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1.
Protein J ; 43(2): 362-374, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38431536

RESUMEN

Protein aggregation is related to numerous pathological conditions like Alzheimer's and Parkinson's disease. In our study, we have shown that an already existing FDA-approved drug; methotrexate (MTX) can be reprofiled on preformed α-chymotrypsinogen A (α-Cgn A) aggregates. The zymogen showed formation of aggregates upon interaction with mercuric ions, with increasing concentration of Hg2Cl2 (0-150 µM). The hike in ThT and ANS fluorescence concomitant with blue shift, bathochromic shift and the hyperchromic effect in the CR absorbance, RLS and turbidity measurements, substantiate the zymogen ß-rich aggregate formation. The secondary structural alterations of α- Cgn A as analyzed by CD measurements, FTIR and Raman spectra showed the transformation of native ß-barrel conformation to ß-inter-molecular rich aggregates. The native α- Cgn A have about 30% α-helical content which was found to be about 3% in presence of mercuric ions suggesting the formation of aggregates. The amorphous aggregates were visualized by SEM. On incubation of Hg2Cl2 treated α- Cgn A with increasing concentration of the MTX resulted in reversing aggregates to the native-like structure. These results were supported by remarkable decrease in ThT and ANS fluorescence intensities and CR absorbance and also consistent with CD, FTIR, and Raman spectroscopy data. MTX was found to increase the α-helical content of the zymogen from 3 to 15% proposing that drug is efficient in disrupting the ß-inter-molecular rich aggregates and reverting it to native like structure. The SEM images are in accordance with CD data showing the disintegration of aggregates. The most effective concentration of the drug was found to be 120 µM. Molecular docking analysis showed that MTX molecule was surrounded by the hydrophobic residues including Phe39, His40, Arg145, Tyr146, Thr151, Gly193, Ser195, and Gly216 and conventional hydrogen bonds, including Gln73 (bond length: 2.67Å), Gly142 (2.59Å), Thr144 (2.81Å), Asn150 (2.73Å), Asp153 (2.71Å), and Cys191 (2.53Å). This investigation will help to find the use of already existing drugs to cure protein misfolding-related abnormalities.


Asunto(s)
Quimotripsinógeno , Reposicionamiento de Medicamentos , Metotrexato , Metotrexato/química , Metotrexato/farmacología , Reposicionamiento de Medicamentos/métodos , Quimotripsinógeno/química , Agregado de Proteínas/efectos de los fármacos , Cloruro de Mercurio/química , Humanos , Simulación del Acoplamiento Molecular , Estructura Secundaria de Proteína
2.
Int J Biol Macromol ; 174: 153-161, 2021 Mar 31.
Artículo en Inglés | MEDLINE | ID: mdl-33484803

RESUMEN

Heavy metal based toxicity has a direct relation with the perturbation of protein structure. We have investigated the progressive unfolding of ovalbumin, in the presence of increasing concentration mercury (0-6.25 µM) using different spectroscopic techniques. Formation of amorphous aggregate has been observed at the physiological pH. Initial addition of HgCl2 resulted in the association of monomers to oligomers that proceeded to non-fibrillar aggregates on further addition. The sigmoidal curve obtained from the Stern-Volmer plot clearly divided into three stage transition. A strong lag phase is observed indicating the time dependence for the association of competent monomers. The second stage was resolved into non-cooperative binding. These results match very well with the data from atomic force microscopy and the free energy change observed in the regions. Raman spectroscopic studies indicated toxic antiparallel ß-sheets structure. Time dependent atomic force microscopy study revealed the off-pathway nature of amorphous aggregates. At molten globular state, similar quenching behaviour is observed. The atomic force microscopy images clearly indicate at pH 2.2 the initiation of fibril formation occurs at lower concentration of HgCl2 itself. Our results revealed the conformation switch of ovalbumin upon the contact of an environmental toxin and its possible way of toxicity.


