1,3-dipolar cycloaddition of CS2 to the coordinated azide in the cyclopalladated [Pd(bzan)(mu-N-3)](2). Crystal and molecular structure of di(mu-N,S-1,2,3,4-thiatriazole-5-thiolate)bis[(benzylideneaniline-C-2,N)palladium(II)]

The compound [Pd(bzan)(mu -N-3)](2) 1, bzan = benzylideneaniline, was prepared from [Pd(bzan) (mu -OOCCH3)](2) by an anion exchange reaction. The 1,3-dipolar cycloaddition of carbon disulfide to the bridged coordinated azide in the cyclometallated compound I was investigated. The species resulting from this reaction, di(mu -N,S-1,2,3,4-thiatriazol-5-thiolate)bis[(benzylideneaniline)palladium(II)] 2, was characterized by IR spectroscopy and X-ray diffraction. The compound 2 is a dimer containing two [Pd(benzylideneaniline)] moieties connected by two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination geometry for the palladium atoms.

Manipulation of anchoring strength in an azo-dye side chain polymer by photoisomerization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crystal structure of bis(acetylacetonato)bis(quinoline)nickel(II), Ni(C5H14O2N)(2)(C9H7N)(2)

C28H28N2NiO4, triclinic, P (1) over bar (no. 2), a = 7.9202(6) angstrom, b = 8.0496(6) angstrom, c = 10.246(1) angstrom, alpha = 97.15(1)degrees, beta = 106.68(1)degrees, gamma = 94.686(9)degrees, V = 616.1 angstrom(3), Z = 1, R-gt(F) = 0.028, wR(ref)(F-2) = 0.078, T = 293 K.

Characterization of electrodes chemically modified with Mn(III) porphyrin/polypyrrole films as catalytic surfaces for an azo dye

In this study we describe the electrochemical behavior of 5,10,15,20-tetrakis(2'-aminophenylporphyrin)manganese(III) chloride supported on a glassy carbon electrode, as well as the electrochemical preparation and characterization of thin films based on pyrrole-3-carboxylic acid. The electrocatalytic action of the electrode modified with the Mn(III) porphyrin toward an azo dye was tested, and the characteristic strong interaction between the incorporated metalloporphyrin and RR120 dye was verified. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.

Mutagenic compounds generated from the chlorination of disperse azo-dyes and their presence in drinking water

The water produced by the Cristais River Drinking Water Treatment Plant (CR-DWTP) repeatedly produced mutagenic responses that could not be explained by the presence of disinfection byproducts (DBPs) generated by the reaction of humic acids and chlorine. In order to determine the possible role of chlorinated dye products in this mutagenic activity, solutions of a black dye commercial product (BDCP) composed of C. I. Disperse Blue 373, C. I. Disperse Orange 37, C. I. Disperse Violet 93, and chemically reduced BDCP (R-BDCP) were chlorinated in a manner similar to that used by the CR-DWTP. The resulting solutions were extracted with XAD-4 along with one drinking water sample collected from the CR-DWTP. All extracts showed mutagenic activity in the Salmonella/microsome assay. Dye components of the BDCP as well as its reduced chlorinated (Cl-R-BDCP) derivative were detected in the drinking water sample by analysis with a high performance liquid chromatography/diode array detector (HPLC/DAD). The mutagenicity results of these products suggest that they are, at least in part, accounting for the mutagenic activity detected in the drinking water samples from the Cristais River. The data obtained in this study have environmental and health implications because the chlorination of the BDCP and the R-BDCP leads to the formation of mutagenic compounds (Cl-BDCP and Cl-R-BDCP), which are potentially important disinfection byproducts that can contaminate the drinking water as well as the environment.

