Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Effects of Cr(III) organic compounds on Lactobacillus plantarum

Biotransformation of Cr(VI) to less toxic Cr(III) has been known to produce insoluble Cr(III) compounds and soluble Cr(III) organic complexes. However, recent research reports have indicated that Cr(III) organic complexes are relatively stable in the environment. Little has been reported on the fate and toxic effects of Cr(III) organic compounds on organisms. In this study, the toxic effects of the soluble Cr(III) organic complexes [Cr(III) citrate, Cr(III) histidine, Cr(III) lactate and Cr(III) glutamate] to a local strain of Lactobacillus plantarum isolated from sauerkraut was investigated. Growth inhibition, viable cell count and lactic acid inhibition were measured to determine the toxicity potential of the test compounds. The EC₅₀ values of Cr(III) citrate, Cr(III) histidine, Cr(III) lactate, and Cr(III) glutamate, calculated from the percent growth inhibition were found to be 56 mg L^?1, 70 mg L^?1, 81 mg L^?1, and 85 mg L^?1, respectively. Similar trend was observed in the viable cell counts and lactic acid production. Cr(VI) was observed to be more toxic than the Cr(III) organic compounds, while inorganic Cr(III) was the least toxic. The severity seemed to increase with increase in chromium compounds’ concentration. The results showed that Cr(III) citrate was the most toxic Cr(III) organic compound, while Cr(III) glutamate was the least.     

Statistical interpolation model for the description of ground pollution due to the TCDD produced in the 1976 chemical accident at seveso in the heavily contaminated zone “A”;

The influence of NTA on chromium genetic activity was studied in the D7 strain of Saccharomyces cerevisiae. At low dose (subgenotoxic) of sodium chromate (CrVI) (5mM), NTA increased the point mutation while at higher dose (25 mM) of chromate in the presence of NTA a decrease of point reverse mutation was observed. Probably NTA affected either the uptake of Cr(VI) favouring the intracellular reduction to Cr(III), or the recombinational repair of DNA breaks induced by chromate oxiding activity.

An increase of point (reverse) mutation was obtained in the experiments with NTA and chromium chloride, suggesting the hypothesis that NTA might interact with Cr(III) forming NTA‐Cr(III) complexes able to permeate cellular membranes and bind to DNA. In addition NTA genetic inactivity was confirmed.     

Induction of gene mutations in salmonella and Drosophila by soluble Cr(Vi) compounds: Synergistic effects of nitrilotriacetic acid

The interaction between NTA and soluble Cr(VI) (K₂Cr₂O₇) was studied by the Ames test on S. typhimurium and the sex‐linked recessive lethal test on D. melanogaster. In both systems a synergistic effect of NTA on Cr(VI) mutagenicity took place at sub‐toxic doses of Cr(VI). The synergism could depend on the action of NTA on intracellular Cr(VI) reduction, as more Cr(VI) was reduced in vitro to Cr(III) by Salmonella and Drosophila protein extracts in the presence of NTA. A similar enhancement of soluble Cr(VI) mutagenicity was produced by low doses of EDTA.     

密度泛函理论方法研究铝-麦芽酚配合物的形态结构与水交换反应

在B3LYP/6-311+G(d,p)基组水平下采用密度泛函理论方法系统开展了以下工作:(1)优化得到1∶1、1∶2和1∶3铝-麦芽酚配合物10种可能构型的静态结构、NPA电荷以及能量参数,计算得到Al(ma)3配合物4种异构体的核磁共振、紫外和红外等光谱学数据并与文献实验值比较,证明本文采用的计算方法和模型适用于铝-麦芽酚体系的研究;(2)模拟1∶1和1∶2铝-麦芽酚配合物9种可能位点的水交换反应,其中3个位点计算得到的水交换反应速率对数log kex(s-1)分别为2.4(Al(ma)(H2O)2+4(cis to ma))、2.6(cis-Al(ma)2(H2O)+2(I))和3.0(trans-Al(ma)2(H2O)+2(I)),与实验值2.5(Al(ma)2+)和3.3(Al(ma)+2)相符,说明相应位点为反应活性位点;(3)探讨铝-麦芽酚配合物毒性与其形态结构之间的相关机制。     

Exposure-response of Cr(III)-organic complexes to <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