Asunto(s)
Metales Pesados/toxicidad , Agregado de Proteínas/efectos de los fármacos , Desplegamiento Proteico/efectos de los fármacos , Amiloide/química , Ambiente , Concentración de Iones de Hidrógeno , Cinética , Cloruro de Mercurio/química , Cloruro de Mercurio/toxicidad , Mercurio/química , Mercurio/toxicidad , Metales Pesados/química , Microscopía de Fuerza Atómica/métodos , Conformación Molecular , Ovalbúmina/química , Ovalbúmina/efectos de los fármacos , Transición de Fase , Proteínas/química , Proteínas/efectos de los fármacos , Espectrometría Raman/métodos
3.
Environ Geochem Health ; 43(6): 2433-2442, 2021 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-32488795

RESUMEN

Human activities, especially in industry, have contributed to soil contamination with heavy or toxic metals. The objective of this study was to determine the chelating effect and antioxidant activity of pyrogallol, as well as to evaluate its cytoprotective activity in prokaryotic and eukaryotic models, animal and plant, respectively, against toxic mercury chloride action. Antioxidant activity was determined by DPPH where pyrogallol showed considerable action, chelating even iron ions. For the microbiologic activity assays, microdilution was performed to obtain the minimal inhibitory concentration, minimum bactericidal and minimum fungicide concentration, from which the sub-inhibitory concentrations were determined. The product did not conferred cytoprotection to the tested bacteria and fungi. To evaluate plant cytoprotection, Lactuta sativa seeds were used together with the product at a sub-allelopathic concentration with different HgCl2 concentrations. In this case, the tannin conferred cytoprotection to the plant model, allowing the best growth and development of caulicles and radicles, thus preserving tissues necessary for plant survival. From the results, it is observable that pyrogallol possesses cytoprotective action in the eukaryotic plant model, this action being useful as an alternative which favors the growth of plants in contaminated areas, as the recovering of crop fields or reforestation projects.


Asunto(s)
Lactuca/efectos de los fármacos , Cloruro de Mercurio/toxicidad , Pirogalol/farmacología , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Alelopatía , Antioxidantes/química , Antioxidantes/farmacología , Quelantes/química , Quelantes/farmacología , Germinación/efectos de los fármacos , Quelantes del Hierro/química , Quelantes del Hierro/farmacología , Cloruro de Mercurio/química , Pruebas de Sensibilidad Microbiana , Pirogalol/química , Semillas/efectos de los fármacos , Contaminantes del Suelo/toxicidad
4.
J Membr Biol ; 253(4): 357-371, 2020 08.
Artículo en Inglés | MEDLINE | ID: mdl-32748041

RESUMEN

The existence of mercury in various forms, e.g., elemental, organic, and inorganic has been known for decades. In any of these forms, it is poisonous to metabolism. In this, an investigation about the effect of the inorganic form of mercury, i.e., mercuric chloride (HgCl2) to the mitochondrial voltage-dependent anion channel (VDAC), has been done after isolation from the cardiac and brain tissues of Wistar rats. In vitro electrophysiology experiments were performed in Cardiolipin planar lipid bilayer membrane (BLM) to study the change in the conductance, selectivity, and gating charge of VDAC post HgCl2 treatment. A reduction in mean conductance of VDAC from 4.3 ± 0.18 to 1.66 ± 0.11 nS was observed. Further, the Gating charge calculated before (± 3.5) and after HgCl2 treatment (± 2.3) showed significant difference. Later, VDAC's behavior was studied at different concentrations of HgCl2 ranging from 0.1 µM to 1 mM. The Inhibitory concentration (IC50) was calculated from the linear regression plot. The IC50 was found to be 488.1 µM. In the asymmetrical HgCl2 (5:1), a permeability ratio of cation to anion was found to be 4.2. It is interpreted that VDAC functioning is affected due to the application of 4 mM HgCl2 and a reduction in the conductance, gating charge, and permeability of VDAC was detected. The results provide clues to HgCl2-induced toxicity mediated through VDAC in the Cardiolipin BLM.


