RESUMEN
We have previously synthesized and characterized the chrysin coordination complex with the oxidovanadium(IV) cation (VIVO(chrys)2) and characterized in ethanolic solution and in solid state. Because suitable single crystals for X-ray diffraction determinations could not be obtained, in the present work, we elucidate the geometrical parameters of this complex by computational methodologies. The optimization and vibrational investigation were carried out both in ethanolic solution and in gas phase. The computational results support the experimentally proposed geometries of the VIVO(chrys)2 complex, thus leading to the conclusion that the complex exists as conformers with trans-octahedral geometry in ethanolic solution and as conformers with cis-octahedral geometry in the solid state. The complex also exists as conformers with trans-octahedral geometry in aqueous media. The active species formed after dissolution in DMSO showed anticancer and antimetastatic behavior in human lung cell line A549 with moderate binding (Kaca. 105 M-1) to bovine serum albumin (BSA). The interaction through hydrogen bonding and van der Waals forces resulted in a spontaneous process. Site marker competitive experiments showed binding sites for chrysin mainly located in site II (subdomain IIIA) and in site I (subdomain IIIA) for the complex. FT-IR spectral measurements showed evidences of the alterations of protein secondary structure in the presence of chrysin and VIVO(chrys)2.
Asunto(s)
Antineoplásicos/farmacología , Movimiento Celular/efectos de los fármacos , Complejos de Coordinación/farmacología , Flavonoides/farmacología , Albúmina Sérica Bovina/metabolismo , Compuestos de Vanadio/farmacología , Células A549 , Animales , Antineoplásicos/química , Antineoplásicos/metabolismo , Sitios de Unión , Bovinos , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/química , Complejos de Coordinación/metabolismo , Flavonoides/química , Flavonoides/metabolismo , Humanos , Estructura Molecular , Unión Proteica , Conformación Proteica/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Albúmina Sérica Bovina/química , Compuestos de Vanadio/química , Compuestos de Vanadio/metabolismoRESUMEN
The luteinizing hormone receptor (LHR), a G protein-coupled receptor (GPCRs), can initiate signaling in the presence of some vanadium-containing compounds as a result of vanadium compound interactions with the membrane lipids and/or the cell membrane lipid interface. The ability of LHR expressed in CHO cells to initiate signaling in the presence of highly charged and water-soluble polyoxovanadates (POV) including Na3[H3V10O28] (V10) and two mixed-valence heteropolyoxovanadates, K(NH4)4[H6V14O38(PO4)]·11H2O (V14) and [(CH3)4N]6[V15O36(Cl)] (V15), was investigated here. Interactions of the vanadium compounds with CHO cells decreased the packing of membrane lipids, drove aggregation of LHR and increased signal transduction by LHR. Cell responses were comparable to, or in the case of V14 and V15, greater than those seen for cells treated with human chorionic gonadotropin (hCG), a naturally-occurring LHR ligand produced in early pregnancy in humans. POV effects were observed for CHO cells where LHR was expressed at 10 000 or 32 000 LHR per cell but not when LHR was overexpressed with receptor numbers >100 000 LHR per cell. To determine which POV species were present in the cell medium during cell studies, the speciation of vanadate (V1), V10, V14 or V15 in cell medium was monitored using 51V NMR and EPR spectroscopies. We found that all the POVs initiated signaling, but V15 and V10 had the greatest effects on cell function, while V1 was significantly less active. However, because of the complex nature of vanadium compounds speciation, the effects on cell function may be due to vanadium species formed in the cell medium over time.
