Interactions of biotin with metal ions. X-ray crystal structure of the polymeric biotin--silver(I) nitrate complex: metal bonding to thioether and ureido carbonyl groups

X-ray structure analysis of the silver(I) complex of d-(+)-biotin, [Ag(biotin)(NO3)] X 0.5H2O, shows the complex to be polymeric with the silver ion coordinated tetrahedrally to nitrate and to three different biotin molecules. Binding to the latter involves two thioether sulfur atoms in the cis and trans direction with respect to the ureido ring, and one ureido carbonyl oxygen atom. The biotin carboxylate group is probably protonated and not coordinated with the silver ion.     

Interaction of adenosine 5'-triphosphate with metal ions X-ray structure of ternary complexes containing Mg(II), Ca(II), Mn(II), Co(II), ATP and 2,2'-dipyridylamine

The X-ray structures of the isomorphous Mg2+, Ca2+, Mn2+ and Co2+ complexes of ATP have been determined. The metal ions are wrapped in hexa-coordination by the alpha, beta and gamma phosphate groups of two ATP molecules thus blocking the interaction of the metal ions with the adenine base. A second metal ion which is fully hydrated, M(H2O)2+(6), is engaged in a strong hydrogen bond with the gamma phosphate group of ATP and suggests a possible step in facilitating the cleavage between the beta and gamma phosphates in phosphoryl transfer reactions.     

Interaction of beta-cyclodextrin with cadmium(II) ions

Reduction of Cd(II) on a dropping mercury electrode was used to study interaction of β-cyclodextrin with Cd(II) ions. It was found that Cd(II) forms Cdβ-CD(OH)₂²⁻ hydroxy-complex with the anion of β-cyclodextrin in alkaline solutions (pH>11), the logarithm of stability constant being 10.4±0.1 (20 °C; I=1.0). The calculated value of the diffusion coefficient equal to 1.0×10⁻⁶ cm²/s shows a large size Cd(II) complex species formation in alkaline solutions containing β-CD.     

Characterization and crystal structure of cadmium(II) halide complexes with amino acids and their derivatives: VII. Crystal structures of aquadibromo(3-aminopropanoic acid)cadmium(II), dichloro(4-aminobutanoic acid)cadmium(II), diaquabis(aminohexanoic acid)cadmium(II) tetrachlorocadmium(II), and dibromo(azetidine-3-carboxylic acid)cadmium(II)

Seven cadmium complexes: [CdX2(Hapro)(H2O)n] (X: Cl(1), Br(2)), [CdX2(Hgaba)] (X: Cl(3), Br(4)), [Cd(Hahex)2(H2O)2][CdCl4] (5), and [CdX2(Haze-3)](H2O)n (X: Cl(6), Br(7)) have been prepared and investigated by means of IR and FT Raman spectra. The crystal and molecular structures of 2, 3, 5 and 7 were determined by a single-crystal X-ray diffraction method. In complex 2, the cadmium atom is in a distorted octahedral geometry, ligated by two carboxyl oxygen atoms of Hapro, a water molecule, and three bromine atoms; one is terminal and each of the other two is bridging two cadmium atoms to make a polymer. The structure of 3 consists of one-dimensional polymers bridged by two chlorine atoms and a carboxyl group. The carboxyl oxygen atoms of Hgaba coordinate forkedly to two cadmium atoms. The cadmium atom of [Cd(Hahex)2(H2O)2]2+ in complex 5 is in a distorted octahedral geometry, ligated by four carboxyl oxygen atoms of two molecules of Hahex and by two water molecules. [Cd(Hahex)2(H2O)2]2+ exists between two layers which are formed of infinite [CdCl4]2- chains. The carboxyl oxygen atoms of Hahex coordinate to the same cadmium atom. In complex 7, the cadmium atom is ligated by two carboxyl oxygen atoms and four bridging bromine atoms to make a polymer.     