Asunto(s)
Activación del Canal Iónico/efectos de los fármacos , Membrana Dobles de Lípidos , Cloruro de Mercurio/metabolismo , Canales Aniónicos Dependientes del Voltaje/metabolismo , Cardiolipinas/química , Cardiolipinas/farmacología , Permeabilidad de la Membrana Celular , Fenómenos Electrofisiológicos , Concentración 50 Inhibidora , Membrana Dobles de Lípidos/química , Potenciales de la Membrana , Cloruro de Mercurio/química , Cloruro de Mercurio/farmacología , Modelos Moleculares , Modelos Teóricos , Conformación Molecular , Relación Estructura-Actividad , Canales Aniónicos Dependientes del Voltaje/química , Canales Aniónicos Dependientes del Voltaje/aislamiento & purificación
5.
Molecules ; 25(15)2020 Jul 27.
Artículo en Inglés | MEDLINE | ID: mdl-32727057

RESUMEN

Optically active (-)589ethyl (S)-2-phenylbutyl thioether, (-)(S)C-Et(PhBu)S (I), and its new diastereoisomeric mercury (II) chloride adduct, 1:2, (-)[(S)S(S)C-Et(PhBu)S.(HgCl2)2]2, (II) were stereoselectively synthesized; the absorbance (UV) and circular dichroism (CD) spectra were measured and the crystal and molecular structure of complex (II) was determined by single-crystal X-ray diffraction. Two different Hg centres are present whose coordination environments are built by two short bonds to chloride ligands in one case, and to one chloride and one sulphur in the other one. These originate digonal units. Electroneutrality is achieved by a further chlorine, which can be considered prevalently ionic and bonded to the two Hg centres, forming square bridging systems nearly perpendicular to the digonal molecules. The coordination polyhedra can be interpreted as 2 + 4 tetragonally-compressed octahedra with the four longer contacts lying in the equatorial plane. IR spectroscopic data are consistent with the presence of one bent and one linear Cl-Hg-Cl moiety. The absolute configurations at both stereogenic centres of the formed diastereoisomeric complex (II) are (S). The (S)S absolute configuration at the stereogenic sulphur atom bonded to the mercury(II) atom in complex (II) has been related with the negative Cotton effect assigned in its circular dichroism (CD) spectrum to a charge-transfer transition at ca. 230 nm. The stereoselective oxidation of (I) and (II) with hydrogen peroxide, induced by the stereogenic carbon atom (S)C of the enantiopure sulphide, gave (-)598ethyl (S)C-2-phenylbutyl(S)S-sulphoxide, (-)598[(S)S(S)C-Et(PhBu)SO], (III), having 18.1% de. Oxidations carried out in the presence of a 200 molar excess of mercury(II) chloride gave (-)598ethyl (S)C-2-phenylbutyl(R)S-sulphoxide, (-) 598[(R)S(S)C-Et(PhBu)SO], (IV) with 31% de, showing the cooperative influence of mercury(II) chloride on the selectivity of the oxidation reaction.


Asunto(s)
Cloruro de Mercurio/química , Compuestos Organometálicos/química , Compuestos de Sulfhidrilo/química , Dicroismo Circular/métodos , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Oxidación-Reducción , Estereoisomerismo
6.
J Biochem ; 167(3): 333-341, 2020 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-31725161

