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[Chromates: resistance and detoxification in bacteria].

Derivatives of hexavalent chromium (chromates and dichromates) are highly toxic and have been shown to be mutagens and carcinogens. These compounds are often disposed to the environment as a result of diverse industrial procedures. The presence of chromates selects bacterial strains possessing chromate resistance determinants, commonly carried by plasmids. Some bacteria are able to reduce hexavalent chromium to trivalent chromium which is much less toxic. Bacterial strains combining both properties, resistance to and reduction of chromate, are potentially useful for decontamination of sewage or other refuse contaminated by chromates.

Amino Acid Sequence↗

Synthesis, characterization, and in vitro cytotoxic effects of K4 [PtCl2ATP].

An antineoplastic agent, cis-K4 [PtCl2ATP] has been synthesized and characterized, using elemental analysis, solution conductance, thermoanalysis, infrared, NMR spectroscopy, and circular dichroism studies. The in vitro cytotoxic effect imparted by this compound on Dalton's Lymphoma cells has been assessed by Trypan blue dye exclusion method and 51Cr release assays.

Adenosine Triphosphate↗

Specificity and inducibility of the metabolic reduction of chromium(VI) mutagenicity by subcellular fractions of rat tissues.

The mutagenicity of sodium dichromate in the Ames test was decreased as a consequence of chromium(VI) reduction by tissue postmitochondrial (S-9 or S-12) fractions from untreated rats with the following rank of efficiency: liver; kidney; and lung. The effects of lung preparations were significantly enhanced following the intratracheal administration of high doses (0.25 mg/kg) of dichromate itself, 5 times per week for 4 weeks (i.e., 20 fractionated instillations). No changes were conversely detected following single weekly doses of 1.25 mg/kg for the same period (i.e., four cumulative instillations). The local stimulation of chromium(VI) metabolism was also confirmed by testing the mutagenicity of calcium chromate and chromium trioxide, whereas the metabolism of a number of other activatable or deactivatable mutagens was not significantly affected by intratracheal treatment with chromium(VI). Of three enzyme inducers injected i.p. which modified the spectral properties and/or concentration of cytochromes P-450 in liver and lung microsomes, only Aroclor 1254 proved to stimulate chromium(VI) metabolism in lung cells. In liver cells, Aroclor 1254 and to a lower extent phenobarbital induced chromium(VI) reduction, while 3-methylcholanthrene was ineffective. Pretreatment of rats with these three compounds resulted in a selective induction of the metabolic activation of promutagens [benzo(a)pyrene and its trans-7,8-diol, 2-aminofluorene, aflatoxin B1] and of the metabolic deactivation of direct-acting mutagens [2-methoxy-6-chloro-9-[3-(2-chloroethyl)-aminopropylamino] acridine X 2HCl, epichlorohydrin, 4-nitroquinolino-N-oxide] by S-12 and microsomal fractions. These findings indicate that, in addition to already recognized detoxification mechanisms operating outside target cells (26), specific and inducible chromium-reducing pathways, mediating threshold phenomena in chromium carcinogenesis, do also occur in the intracellular environment.

Animals↗

Diamond paste-based electrodes for determination of Cr(III) in pharmaceutical compounds.

A new class of monocrystalline diamond paste-based electrodes is proposed for the determination of chromium(III) at trace levels in vitamins. Three types of monocrystalline diamond-natural diamond 1mu (natural diamond), synthetic diamond 50mu (synthetic-1), and synthetic diamond 1mu (synthetic-2)-were used for electrode construction. The linear concentration ranges are between 10(-10) and 10(-8); 10(-9) and 10(-7), and 10(-10) to 10(-8) mol L(-1), with limits of detection of 10(-12), 10(-12), and 10(-11) mol L(-1), when natural diamond, synthetic-1, and synthetic-2, respectively, are used as electrode materials. For electrodes based on natural diamond and synthetic-1 it was found that Cr(III) yields a peak at about +0.275+/-0.015 V (vs. Ag/AgCl) within a predetermined positive potential range situated between +0.4 and +0.2 V, while for the electrode based on synthetic-2 the peaks are found at +0.300+/-0.015 V (vs. Ag/AgCl). The proposed method is reliable for the determination of chromium(III) at trace levels in two vitamin tablets (RSD<0.2%).

Chromium↗

Exposure, metabolism, and toxicity of rare earths and related compounds.

For the past three decades, most attention in heavy metal toxicology has been paid to cadmium, mercury, lead, chromium, nickel, vanadium, and tin because these metals widely polluted the environment. However, with the development of new materials in the last decade, the need for toxicological studies on those new materials has been increasing. A group of rare earths (RE) is a good example. Although some RE have been used for superconductors, plastic magnets, and ceramics, few toxicological data are available compared to other heavy metals described above. Because chemical properties of RE are very similar, it is plausible that their binding affinities to biomolecules, metabolism, and toxicity in the living system are also very similar. In this report, we present an overview of the metabolism and health hazards of RE and related compounds, including our recent studies.

