[Correlations between solubility of metal compounds and their toxicity, distribution and elimination from the body (review)].
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Selenium and the brain: a review.
Similar to other tissues selenium from selenomethionine is deposited in the brain at higher concentrations than selenium in other forms. Vitamin E has a greater effect than selenium in reducing lipid peroxidation in various brain regions. Selenium does not have as great effect on glutathione peroxidase (GPX) activity in the brain as in most other organs. Prolonged selenium and iodine deficiencies will compromise thyroid hormone homeostatus in the brain and this is due to changes in deiodinases activities and lipid peroxidation. Even though selenium deficiency results in reduced GPX activity and selenium content in the brain, there is no reduction in thioredoxin reductase activity or selenoprotein W levels. Selenoprotein P is taken up in greater amounts by the brain but not by other organs in selenium deficient animals, suggesting a critical function of this selenoprotein in this organ. Selenium will influence compounds with hormonal activity (and neurotransmitters) in the brain, and this is postulated to be the reason selenium affects moods in humans and behavior in animals. Even though selenium counteracts the neurotoxicity of mercury, cadmium, lead and vanadium, it causes them to accumulate in the brain, presumably in a nontoxic complex.
Animals↗
Catalase degrades diperoxovanadate and releases oxygen.
On incubation with catalase diperoxovanadate was found to be degraded, showing a decrease in its absorbance at 356 nm and a loss of its peak with a chemical shift at -706 ppm in its 51V NMR spectrum. The products of the reaction had an absorption peak at 266 nm and chemical shifts at -569 and -578 ppm in NMR spectra assigned to dimer and tetramer of vanadate, respectively. Catalase released half the molecular equivalent of oxygen during this degradation of diperoxovanadate with a rate two orders of magnitude lower than that seen with H2O2. By substituting for and not releasing H2O2, diperoxovanadate supported scopoletin oxidation by horseradish peroxidase, as indicated by the reaction being not sensitive to catalase, unlike that seen with H2O2. Catalase-dependent oxygen release was sensitive to azide with both H2O2 and diperoxovanadate as substrates, whereas EDTA selectively inhibited this reaction with diperoxovanadate. The results bring out the potential of catalase in degrading diperoxovanadate and suggest caution in the use of this enzyme to destroy excess H2O2 during preparation of this compound.
Animals↗
A new class of ferromagnetically-coupled mixed valence vanadium(IV/V) polyoxometalates.
Reaction of [V(VI)OCl(2)(thf)(2)] with a bidentate nitrogen-donor ligand (L: phen=1,10-phenanthroline, 5-mephen=5-methyl-1,10-phenanthroline, bipy=2,2'-bipyridine, 5,5'-me(2)bipy=5,5'-dimethyl-2,2'-bipy) in methyl alcohol, in the presence of triethylamine, leads to the formation of hexameric [V(2) (IV)V(4) (V)] oxo-alkoxo-vanadates of the general formula [V(6)O(12)(mu(2)-OCH(3))(4)(L)(4)].x H(2)O [L=phen (1.4 H(2)O), 5-mephen (2.6 H(2)O), bipy (3.4 H(2)O), 5,5'-me(2)bipy (4.H(2)O)]. X-ray structure analysis of 1.2 H(2)O and 4.8 CH(3)OH revealed a pair of V(3)O(13)N(4) trimeric units sharing two corners, with a centrosymmetric planar V(6)-core. In addition, a fully oxidized V(V) species [V(V) (4)O(8)(OCH(3))(2)(mu(3)-OCH(3))(2)(5,5'-me(2)bipy)(2)].3 CH(3)OH (5.3 CH(3)OH) was isolated from the reaction mixture used for the synthesis of 4.H(2)O. The crystal structure of 5.3 CH(3)OH revealed a dicubane-like framework with two missing vertices. Electron paramagnetic resonance (EPR) and variable temperature magnetic susceptibility studies for the hexamers 1.4 H(2)O and 3.4 H(2)O showed the complete localization of the single 3d electrons on the V(IV) ions and unusual ferromagnetic interaction between the two paramagnetic vanadium(IV) ions separated by a distance of about 5.1 A. Furthermore, intermolecular antiferromagnetic interactions through pi-contacts of phenyl rings were observed for these species below 8 K. The ferromagnetic exchange coupling observed in the hexanuclear compounds 1.4 H(2)O and 3.4 H(2)O is also discussed using ab initio UHF calculations on a model compound. The value of the exchange coupling constant (3.7 cm(-1)) for this model compound, calculated using the broken symmetry approach, is in good agreement, both in sign and magnitude, with the experimental J values (6.00 cm(-1) for 1.4 H(2)O and 8.54 cm(-1) for 3.4 H(2)O).