RESUMEN

A novel enzyme, thiourocanate hydratase, which catalyses the conversion of thiourocanic acid to 3-(5-oxo-2-thioxoimidazolidin-4-yl) propionic acid, was isolated from the ergothioneine-utilizing strain, Burkholderia sp. HME13. When the HME13 cells were cultured in medium containing ergothioneine as the sole nitrogen source, thiourocanate-metabolizing activity was detected in the crude extract from the cells. However, activity was not detected in the crude extract from HME13 cells that were cultured in Luria-Bertani medium. The gene encoding thiourocanate hydratase was cloned and expressed in Escherichia coli, and the recombinant enzyme was purified to homogeneity. The enzyme showed maximum activity at pH 7.5 and 55°C and was stable between pH 5.0 and 10.5, and at temperatures up to 45°C. The Km and Vmax values of thiourocanate hydratase towards thiourocanic acid were 30 µM and 7.1 µmol/min/mg, respectively. The enzyme was strongly inhibited by CuCl2 and HgCl2. The amino acid sequence of the enzyme showed 46% identity to urocanase from Pseudomonas putida, but thiourocanate hydratase had no urocanase activity.


Asunto(s)
Burkholderia/enzimología , Hidroliasas/metabolismo , Secuencia de Aminoácidos , Burkholderia/genética , Catálisis , Clonación Molecular , Cobre/química , Escherichia coli/metabolismo , Hidroliasas/antagonistas & inhibidores , Hidroliasas/química , Hidroliasas/genética , Concentración de Iones de Hidrógeno , Cinética , Espectrometría de Masas , Cloruro de Mercurio/química , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Proteínas Recombinantes/metabolismo , Especificidad por Sustrato , Temperatura , Urocanato Hidratasa/genética
7.
Environ Sci Pollut Res Int ; 26(31): 32322-32332, 2019 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-31598926

RESUMEN

Mercury exposure has been shown to affect the reproductive system in many organisms, although the molecular mechanisms are still elusive. In the present study, we exposed Drosophila melanogaster Canton-S adult females to concentrations of 0 mM, 0.1 mM, 0.3 mM, 3 mM, and 30 mM of mercury chloride (HgCl2) for 24 h, 48 h, or 72 h to determine how mercury could affect fertility. Alkaline assays performed on dissected ovaries showed that mercury induced DNA damage that is not only dose-dependent but also time-dependent. All ovaries treated for 72 h have incorporated mercury and exhibit size reduction. Females treated with 30 mM HgCl2, the highest dose, had atrophied ovaries and exhibited a drastic 7-fold reduction in egg laying. Confocal microscopy analysis revealed that exposure to HgCl2 disrupts germinal and somatic cell organization in the germarium and leads to the aberrant expression of a germline-specific gene in somatic follicle cells in developing egg chambers. Together, these results highlight the potential long-term impact of mercury on germline and ovarian cells that might involve gene deregulation.


Asunto(s)
Drosophila melanogaster/genética , Cloruro de Mercurio/metabolismo , Mercurio/metabolismo , Animales , Daño del ADN , Drosophila melanogaster/química , Femenino , Fertilidad , Células Germinativas , Cloruro de Mercurio/química , Mercurio/química , Ovario
8.
ACS Appl Mater Interfaces ; 11(8): 8400-8411, 2019 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-30724070

RESUMEN

The development of novel methods to detect mercury is of paramount importance owing to the impact of this metal on human health and the environment. We observed that flavin mononucleotide (FMN) and its helical assembly with a single-walled carbon nanotube (SWNT) selectively bind Hg2+ arising from HgCl2 and MeHgCl. Absorption spectroscopic studies show that FMN preferentially forms a 2:1 rather than a 1:1 complex with Hg2+ at high FMN concentrations. On the basis of the analogy to the thymine-Hg-thymine complex, it is proposed that the 2:1 complex between FMN and Hg2+ comprises a Hg-bridged pair of FMN groups, regardless of the presence of SWNT. Upon addition of as little as a few hundred nanomoles of Hg2+, both FMN and FMN-SWNT exhibit absorption and photoluminescence (PL) changes. Moreover, FMN-SWNT displays simultaneous multiple sigmoidal changes in PL of SWNT tubes having different chiral vectors. Assessment of binding affinities using the Hill equation suggests that 2:1 and 1:1 complexes form between Hg2+ and FMN groups on the FMN-SWNT. Theoretical calculations indicate that optical changes of the FMN-SWNT originate from Hg-mediated conformational changes occurring on the helical array of FMN on the SWNT. High-resolution transmission electron microscopy revealed that the presence of Hg2+ in complexes with the FMN-SWNT enables visualization of helical periodic undulation of FMN groups along SWNT without the need for staining. Circular dichroism (CD) study revealed that FMN-SWNT whose CD signal mainly originates from FMN decreases dichroic bands upon the addition of Hg2+ owing to the formation of a centrosymmetric FMN-Hg-FMN triad on SWNT. The binding mode specificity and multimodal changes observed in response to Hg2+ ions suggest that systems based on FMN-SWNT can serve as in vivo NIR beacons for the detection of various mercury derivatives.


