Metal(loid)s and radionuclides cytotoxicity in Saccharomyces cerevisiae. Role of YCF1, glutathione and effect of buthionine sulfoximine

The presence of heavy metal(loid)s in soils and waters is an important issue with regards to human health. Taking into account speciation problems, in the first part of this report, we investigated under identical growth conditions, yeast tolerance to a set of 15 cytotoxic metal(loid)s and radionuclides. The yeast cadmium factor 1 (YCF1) is an ATP-Binding Cassette transporter mediating the glutathione detoxification of heavy metals. In the second part, metal(loid)s that could be handled by YCF1 and a possible re-localisation of the transporter after heavy metal exposure were evaluated. YCF1 and a C-terminal GFP fusion, YCF1-GFP, were overexpressed in wild-type and Deltaycf1 strains. Both forms were functional, conferring a tolerance to Cd, Sb, As, Pb, Hg but not to Ni, Zn, Cu, Ag, Se, Te, Cr, Sr, Tc, U. Confocal experiments demonstrated that during exposure to cytotoxic metals, the localisation of YCF1-GFP was restricted to the yeast vacuolar membrane. In the last part, the role of glutathione in this resistance mechanism to metal(loid)s was studied. In the presence of heavy metals, application of buthionine sulfoximine (BSO), a well-known inhibitor of gamma-glutamylcysteine synthetase, led to a decrease in the cytosolic pool of GSH and to a limitation of yeast growth. Surprisingly, BSO was able to phenocopy the deletion of gamma-glutamylcysteine synthetase after exposure to Cd but not to Sb or As. In the genetic context of gsh1 and gsh2 yeast mutants, the critical role of GSH for Cd, As, Sb and Hg tolerance was compared to that of wild-type and Deltaycf1.     

Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV–visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.     

Increased Zn/Glutathione Levels and Higher Superoxide Dismutase-1 Activity as Biomarkers of Oxidative Stress in Women with Long-Term Dental Amalgam Fillings: Correlation between Mercury/Aluminium Levels (in Hair) and Antioxidant Systems in Plasma

Background

The induction of oxidative stress by Hg can affect antioxidant enzymes. However, epidemiological studies have failed to establish clear association between dental fillings presence and health problems.

Objectives

To determine whether heavy metals (in hair), antioxidant enzymes (SOD-1) and glutathione levels could be affected by the chronic presence of heavy metals in women who had dental amalgam fillings.

Materials and Methods

55 hair samples (42 females with amalgam fillings and 13 female control subjects) were obtained. All subjects (mean age 44 years) who had dental amalgam filling for more than 10 years (average 15 years). Certain metals were quantified by ICP-MS (Mass Spectrophotometry) in hair (μg/g: Al, Hg, Ba, Ag, Sb, As, Be, Bi, Cd, Pb, Pt, Tl, Th, U, Ni, Sn, Ti) and SOD-1 and Glutathione (reduced form) levels in plasma. Data were compared with controls without amalgams, and analyzed to identify any significant relation between metals and the total number of amalgam fillings, comparing those with four or less (n = 27) with those with more than four (n = 15). As no significant differences were detected, the two groups were pooled (Amlgam; n = 42).

Findings

Hg, Ag, Al and Ba were higher in the amalgam group but without significant differences for most of the heavy metals analyzed. Increased SOD-1 activity and glutathione levels (reduced form) were observed in the amalgam group. Aluminum (Al) correlated with glutathione levels while Hg levels correlated with SOD-1. The observed Al/glutathione and Hg/SOD-1 correlation could be adaptive responses against the chronic presence of mercury.

Conclusions

Hg, Ag, Al and Ba levels increased in women who had dental amalgam fillings for long periods. Al correlated with glutathione, and Hg with SOD-1. SOD-1 may be a possible biomarker for assessing chronic Hg toxicity.     

Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b

Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV–visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.     