Asunto(s)
Aniones/metabolismo , Polielectrolitos/metabolismo , Receptores Acoplados a Proteínas G/metabolismo , Compuestos de Vanadio/metabolismo , Animales , Células CHO , Membrana Celular/metabolismo , Gonadotropina Coriónica/metabolismo , Cricetulus , Espectroscopía de Resonancia por Spin del Electrón , Espectroscopía de Resonancia Magnética , Receptores Acoplados a Proteínas G/genética , Vanadatos/metabolismoRESUMEN
Fungi are well known to strongly interact with metals, thereby influencing metal biogeochemistry in the terrestrial environment. To assess and quantify potential fungi-vanadium (V) interactions, Amanita muscaria, Armillaria cepistipes, Xerocomus badius and Bjerkandera adusta were cultured in media containing soluble V (VOSO4 or NaVO3) or solid-phase V of different chemical forms and oxidation state (V2O3, VO2, V2O5, or V-Ti magnetite slag). All fungi underwent physiological and structural changes, as revealed by alterations in FT-IR peak positions and intensities relative to the control, and morphological changes of mycelia, as observed by scanning electron microscopy. The diametric growth size generally decreased with decreasing oxidation state of V and with increasing concentrations of VOSO4 and NaVO3, implying that V toxicity is dependent on V speciation. The tolerance index, the ratio of treated and control mycelium (dry weight), shows different tendencies, suggesting additional factors influencing fungi weight, such as the formation of extrahyphal crystals. Vanadium accumulation from VOSO4 and NaVO3 medium in all fungi (up to 51.3â¯mgâ¯g-1) shows the potential of fungi to immobilise soluble V, thereby reducing its impacts on environmental and human health. Uptake and accumulation of V in slag was insignificant, reflecting the association of slag V with insoluble crystalline materials. The fungal accumulation of V in medium amended with V-oxides demonstrates the ability of fungi to solubilise solid-phase V compounds, thereby introducing previously immobile V into the V biogeochemical cycle and into the food chain where it may impact ecological and human health. A.muscaria lowered the pH of the medium substantially during cultivation, indicating acidolysis and complexolysis via excretion of organic acids (e.g. oxalic acid). Oxidation of VOSO4 was observed by a colour change of the medium to yellow during B. adusta cultivation, revealing the role of fungally-mediated redox transformation in V (im)mobilisation. The calculated removal efficiencies of soluble V were 40-90% for A. cepistipes and X. badius, but a much lower recovery (0-20%) was observed from V oxides and slag (0-20%) by all fungi. This suggests the probable application of fungi for bio-remediation of mobile/soluble V in contaminated soils but not of V incorporated in the lattice of soil minerals.
Asunto(s)
Basidiomycota , Biodegradación Ambiental , Contaminantes del Suelo , Vanadio , Basidiomycota/química , Basidiomycota/efectos de los fármacos , Basidiomycota/metabolismo , Minerales , Oxidación-Reducción , Contaminantes del Suelo/aislamiento & purificación , Contaminantes del Suelo/metabolismo , Contaminantes del Suelo/toxicidad , Vanadio/aislamiento & purificación , Vanadio/metabolismo , Vanadio/toxicidad , Compuestos de Vanadio/aislamiento & purificación , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/toxicidadRESUMEN
Dog's tail grass (Setaria viridis) presented strong tolerance and high accumulation of vanadium in field conditions. Liquid digestate containing high levels of nutrients could alleviate vanadium toxicity and accelerate the growth of dog's tail grass. To elucidate the detoxification potential and mechanism of liquid digestate, dog's tail grass was grown in soil solution containing 0.14-55.8 mg L-1 of vanadium. Parameters including germination index (GI), tolerance index (TI), seedlings' fresh weight, seedlings' vanadium accumulation, antioxidant enzymes activity, malonaldehyde (MDA) content, and V5+ species, were measured after addition of 1%, 5%, 10% and 15% liquid digestate. The results showed that a vanadium level of 10.9 mg L-1was a threshold value for toxicity; furthermore, the GI and TI decreased by 50% when vanadium content reached 36.8 mg L-1. The MDA content was reduced, and the other parameters were markedly enhanced, after addition of 5% and 10% liquid digestate with vanadium levels above 36.8 mg L-1. V5+ species was the dominant vanadium species in solution and the addition of liquid digestate reduced V5+ concentrations. The detoxification of vanadium by liquid digestate was a combined effect of direct reduction of V5+ species and plant nutrition.
Asunto(s)
Contaminantes Ambientales/metabolismo , Contaminantes Ambientales/toxicidad , Restauración y Remediación Ambiental/métodos , Poaceae/crecimiento & desarrollo , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/toxicidad , Antioxidantes/metabolismo , Germinación , Malondialdehído , Poaceae/metabolismo , Plantones/crecimiento & desarrollo , Semillas/crecimiento & desarrollo , Contaminantes del SueloRESUMEN
The impact of vanadium (V) and magnesium (Mg) as sodium metavanadate (SMV, 0.125â¯mgâ¯V/ml) and magnesium sulfate (MS, 0.06â¯mgâ¯Mg/ml) on lipid peroxidation (LPO) and selected elements in the rat erythrocytes (RBCs) was investigated. Relationships between some indices determined in RBC were also studied. SMV alone (Group II) elevated the malondialdehyde level (MDARBC) (by 95% and 60%), compared with the control (Group I) and MS-supplemented rats (Group III), respectively, reduced the concentration of CuRBC (by 23.5%), in comparison with Group I, but did not change the levels of NaRBC, KRBC, and CaRBC, whereas MS alone (Group III) only reduced the CuRBC concentration (by 22%), compared with Group I. The SMV + MS combination (Group IV) reduced and elevated the CuRBC (by 24%) and CaRBC (by 111%) concentrations, respectively, in comparison with Groups I and III, and these changes were induced by the V-Mg antagonistic and synergistic interaction, respectively. The combined SMV + MS effect also enhanced the MDARBC level, compared with Groups I (by 79%) and III (by 47%) and slightly limited its concentration, compared with Group II, which, in turn, resulted from the distinct trend toward the V-Mg antagonistic interaction. We can conclude that V (as SMV) is able to stimulate LPO in rat RBCs and that V-Mg interactive effects are involved in changes in CuRBC, CaRBC, and MDARBC. Further studies are needed to elucidate the exact mechanisms of the V-Mg antagonistic/synergistic interactions and to provide insight into the biochemical mechanisms of changes in rats suffering from anemia [1], characterized by a disrupted antioxidant barrier in RBCs [2] and an intensified free radical process in these cells.