Journal Article↗
Effects of reducing reagents and temperature on conversion of nitrite and nitrate to nitric oxide and detection of NO by chemiluminescence.
To measure the concentration of nitrites and nitrates by chemiluminescence, we examined the efficiency of five reducing agents [V(III), Mo(VI) + Fe(II), NaI, Ti(III), and Cr(III)] to reduce nitrite (NO2-) and (or) nitrate (NO3-) to nitric oxide (NO). The effect of each reducing agent on the conversion of different amounts of NO2- and (or) NO3- (100-500 pmol, representing concentrations of 0.4 to 2 mu molar) to NO was determined at 20 degrees C for NO2- and at 80 degrees C for NO3-. The effect of temperature from 20 to 90 degrees C on the conversion of a fixed amount of NO2- or NO3- (400 pmol or 1.6 mu molar) to NO was also determined. These five reducing agents are similarly efficient for the conversion of NO2- to NO at 20 degrees C. V(III) and Mo(VI) + Fe(II) can completely reduce NO3- to NO at 80 degrees C. NaI and Cr(III) were unable to convert NO3- to NO. Increased temperature facilitated the conversion of NO3- to NO, rather than that of NO2- to NO. We evaluated the recovery of NO2- and NO3- from plasmas of pig and of dog. Recovery from plasma of both animals was reproducible and near quantitative.
Animals↗
Two novel vanadium tellurites covalently bonded with metal-organic complex moieties: M(phen)V(2)TeO(8) (M = Cu, Ni).
Two novel two-dimensional organic-inorganic hybrid vanadium tellurites M(phen)V(2)TeO(8) (M = Cu (1), Ni (2)) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, EPR spectrum, XPS spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9.2193(18) A, b = 7.9853(16) A, c = 21.401(4) A, beta = 97.54(3) degrees, and Z = 4. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9.2163(18) A, b = 7.9897(16) A, c = 21.386(4) A, beta = 97.52(3) degrees, and Z = 4. Compounds 1 and 2 are isostructural, and both exhibit interesting two-dimensional networks with [V(2)TeO(8)]( infinity ) double-chain-like ribbons bridged by metal-organic complex moieties [M(phen)](2+) (M = Cu and Ni). Furthermore, the three-dimensional supramolecular architectures of compounds 1 and 2 are formed by pi-pi stacking interactions of phen groups between adjacent layers.
Journal Article↗
Potent dual anti-HIV and spermicidal activities of novel oxovanadium(V) complexes with thiourea non-nucleoside inhibitors of HIV-1 reverse transcriptase.