Potential health risk of selected metals for Polish consumers of oolong tea from the Fujian Province,China

The influence of environmental pollution on the heavy metal content in oolong teas from the Fujian Province, China, and the health risk for the Polish consumers were studied. Average contents of the metals in made oolong tea leaves were (mg kg^?1): Al 1452, Cd 0.08, Co 0.23, Cr 1.59, Cu 10.5, Fe 140, Hg 0.10, Mn 1465, Mo 0.63, Ni 3.45, Pb 1.99, Sb 0.78, Se 5.15, Sn 3.16, Tl 0.28, and Zn 26.9. The metals easily released from leaves to infusions were: Tl, Se, Cd, Sn, Sb, Ni, Al, and Pb. No concentration of As, Hg, Mo, or Pb was found in the first infusion and no As, Co, Hg, or Mo was found in the second one. The hazard quotient values for particular metals found in the infusions and tea leaves and the appraised combined hazard index (HI) amounted to <1. The highest HI values, resulting from the consumption of both infusions, did not exceed 5.88E-03, or 6.94E-04a in the case of tea leaves. No health hazard for the Polish consumers of oolong teas was identified at any of the examined stages of consumption. However, we recommend discarding the first tea infusion to reduce the metal concentrations before consumption.     

Peptidic models for the binding of Pb(II), Bi(III) and Cd(II) to mononuclear thiolate binding sites

Herein, we evaluate the binding of Pb(II) and Bi(III) to cysteine-substituted versions of the TRI peptides [AcG-(LKALEEK)₄G-NH₂] which have previously been shown to bind Hg(II) and Cd(II) in unusual geometries as compared with small-molecule thiol ligands in aqueous solutions. Studies of Pb(II) and Bi(III) with the peptides give rise to complexes consistent with the metal ions bound to three sulfur atoms with M–S distances of 2.63 and 2.54 Å, respectively. Competition experiments between the metal ions Pb(II), Cd(II), Hg(II) and Bi(III) for the peptides show that Hg(II) has the highest affinity, owing to the initial formation of the extremely strong HgS₂ bond. Cd(II) and Pb(II) have comparable binding affinities at pH > 8, while Bi(III) displays the weakest affinity, following the model, M(II) + (TRI LXC)₃ ^3? → M(II)(TRI LXC)₃ ^?. While the relevant equilibria for Hg(II) binding to the TRI peptides corresponds to a strong first step forming Hg(TRI LXC)₂(HTRI LXC), followed by a single deprotonation to give Hg(TRI LXC)₃ ^?, the binding of Cd(II) and Pb(II) is consistent with initial formation of M(II)(TRI LXC)(HTRI LXC)₂ ⁺ at pH < 5 followed by a two-proton dissociation step (pK _a2) yielding M(II)(TRI LXC)₃ ^?. Pb(II)(TRI LXC)(HTRI LXC)₂ ⁺ converts to Pb(II)(TRI LXC)₃ ^? at slightly lower pH values than the corresponding Cd(II)–peptide complexes. In addition, Pb(II) displays a lower pK _a of binding to the “d”-substituted peptide, (TRI L12C, pK _a2 = 12.0) compared with the “a”-substituted peptide, (TRI L16C, pK _a2 = 12.6), the reverse of the order seen for Hg(II) and Cd(II). Pb(II) also showed a stronger binding affinity for TRI L12C (K _bind = 3.2 × 10⁷ M^?1) compared with that with TRI L16C (K _bind = 1.2 × 10⁷ M^?1) at pH > 8.     