Asunto(s)
Eritrocitos/metabolismo , Sulfato de Magnesio/metabolismo , Óxidos/metabolismo , Compuestos de Vanadio/metabolismo , Animales , Calcio/metabolismo , Cobre/metabolismo , Eritrocitos/citología , Eritrocitos/efectos de los fármacos , Peroxidación de Lípido/efectos de los fármacos , Sulfato de Magnesio/química , Sulfato de Magnesio/farmacología , Masculino , Malondialdehído/metabolismo , Óxidos/química , Óxidos/farmacología , Ratas , Ratas Wistar , Compuestos de Vanadio/química , Compuestos de Vanadio/farmacologíaRESUMEN
Solid wastes are currently produced in large amounts. Although bioleaching of metals from solid wastes is an economical and sustainable technology, it has seldom been used to recycle metals from abandoned catalyst. In this study, the bioleaching of vanadium from V2O5-WO3/TiO2 catalyst were comprehensively investigated through five methods: Oligotrophic way, Eutrophic way, S-mediated way, Fe-mediated way and Mixed way of S-mediated and Fe-mediated. The observed vanadium bioleaching effectiveness of the assayed methods was follows: S-mediatedâ¯>â¯Mixedâ¯>â¯Oligotrophicâ¯>â¯Eutrophicâ¯>â¯Fe-mediated, which yielded the maximum bioleaching efficiencies of approximately 90%, 35%, 33%, 20% and 7%, respectively. The microbial community analysis suggested that the predominant genera Acidithiobacillus and Sulfobacillus from the S-mediated bioleaching way effectively catalyzed the vanadium leaching, which could have occurred through the indirect mechanism from the microbial oxidation of S0. In addition, the direct mechanism, involving direct electron transfer between the catalyst and the microorganisms that attached to the catalyst surface, should also help the vanadium to be leached more effectively. Therefore, this work provides guidance for future research and practical application on the treatment of waste V2O5-WO3/TiO2 catalyst.
Asunto(s)
Biodegradación Ambiental , Vanadio/metabolismo , Catálisis , Titanio/metabolismo , Tungsteno/metabolismo , Compuestos de Vanadio/metabolismoRESUMEN
Nanomaterials with enzyme-like activity (nanozymes) attract significant interest owing to their applications in biomedical research. Particularly, redox nanozymes that exhibit glutathione peroxidase (GPx)-like activity play important roles in cellular signaling by controlling the hydrogen peroxide (H2 O2 ) level. Herein we report, for the first time, that the redox properties and GPx-like activity of V2 O5 nanozyme depends not only on the size and morphology, but also on the crystal facets exposed on the surface within the same crystal system of the nanomaterials. These results suggest that the surface of the nanomaterials can be engineered to fine-tune their redox properties to act as "nanoisozymes" for specific biological applications.
Asunto(s)
Glutatión Peroxidasa/química , Nanoestructuras/química , Compuestos de Vanadio/química , Cristalografía por Rayos X , Glutatión Peroxidasa/metabolismo , Peróxido de Hidrógeno/química , Modelos Moleculares , Tamaño de la Partícula , Propiedades de Superficie , Compuestos de Vanadio/metabolismoRESUMEN
Vanadium compounds have been known to have beneficial therapeutic properties since the turn of the century, but it was not until 1965 when it was discovered that those effects could be extended to treating cancer. Some vanadium compounds can combat common markers of cancer, which include metabolic processes that are important to initiating and developing the phenotypes of cancer. It is appropriate to consider vanadium as a treatment option due to the similarities in some of the metabolic pathways utilized by both diabetes and cancer and therefore is among the few drugs that are effective against more than one disease. The development of vanadium compounds as protein phosphatase inhibitors for the treatment of diabetes may be useful for potential applications as an anticancer agent. Furthermore, the ability of vanadium to redox cycle is also important for biological properties and is involved in the pathways of reactive oxygen species. Early agents including vanadocene and peroxovanadium compounds have been investigated in detail, and the results can be used to gain a better understanding of how some vanadium compounds are modifying the metabolic pathways potentially developing cancer. Considering the importance of coordination chemistry to biological responses, it is likely that proper consideration of compound formulation will improve the efficacy of the drug. Future development of vanadium-based drugs should include consideration of drug formulation at earlier stages of drug development.