Hexavalent chromium [Cr(VI)] bioreduction produces soluble Cr(III)-organic complexes. The Cr(III)-organic complexes are relatively stable once they are formed, and no data about their toxicity were reported. Therefore, this study aims to investigate the bioavailability and toxicity of the soluble Cr(III)-organic complexes. Saccharomyces cerevisiae L-1 wild type yeast strain was chosen as the model organism and Cr(III)-citrate was selected as the representative compound of the Cr(III)-organic complexes. The short-term chronic aquatic toxicity tests of the Cr(III)-citrate was explored by measuring growth inhibition, direct viable cell count, dry biomass, biosorption, and the amount of CO₂ production. Cr(III)-citrate exerted a toxicity of 51 mg/L with an EC ₅₀, which was calculated from the percent growth inhibition. These toxicity data would be helpful to define the toxic potential of the organo-chromium-III compounds in the environment.     

Synthesis,structural characterization and antimicrobial activity of nickel(II) tetrathiocyanato dicuperate(I) complexes with some acyl hydrazones

Heterobimetallic complexes of the type Ni[Cu(SCN)₂]₂ · L (where L = acetophenone benzoylhydrazone, acetophenone isonicotinoyl hydrazone, acetophenone salicyloylhydrazone (ash), acetophenone anthraniloylhydrazone, p-hydroxy acetophenone benzoylhydrazone, p-hydroxy acetophenone isonicotinoyl hydrazone p-hydroxy acetophenone salicyloylhydrazone (phash), p-hydroxy acetophenone anthraniloyl hydrazone), were synthesized and characterized. The complexes are polymeric, insoluble in common organic solvents and are nonelectrolytes. Magnetic moments and electronic spectral studies suggest a spin-free octahedral geometry for the complexes. IR spectra show the bidentate nature of all the ligands bonding through >C=O and >C=N–groups. The SCN group acts as a bridge between two metal centers. X-ray powder diffraction parameters for Ni[Cu(SCN)₂]₂ · ash and Ni[Cu(SCN)₂]₂ · phash correspond to orthorhombic and tetrahedral crystal lattices, respectively, for these complexes. The complexes show a significant antifungal activity against Rizoctonia, Stemphylium and Aspergillus sp. and antibacterial activity against Clostridium and Pseudomonas sp. The metal complexes are more active than the ligands.     

Spectroscopic studies and biological evaluation of some transition metal complexes of a novel Schiff base ligands derived from 5-arylazo-salicyladehyde and o-amino phenol

Synthesis and characterization of Cu(II), Ni(II), and Zn(II) Schiff bases complexes resulted from the condensation of salicylaldehyde derivatives with o-amino phenol were discussed using elemental analysis (carbon, hydrogen, and nitrogen), molar conductance, magnetic measurements, mass spectra, and electronic spectra. The essential bands of infrared, ¹HNMR, and UV-Vis spectra as well as thermogravimetric analysis corresponding to the active groups within the three ligands and their complexes were interpreted. The dehydration and decomposition processes of the [Cu(H₂L₁)(H₂O)](OAc)₂, [Ni(H₂L₁)(H₂O)]SO₄ · H₂O, [Zn(H₂L₁)(H₂O)]SO₄ · H₂O, [Cu(H₂L₂)(H₂O)](OAc)₂, [Ni(H₂L₂)(H₂O)]SO₄ · H₂O, [Zn(H₂L₂)(H₂O)]SO₄ · 2H₂O, [Cu(H₂L₃)(H₂O)](OAc)₂ · H₂O, [Ni(H₂L₃)(H₂O)]SO₄ · 2H₂O, [Zn(H₂L₃)(H₂O)]SO₄ complexes were studied thermodynamically using the integral method applying the Coats–Redfern and Horowitz–Metzger equations and the thermodynamic parameters were calculated. It was found from the elemental analysis and the thermal studies, that the ligand behaves as tridentate ligand forming chelates with 1 : 1 (metal : ligand) stoichiometrically. The molar conductance measurements of the complexes in dimethyl sulfoxide solvent indicate that the complexes have an electrolytic nature. The biological activities of the three ligands in comparison with metal(II) complexes were studied against different Gram positive and Gram negative bacteria.     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Acid-base responses to lethal aquatic hypercapnia in three marine fishes