豚草叶片和果实气体交换特性与11种土壤重金属相关性

对10个样地中Cu、Pb、Zn、Mn、Cr、Co、Ni、Cd、As、Sb和Hg11种土壤重金属含量及样地内豚草叶片和果实气体交换特性进行测定.结果表明,样地内豚草叶片的净光合速率在1·88~9·41μmol·m-2·s-1,而果实的净光合速率最高可达2·81μmol·m-2·s-1.叶片的呼吸速率、气孔导度、光合速率和水分利用效率的平均值分别为1·81μmol·m-2·s-1、75·7mmol·m-2·s-1、6·05μmol·m-2·s-1和4·72μmol·mmol-1,分别是果实的5·26、0·64、1·31和1·69倍,说明非同化器官幼嫩果实具有与叶片相当,甚至更强的呼吸、光合能力和水分利用效率;研究地点重金属Ni达到轻微污染水平,其它重金属含量都接近或者显著低于重金属污染的阈值.相关分析和多元回归分析显示,大部分土壤重金属(如Cu、Pb、Zn、Cd、As、Sb和Hg)含量的高低对豚草气体交换特性没有显著影响,仅部分重金属含量与豚草的叶片、果实气体交换特性密切相关,如Ni和Cr对豚草叶片、果实的气孔导度及水分利用效率显著相关;Cr与豚草叶片饱和光合速率显著相关;而As与豚草果实的气孔导度显著相关.表明大部分土壤重金属对叶片和球果的气体交换没有直接影响,而Ni、Cr和As可以在轻微污染甚至没有达到污染水平时影响豚草的气体交换特性.     

Silver(I), mercury(II), cadmium(II), and zinc(II) target exposed enzymic iron-sulfur clusters when they toxify Escherichia coli

The toxicity of soft metals is of broad interest to microbiologists, both because such metals influence the community structures in natural environments and because several metals are used as antimicrobial agents. Their potency roughly parallels their thiophilicity, suggesting that their primary biological targets are likely to be enzymes that contain key sulfhydryl moieties. A recent study determined that copper poisons Escherichia coli in part by attacking the exposed [4Fe-4S] clusters of dehydratases. The present investigation sought to test whether other soft metals also target these enzymes. In vitro experiments revealed that low-micromolar concentrations of Ag(I) and Hg(II) directly inactivated purified fumarase A, a member of the dehydratase family. The enzyme was also poisoned by higher levels of Cd(II) and Zn(II), but it was unaffected by even millimolar concentrations of Mn(II), Co(II), Ni(II), and Pb(II). Electron paramagnetic resonance analysis and measurements of released iron confirmed that damage was associated with destruction of the [4Fe-4S] cluster, and indeed, the reconstruction of the cluster fully restored activity. Growth studies were then performed to test whether dehydratase damage might underlie toxicity in vivo. Barely toxic doses of Ag(I), Hg(II), Cd(II), and Zn(II) inactivated all tested members of the [4Fe-4S] dehydratase family. Again, activity was recovered when the clusters were rebuilt. The metals did not diminish the activities of other sampled enzymes, including NADH dehydrogenase I, an iron-sulfur protein whose clusters are shielded by polypeptide. Thus, the data indicate that dehydratases are damaged by the concentrations of metals that initiate bacteriostasis.     

EFFECTS OF HEAVY METALS ON SURVIVAL AND GROWTH OF BIOMPHALARIA GLABRATA SAY (GASTROPODA: PULMONATA) AND INTERACTION WITH SCHISTOSOME INFECTION

The effects of dissolved Pb, Cd and Hg on growth and survivalof adult Biomphalaria glabrata Say. uninfected and infectedwith Schistosoma mansoni Sambon, were examined. Pb at concentrationsfrom 0.25–100 µM, Cd from 0.075–0.25 µMand Hg from 0.25–1 µM significantly reduced growthand survival of normal snails. With each metal the effects increasedwith increasing concentration. The LC 25 at 2 wks exposure was82 ± 19, 0.22 ± 0.04 and 0.94 ± 0.13 µM(x ± S.E.) for Pb, Cd and Hg, respectively. Snails exposedto heavy metals continued to be reproductively active, but theegg production was highly variable and no significant effectof heavy metal exposure was demonstrated. Infection also decreasedsurvival and growth of snail hosts and infected individualsexposed to heavy metals displayed the greatest mortality. TheLC 25 for infected snails at 2 wks exposure was 8 ± 3,0.9 ± 0.02 and 0.29 ± 0.08 for Pb, Cd and Hg respectively.A significant interaction between heavy metal exposure and infectionwas apparent. Infected snails were not reproductively active.Cercarial shedding by infected snails was significantly reducedin the presence of heavy metals and by 6 wks shedding had ceasedat the highest metal concentrations. (Received 20 May 1996; accepted 31 July 1996)     