Asunto(s)
Mononucleótido de Flavina/química , Mercurio/química , Nanotubos de Carbono/química , Dicroismo Circular , Teoría Funcional de la Densidad , Cloruro de Mercurio/química , Compuestos de Metilmercurio/química , Microscopía Electrónica de Transmisión , Espectroscopía Infrarroja por Transformada de Fourier , Timina/química
9.
J Microbiol Biotechnol ; 29(2): 274-282, 2019 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-28783894

RESUMEN

Mercury-resistant (HgR) bacteria were isolated from heavy metal polluted wastewater and soil collected near to tanneries of district Kasur, Pakistan. Bacterial isolates AZ-1, AZ-2 and AZ-3 showed resistance up to 40 µg/ml against mercuric chloride (HgCl2). 16S rDNA ribotyping and phylogenetic analysis were performed for the characterization of selected isolates as Bacillus sp. AZ-1 (KT270477), Bacillus cereus AZ-2 (KT270478) and Bacillus cereus AZ-3 (KT270479). Phylogenetic relationship on the basis of merA nucleotide sequence confirmed 51- 100% homology with the corresponding region of the merA gene of already reported mercuryresistant Gram-positive bacteria. The merE gene involved in the transportation of elemental mercury (Hg0) via cell membrane was cloned for the first time into pHLV vector and transformed in overexpressed C43(DE3) E. coli cells. The recombinant plasmid (pHLMerE) was expressed and the native MerE protein was obtained after thrombin cleavage by size exclusion chromatography (SEC). The purification of fusion/recombinant and native protein MerE by Ni-NTA column, dialysis and fast protein liquid chromatography (FPLC/SEC) involved unfolding/refolding techniques. A small-scale reservoir of wastewater containing 30 µg/ml of HgCl2 was designed to check the detoxification ability of selected strains. It resulted in 83% detoxification of mercury by B. cereus AZ-2 and B. cereus AZ-3, and 76% detoxification by Bacillus sp. AZ-1 respectively (p < 0.05).


Asunto(s)
Bacillus cereus/química , Proteínas Bacterianas/genética , Proteínas Bacterianas/aislamiento & purificación , Farmacorresistencia Bacteriana , Proteínas de la Membrana/genética , Proteínas de la Membrana/aislamiento & purificación , Mercurio/metabolismo , Secuencia de Aminoácidos , Bacillus cereus/clasificación , Bacillus cereus/genética , Bacillus cereus/aislamiento & purificación , Proteínas Bacterianas/química , Proteínas Bacterianas/metabolismo , Secuencia de Bases , Transporte Biológico , Análisis por Conglomerados , Escherichia coli/química , Escherichia coli/genética , Escherichia coli/metabolismo , Expresión Génica , Inactivación Metabólica , Proteínas de la Membrana/química , Proteínas de la Membrana/metabolismo , Cloruro de Mercurio/química , Cloruro de Mercurio/metabolismo , Mercurio/química , Proteínas Recombinantes de Fusión/química , Proteínas Recombinantes de Fusión/genética , Proteínas Recombinantes de Fusión/aislamiento & purificación , Proteínas Recombinantes de Fusión/metabolismo , Microbiología del Suelo , Aguas Residuales/química , Aguas Residuales/microbiología
10.
Molecules ; 23(11)2018 Nov 10.
Artículo en Inglés | MEDLINE | ID: mdl-30423803

