion of the Cu(ii) coordination sphere in the solid phase.

Eight- and six-coordinated Mn(II) complexes of heteroaromatic alcohol and aldehyde: crystal structure, spectral, magnetic, thermal and antibacterial activity studies.

Crystal, molecular and electronic structure of new manganese(II) compounds: [Mn(2-CH2OHpy)2(NO3)2] (1), [Mn(4-CHO-5-MeIm)2(NO3)2] (2) and [Mn(4-CHO-5-MeIm)2Cl2] (3), where 2-hydroxymethylpyridine (2-CH2OHpy) and 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm), have been characterised using X-ray, spectroscopic, magnetic and TG/DTG data. In compounds 1 and 2, the Mn(II) ion is eight-coordinated forming distorted pseudo-dodecahedron, that is rather unusual for the manganese(II) complexes, whereas in 3 the Mn(II) ion environment is a distorted octahedron. The high coordination number (CN=8) of 1 and 2 results from bidentate character of the nitrate ligands.

Hydroxide-bridged cubane complexes of nickel(II) and cadmium(II): magnetic, EPR, and unusual dynamic properties.

The reactions of M(ClO4)2·xH2O (M = Ni(II) or Cd(II)) and m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) in the presence of triethylamine lead to the formation of hydroxide-bridged cubane compounds of the formula [M4(μ3-OH)4(μ-Lm)2(solvent)4](ClO4)4, where solvent = dimethylformamide, water, acetone. In the solid state the metal centers are in an octahedral coordination environment, two sites are occupied by pyrazolyl nitrogens from Lm, three sites are occupied by bridging hydroxides, and one site contains a weakly coordinated solvent molecule. A series of multinuclear, two-dimensional and variable-temperature NMR experiments showed that the cadmium(II) compound in acetonitrile-d3 has C2 symmetry and undergoes an unusual dynamic process at higher temperatures (ΔGLm‡ = 15.