Animals↗

Paper electrophoresis in the study of mixed ligand complexes in solution. The system Fe(III)- and Cr(III)-methyl cysteine-penicillamine.

A method involving use of paper electrophoresis is described for the study of equilibria in mixed ligand [methyl cysteine-penicillamine] complex systems in solution. The concentration of the primary ligand methyl cysteine was kept constant, while that of secondary ligand penicillamine was varied. The plots of -log [penicillamine] against mobility were used to obtain information on the formation of mixed complex and to calculate its stability constants. The binary equilibria M(III)-methyl cysteine have also been studied since this is a pre-requisite for the investigation of mixed complexes. The stability constants of [Fe(III)- methyl cysteine-penicillamine] and [Cr(III)-methyl cysteine-penicillamine] complexes were found to be 7.40 +/- 0.13 and 4.80 +/- 0.07 (log K values) for Fe(III) and Cr(III) complexes, respectively, at mu = 0.1 mol/L and at a temperature of 35 degrees C.

Chelating Agents↗

Influence of chromium on some physiological variables of Anabaena doliolum: interaction with metabolic inhibitors.

The impact of 2,4-dinitrophenol and chlorophenyl dimethylurea on ATP content, carbon fixation, O2 evolution, nitrogenase activity and Cr uptake of Anabaena doliolum has been studied. 2,4-Dinitrophenol has been found to be more toxic than chlorophenyldimethylurea for all these processes. However, when Cr toxicity to above variables was assessed in their presence the interaction was less than additive. An initial (10-15 min) concentration-dependent rapid Cr uptake, followed by a slow one, indicates a biphasic uptake. A significant inhibition of Cr uptake in the presence of both these metabolic inhibitors suggests the involvement of metabolic processes in Cr uptake.

2,4-Dinitrophenol↗

Toxicity of chromium and tin to Anabaena doliolum. Interaction with sulphur-containing amino acids and thiols.

Toxicity of chromium and tin on growth, heterocyst differentiation, nitrogenase activity and 14CO2 uptake of Anabaena doliolum and its amelioration by sulphur-containing amino acids and thiols has been studied. The final growth yield was found to be approximately 51% and 58% of control at sublethal concentration of chromium and tin respectively. Among various amino acids tested, cysteine (0.05 mM) significantly restored growth, heterocyst differentiation, nitrogenase and 14CO2 uptake of test alga. Dithiothreitol (1 mM) restored all the parameters and processes better than monothiol, mercaptoethanol. It is obvious from present investigation that sulphur-containing amino acids and thiols, viz. cysteine, methionine, cystine, mercaptoethanol and dithiothreitol, may appreciably alleviate the toxicity of heavy metals in N2-fixing cyanobacteria if present in an aquatic ecosystem.

Amino Acids, Sulfur↗

The action of chromium on serum lipids and on atherosclerosis in cholesterol-fed rabbits.

Eight rabbits, fed on a 1% cholesterol diet for 30 days, were injected daily with potassium chromate for a further 60 days. A 50% reduction in aortic intimal plaque area and in aortic total cholesterol content was observed. However, although levels of serum cholesterol and triglycerides were consistently lower and levels of high density lipoprotein fractions consistently higher in the chromium-treated as compared to the control rabbits, these differences did not reach statistical significance. A further 6 rabbits were injected with potassium chromate and fed on a 1% cholesterol diet for 12 weeks. Mean aortic cholesterol content (+/-SEM) was 40.23 mg/10 cm aortic length (+/-7.50) as compared to 66.24 mg/10 cm (+/- 7.89) in a control group (P less than 0.05), whereas the area of aortic intima covered by macroscopic plaques was 67.5% (+/-2.79) and 81.1% (+/-3.14) (P less than 0.01) respectively.

Animals↗

Hexavalent chromium and ascorbic acid interaction on proliferation of the human cell line NHIK3025.

When cells from the human cell line NHIK3025 were cultured for 4 days, with hexavalent chromium (K2Cr2O7) at a concentration of 8 . 10(-7)M, the relative cell number was reduced to 38%. This effect of hexavalent chromium was abolished if ascorbic acid and chromate were added simultaneously to the incubation medium, but not if ascorbic acid was added 24 h prior to chromate addition. Dehydroascorbic acid was not able to reduce the effect of K2Cr2O7 either when added simultaneously or when added 24 h prior to chromate exposure. Therefore, the cells could only be protected against the toxic effect of hexavalent chromium when ascorbic acid was added at the same time as K2Cr2O7.

