Rare-earth chromium citrates as precursors for rare-earth chromites: lanthanum biscitrato chromium(III) dihydrate, La[Cr(C6H5O7)2]·2H

The thermal decomposition of lanthanum biscitrato chromium(III) dihydrate has been studied in static air and dynamic argon atmospheres. The complex decomposes in four steps: dehydration, decomposition of the citrate to an intermediate oxycarbonate, formation of LaCrO4(V) from oxycarbonate, and finally decomposition of LaCrO4(V) to LaCrO3. Formation of LaCrCrO4(V) requires the presence of oxygen The decomposition behaviour of a mechanical mixture of lanthanum citrate hydrate and chromium citrate hydrate was compared with that of the citrato complex. Both the starting material and the intermediates were characterized by X-ray diffraction, IR electronic and ESR spectroscopy, surface area and magnetic susceptibility measurements, as well as by chemical analysis. A scheme is proposed for the decomposition of lanthanum biscitrato chromium(III) dihydrate in air. LaCrO3 can be obtained at temperatures as low as 875 K by isothermal decomposition of the complex.

NQR study of complexes between p-dichlorobenzene and some aromatic π acceptors

The charge-transfer complexes of p-dichlorobenzene (PDB) with some aromatic π acceptors such as m-nitrobenzaldehyde (MNB), picric acid (PA), p-nitrobenzoic acid (PNB), and m-dinitrobenzene (MDNB) were prepared by slowly adding the acceptor to the molten donor and then cooling the mass to 15°C. The NQR frequencies of these complexes were measured at room temperature. Contrary to the theoretical prediction, the NQR shift is positive, indicating that the NQR shift in donor-acceptor complexes is indirectly related to the charge-transfer interaction. Bond properties are discussed in terms of frequency shift.

Quinone studies. Part III. Metal ion-catalysed oxidation of halophenols and halonaphthols by peroxidisulphate

Oxidation of representative halophenols and halonaphthols by peroxidisulphate has been examined. The influence of metallic ions, viz. Cu2+, Fe3+, Ag+, on the above reaction has been studied. Cu2+ ion-catalyzed oxidation gives halo-1, 4-quinones in excellent yield. Potassium bis(biureto)cuprate(III) complex also oxidises halophenols to halo-1, 4-quinones.

Computer simulation of protein—carbohydrate complexes: application to arabinose-binding protein and pea lectin

The CCEM method (Contact Criteria and Energy Minimisation) has been developed and applied to study protein-carbohydrate interactions. The method uses available X-ray data even on the native protein at low resolution (above 2.4 Å) to generate realistic models of a variety of proteins with various ligands.The two examples discussed in this paper are arabinose-binding protein (ABP) and pea lectin. The X-ray crystal structure data reported on ABP-β-l-arabinose complex at 2.8, 2.4 and 1.7 Å resolution differ drastically in predicting the nature of the interactions between the protein and ligand. It is shown that, using the data at 2.4 Å resolution, the CCEM method generates complexes which are as good as the higher (1.7 Å) resolution data. The CCEM method predicts some of the important hydrogen bonds between the ligand and the protein which are missing in the interpretation of the X-ray data at 2.4 Å resolution. The theoretically predicted hydrogen bonds are in good agreement with those reported at 1.7 Å resolution. Pea lectin has been solved only in the native form at 3 Å resolution. Application of the CCEM method also enables us to generate complexes of pea lectin with methyl-α-d-glucopyranoside and methyl-2,3-dimethyl-α-d-glucopyranoside which explain well the available experimental data in solution.

An ultraviolet photoelectron spectroscopic study of BF3–donor complexes

He i spectra of strong n–v type adducts of BF3 with H2O, CH3OH, (C2H5)2O, and CH3CN as well as of weak complexes of BF3 with NO and H2S are reported along with assignments based on MO calculations. The energy of the fluorine orbitals of BF3 is shown to be shifted in proportion to the strength of the donor–acceptor interaction. BF3 seems to form a contact pair with CS2.

Biosorption of iron(III) from aqueous solutions using the husk of Cicer arientinum

Iron is a major pollutant released as a by-product during several industrial operations especially during acid mining of metal ores. In this paper, the use of Bengal gram husk (husk of channa dal, Cicer arientinum) in the biosorption of Fe(III) from aqueous solutions is discussed. Parameters like agitation time, adsorbent dosage and pH were studied at different Fe(Ill) concentrations. The adsorption data fit well with Langmuir and Freundlich isotherm models. The adsorption capacity (q(max)) calculated from the Langmuir isotherm was 72.16 mg of Fe(III)/g of the biosorbent at an initial pH of 2.5. Desorption Studies were performed at different concentrations of hydrochloric acid showing that quantitative recovery of the metal ion is possible. The infrared spectra of the biomass before and after treatment with Fe(III), revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Fe(III) ions.

Crystal structure of 2-thiophene-2-yl-3(thiophene-2-carboxylideneamino)-1,2-dihydroquinazolin-4(3H)-one and the synthesis, spectral and thermal studies of its transition metal(II) complexes

The synthesis of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of a new ligand 2-thiophene-2-yl-3(thiophene-2-carboxylidene-amino)-1,2-dihydroquinazolin-4(3H)-one (TTCADQ) is described. The ligand and metal complexes were characterized by elemental analysis, conductivity measurements, spectral (u.v.-vis., i.r., 1D n.m.r., 2D hetcor and e.p.r.) and thermal studies. The formation of 1,2-dihydroquinazolin-4(3H)-one rather than hydrazone, in the reaction of aromatic aldehyde and o-aminobenzoylhydrazide is proved by single crystal X-ray diffraction and 2D hetcor n.m.r. studies. On the basis of elemental analysis, u.v.-vis.spectroscopy and magnetic moment studies, six coordinate geometry for all the complexes was proposed. The i.r. spectral studies reveal the bidentate behaviour of the ligand.

Photocytotoxic and anaerobic DNA cleavage activity of binuclear 3,3 '-dithiodipropionic acid cobalt(II) complexes having phenanthroline bases

Dicobalt(II) complexes [{(B)Co-11)(2)(mu-dtdp)(2)] (1-3) of 3,3'-dithiodipropionic acid (dtdp) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 2) and dipyrido13,2-a:2',3'-clphenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The elemental analysis and mass spectral data suggest binuclear formulation of the complexes. The redox inactive complexes have magnetically non-interacting dicobalt(II) core showing magnetic moment of similar to 3.9 p per cobalt(II) center. The complexes show good binding propensity to calf thymus DNA giving K-b values within 4.3 x 10(5)-4.0 x 10(6) M-1. Thermal melting and viscosity data predict DNA groove binding and/or partial intercalative nature of the complexes. The complexes show significant anaerobic DNA cleavage activity in green light under argon atmosphere possibly involving radical species generated from the disulfide moiety in a type-I pathway. The DNA cleavage reaction under aerobic medium in green light is found to involve hydroxyl radical species. The dppz complex 3 exhibits significant photocytotoxicity in HeLa cervical cancer cells with an IC50 value of 2.31 mu M in UV-A light of 365 nm, while it is essentially non-toxic in dark giving an IC50 value of >200 mu M. A significant reduction of the dark toxicity of the organic dppz base (IC50 = 8.3 mu M in dark) is observed on binding to the cobalt(II) center while essentially retaining its photocytotoxicity in UV-A light (IC50 = 0.4 mu M). (C) 2010 Elsevier Ltd. All rights reserved.