高原鼢鼠和高原鼠兔骨骼中非必需微量元素的测定

铅、镉、砷、汞、锑和铋等元素是人与动物生命活动非必需且有害的微量元素[1] 。哺乳类动物体内的这些微量元素主要由食物链传递所产生[2 ,3] 。本文对高原鼢鼠 (Ｍｙｏｓｐａｌａｘｂａｉｌｅｙｉ)和高原鼠兔(Ｏｃｈｏｔｏｎａｃｕｒｚｏｎｉａｅ)骨骼中非必需微量元素砷、锑、汞、铋、铅、镉的分布、种间含量差异及其相关性进行了分析和讨论 ,为高寒草甸生态系统研究小哺乳动物的营养生态学、化学生态学以及生态系统的物质循环[4 ,5] 等提供基础资料。1　材料与方法1 1　样品预处理1994年 5～ 6月在中国科学院海北高寒草甸生态系统定位站…     

What are “heavy metals” in Plant Sciences?

Plants do not have the ability to sense physical properties of metals, e.g. specific weight. The term “heavy metal” was defined mainly by the specific weight of metals. The definition was often connected with the expectation that the substance should be toxic. This definition is not acceptable and also inconsistent in use as already stressed in literature. However, in Plant Sciences, the term is so widely used that it is hardly possible to eliminate it. We suggest instead defining the term in a more unequivocal way. This should be done on the basis of the periodic system of elements. Here, we suggest introducing the following three subgroups forming the group of heavy metals for use in Plant Sciences. 1st subgroup: all transition elements except La and Ac (Transition metals). 2nd subgroup: rare earth elements, subdivided in the series of lanthanides and the series of actinides including La and Ac themselves (Rare earth metals). 3rd subgroup: a heterogenous group p-elements including the metal Bi, the amphoterous oxides forming elements Al, Ga, In, Tl, Sn, Pb, Sb and Po, and the metalloids Ge, As and Te. We suggest using the term “lead-group” for this 3rd subgroup of heavy metals as in Toxicology and Environmental Sciences, Pb is the most prominent representative of this group.     

贵州水银洞金矿紫茎泽兰重金属元素测定与分析

利用原子吸收法对贵州水银洞金矿紫茎泽兰及其基质中Cr、Pb、Zn、Cd、Hg和As含量进行了测定和分析。结果表明,贵州水银洞金矿废水处理区土壤Hg(12.575 mg·kg^-1)和As(501.374 mg·kg^-1)已严重超标,Hg和As的平均含量分别是国家土壤环境质量三级标准(GB15618-1995)的8.383倍和12.534倍,污染极为严重;紫茎泽兰对该矿区不同的重金属富集能力不同,尤其对该矿区Cr有较强的富集作用,具有一定的Cr污染修复潜力。紫茎泽兰对所测定的6种重金属元素的吸收转移能力有较大的差异,整个植株对Pb、Zn 和Cr具有很强的吸收转移能力。其茎、叶对不同的重金属元素的吸收转移能力也呈现出很大的差异,紫茎泽兰茎对Cr、Pb和Cd具有很强的吸收转移能力,而叶对Zn、Pb和Hg具有很强的吸收转移能力。除As外,紫茎泽兰对Cr、Pb、Zn、Cd和Hg都具有不同程度的耐受能力,对该矿区的生态恢复具有重要的作用。     

Concentrations of Metals in Soils in the Neighborhood of a Hazardous Waste Incinerator: Assessment of the Temporal Trends