We have previously demonstrated that tetrahedral bis(cyclopentadienyl)vanadium(IV) complexes and square pyramidal oxovanadium(IV) complexes of vanadium are rapid and selective spermicidal agents at low micromolar concentrations. This study investigated the potential utility of oxovanadium in combination with thiourea non-nucleoside inhibitors (NNIs) of HIV-1 reverse transcriptase (RT) for the development of an effective dual-function anti-HIV spermicide. Two rationally designed substituted phenyl-ring containing pyridyl thiourea NNIs, N-[2-(2-chlorophenethyl)]-N(')-[2-(5-bromopyridyl)-thiourea) [1] and N-[2-(2-methoxyphenethyl)]-N(')-[2-(pyridyl)-thiourea [2] that exhibited subnanomolar IC(50) values against the drug-sensitive, drug-resistant, and multidrug-resistant strains of HIV-1, were complexed with oxovanadium. The oxovanadium-thiourea [OVT] NNIs, C(29)H(27)Br(2)Cl(2)N(6)O(2)S(2)V [3], and C(31)H(35)N(6)O(4)S(2)V [4], were synthesized by reacting VOSO(4), a V(IV) compound, with the corresponding deprotonated thiourea NNI compounds as ligands. Elemental analysis showed that each OVT-NNI used two thiourea molecules as ligands. The existence of the Vz.dbnd6;O bond (968cm(-1)) was confirmed by IR spectroscopy. No d-d bands were observed in the visible spectra of OVT-NNIs and their EPR spectra were featureless, indicating that the vanadium centers were oxidized to V(V). The new OVT-NNIs as well as their thiourea NNI ligands were evaluated for (i) anti-HIV activity using the cell-free recombinant RT inhibition assays, (ii) cellular HIV replication assays, (iii) spermicidal activity against human sperm by computer-assisted sperm analysis (CASA), and (iv) cytotoxicity against normal human female genital tract epithelial cell using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) dye-reduction assays. Similar to thiourea NNIs 1 and 2, the OVT-NNIs 3 and 4, exhibited potent anti-HIV activity with submicromolar IC(50[p24]) values (0.08 and 0.128 microM, respectively) and submicromolar IC(50[RT]) values (2.1 and 0.87 microM, respectively). Notably, OVT-NNIs were spermicidal against human sperm at low micromolar concentrations (IC(50)=34 and 55 microM, respectively) and induced rapid sperm immobilization (T(1/2)=12 and 240s) when compared with their respective thiourea NNI ligands (EC(50)=>400 microM and T(1/2)=>180min). Moreover, OVT-NNIs displayed high selectivity indices against normal female genital tract epithelial cells (IC(50) values >250 microM) when compared to the detergent-type spermicide, nonoxynol-9, which was cytotoxic at spermicidal concentrations (IC(50) values 32-64 microM). This is the first report on the dual anti-HIV and spermicidal activities of a vanadium/oxovanadium complex. Our discovery of potent anti-HIV and rapid spermicidal activities of OVT-NNIs may be useful for the development of an effective and safe vaginal anti-HIV spermicide for women who are at high risk for acquiring HIV/AIDS by heterosexual transmission.
Anti-HIV Agents↗
An organically templated cobalt-vanadium oxide with beta cage units: hydrothermal synthesis and x-ray structural characterization of (C(2)H(10)N(2))[Co(2)(C(2)O(4))V(4)O(12)].
A novel organically templated cobalt-vanadium oxalate, (C(2)H(10)N(2))[Co(2)(C(2)O(4))V(4)O(12)], was synthesized under mild hydrothermal conditions and characterized by single-crystal/powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The compound crystallizes in an orthorhombic system with space group Cmcm and cell parameters a = 11.527(2) A, b = 9.9476(18) A, c = 14.780(3) A. The compound possesses 3-dimensional topologies with sodalite analogue structure and is constructed by C(2)O(4)-incorporated beta cage units. On the basis of the results of TG/DTA analyses, the structure is thermally stable up to approximately 573 K.
Journal Article↗
Cell apoptosis induced by carcinogenic metals.
Well-documented evidence suggests that environmental and occupational exposure of toxic metals or metal-containing compounds can cause a number of human diseases, including inflammation and cancer, through DNA damage, protein modifications, or lipid peroxidation. This mini-review addresses the mechanisms of cell death induced by some carcinogenic metals, including arsenic (III), chromium (VI) and vanadium (V). A possible contribution of reactive oxygen species to metal-induced cell death is also discussed.
Animals↗
Vanadium: genetical and biochemical investigations.
Ammonium metavanadate was studied for its ability to induce mitotic gene conversion and reverse point mutation in the D7 strain of Saccharomyces cerevisiae. Metavanadate increased the convertant and revertant frequencies; the highest activity was observed without metabolic activation. This indicated that the S9 hepatic fraction and yeast cells in logarithmic phase (and containing a high level of cytochrome P450) biotransform vanadate, probably reducing it to vanadyl. In addition, the effect of ammonium metavanadate on the hepatic monooxygenase system was studied in mice by measuring the level of cytochrome P450 and determining the activities of aminopyrine N-demethylase, p-nitroanisole O-demethylase and 7-ethoxycoumarin O-deethylase in mouse liver microsomal fraction. The results indicated that this compound reduced mono-oxygenase activity and also the level of cytochrome P450.