Interactions of metal ions with mu-monothiopyrophosphate.

mu-Monothiopyrophosphate (MTP) binds monovalent and divalent metal ions with dissociation constants (Kd) similar to those for pyrophosphate (PPi). The values of Kd for metal-MTP complexes are the following, as measured kinetically in the hydrolysis of MTP (microM): Mg2+, 32 +/- 4; Mn2+, 5.4 +/- 1.4; and Co2+, 27 +/- 15. The thermodynamically measured (EPR) values for Mg2+ and Co2+ are 28 +/- 13 microns and 11 +/- 4 microM, respectively; and the Kd for the complex MnPPi is 3.4 +/- 0.5 microM. The metal-MTP complexes undergo hydrolysis at rates modestly faster or slower than the rate at which MTP itself reacts. The complexes MgMTP2-, CoMTP2-, and MnMTP2- undergo hydrolytic cleavage with release of thiophosphate with observed first-order rate constants of 1.6 x 10(-2) min-1, 2.3 x 10(-2) min-1, and 0.6 x 10(-2) min-1, respectively, at 35 degrees C, compared with 1.1 x 10(-2) min-1 for MTP4- under the same conditions. Alkali metal cations also stimulate or retard the hydrolysis of MTP. At 25 degrees C and pH 12.2, the observed rate constant for tetramethylammonium MTP4- is 2.1 x 10(-3) min-1, and the estimated rate constants (min-1) for saturating alkali metals under the same conditions are as follows: Li+, 0.25 x 10(-3); Na+, 3.9 x 10(-3), K+, 6.7 x 10(-3); and Cs+, 6.7 x 10(-3). Divalent metal ions markedly retard the hydrolysis of MTP at pH 7 and 8 because complexation shifts the pH rate profile more than 2 pH units toward the acid side.(ABSTRACT TRUNCATED AT 250 WORDS)     

Interactions of DNA with divalent metal ions. II. Proton relaxation enhancement studies

The extent and modes of binding of the divalent metal ions Mn²⁺ and Co²⁺ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA–bound Mn²⁺ and Co²⁺ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn²⁺ and Co²⁺ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn²⁺ and Co²⁺ upon binding to DNA. An average 2–3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn²⁺ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn²⁺ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.     

Sugar adducts with alkaline earth metal ions. Interaction of L-arabinose with Sr(II) and Ba(II) ions and the effects of metal ion binding on the sugar anomeric configurations

The reaction between L-arabinose and hydrated Sr(II) or Ba(II) halide salts has been studied in H2O solution and adducts of the type M(L-arabinose)X(2).4H(2)O, where M = Sr(II) or Ba(II) and X = Cl- or Br- have been isolated and characterized by means of Fourier transform infrared spectroscopy, 1H-NMR spectroscopy, molar conductivity and X-ray powder diffraction measurements. Due to the marked spectral similarities with those of the structurally known Ca(L-arabinose)X2 . 4H2O (X= Cl- or Br-) compounds, the Sr(II) and the BA(II) ions are eight-coordinated, binding to two l-arabinose molecules via O1, O5 of the first and O3, O4 of the second sugar moiety and to four H2O molecules. 1H-NMR spectroscopy indicated that the free L-arabinose has the beta-anomer configuration in aqueous solution, whereas the alpha-anomer isomer is preferred by Mg(II), Ca(II), Sr(II) and Ba(II) ions, on complexation.     

Interactions of Hg(II) ions with DNA as revealed by CD measurements.

The circular dichroism spectra of Hg(II) complexes with native calf thymus DNA, chemically methylated Streptomyces chrysomallus DNA and with Ag(I)-DNA complexes were measured in the region of 220 - 340 nm. As a main result a conversion of the conservative CD spectrum of DNA to a distinct nonconservative type of CD spectrum for the complexes occurs with increasing Hg(II) concentration. The CD spectra of the Hg(II) complexes as well as some additional arguments strongly support the idea, that DNA in the complex undergoes a structural transition to a more condensed state with 4 -like character.     

Removal characteristics of metal ions using degreased coffee beans: adsorption equilibrium of cadmium(II)

The feasibility of using coffee beans after being dripped and degreased (DCB) as an adsorbent for base metals such as copper(II), zinc(II), lead(II), iron(III) and cadmium(II) were examined. The compositions of the DCB were characterized by Fourier transform infrared spectroscopy, scanning electronic micrograph and fluorescent X-ray. It was found that DCB contain sulfur and calcium from the analysis using fluorescent X-ray. The plant cell wall in DCB has the porous structure from the scanning electron microscopy (SEM) analysis, and the specific surface area was determined to be 1.2 m2/g using the specific surface area analyzer. Batch adsorption experiments on DCB were carried out at various pHs in order to elucidate the selectivity of metal ions. All metals were adsorbed at low pH region (3.0-5.0). Of particular interest was the adsorption characteristics of cadmium(II) on DCB. The adsorption isotherm for cadmium(II) at pH 8 fitted with a Langmuir equation to yield an adsorption equilibrium constant of 55.2 mmol dm(-3) and an adsorption capacity of 5.98 x 10(-2) mmol g(-1). The desorption of cadmium(II) was easily achieved over 90% by a single batchwise treatment with an aqueous solution of hydrochloric acid or nitric acid at more than 0.01 mol dm(-3). These results suggested that DCB behaves as a cation exchanger.     