RESUMEN

A series of 2-alkyl-2-(N-arylsulfonylindol-3-yl)-3-N-acyl-5-aryl-1,3,4-oxadiazolines were expeditious prepared under microwave-assisted, catalyzed by HgCl2 and solvent-free conditions. This method has the advantage of low catalyst loading and recovering catalyst, ease reaction and repaid reaction times, easy separation products and excellent yields, and more conducive to the large-scale synthesis products. Furthermore, compounds 3s, 3y, 3a', 3b', 3f', 3i', 3q', and 3r' exhibited more potent anti-HIV-1 activity with EC50 values of 3.35, 6.12, 3.63, 9.54, 1.79, 0.51, 3.00, and 4.01 µg/mL, and TI values of 32.66, >32.68, 31.22, 13.94, 24.27, 39.59, 26.01, and 24.51, respectively. Especially compound 3i' displayed the highest anti-HIV-1 activity with TI values of 39.59.


Asunto(s)
Fármacos Anti-VIH/síntesis química , Fármacos Anti-VIH/farmacología , Técnicas de Química Sintética , VIH-1/efectos de los fármacos , Cloruro de Mercurio , Oxadiazoles/síntesis química , Oxadiazoles/farmacología , Solventes , Fármacos Anti-VIH/química , Catálisis , Cloruro de Mercurio/química , Pruebas de Sensibilidad Microbiana , Oxadiazoles/química
11.
Sci Rep ; 8(1): 12074, 2018 08 13.
Artículo en Inglés | MEDLINE | ID: mdl-30104676

RESUMEN

The assessment of neuronal number, spatial organization and connectivity is fundamental for a complete understanding of brain function. However, the evaluation of the three-dimensional (3D) brain cytoarchitecture at cellular resolution persists as a great challenge in the field of neuroscience. In this context, X-ray microtomography has shown to be a valuable non-destructive tool for imaging a broad range of samples, from dense materials to soft biological specimens, arisen as a new method for deciphering the cytoarchitecture and connectivity of the brain. In this work we present a method for imaging whole neurons in the brain, combining synchrotron-based X-ray microtomography with the Golgi-Cox mercury-based impregnation protocol. In contrast to optical 3D techniques, the approach shown here does neither require tissue slicing or clearing, and allows the investigation of several cells within a 3D region of the brain.


Asunto(s)
Encéfalo/citología , Imagenología Tridimensional/métodos , Neuronas , Microtomografía por Rayos X/métodos , Animales , Encéfalo/diagnóstico por imagen , Imagenología Tridimensional/instrumentación , Cloruro de Mercurio/química , Ratones , Tinción con Nitrato de Plata/métodos , Sincrotrones , Fijación del Tejido/métodos , Microtomografía por Rayos X/instrumentación
12.
Chemosphere ; 193: 1094-1104, 2018 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-29874737

RESUMEN

Marine environments are affected by large amounts of toxicants among those mercury (Hg). The aim of this study was to assess potential neurotoxic effects of Hg in the peacock blenny Salaria pavo. A sublethal contamination to 66 µg HgCl2 L-1 over periods of 1, 4, 10 and 15 days was performed. Total Hg concentrations measured in the brain highlighted the detection of Hg at days 1 and 4 following the exposure but no concentration of the metal was further detected. Partial-length cDNA of genes coding ABC transporters (abcb1, abcc1, abcc2, abcg2) and acetylcholinesterase (ache) were characterized. Results from mRNA expression levels displayed an up-regulation of abcb1 mRNA while a down-regulation of abcc1 and abcc2 mRNA was observed. No change in abcg2 and ache mRNA expression was noted throughout the experiment. At each sampling time, Hg exposure did not affect the activity of the AChE enzyme. The histological analysis indicated that fish exhibited several damages in the optic tectum and the cerebellum and 3 reaction patterns were identified for each organ: circulatory disturbances, regressive and progressive changes. Molecular, physiological and histological biomarkers assessed in the present study highlighted that peacock blennies were able to detoxify Hg from the brain tissue by developing defense mechanisms. More globally, neurotoxic effects of a sublethal Hg exposure in the brain of peacock blennies and the adaptation capacity of this species were evaluated.