7-Alkoxycoumarin O-Dealkylase↗
Competing Magnetic Exchange Interactions in Tetranuclear d(1) Systems: Synthesis, Structure, and Magnetochemistry of a Neutral Vanadium(IV) Complex with a {(VO)(4)(&mgr;(3)-OR)(2)(&mgr;(2)-OR)(4)}(2+) Core.
The complex [{VO(L)}(2){VO(acac)}(2)(&mgr;(2)-OMe)(2)] 1 can be synthesized by reaction of the Schiff base ligand N,N-bis(2-hydroxyethyl)-N'-(2-pyrrolylmethylidene)ethylenediamine (H(2)L) with [VO(acac)(2)] (Hacac = 2,4-pentanedione). The compound 1.MeOH has been characterized by IR, UV/vis, and ESR spectroscopy as well as magnetic susceptibility measurements. A single-crystal diffraction study performed on 1. MeOH gives the following crystal data: triclinic, P&onemacr;, a = 7.352(2) Å, b = 12.584(4) Å, c = 12.826(4) Å, alpha = 107.61(2) degrees, beta = 102.96(2) degrees, gamma = 95.25(2) degrees, Z = 1. The tetranuclear {(VO)(4)(&mgr;(3)-OR)(2)(&mgr;(2)-OR)(4)}(2+) core of 1 is composed of three different types of edge-shared binuclear units, an anti-coplanar, two syn-coplanar, and two twist configurations. Consistent with this connectivity pattern, analysis of the magnetic data reveals competing ferromagnetic and antiferromagnetic exchange interactions within the tetranuclear core structure. Both ESR and magnetic data indicate a singlet ground state for 1. In addition, the general magnetic behavior of oxovanadium(IV) clusters is discussed on the basis of classification schemes derived from simple binuclear fragmentation patterns. Consistent with the superexchange mechanism expected to be operative for binuclear oxovanadium(IV) units with syn-coplanar configuration, the corresponding magnetic exchange parameter J(sc) of 1 (V.V = 3.410(2) Å) is determined to be antiferromagnetic at -153 cm(-)(1).
Journal Article↗
Imidovanadium(v) complexes as reaction partners for kinetically stabilized phosphaalkynes: synthesis of 1,2,4-azaphosphavanada(v)-cyclobutenes, 1,3,5-triphosphabenzenes, and 1H-1,2,4-azadiphospholes.
Cycloaddition reactions of the kinetically stabilized phosphaalkynes 1 with the imidovanadium(v) trihalides 9 furnish the 1,2,4-azaphosphavanada(v)cyclobutenes 10. The stability of these novel metallacyclic compounds depends solely on the substitutents of the imido unit. Thus, the imidovanadium(v) species 9 with tertiary alkyl groups on the N atom form stable addition products with 1 while in the cases of compounds 9 with a lower degree of substitution at N (primary and secondary alkyl groups) the primarily formed adducts 10 undergo irreversible decomposition to afford the 1H-1,2,4-azadiphospholes 13. Reactions of an excess of the phosphaaalkyne 1 with the vanadium complexes 9 furnish the corresponding triphosphabenzenes 8 in good yields (36-68%). A catalytic reaction course has been demonstrated for the all-tert-butyl system 1a/9a in which the metallacyclic species 10a serves as the catalytically active species. Poisoning of the catalyst leads to a second reaction pathway, which results in formation of the azatetraphosphaquadricyclanes 16. By means of the stepwise use of different phosphaalkynes 1a,b this methodology provides the first access to the differently substituted triphosphabenzenes through cyclotrimerization.
Journal Article↗
Amelioration of radiation-induced oxidative stress and biochemical alteration by SOD model compounds in pre-treated gamma-irradiated rats.