The concentrations of arsenic (As), beryllium (Be), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb), antimony (Sb), tin (Sn), thallium (Tl), and vanadium (V) were determined in 30 soil samples collected in April 2011 near a hazardous waste incinerator (HWI; Constantí, Catalonia, Spain), which is under regular operations since 1999. The results were compared with those of recent surveys performed in the same zone, as well as with data from a background study (1996?C1998). We also assessed the human health risks derived from metal exposure in the area under potential influence of the emissions of the HWI. Manganese was the most abundant element in soils, with a mean value of 316.4???g/g, followed by Pb and Cu (mean values, 42.5 and 38.2???g/g, respectively). In contrast, Sb, Cd, and Tl presented the lowest values (0.12, 0.27, and 0.29???g/g, respectively), while Hg was below its limit of detection. In the period 1998?C2011, only As, Cr, Sn, Tl, and V levels presented significant increases in soils. The estimated carcinogenic and noncarcinogenic risks derived from exposure to these metals from soils should not mean any special concern for the population living in the surroundings of the HWI.     

Heavy metal risk assessment of European eels (Anguilla anguilla,Linnaeus, 1758) from the Asi (Orontes) River,Turkey

The muscle tissues of a total 154 sampled eels from the Asi (Orontes) River were analyzed between January and December 2018 to determine the content of heavy metals (Hg, Pb, Cd and As). Determination of heavy metals in muscle tissue was carried out with an Inductively Coupled Plasma Mass Spectrometer (ICP-MS). To express the risk level for human consumption of heavy metal contaminated eels we used common concepts and criteria such as Hazard Index (HI), Target Hazard Quotient (THQ) and Total THQ (TTHQ). From the human health point of view, the indices HI, THQ, TTHQ values of Hg, Cd, Pb and As indicate no risks for the consumers at assumed intake levels per unit time.     

Characterization of a metalloregulatory bismuth(III) site in Staphylococcus aureus pI258 CadC repressor

Staphylococcus aureus pI258 CadC is a metal sensor protein that regulates the expression of the cad operon which encodes metal ion resistance proteins involved in the efficient efflux of Cd(II), Pb(II), Zn(II) and, according to one report, Bi(III) ions. In this paper, direct evidence is presented that Bi(III) binds to CadC and negatively regulates cad operator/promoter (O/P) binding. Optical absorption spectroscopy reveals that dimeric CadC binds approximately 0.8 mol equivalents of Bi(III) per CadC monomer to form a coordination complex characterized by three S(-)-->Bi(III) ligand-to-metal charge transfer transitions, with the longest wavelength absorption band centered at 415 nm (epsilon(415)=4000 M(Bi)(-1) cm(-1)). UV-Vis absorption spectra of wild-type and mutant Cys-->Gly (Ser) substitution CadC mutants compared to [Bi(DTT)(2)], [Bi(GSH)(3)] and [Bi(NAC)](3) model complexes reveal that Cys7, Cys11, Cys60 and Cys58 directly coordinate Bi(III) in a tetrathiolate coordination complex. The apparent affinity derived from a Bi(III)-displacement optical titration with Cd(II) is estimated to be K(Bi)< or =10(12) M(-1). Apo-CadC binds with high affinity [ K(a)=1.1(+/-0.3)x10(9) M(-1); 0.40 M NaCl, pH 7.0, 25 degrees C] to a 5'-fluorescein-labeled cad O/P oligonucleotide,while the binding of one molar equivalent of Bi(III) per CadC monomer (Bi(1)-CadC) reduces the affinity by approximately 170-fold. Strikingly, Bi(III)-responsive negative regulation of cad O/P binding is abrogated for Bi(1)-C60G CadC and severely disrupted in Bi(1)-C7G CadC, whose relative affinity is reduced only 10-fold. The mechanism of Bi(III)-responsive metalloregulation is discussed, based on the findings presented here. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00775-001-0336-9.     