Asunto(s)
Encéfalo/efectos de los fármacos , Proteínas de Peces/metabolismo , Cloruro de Mercurio/química , Mercurio/química , Perciformes/metabolismo , Animales , Proteínas de Peces/genética
13.
Chem Commun (Camb) ; 54(54): 7439-7442, 2018 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-29771257

RESUMEN

Mercury-binding protein profiles in rat plasma at different levels of mercury exposure in vitro and in vivo were systematically investigated using column gel electrophoresis coupled with inductively coupled plasma-mass spectrometry. The current finding provided various protein candidates that may play critical roles in mercury binding and transporting in plasma.


Asunto(s)
Proteínas Portadoras/sangre , Mercurio/química , Animales , Apolipoproteínas/metabolismo , Glutatión Peroxidasa/metabolismo , Hemoglobinas/metabolismo , Masculino , Cloruro de Mercurio/química , Ratas Wistar , Selenoproteína P/metabolismo , Albúmina Sérica/metabolismo , Transferrina/metabolismo
14.
Bull Exp Biol Med ; 163(6): 726-730, 2017 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-29063335

RESUMEN

The study showed that dinitrosyl iron complex (NO)2Fe(RS)2 containing the thiolate ligands, which is the basic physiological donor of NO, can transfer NO to other molecule only at the moment of rearrangement. This rearrangement can occur during interaction of the complex with more effective iron chelators than the thiolate ligands. In the absence of NO trap, a new complex is formed with a new ligand. NO transfer to a trap can also occur under the action of the agents such as mercury salts or ROS, which interact with the thiolate ligands. Probably, the ligands in the dinitrosyl iron complexes are the structures responsible for interaction of these complexes with physiological targets and for specificity and effectiveness of this interaction.


Asunto(s)
Hierro/química , Donantes de Óxido Nítrico/química , Óxido Nítrico/química , Óxidos de Nitrógeno/química , S-Nitrosoglutatión/química , Animales , Pollos , Quelantes del Hierro/química , Ligandos , Cloruro de Mercurio/química , Oxihemoglobinas/química , Fenantrolinas/química , Soluciones
15.
Talanta ; 171: 262-269, 2017 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-28551139

RESUMEN

It has been broadly recognized that the antagonism between selenium (Se) and mercury (Hg) can reduce the toxicity of mercury in organism. Glutathione (GSH) can participate in the metabolism of Se and Hg in vivo and promote the formation of low-toxic Hg-Se complexes, which is a vital way of detoxification for Hg. In this paper, the reaction mechanism of GSH-Se(IV) binary system, GSH-Hg(II) binary system and GSH-Se(IV)-Hg(II) ternary system were systematically studied from the aspects of stoichiometry, thermodynamics and kinetics, via hyphenated techniques including high performance liquid chromatography (HPLC)-ultraviolet (UV) detection, HPLC-inductively coupled plasma mass spectrometry (ICP-MS) and HPLC-electrospray ionization mass spectrometry (ESI-MS). For GSH-Se(IV) binary system, selenodiglutathione (GSSeSG) was the crucial intermediate; the reaction was exothermic and irreversible at constant pressure; it followed second-order kinetics with a fast kinetics (rate constant (k)=4534.2mol-1Ls-1). For GSH-Se(IV)-Hg(II) ternary system, GSSeSeSG would form by the extremely weak dissociation of two molecules of GSSeSG; Hg(II) would rapidly coordinate with GSSeSeSG to generate (HgxSey)n(GS)m precipitates. The mechanism of GSH-Se(IV)-Hg(II) antagonism system involves two processes, the competitive combination of Hg and Se with GSH and the formation of (HgxSey)n(GS)m complexes.