INTRODUCTION: The role of metalloelements in tissue maintenance, function and response to injury offer a new approach to decreasing and/or treating radiation injury. We investigated the roles of CuL(2)SO(4), [MnL(2)O](2)Cl(4)(H(2)O)(2) and [(VL(2)O)(VL(2)H(2)O)]Cl(6) complexes (L=2-methylaminopyridine) of SOD-mimetic activities, in ameliorating the radiation-induced oxidative stress and alterations in some biochemical parameters in liver, kidney, spleen and brain in pretreated female rats exposed to gamma-irradiation. METHODS: Both untreated-rats and rats treated with the above complexes were subjected to whole-body gamma-irradiation (6 Gy). 5'-Nucleotidase (5'-NT), acetylcholinesterase (AChE), adenosne triphosphatase (ATPase), superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GSSG-R) were assessed as well as liver DNA and RNA contents and total protein concentration were estimated in tissue homogenates of the above organs. The same parameters were assessed in non-irradiated treated rats and normal control rats. Results were compared to irradiated non-treated and normal control rats. RESULTS: Pretreatment of gamma-irradiated rats with Mn(IV) or V(IV) complex produced a significant decrease in liver 5'-NT activity compared to the corresponding value of the untreated irradiated rats. In contrast, liver DNA and RNA contents and brain AChE and ATPase activities were significantly increased in irradiated rat group pre-treated with these metal complexes. Cu II, Mn IV or V IV complex inoculation prior to irradiation of normal rats exhibited a significant increase in SOD, CAT, GSSG-R activities and protein content of liver, kidney, spleen and brain homogenates compared with that of the untreated irradiated rats. The treatment of non-irradiated rats with these complexes produced a highly significant increase in mean activities of SOD and CAT, with no changes in other parameters vs. controls. CONCLUSIONS: Cu(II), Mn(IV) and V(IV) 2-methylaminopyridine complexes offer a physiological approach to ameliorate the radiation-induced biochemical alterations. In addition, they provide sufficient protection against radiation injury of radiosensitive tissues.
5'-Nucleotidase↗
Effect of oxovanadium(IV) complexes on nondiabetic and streptozotocin-diabetic rats.
The effects of vanadium complexes with organic ligands, [VO(phen)2]SO4.3H2O, [VO(bpy)2]SO4.2H2O, and [VOCl2(Hmcp)2H2O], on blood glucose and plasma lipid levels were studied in nondiabetic and streptozotocin-diabetic rats and compared to that of [VO(mal)2] (the reference compound). The present results provide evidence that the compounds examined possess lower toxicity than [VO(mal)2]. One of the compounds examined, viz. [VO(bpy)2]SO4.2H2O, decreases, statistically significantly, the glucose level and a second one, viz. [VOCl2(Hmcp)2H2O], decreases, also significantly, the total cholesterol level.
Animals↗
V4S9Br4: a novel high-spin vanadium cluster thiobromide with square-planar metal core.
The novel vanadium thiobromide, V4S9Br4, with a square-planar metal cluster core was synthesized and characterized by single-crystal X-ray diffraction, measurements of magnetic properties and the heat capacity, and DFT calculations of the electronic structure. At the room temperature, the compound displays paramagnetic properties with an independent spin on each V atom and with a weak exchange constant (J approximately 10 cm(-1)). The paramagnetic state is transformed into a low-spin state (AF-type ordering) at low temperatures. This change is accompanied by a heat-capacity anomaly. The observed magnetic and heat-capacity anomalies can be explained by the thermal excitation of electrons on the closely spaced molecular energy levels in the presence of the Jahn-Teller effect.
Journal Article↗
Peroxide(s) of vanadium: a novel and potent insulin-mimetic agent which activates the insulin receptor kinase.
The actions of insulin, vanadate (V) and hydrogen peroxide (H2O2) on IGF-II binding and insulin receptor tyrosine kinase activity were studied in rat adipocytes. Incubating adipocytes with a combination of V plus H2O2 resulted in a potent synergistic effect on both the increase in IGF-II binding and the activation of the insulin receptor kinase. Catalase, which removes H2O2, abolished this synergism if added at the time of mixing of V plus H2O2 but not if added 10 min. later, suggesting that the formation of peroxide(s) of vanadate generated a potent insulin mimicker. The data support a critical role for the insulin receptor kinase in insulin action. The novel insulin-mimetic compound, a presumed peroxide of vanadate, could prove useful for investigating insulin action and may be valuable for treating insulin resistance.