Dose- and sex-related carcinogenesis by N-bis(2-hydroxypropyl)nitrosamine in Wistar rats

An initiation-promotion medium-term bioassay for detection of chemical carcinogens, developed in the male F344 rat, uses 0.1% N-bis(2-hydroxypropyl)nitrosamine (DHPN) among five genotoxic chemicals for the initiation of carcinogenesis in multiple organs. To establish this bioassay in the Wistar strain, the effects of two dose levels of DHPN were evaluated on the main DHPN rat target organs: lung, thyroid gland, kidneys and liver. Four groups of male and female animals were studied: Control--untreated group; Multi-organ initiated group (also referred to as DMBDD, based on the initials of the five initiators)-treated sequentially with N-diethylnitrosamine (DEN, i.p.), N-methyl-N-nitrosourea (MNU, i.p.), N-butyl-N-(4-hydroxy butyl)nitrosamine (BBN, drinking water), N, N'-dimethylhydrazine (DMH, s.c.) and DHPN (drinking water) for 4 weeks; a third group treated with 0.1% DHPN in drinking water for 2 weeks and the last group treated with 0.2% DHPN in drinking water for 4 weeks. The animals were sacrificed after 30 weeks. DHPN at 0.2% induced preneoplasia in the liver and kidneys of rats of both sexes, the number and area of the putative preneoplastic liver glutathione S-transferase-positive hepatocyte foci being significantly increased in these animals. It also induced benign and malignant tumors in female and in male rats. However, there was no relationship between the increased incidence of preneoplastic lesions and tumor development in the 0.2% DHPN-exposed groups of both sexes. DHPN at 0.1% induced only a few preneoplastic lesions in the liver and kidney and no tumors in both male and female rats. A clear dose and sex-related carcinogenic activity of DHPN was registered, although Wistar rats of both sexes showed a relative resistance to the carcinogenic activity of this compound.

Electrosynthesis of binuclear ruthenium complexes from [RuCl3(dppb)(L)] precursors [L = pyridine, 4-methylpyridine or dimethyl sulfoxide; dppb=1,4-bis(diphenylphosphino)butane]

Electrolysis has been examined as a method of synthesis for [(L)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] complexes, where dppb = 1,4-bis(diphenylphosphino)butane and L = pyridine (py), 4-methylpyridine (4-pic) or dimethyl sulfoxide (DMSO), by using [RuCl3(dppb)(L)] as precursors. The products of the electrolysis were characterized by P-31-{H-1} NMR, cyclic voltammetry and near infrared spectroscopy. The presence of the [Ru2Cl5(dppb)(2)] complex in the electrochemical cell suggests a mechanism by which the starting original species from the bulk solution reacts with the reduced form [RuCl2(dppb)(L)] generated at the surface of the electrode. The crystal structure of the precursor mer-[RuCl3(dppb)(4-pic)] was determined by X-ray diffraction.

Novel stereoselective addition of some nucleophiles to 2,3-bis(methylsulfanyl) norbornenobenzoquinone

2,3-Bis(methylsulfanyl)norbomenobenzoquinone undergoes reaction with nitrogen, oxygen, sulfur or carbon nucleophiles to give the trisubstituted adducts containing the new substituent at the ring junction. Their configurations are assigned by H-1 NMR spectroscopy and NOE enhancement experiments. (C) 1997 Elsevier B.V. Ltd.

Thermal study of cyclopalladated complexes of the type [Pd-2(dmba)(2)X-2(bpe)] - (X=NO3-, Cl-, N-3(-), NCO-, NCS-; bpe=trans-1,2-bis(4-pyridyl)ethylene)

The synthesis, characterization and thermal analysis of the novel cyclometallated compounds [Pd-2(dmba)(2)Cl-2(mu-bpe)] (1), [Pd-2(dmba)(2)(N-3)(2)(mu-bpe)] (2), [Pd-2(dmba)(2)(NCO)(2)(mu-bpe)] (3), [Pd-2(dmba)(2)(SCN)(2)(mu-bpe)] (4), [Pd-2(dmba)(2)(NO3)(2)(mu-bpe)] (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene; dmba=N,N-dimethylbenzylamine) are described. The thermal stability of [Pd-2(dmba)(2)X-2(mu-bpe)] complexes varies in the sequence 1 > 4 > 3 > 2 > 5. The final residues of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.