Ocean sequestration of CO₂ is proposed as a possible measure to mitigate environmental changes due to the increasing atmospheric concentration of the gas. However, toxic effects of CO₂ on marine organisms are poorly understood. We therefore studied acid–base responses and mortality during exposure to fatal levels of CO₂ in three marine fishes (Japanese flounder, Paralichthys olivaceus; yellowtail, Seriola quinqueradiata; and starspotted dogfish, Mustelus manazo). The teleosts died during exposure to seawater equilibrated with a gas mixture containing 5% CO₂ (water PCO₂ 4.95 kPa); 100% mortality occurred within 8 h for yellowtail and within 48 h for flounder. Only 20% mortality was recorded at 72 h for the dogfish during exposure to 7% CO₂ (water PCO₂ 6.96 kPa). Arterial pH (pH_a) initially decreased, but completely recovered within 1–24 h for the teleosts at 1% and 3%, although the recovery was slower and complete only at 1% (water PCO₂ 0.99 kPa) for the dogfish. During exposure to 5%, the flounder died after the pH_a had been completely restored, suggesting that the mortality was not due to plasma acidosis. During exposure to 1% hypercapnia, plasma [Cl^–] appeared to be the main counter ion to balance increases in plasma [HCO₃^-]. There was a 1:1 stoichiometry for the rise in [HCO₃^-] and the fall in [Cl^–] for the teleosts, whereas the ratio was 1:0.4 for the dogfish at 1% CO₂. At the higher levels of hypercapnia, the rise in [HCO₃^-] consistently exceeded the fall in [Cl^–], and plasma [Na⁺] significantly increased.These results do not agree with the generally accepted model for acid–base regulation in marine fish in which Na⁺/H⁺ exchangers are assumed to play a predominant role, and indicate that an acid–base regulatory mechanism differs between teleost and elasmobranch fishes, as well as the intensity of acidic stress.Communicated by T. Ikeda, Hakodate     

Bioavailability and metabolism of hexavalent chromium compounds †

Intratracheal instillation of ⁵¹CrCl₃ in anaesthetized rabbits resulted in partial absorption. In blood, the absorbed material was entirely confined to the plasma compartment. Only trace amounts were deposited in liver and kidney. By contrast, after similar application of Na, ⁵¹CrO₄ the bulk of blood radioactivity was present in red blood cells (RBC). Substantial deposition occurred in liver and kidneys. It is concluded that Cr(VI) may enter the body unreduced via the lung and is partially deposited in cells over a prolonged period of time.

Since chromium was accumulated in liver after administration of Cr(VI) we investigated the intracellular disposition of Cr(VI) in the isolated perfused liver. No significant sex differences in chromium distribution were observed. At the end of the experiments (1 h), 60% of the applied dose (312μg Cr/liver) was located in the cytosol, whilst 14% was in the mitochondria, 9% in the microsomal pellet and 2% was associated with the nuclei. Gel chromatography of the cytosolic compartment showed that the overwhelming part of chromium was eluted in fractions with an apparent molecular weight of 6,000 dalton. These fractions exhibited absorption maxima at 410nm and 548nm. It is concluded, that cytosolic reduction might be the main intracellular redox pathway for chromates. This view was confirmed by monitoring the reaction of Cr(VI) with GSH in vitro. GSH reduced Cr(VI) without further cofactors under formation of GSH‐chromium complexes, which possibly represent major intermediates in the metabolism of Cr(VI).     

Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Synthesis,structural elucidation,electro-chemical behaviour and fungitoxic activity of transition metal(II) mixed-ligand complexes with some Schiff bases

The Schiff bases, potassium salt of salicylidene-β-alanine [KHL], bis(benzylidene)ethylenediamine [SB¹] and thiophene-o-carboxaldene-p-toluidine [SB²], and mixed-ligand complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have been prepared. They were characterized by elemental analyses, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.), infrared spectra and electronic spectra. The mixed-ligand complexes were found to have the general composition [M(L)(SB)(H₂O)]. All the mixed-ligand complexes were found to have six-coordinated octahedral geometry. The fungitoxic activity of the ligands, metal salts, control (DMSO), bavistin, emcarb, and mixed-ligand complexes were screened against Aspergillus niger, Fusarium oxysporum and Aspergillus flavus. All the mixed-ligand complexes show higher fungitoxic activity as compared to the Schiff bases, metal nitrate and control (dimethyl sulphoxide, DMSO), and moderate fungitoxic activity as compared to the fungicides (bavistin and emcarb).     

Genotoxicity of chromium in vitro on yeast: Interaction with DNA†

The genotoxicity of chromium chloride was investigated in cells of D₇ strain of Saccharomyces cerevisiae harvested either from logarithmic or stationary growth phase.