Asunto(s)
Anticarcinógenos/uso terapéutico , Antineoplásicos/uso terapéutico , Neoplasias/tratamiento farmacológico , Neoplasias/prevención & control , Compuestos de Vanadio/uso terapéutico , Animales , Anticarcinógenos/efectos adversos , Anticarcinógenos/química , Anticarcinógenos/metabolismo , Antineoplásicos/efectos adversos , Antineoplásicos/química , Antineoplásicos/metabolismo , Complejos de Coordinación , Suplementos Dietéticos/efectos adversos , Composición de Medicamentos , Descubrimiento de Drogas/métodos , Humanos , Estructura Molecular , Neoplasias/metabolismo , Neoplasias/patología , Relación Estructura-Actividad , Compuestos de Vanadio/efectos adversos , Compuestos de Vanadio/química , Compuestos de Vanadio/metabolismoRESUMEN
The interaction of the potential anti-tumor agent vanadocene dichloride ([Cp2VCl2] or VDC) with some relevant bioligands of the cytosol such as proteins (Hb), amino acids (glycine and histidine), NADH derivatives (NADH, NADPH, NAD(+) and NADP(+)), reductants (GSH and ascorbic acid), phosphates (HPO4(2-), P2O7(4-), cAMP, AMP, ADP and ATP) and carboxylate derivatives (lactate) and its uptake by red blood cells were studied. The results indicated that [Cp2VCl2] transforms at physiological pH into [Cp2V(OH)2] and that only HPO4(2-), P2O7(4-), lactate, ATP and ADP form mixed species with the [Cp2V](2+) moiety replacing the two hydroxide ions. EPR and electronic absorption spectroscopy, agarose gel electrophoresis and spin trapping measurements allow excluding any direct interaction and/or intercalation with DNA and the formation of reactive oxygen species (ROS) in Fenton-like reactions. Uptake experiments by erythrocytes suggested that VDC crosses the membrane and enters inside the cells, whereas 'bare' V(IV) transforms into V(IV)O species with loss of the two cyclopentadienyl rings. This transformation in the cellular environment could be related to the mechanism of action of VDC.
Asunto(s)
Antineoplásicos/farmacología , Compuestos de Vanadio/farmacología , Antineoplásicos/metabolismo , ADN/efectos de los fármacos , Eritrocitos/efectos de los fármacos , Humanos , Ligandos , Especies Reactivas de Oxígeno/metabolismo , Compuestos de Vanadio/metabolismoRESUMEN
Oxovanadium(IV)-salen complexes bind with bovine serum albumin (BSA) and ovalbumin (OVA) strongly with binding constant in the range 10(4)-10(7) M(-1) at physiological pH (7.4) confirmed using UV-visible absorption, fluorescence spectral and circular dichroism (CD) study. CD results show that the binding of oxovanadium(IV) complexes induces the conformational change with the loss of α-helicity in the proteins. Docking studies indicate that mode of binding of oxovanadium(IV)-salen complexes with proteins is hydrophobic in nature.
Asunto(s)
Etilenodiaminas/química , Compuestos Organometálicos/metabolismo , Ovalbúmina/metabolismo , Albúmina Sérica Bovina/metabolismo , Espectrometría de Fluorescencia/métodos , Compuestos de Vanadio/metabolismo , Animales , Bovinos , Dicroismo Circular , Interacciones Hidrofóbicas e Hidrofílicas , Simulación del Acoplamiento Molecular , Compuestos Organometálicos/química , Ovalbúmina/química , Unión Proteica , Estructura Secundaria de Proteína , Albúmina Sérica Bovina/química , Termodinámica , Compuestos de Vanadio/químicaRESUMEN
Vanadium is special in at least two respects: on the one hand, the tetrahedral anion vanadate(v) is similar to the phosphate anion; vanadate can thus interact with various physiological substrates that are otherwise functionalized by phosphate. On the other hand, the transition metal vanadium can easily expand its sphere beyond tetrahedral coordination, and switch between the oxidation states +v, +iv and +iii in a physiological environment. The similarity between vanadate and phosphate may account for the antidiabetic potential of vanadium compounds with carrier ligands such as maltolate and picolinate, and also for vanadium's mediation in cardiovascular and neuronal defects. Other potential medicinal applications of more complex vanadium coordination compounds, for example in the treatment of parasitic tropical diseases, may also be rooted in the specific properties of the ligand sphere. The ease of the change in the oxidation state of vanadium is employed by prokarya (bacteria and cyanobacteria) as well as by eukarya (algae and fungi) in respiratory and enzymatic functions. Macroalgae (seaweeds), fungi, lichens and Streptomyces bacteria have available haloperoxidases, and hence enzymes that enable the 2-electron oxidation of halide X(-) with peroxide, catalyzed by a Lewis-acidic V(V) center. The X(+) species thus formed can be employed to oxidatively halogenate organic substrates, a fact with implications also for the chemical processes in the atmosphere. Vanadium-dependent nitrogenases in bacteria (Azotobacter) and cyanobacteria (Anabaena) convert N2 + H(+) to NH4(+) + H2, but are also receptive for alternative substrates such as CO and C2H2. Among the enigmas to be solved with respect to the utilization of vanadium in nature is the accumulation of V(III) by some sea squirts and fan worms, as well as the purport of the nonoxido V(IV) compound amavadin in the fly agaric.