Complex-formation and redox reactions of bilirubin and biliverdin with zinc(II), cadmium(II) and copper(II) ions

Transition metal complexes of bilirubin and biliverdin were studied spectrophotometrically, in DMSO and in a boric acid-NaOH buffer mixture at pH 10.5. In the zinc(II) and cadmium(II)- bilirubin systems, 2:1 complexes are formed. Both in aqueous and in DMSO medium, the copper(II) ion oxidizes bilirubin to biliverdin. With all three metal ions, biliverdin forms 1:1 complexes, the stabilities of which are higher than those of the corresponding bilirubin complexes. Accordingly, these metal ions accelerate the oxidative transformations of bilirubin.     

Differences in the binding modes of phytochelatin to cadmium (II) and Zinc(II) ions

An ¹H NMR (nuclear magnetic resonance) spectroscopic structural analysis of Cd²⁺ complexes formed with the pentapeptide phytochelatin, (NH₃)⁺−(ψ-Glu-Cys)₂−Gly−COO−(PC₂), at a pH of 7.5 showed that the two thiol groups of the Cys residues and either the carbonyl or amide group of the peptide bond between Glu1 and Cys1 act as possible donor groups in the complexes at Cd²⁺/PC₂ ratios up to 0.4. As the ratio increases, the carboxylate group of Glu2 and either the carbonyl or amide group of the peptide bond between Cys1 and Glu2 comes to serve as a donor group. The manner in which Cd²⁺ forms complexes with PC₂ is distinctly different from Zn²⁺ and might account for the role of phytochelatin in Cd²⁺ detoxification. Electron absorption spectrometry demonstrated that the Cd²⁺ complexes are coordinated in a tetrahedral fashion by four thiol groups and that several sulfur atoms might bridge Cd²⁺ ions, resulting in the formation of polynuclear complexes. This contrasts with Zn²⁺ complex formation, which consists exclusively of a 1:1 complex.     

Speciation of ternary complexes of lead(II), cadmium(II) and mercury(II) with L-dopa and phenanthroline in propanediol-water mixtures

Abstract

The formation constants of ternary complexes of title systems have been determined pH-metrically in biologically relevant conditions at an ionic strength of 0.16 mol dm^-3 and 303 K. The overall stability constants have been evaluated using MINIQUAD75 computer program. The complexation equilibria have been derived on the basis of species distribution diagram. In the present study L-Dopa and 1, 10-phenanthroline are found to be compatible ligands, proving greater stability of ternary complexes as compared to binary ones. The trend in variation of stability constants with change in dielectric constant of medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of propanediol-water mixtures are also presented. The factors responsible for the compatibility of both the ligands have also been discussed.     

Interactions of metal ions with two quinolone antimicrobial agents (cinoxacin and ciprofloxacin). Spectroscopic and X-ray structural characterization. Antibacterial studies

Several novel metal-quinolone compounds have been synthesized and characterized by analytical, spectroscopic and X-ray diffraction methods. The crystal structure of the four compounds, Na(2)[(Cd(Cx)3)(Cd(Cx)3(H2O))].12H2O, [Co(Cp)2(H2O)2].9H2O, [Zn(Cp)2(H2O)2].8H2O and [Cd(HCp)2(Cl)2].4H2O, is presented and discussed: HCx=1-ethyl-1,4-dihydro-4-oxo(1,3)-dioxolo(4,5-g)cinnoline-3-carboxylic acid and HCp=1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid. In all these compounds the quinolone acts as a bidentate chelate ligand that binds through one carboxylate oxygen atom and the exocyclic carbonyl oxygen atom. Complexes of ciprofloxacin were screened for their activity against several bacteria, showing activity similar to that of the ligand. In addition, the number of bacteria killed after 3 h of incubation with the ligand, [Co(Cp)2(H2O)2].9H2O, Ni(Cp)2.10H2O and Cu(Cp)2.6H2O, was determined against S. aureus ATCC25923. There is a direct relationship between the growth rate and the lethal rate. Against growing bacteria, the ligand is the most bactericidal and Cu(Cp)2.6H2O is the less bactericidal. On the contrary, against non-dividing bacteria, the complexes were more bactericidal than the ligand, with Cu(Cp)(2).6H(2)O the most bactericidal compound.     