Cycloaddition reaction of the azido-bridged cyclometallated complex [Pd(dmba)N-3](2) with CS2. Crystal and molecular structure of DI(mu, N,S-1,2,3,4-thiatriazole-5-thiolate) bis[(N,N-dimethylbenzyl-amine-C-2,N)palladium(II)]

The 1,3-dipolar cycloaddition of carbon disulfide to the coordinated azide in the cyclometallated compound [Pd(dmba)(N-3)](2) (1), dmba = N,N-dimethylbenzylamine, was investigated. The compound obtained di(mu, N,S-1,2,3,4-thiatriazole-5-thiolate)-bis[(N,N-dimethylbenzylamine-C-2,N)palladium(II)] (2), was characterized by IR spectroscopy and X-ray diffraction. Complex (2) is dimeric with the two [Pd(N,N-dimethylbenzylamine)] moieties being connected by the two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination for the palladium atoms.

Studies of adsorptive interaction between Aspergillus niger and the reactive azo dye Procion Blue MX-G

Aspergillus niger on paramorphogenic form showed to be efficient adsorbent to reactive azo dye Procion Blue MX-G, where it has obtained rates of colour removal above 99% in acid pH, at 120 minutes of equilibrium time. Temperature did not exert expressive influence in the process, and the applicability of Freundlich's, isotherm suggest the occurrence of various molecules layers of adsorbed dye on the substratum surface.

Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes

The feasibility of the photobleaching of a textile azo dye, reactive orange 16 (C.I. 17757), in aqueous solution using titanium dioxide thin-film electrodes prepared by the sol-gel method was investigated. The best conditions for maximum photoelectrocatalytic degradation were found to be pH > 10 for Na2SO4 medium and pH < 6 for NaCl. In both situations, an applied potential of +1.0 V and low dye concentration are recommended, when 100% of color removal is obtained after 20 min of photoelectrocatalysis. The effects of side reaction pathway on the degradation rate of dye in sulfate and chloride medium were presented and the best performance are optimized to situations closed to that verified in the textile effluent. The influence of variables as applied potential, pH, supporting electrolyte and dye concentration on the kinetics of photoelectrochemical degradation also were investigated. Oxalic acid is identified by HPLC and UV-Vis spectrophotometric methods as the main degradation product generated after 180 min of photoelectrocatalysis of 4 x 10(-5) mol l(-1) dye in sodium sulphate pH 12 and NaCl pH 4.0 and a maximum reduction of 56 and 62% TOC was obtained, respectively. (C) 2004 Elsevier Ltd. All rights reserved.

Crystal structure of bis(benzyltriethylammonium) hexachlorotellurate(IV), [C7H7(C2H5)(3)N](2)(TeCI6)

C26H44Cl6N2Te, monoclinic, P12(1)/n1 (no. 14), a = 9.3981(5) Angstrom, b = 14.606(1) Angstrom, c = 12.4524(7) Angstrom, beta = 108.335(5)degrees, V = 1622.6 Angstrom(3), Z = 2, R-gt(F) = 0.024, wR(ref)(F-2) = 0.065, T = 293 K.

Crystal structure of bis(acetylacetonato)-bis(3-methylpyridine)-nickel(II) dihydrate, Ni(C6H7N)(2)(C5H7O2)(2)center dot 2H(2)O

C22H32N2NiO6, triclinic, P (1) over bar (no. 2), a = 8.335(1) angstrom, b = 9.314(1) angstrom, c = 17.045(2) angstrom, alpha = 88.45(1)degrees, beta = 82.12(1)degrees, gamma = 70.296(9)degrees, V = 1233.7 angstrom(3), Z = 2, R-gt(F) = 0.050, wR(ref)(F-2) = 0.177, T = 293 K.