Asunto(s)
Compuestos de Vanadio/metabolismo , Vanadio/metabolismo , Animales , Bacterias/química , Bacterias/enzimología , Bacterias/metabolismo , Descubrimiento de Drogas , Humanos , Modelos Moleculares , Nitrogenasa/química , Nitrogenasa/metabolismo , Peroxidasa/química , Peroxidasa/metabolismo , Vanadio/análisis , Vanadio/farmacología , Compuestos de Vanadio/análisis , Compuestos de Vanadio/farmacologíaRESUMEN
Three dioxidovanadium(V) complexes [VO2L(1-3)] (1-3) [HL(1)=1-napthoyl hydrazone of 2-acetyl pyridine, HL(2)=2-furoyl hydrazone of 2-acetyl pyridine and H2L(3)=isonicotinoyl hydrazone of 2-hydroxy benzaldehyde] have been reported. All the complexes were characterized by various spectroscopy (IR, UV-visible and NMR) and the molecular structures of 1 and 2 were characterized by single crystal X-ray diffraction technique. Structural report established five-coordinate geometries, distorted toward square pyramidal for each of 1 and 2, based on a tridentate -O,N,N coordinating anion and two oxido-O atoms. The experimental results show that the complexes interact with calf-thymus DNA (CT-DNA) possibly by a groove binding mode, with binding constants of ~10(5)M(-1). All complexes show good photo-induced cleavage of pUC19 supercoiled plasmid DNA with complex 1 showing the highest photo-induced DNA cleavage activity of ~68%. 1-3 also exhibit moderate binding affinity in the range of 10(3)-10(4)M(-1) towards bovine serum albumin (BSA), while all the complexes show good photo-induced BSA cleavage activity. Moreover the antiproliferative activity of all these complexes was studied, which reveal all compounds are significantly cytotoxic towards the HeLa cell line.
Asunto(s)
Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/metabolismo , Complejos de Coordinación/farmacología , División del ADN , ADN/metabolismo , Hidrazonas/metabolismo , Hidrazonas/farmacología , Albúmina Sérica Bovina/metabolismo , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/farmacología , Complejos de Coordinación/síntesis química , Complejos de Coordinación/química , Cristalografía por Rayos X , Células HeLa , Humanos , Hidrazonas/síntesis química , Hidrazonas/química , Ligandos , Estructura Molecular , Unión Proteica , Bases de Schiff/química , Rayos Ultravioleta , Compuestos de Vanadio/química , Difracción de Rayos XRESUMEN
The interaction of V(IV)O(2+) ion with hemoglobin (Hb) was studied with the combined application of spectroscopic (EPR), spectrophotometric (UV-vis), and computational (DFT methods) techniques. Binding of Hb to V(IV)O(2+) in vitro was proved, and three unspecific sites (named α, ß, and γ) were characterized, with the probable coordination of His-N, Asp-O(-), and Glu-O(-) donors. The value of log ß for (VO)Hb is 10.4, significantly lower than for human serum apo-transferrin (hTf). In the systems with V(IV)O potential antidiabetic compounds, mixed species cis-VOL2(Hb) (L = maltolate (ma), 1,2-dimethyl-3-hydroxy-4(1H)-pyridinonate (dhp)) are observed with equatorial binding of an accessible His residue, whereas no ternary complexes are observed with acetylacetonate (acac). The experiments of uptake of [VO(ma)2], [VO(dhp)2], and [VO(acac)2] by red blood cells indicate that the neutral compounds penetrate the erythrocyte membrane through passive diffusion, and percent amounts higher than 50% are found in the intracellular medium. The biotransformation of [VO(ma)2], [VO(dhp)2], and [VO(acac)2] inside the red blood cells was proved. [VO(dhp)2] transforms quantitatively in cis-VO(dhp)2(Hb), [VO(ma)2] in cis-VO(ma)2(Hb), and cis-VO(ma)2(Cys-S(-)), with the equatorial coordination of a thiolate-S(-) of GSH or of a membrane protein, and [VO(acac)2] in the binary species (VO)xHb and two V(IV)O complexes with formulation VO(L(1),L(2)) and VO(L(3),L(4)), where L(1), L(2), L(3), and L(4) are red blood cell bioligands. The results indicate that, in the studies on the transport of a potential pharmacologically active V species, the interaction with red blood cells and Hb cannot be neglected, that a distribution between the erythrocytes and plasma is achieved, and that these processes can significantly influence the effectiveness of a V drug.