Ascorbic Acid↗

Study of the removal of mercury(II) and chromium(VI) from aqueous solutions by Moroccan stevensite.

The objective of the present study was to investigate the adsorption of the heavy metals mercury(II) and chromium(VI), from aqueous solutions, onto Moroccan stevensite. A mineralogical and physicochemical characterization of natural stevensite was carried out. In order to improve the adsorption capacity of stevensite for Cr(VI), a preparation of stevensite was carried out. It consists in saturating the stevensite by ferrous iron Fe(II) and reducing the total Fe by Na(2)S(2)O(4). Then, the adsorption experiments were studied in batch reactors at 25+/-3 degrees C. The influence of the pH solution on the Cr(VI) and Hg(II) adsorption was studied in the pH range of 1.5-7.0. The optimum pH for the Cr(VI) adsorption is in the pH range of 2.0-5.0 while that of Hg(II) is at the pH values above 4.0. The adsorption kinetics were tested by a pseudo-second-order model. The adsorption rate of Hg(II) is 54.35 mmol kg(-1)min(-1) and that of Cr(VI) is 7.21 mmol kg(-1)min(-1). The adsorption equilibrium time for Hg(II) and Cr(VI) was reached within 2 and 12 h, respectively. The adsorption isotherms were described by the Dubinin-Radushkevich model. The maximal adsorption capacity for Cr(VI) increases from 13.7 (raw stevensite) to 48.86 mmol kg(-1) (modified stevensite) while that of Hg(II) decreases from 205.8 to 166.9 mmol kg(-1). The mechanism of Hg(II) and Cr(VI) adsorption was discussed.

Adsorption↗

Fluorescence resonance energy transfer from tryptophan to a chromium(III) complex accompanied by non-specific cleavage of albumin: a step forward towards the development of a novel photoprotease.

A chromium(III) complex, transdiaqua [N, N'-propylenebis(salicylideneimino)chromium(III)]perchlorate ([Cr(salprn)(H2O)(2)]ClO(4)) in the presence of sodium azide and upon photoexcitation was found to bring about non-selective cleavage of bovine serum albumin (BSA). Electron paramagnetic resonance (EPR) evidence has been obtained for the formation of a Cr(V) species upon photolysis of a solution containing the chromium(III) complex and sodium azide. This Cr(V) species non-selectively cleaves BSA. The fluorescence excitation spectrum of BSA-[Cr(salprn)(H2O)(2)]+ adduct showed a band at lambda(max)(ex) nm due to charge transfer transition of the chromium(III) complex as well as a prominent band at 290 nm attributable to tryptophan absorption. This indicated an efficient Forster type fluorescence energy transfer (FRET) from the tryptophan residues to the chromium(III) complex indicating that the Cr(III) complex binds in the vicinity of the tryptophan residue.

Animals↗

Hardening of aged duplex stainless steels by spinodal decomposition.

Mechanical properties, such as hardness and impact toughness, of ferrite-containing stainless steels are greatly affected by long-term aging at intermediate temperatures. It is known that the alpha-alpha' spinodal decomposition occurring in the iron-chromium-based ferrite is responsible for this aging susceptibility. This decomposition can be characterized unambiguously by atom probe analysis, allowing comparison both with the existing theories of spinodal decomposition and the evolution of some mechanical properties. It is then possible to predict the evolution of hardness of industrial components during service, based on the detailed knowledge of the involved aging process.

Chromium↗

Development of an 19F NMR method for the analysis of fluorinated acids in environmental water samples.

This investigation was carried out to evaluate 19F NMR as an analytical tool for the measurement of trifluoroacetic acid (TFA) and other fluorinated acids in the aquatic environment. A method based upon strong anionic exchange (SAX) chromatography was also optimized for the concentration of the fluoro acids prior to NMR analysis. Extraction of the analyte from the SAX column was carried out directly in the NMR solvent in the presence of the strong organic base, DBU. The method allowed the analysis of the acid without any prior cleanup steps being involved. Optimal NMR sensitivity based upon T1 relaxation times was investigated for seven fluorinated compounds in four different NMR solvents. The use of the relaxation agent chromium acetylacetonate, Cr(acac)3, within these solvent systems was also evaluated. Results show that the optimal NMR solvent differs for each fluorinated analyte. Cr(acac)3 was shown to have pronounced effects on the limits of detection of the analyte. Generally, the optimal sensitivity condition appears to be methanol-d4/2M DBU in the presence of 4 mg/mL of Cr-(acac)3. The method was validated through spike and recovery for five fluoro acids from environmentally relevant waters. Results are presented for the analysis of TFA in Toronto rainwater, which ranged from < 16 to 850 ng/L. The NMR results were confirmed by GC-MS selected-ion monitoring of the fluoroanalide derivative.

Air Pollutants↗