Adipose Tissue↗
Diabetes-induced abnormalities in the myocardium.
One of the leading causes of mortality in diabetics is myocardial disease. In the past few years this subject has generated a significant amount of interest with the result that myocardial problems associated with diabetes are far better understood. Though originally thought to occur as a result of atherosclerosis, various studies have shown that heart disease can occur in the absence of atherosclerosis, suggesting a diabetic cardiomyopathy. Using diabetic animals, it has been possible to characterize diabetes-induced myocardial abnormalities. Diabetic rat hearts do not respond to conditions of high stress as well as controls. The functional depression is accompanied by altered cardiac enzyme systems. A decrease in myosin ATPase activity which appears to be a result of diabetes-induced hypothyroidism is seen. Also, a depression of sarcoplasmic reticular calcium ATPase, along with a depression of calcium uptake by the SR, is seen in diabetic rat hearts. Na+, K+ ATPase activity has also been shown to be depressed and the depression appears to correlate with depressed atrial contractility. High levels of circulating fats in diabetics may alter the integrity of membranes leading to altered enzyme activities. Insulin treatment has been relatively successful at reversing or preventing myocardial changes in the diabetic rat. Other treatments that have been studied include thyroid hormone treatment, since the depression of myosin ATPase can be corrected by such treatment; and carnitine treatment, as the elevation of long chain acyl carnitines (LCAC) and the resulting depression of calcium uptake in the SR can be so normalized. These treatments have not been successful at normalizing cardiac function. A combination of the two treatments normalized function only partially, suggesting that factors besides myosin ATPase and SR calcium uptake are involved. Other treatments that have been tried include vanadate, methyl palmoxirate, and choline and methionine. Vanadate treatment has proved to be encouraging in that it normalizes both function and hyperglycemia. Methyl palmoxirate, a fatty acid analog, normalized only the elevation of LCAC but did not affect function. Methionine and choline were only partially successful in preventing the functional alterations of diabetic rat hearts. The purpose of the present article is to review our understanding of diabetes-induced myocardial problems and their possible causes. Findings from our laboratory and others are described in which attempts have been made to normalize cardiac function.
Adenosine Triphosphatases↗
A vanadium and iron cluster accumulates on VnfX during iron-vanadium-cofactor synthesis for the vanadium nitrogenase in Azotobacter vinelandii.
The vnf-encoded nitrogenase from Azotobacter vinelandii contains an iron-vanadium cofactor (FeV-co) in its active site. Little is known about the synthesis pathway of FeV-co, other than that some of the gene products required are also involved in the synthesis of the iron-molybdenum cofactor (FeMo-co) of the widely studied molybdenum-dinitrogenase. We have found that VnfX, the gene product of one of the genes contained in the vnf-regulon, accumulates iron and vanadium in a novel V-Fe cluster during synthesis of FeV-co. The electron paramagnetic resonance (EPR) and metal analyses of the V-Fe cluster accumulated on VnfX are consistent with a VFe7-8Sx precursor of FeV-co. The EPR spectrum of VnfX with the V-Fe cluster bound strongly resembles that of isolated FeV-co and a model VFe3S4 compound. The V-Fe cluster accumulating on VnfX does not contain homocitrate. No accumulation of V-Fe cluster on VnfX was observed in strains with deletions in genes known to be involved in the early steps of FeV-co synthesis, suggesting that it corresponds to a precursor of FeV-co. VnfX purified from a nifB strain incapable of FeV-co synthesis has a different electrophoretic mobility in native anoxic gels than does VnfX, which has the V-Fe cluster bound. NifB-co, the Fe and S precursor of FeMo-co (and presumably FeV-co), binds to VnfX purified from the nifB strain, producing a shift in its electrophoretic mobility on anoxic native gels. The data suggest that a precursor of FeV-co that contains vanadium and iron accumulates on VnfX, and thus, VnfX is involved in the synthesis of FeV-co.
Azotobacter vinelandii↗