Interaction of metal ions with nucleic acids and related compounds. II. Studies on Au(III)-nucleic acid system

The nature of interaction of Au(III) with nucleic acids was studied by using methods such as uv and ir spectrophotometry, viscometry, pH titrations, and melting-temperature measurements. Au(III) is found to interact slowly with nucleic acids over a period of several hours. The uv spectra of native calf-thymus DNA 9pH 5.6 acetate buffer containing (0.01M NaCIO₄) showed a shift in λ max to high wavelengths and an increase in optical density at 260 nm. There was a fourfold decrease in viscosity (expressed as η_sp/c). The reaction was faster at pH 4.0 and also with denatured DNA (pH 5.6) and whole yeast RNA (pH 5.6). The order of preference of Au(III) (as deduced from the time of completion of reaction) for the nucleic acids in RNA > denatured DNA > DNA. The reaction was found to be completely reversible with respect KCN. Infrared spectra of DNA-Au(III) complexes showed binding to both the phosphate and bases of DNA. The same conclusions were also arrived at by melting-temperature studies of Au(III)-DNA system. pH titrations showed liberation of two hydroxylions at r = 0.12 [r = moles of HAuCl₄ added per mole of DNA-(P)] and one hydrogen ion at r = 0.5. The probable binding sites could be N(1)/N(7) of adenine, N(7) and/or C(6)O of guanine, N(3) of cytosine and N(3) of thymine. DNAs differing in their (G = C)-contents [Clostridium perfingens DNA(G = C, 29%), salmon sperm DNA (G + C, 42%) and Micrococcus lysodeikticus DNA(G + C, 29%), salmon sperm DNA (G = C, 72%)] behaved differently toward Au(III). The hyperchromicity observed for DNAs differing in (G + C)-content and cyanide reversal titrations indicate selectivity toward ( A + T)-rich DNA at lw values of r. Chemical analysis and job's continuous variation studies indicated the existence of possible complexes above and below r = 1. The results indicate that Au(III) ions probably bind to hte phosphate group in the initial stages of the reaction, particularly at low values of r, and participation of the base interaction also increases. Cross-linking of the two strands by Au(III) may take place, but a complete collapse of the doulbe helix is not envisaged. It is probable that tilting of the bases or rotaiton of the bases around the glucosidic bond, resulting in a significant distrotion of the double helix, might take place due to binding of Au(III) to DNA.     

Interaction of metal ions with humic-like models. Part VII. Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of 2,5-dihydroxybenzoic acid

Complexes of formula M(2,5-DHB)₂4H₂O (M = Mn, Co, Ni, Zn, Cu and Cd; 2,5-DHB = 2,5-dihydroxybenzoate) were prepared and characterized by means of infrared and electronic spectroscopy, and by electron spin resonance. For the Zn complex the crystal and molecular structure was also determined by single-crystal X-ray diffraction analysis. The crystal is orthorhombic, space group Pbca (No. 61), with a = 18.503(4), b = 13.536(3), c = 6.900(2) Å, and Z = 4. The final refinement used 877 reflections and gave a residual R value of 0.041. The complex has slightly compressed octahedral coordination, with the zinc atom bound to two monodentate carboxylate groups lying in trans positions and four water molecules. X-ray data and infrared spectra show the Mn, Co, Ni, Zn and Cd complexes to be isostructural with the Zn compound. The electronic, infrared and ESR spectra of the copper(II) complex are consistent with a CuO_4? based chromophore involving two water molecules and two monodentate carboxylate groups in the metal plane, and long axial contacts.     

Interaction of transition metal ions with Z form poly d(A-C).poly d(G-T) and poly d(A-T) studied by I.R. spectroscopy.

Interactions between Ni2+, Co2+ and purine bases have been studied by I.R. spectroscopy in the case of double stranded regularly alternating purine-pyrimidine polynucleotides poly d(A-T), poly d(A-C).poly d(G-T) and poly d(G-C). The spectra of polynucleotide films have been recorded in hydration and salt content conditions which correspond to the obtention of the classical right-handed (A,B) and left-handed (Z) helical conformations. Selective deuteration of the 8C site of purines has been obtained and is used to detect interactions between the transition metal ions and the adenine or guanine bases. The spectral region between 1500 and 1250 cm-1 corresponding to base in-plane vibrations and involving also the glycosidic linkage torsion is discussed in detail. The selective interaction between the transition metal ion and the 7N site of the purine base is considered to be partly responsible for the stabilization of the base in a syn conformation, which favours the adoption by the polynucleotide (poly d(G-C), poly d(A-C).poly d(G-T) or poly d(A-T)) of a Z type conformation.