A weak induction of mifotic gene conversion and point reverse mutation was obtained when the incubations were performed using phosphate buffer. No genetic effect was observed when the incubations were performed using Tris‐HCl buffer.

The experiments with ⁵¹Cr radiotracer demonstrated that Cr³⁺ ion enters the yeast cells and binds to DNA even if the incubation mixture was performed with Tris HCl buffer. This behaviour could be due to the highest concentration of CrCl₃ that cause some damages to cytoplasmatic membrane.     

Mutagenicity of polyaromatic hydrocarbons by chemical models for cytochrome P450 in Ames assay

DNA damage is an important step in carcinogenesis. The Ames assay is a short-term screening of carcinogens that induce DNA damage. Most carcinogens require enzymatic activation through oxidation by cytochrome P450 (CYP450) in the presence of S9 mix. A combination of iron (Fe)(III) porphyrin and an oxidant is also able to oxidize compounds as an alternative metabolic pathway to CYP450. Previously it was reported that a chemical model containing a water-soluble 5,10,15,20-tetrakis(1-methylpyridinium4-yl)porphyrinatoiron(III) chloride (4-MPy) and tert-butyl hydroperoxide (t-BuOOH) activated aromatic amines and amides. In this study, a chemical model composed of an Fe porphyrin, water-insoluble 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (F₅P) or water-soluble 4-MPy was optimized with an oxidant – t-BuOOH, magnesium monoperoxyphthalate (MPPT), or iodosylbenzene (PhIO). Subsequently the mutagenicity of benzo[a]pyrene (B[a]P) and chrysene in Salmonella typhimurium TA strains was compared. B[a]P was activated by a combination of F₅P or 4-MPy plus MPPT or PhIO in S. typhimurium TA1538. The B[a]P-induced mutagenicity with F₅P plus oxidant was higher than 4-MPy plus oxidant. Mutagenicity of chrysene, a tetracyclic aromatic hydrocarbon, was not detected in the presence of F₅P/PhIO in S. typhimurium TA98, but was activated in the presence of F₅P/MPPT. The F₅P/MPPT activated other polyaromatic hydrocarbons (PAH) in the S. typhimurium TA98 assay including dibenz[a,c]anthracene, dibenz[a,h]anthracene, 3-methylcholanthrene, and benzo[a]anthracene. The results indicated that the F₅P/MPPT was the most efficient model for detecting PAH-induced mutagenicity in the Ames assay.     

Phenol transformation induced by UVA photolysis of the complex FeCl<Superscript>2+</Superscript>

Here we show that the photolysis of FeCl²⁺ upon UV irradiation of Fe(III) at pH 0.5, yielding Cl^• and then Cl₂^−•, upon further reaction with Cl⁻, induces phenol degradation. The photolysis of FeCl²⁺ can be highlighted and studied as the huge interference by FeOH²⁺ can be avoided under such conditions. Our data allowed the assessment of a photolysis quantum yield for FeCl²⁺ of 5.8 × 10⁻⁴ under UVA irradiation, much lower compared to the literature value of 0.5. The discrepancy can be explained if the photolysis process is efficient but photoformed Fe²⁺ and Cl^• undergo recombination inside the solvent cage.     

Toxic effect of transition metal complexes on Salmonella typhi,Escherichia coli and Serratia marcescens

The present article describes the synthesis, structural features and toxicological studies of the complexes of the type [M(L)(dipy-amine)(H₂O)] or [M(L)(bendan)(H₂O)] where M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), H₂L?=?salicylidene-o-aminothiophenol, dipy-amine?=di(2-pyridyal)amine, or bendan?=?bis(benzylidene)1,8-diaminonaphthalene. The complexes have been characterized on the basis of elemental analyses, electronic spectra, magnetic measurement and thermogravimetric analyses. The nature of the bonding has been discussed on the basis of infrared spectral data. A thermal study of the complexes has been carried out to ascertain their thermal stability. Magnetic susceptibility measurements and electronic spectral data suggest a six-coordinated octahedral structure for these complexes. The complexes of Mn(II), Co(II), Ni(II), Cu(II) are paramagnetic, while Zn(II) and Cd(II) are diamagnetic in nature. The toxic effects of the investigated complexes were tested against three Gram-negative bacteria, Salmonella typhi, Escherichia coli and Serratia marcescens by the “Disc Diffusion Method”. It is observed that the complexes show higher toxic effects as compared to the ligands, metal salts and control (DMSO), but moderate toxic effects as compared to the standard drug (tetracycline) and the results are discussed.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.