Asunto(s)
Eritrocitos/metabolismo , Hemoglobinas/metabolismo , Hipoglucemiantes/metabolismo , Compuestos de Vanadio/metabolismo , Adulto , Espectroscopía de Resonancia por Spin del Electrón , Eritrocitos/efectos de los fármacos , Humanos , Hipoglucemiantes/química , Hipoglucemiantes/farmacocinética , Modelos Moleculares , Unión Proteica , Transferrina/metabolismo , Compuestos de Vanadio/química , Compuestos de Vanadio/farmacocinéticaRESUMEN
Vanadium haloperoxidases differ strongly from heme peroxidases in substrate specificity and stability and in contrast to a heme group they contain the bare metal oxide vanadate as a prosthetic group. These enzymes specifically oxidize halides in the presence of hydrogen peroxide into hypohalous acids. These reactive halogen intermediates will react rapidly and aspecifically with many organic molecules. Marine algae and diatoms containing these iodo- and bromoperoxidases produce short-lived brominated methanes (bromoform, CHBr3 and dibromomethane CH2Br2) or iodinated compounds. Some seas and oceans are supersaturated with these compounds and they form an important source of bromine to the troposphere and lower stratosphere and contribute significantly to the global budget of halogenated hydrocarbons. This perspective focuses, in particular, on the biosynthesis of these volatile compounds and the direct or indirect involvement of vanadium haloperoxidases in the production of huge amounts of bromoform and dibromomethane. Some of the global sources are discussed and from the literature a picture emerges in which oxidized brominated species generated by phytoplankton, seaweeds and cyanobacteria react with dissolved organic matter in seawater, resulting in the formation of intermediate brominated compounds. These compounds are unstable and decay via a haloform reaction to form an array of volatile brominated compounds of which bromoform is the major component followed by dibromomethane.
Asunto(s)
Hidrocarburos Bromados/metabolismo , Peroxidasas/metabolismo , Compuestos de Vanadio/metabolismo , Hidrocarburos Bromados/química , Peroxidasas/química , Compuestos de Vanadio/química , VolatilizaciónRESUMEN
Abstract: The objective of the study was to assess the effects of five vanadium organic complexes administered with small insulin injection, on V, Fe, Cu, Zn, Mn, Ca and K concentration in STZ (streptozotocin) diabetic rats tissues during a 5-week treatment with the tested complexes. In all groups of animals, metal concentration in a dry spleen samples was investigated by the proton induced X-ray emission (PIXE) method. Obviously, vanadium tissue concentration was higher in vanadium-treated rats. Concentration of vanadium in the spleen was x = 21.3 microg/g of dry sample. Vanadium administration influenced other metals concentration of rats tissues. The most pronounced influence of vanadium was observed on iron concentration in the spleen. All results were calculated for correlation between different groups of animals. Present study showed small interferences between trace element changes in diabetic, or non diabetic rats after vanadium treatment. Measured elements, especially zinc, manganese and copper, are co-factors of enzymes and their content changes can influence on organism homeostasis in diabetes treatment. Understanding and recognizing these relationship may permit better diabetes treatment in the future.
Asunto(s)
Calcio/metabolismo , Cobre/metabolismo , Diabetes Mellitus Experimental/tratamiento farmacológico , Hipoglucemiantes/farmacología , Hierro/metabolismo , Manganeso/metabolismo , Potasio/metabolismo , Bazo/efectos de los fármacos , Vanadatos/farmacología , Compuestos de Vanadio/farmacología , Zinc/metabolismo , Administración Oral , Animales , Diabetes Mellitus Experimental/inducido químicamente , Diabetes Mellitus Experimental/metabolismo , Hipoglucemiantes/administración & dosificación , Hipoglucemiantes/metabolismo , Insulina/farmacología , Masculino , Ratas , Ratas Wistar , Espectrometría por Rayos X , Bazo/metabolismo , Estreptozocina , Factores de Tiempo , Vanadatos/administración & dosificación , Vanadatos/metabolismo , Compuestos de Vanadio/administración & dosificación , Compuestos de Vanadio/metabolismoRESUMEN
A divanadium(V) complex, [V2O3(o-van-val)2] (o-van-val=Schiff base derived from o-vanillin and L-valine), has been synthesized and structurally characterized. The crystal structure shows that both of the vanadium centers in the complex have a distorted octahedral coordination environment composed of tridentate Schiff base ligand. A V2O3 core in molecular structure adopts intermediate between cis and trans configuration with the O1V1â¯V1AO1A torsion angle 115.22 (28)° and the V1â¯V1A distance 3.455Å. The binding properties of the complex with calf thymus DNA (CT-DNA) have been investigated by UV-vis absorption, fluorescence, CD spectra and viscosity measurement. The results indicate that the complex binds to CT-DNA in non-classical intercalative mode. Meanwhile, the interaction of the complex with bovine serum albumin (BSA) has been studied by UV-vis absorption, fluorescence and CD spectra. Results indicated that the complex can markedly quench the intrinsic fluorescence of BSA via a static quenching process, and cause its conformational change. The calculated apparent binding constant Kb was 1.05×10(6)M(-1) and the binding site number n was 1.18.