A versatile and highly sensitive probe for Hg(II), Pb(II) and Cd(II) detection individually and totally in water samples

The detection of heavy metal ions using enzyme-linked immunosorbent assays (ELISA) has been reported by several research groups. However, highly sensitive and selective detection of total heavy metal ions using ELISA is a major technical limitation. Here we describe the development of a versatile and highly sensitive probe combining goat anti-mice IgG, colloidal gold nanoparticles (AuNPs) and horseradish peroxidase (HRP). We demonstrate the utility of this probe using three kinds of heavy metal complete antigens and three monoclonal antibodies (McAbs) in one ELISA system to establish a high-throughput screening protocol. The procedure was successfully applied to analysis of Hg(II), Pb(II) and Cd(II) individually and totally from different water samples. The sensitivities for the detection of Hg(II), Pb(II) and Cd(II) individually and totally are 27.4, 3.9, 15.8 and 18.2 nM, respectively. And all limit of detection (LODs) are lower than 1.2 nM. The recovery results obtained from the developed technique showed a good correlation (R² = 0.983) with those from ICP-MS. The major advantage of the probe is the versatility and high sensibility. The probe could be potentially used, upon demand, as a sensitive and versatile detector for a broad range of applications.     

防城港临时性海洋倾倒区沉积物重金属污染现状及其生态风险评价

对防城港临时性海洋倾倒区表层沉积物重金属的含量和分布进行了对比分析,并采用污染指数法和Hakanson潜在生态风险指数法对其重金属的污染特征及潜在生态风险程度进行了评价。结果表明,倾倒区沉积物Hg、Pb、As和Zn的含量显著性升高;总体污染程度为中等污染,各重金属元素的污染程度由高到低排序依次为As(3.59)>Hg(2.19)>Pb(1.42)>Zn(1.20)>Cu(1.05)>Cd(0.91),其中As是主要污染因子;该海域表层沉积物重金属总体潜在生态风险程度为中等,各重金属元素的潜在生态风险程度由高到低排序依次为Hg(87.74)>As(35.89)>Cd(27.27)>Pb(7.08)>Cu(5.23)>Zn(1.20),其中Hg为主要潜在生态风险因子。     

Valence tautomerism and macrocycle ruffling in nickel(III) porphyrins

Nonlocal density functional calculations with full geometry optimization have been carried out on the low-lying electronic states of oxidized nickel porphyrins. For [NiIII(P)(Py)2]+, the ground state corresponds to a t2g6(z2)1 configuration and the t2g6(x2-y2)1 configuration is 0.43 eV higher in energy. In contrast, the ground state of [NiIII(P)(CN)2]- corresponds to a t2g6(x2-y2)1 configuration, the t2g6(z2)1 configuration being 0.96 eV higher in energy. The results are consistent with EPR spectroscopic results on the TPP analogs of these complexes. For [Ni(P)(Py)2]+, the a2u- and a1u-type Ni(II) porphyrin cation radical states are higher in energy by 0.63 and 1.23 eV, respectively, relative to the t2g6(z2)1 Ni(III) ground state. The Ni-N(Porphyrin) distance is significantly shorter in [NiIII(P)(Py)2]+ (196 pm) than in [NiIII(P)(CN)2]- (206 pm), which is consistent with the ruffled and planar macrocycle conformations, respectively, in the two complexes.     

Synthesis, characterization, and antibacterial activity of novel Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with vitamin K3-thiosemicarbazone

Vitamin K3-thiosemicarbazone (C12H11N3NaO4S2 x 5H2O, abbreviated as VT), a new Schiff base derivative, has been synthesized. Its crystal structure, determined by X-ray diffraction, is triclinic, space group P1. We have also prepared five novel complexes of VT with transition metals: [M(VT)(2)2H2O] x nH2O, (n = 1 and 2 for M = Cu(II) and Zn(II), respectively) and [M'(HVT)2Cl2] x mH2O, (m = 4, 5, and 7 for M' = Co(II), Mn(II), and Ni(II), respectively). These compounds were characterized by IR and UV-Vis spectroscopy, molar conductivity, thermal analyses, complexometric titration, and elemental analysis. In all the complexes, the VT ligand coordinates through sulfur and oxygen atoms, and the geometry around metal atom is best described as octahedral. In vitro tests of antibacterial activity showed that VT and its complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) all had strong inhibitory actions against G(+) Staphylococcus aureus, G(+) Hay bacillus, and G(-) Escherichia coli.