Asunto(s)
ADN/metabolismo , Sustancias Intercalantes/química , Óxidos/química , Bases de Schiff/química , Albúmina Sérica Bovina/metabolismo , Valina/química , Compuestos de Vanadio/química , Animales , Sitios de Unión , Bovinos , Sustancias Intercalantes/síntesis química , Sustancias Intercalantes/metabolismo , Sustancias Intercalantes/farmacología , Modelos Moleculares , Óxidos/síntesis química , Óxidos/metabolismo , Óxidos/farmacología , Unión Proteica , Bases de Schiff/síntesis química , Bases de Schiff/metabolismo , Bases de Schiff/farmacología , Análisis Espectral , Valina/síntesis química , Valina/metabolismo , Valina/farmacología , Compuestos de Vanadio/síntesis química , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/farmacologíaRESUMEN
Vanadium is the 21st most abundant element in the Earth's crust and the 2nd-to-most abundant transition metal in sea water. The element is ubiquitous also in freshwater and nutrients. The average body load of a human individual amounts to 1 mg. The omnipresence of vanadium hampers checks directed towards its essentiality. However, since vanadate can be considered a close blueprint of phosphate with respect to its built-up, vanadate likely takes over a regulatory function in metabolic processes depending on phosphate. At common concentrations, vanadium is non-toxic. The main source for potentially toxic effects caused by vanadium is exposure to high loads of vanadium oxides in the breathing air of vanadium processing industrial enterprises. Vanadium can enter the body via the lungs or, more commonly, the stomach. Most of the dietary vanadium is excreted. The amount of vanadium resorbed in the gastrointestinal tract is a function of its oxidation state (V(V) or V(IV)) and the coordination environment. Vanadium compounds that enter the blood stream are subjected to speciation. The predominant vanadium species in blood are vanadate and vanadyl bound to transferrin. From the blood stream, vanadium becomes distributed to the body tissues and bones. Bones act as storage pool for vanadate. The aqueous chemistry of vanadium(V) at concentration <10 µM is dominated by vanadate. At higher concentrations, oligovanadates come in, decavanadate in particular, which is thermodynamically stable in the pH range 2.3-6.3, and can further be stabilized at higher pH by interaction with proteins.The similarity between vanadate and phosphate accounts for the interplay between vanadate and phosphate-dependent enzymes: phosphatases can be inhibited, kinases activated. As far as medicinal applications of vanadium compounds are concerned, vanadium's mode of action appears to be related to the phosphate-vanadate antagonism, to the direct interaction of vanadium compounds or fragments thereof with DNA, and to vanadium's contribution to a balanced tissue level of reactive oxygen species. So far vanadium compounds have not yet found approval for medicinal applications. The antidiabetic (insulin-enhancing) effect, however, of a singular vanadium complex, bis(ethylmaltolato)oxidovanadium(IV) (BEOV), has revealed encouraging results in phase IIa clinical tests. In addition, in vitro studies with cell cultures and parasites, as well as in vivo studies with animals, have revealed a broad potential spectrum for the application of vanadium coordination compounds in the treatment of cardiac and neuronal disorders, malignant tumors, viral and bacterial infections (such as influenza, HIV, and tuberculosis), and tropical diseases caused by parasites, e.g., Chagas' disease, leishmaniasis, and amoebiasis.
Asunto(s)
Compuestos de Vanadio , Vanadio/metabolismo , Fragmentación del ADN , Humanos , Compuestos de Vanadio/efectos adversos , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/uso terapéuticoRESUMEN
Transferrin has shown potential in the delivery of anticancer drugs into primarily proliferating malignant cells that over-express transferrin receptors. Constructing transferrin receptor targeted drug delivery system has been widespread concerned. In this study, whether transferrin could transport noncovalent binding drugs into cancer cells has been investigated. Two representative compounds, doxorubicin hydrochloride (Dox) and vanadocene dichloride (Cp(2)VCl(2)), have been chosen to study the interactions with h-Tf and apo-Tf, and the influences in the presence of h-Tf and apo-Tf by using fluorescence spectroscopy, circular dichroism (CD) spectroscopy and MTT assay. The results have shown that both doxorubicin and Cp(2)VCl(2) could bind to h-Tf and apo-Tf but with different binding modes. The results of MTT assay demonstrate that the presence of both h-Tf and apo-Tf has enhanced the antiproliferative activity of Cp(2)VCl(2). However, the anticancer activity of the mixture of doxorubicin and h-Tf is basically the same as that of doxorubicin does. Our studies indicate that transferrin plays an important role in the transport and targeted delivery of Cp(2)VCl(2) into cancer cells.
Asunto(s)
Antineoplásicos/farmacología , Doxorrubicina/farmacología , Sistemas de Liberación de Medicamentos , Terapia Molecular Dirigida , Receptores de Transferrina/metabolismo , Transferrina/metabolismo , Compuestos de Vanadio/farmacología , Antibióticos Antineoplásicos/química , Antibióticos Antineoplásicos/metabolismo , Antibióticos Antineoplásicos/farmacología , Antineoplásicos/química , Transporte Biológico , Línea Celular Tumoral , Proliferación Celular/efectos de los fármacos , Doxorrubicina/química , Doxorrubicina/metabolismo , Portadores de Fármacos , Diseño de Fármacos , Ensayos de Selección de Medicamentos Antitumorales , Fluorescencia , Humanos , Conformación Molecular , Unión Proteica , Especificidad por Sustrato , Transferrina/química , Compuestos de Vanadio/química , Compuestos de Vanadio/metabolismoRESUMEN
Low molecular weight and high molecular weight metal ion binders present in blood plasma are shortly described. The binding of vanadium and ruthenium complexes by these components has received much attention, namely their interactions with human serum albumin and transferrin, and these studies are critically reviewed. The influence of the protein binding on the bioavailability of the prospective drugs, namely on the transport by blood plasma and uptake by cells is also discussed. It is concluded that vanadium compounds are mainly transported in blood by transferrin, but that no study has properly addressed the influence of albumin and transferrin in the vanadium uptake by cells. Ruthenium complexes bind strongly to HSA, most likely at the level of His residues, leading to the formation of stable adducts. If the kinetics of binding to this protein is fast enough, probably they are mainly transported by this serum protein. Nevertheless, at least for a few Ru(III)-complexes, hTf seems to play an active role in the uptake of ruthenium, while HSA may provide selectivity and higher activity for the compounds due to an enhanced permeability effect.
Asunto(s)
Proteínas Sanguíneas/metabolismo , Complejos de Coordinación/sangre , Compuestos de Rutenio/sangre , Compuestos de Vanadio/sangre , Transporte Biológico , Ensayos Clínicos como Asunto , Complejos de Coordinación/química , Complejos de Coordinación/metabolismo , Complejos de Coordinación/uso terapéutico , Humanos , Peso Molecular , Unión Proteica , Rutenio/sangre , Rutenio/química , Rutenio/metabolismo , Compuestos de Rutenio/química , Compuestos de Rutenio/metabolismo , Compuestos de Rutenio/uso terapéutico , Radioisótopos de Rutenio/sangre , Radioisótopos de Rutenio/química , Radioisótopos de Rutenio/metabolismo , Radioisótopos de Rutenio/uso terapéutico , Albúmina Sérica/metabolismo , Análisis Espectral , Transferrina/metabolismo , Vanadio/sangre , Vanadio/química , Vanadio/metabolismo , Compuestos de Vanadio/química , Compuestos de Vanadio/metabolismo , Compuestos de Vanadio/uso terapéuticoRESUMEN
Vanadium is a trace element present in practically all cells in plants and animals. While the essentiality of vanadium for human beings remains to be well established, vanadium has become an increasingly important environmental metal. Vanadium compounds exert a variety of biological activities and responses. At pharmacological doses, vanadium compounds display relevant biological actions such as insulin and growth factor mimetic or enhancing effects, as well as osteogenic and cardioprotective activity. On the other hand, depending on the nature of compounds and their concentrations, toxicological actions and adverse side effects may also be shown. Nevertheless, the toxic effects may be useful to develop new antitumoral drugs. In this review, the authors summarize current knowledge and new advances on in vitro and in vivo effects of inorganic and organically-chelated vanadium compounds. The effects of vanadium derivatives on some cellular signaling pathways related to different diseases are compiled. In particular, the pathways relevant to the insulin mimetic, osteogenic, cadioprotective and antitumoral actions of vanadium compounds have been comprehensively reviewed. The knowledge of these intracellular signaling pathways may facilitate the rational design of new vanadium compounds with promising therapeutic applications as well as the understanding of secondary side effects derived from the use of vanadium as a therapeutic agent.