Asunto(s)
Glutatión/química , Cloruro de Mercurio/química , Cloruro de Mercurio/farmacología , Selenito de Sodio/química , Selenito de Sodio/farmacología , Unión Competitiva , Cinética , Reproducibilidad de los Resultados , Termodinámica
16.
Bull Exp Biol Med ; 162(1): 107-110, 2016 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-27878493

RESUMEN

Studies with the use of highly sensitive enzymatic sensor have shown the presence of various forms of nitrosyl iron complexes, including those undetectable by other methods, in living tissues. All these complexes are long-living compounds and constitute the major part of nitroso compounds in the blood, muscles, liquor, and amniotic fluid.


Asunto(s)
Técnicas Biosensibles/métodos , Donantes de Óxido Nítrico/análisis , Óxido Nítrico/análisis , Compuestos Nitrosos/análisis , Líquido Amniótico/química , Animales , Catalasa/química , Embrión de Pollo , Pollos , Ácido Edético/química , Hemoglobinas/química , Humanos , Peróxido de Hidrógeno/química , Hierro/química , Cloruro de Mercurio/química , Leche/química , Músculo Esquelético/química , Óxido Nítrico/química , Donantes de Óxido Nítrico/química , Nitritos/química , Óxidos de Nitrógeno/química , Compuestos Nitrosos/química , Saliva/química , Semen/química , Compuestos de Vanadio/química
17.
J Org Chem ; 81(21): 10521-10526, 2016 11 04.
Artículo en Inglés | MEDLINE | ID: mdl-27441569

RESUMEN

2-((Phenylsulfonyl)methyl)-4,5-diphenyloxazole is a useful scaffold for synthetic elaboration at the 2-methylene position thereby affording extended oxazoles. The corresponding α-sulfonyl anion reacts smoothly with diverse alkyl halides giving monoalkylated (47-90%), dialkylated (50-97%), and cyclic (59-93%) products. The reductive desulfonylation of the monoalkylated and selected dialkylated products was optimized with a magnesium/mercuric chloride reagent system and afforded desulfonylated products in the range of 66-97%. The anti-inflammatory Oxaprozin was prepared using the α-sulfonyl carbanion strategy along with optimized desulfonylation.


Asunto(s)
Oxazoles/síntesis química , Análisis Espectral/métodos , Alquilación , Cloruro de Magnesio/química , Cloruro de Mercurio/química , Oxazoles/química , Oxidación-Reducción
18.
Huan Jing Ke Xue ; 37(1): 220-7, 2016 Jan 15.
Artículo en Chino | MEDLINE | ID: mdl-27078961

RESUMEN

Mercury removal from aqueous solutions of HgCl2 was studied by indoor simulation experiments, and the effects of three different diameter of particles of Nano-TiO2 ( Nano-Titanium Dioxide) at different dosage, pH, adsorption time and the initial concentration of Hg2+ on the mercury adsorption from simulated wastewater were investigated. The single factor experiments showed that the optimal conditions were: 7.5 g x L(-1) of 5 nm TiO2 or 2.0 g x L(-1) of 100 nm TiO2, pH 8.0, initial concentration of Hg2+ 15 x mg x L(-1) adsorption time 5 min, and under these conditions the adsorption rates reached 99.5% and 99.3%, relatively. When the content of 25 nm TiO2 was 10 g x L(-1), and the other conditions were pH 8.0, initial concentration of Hg2+ 15 mg x L(-1), adsorption time 60 min, the adsorption rate was 62.8%. The Hg(II) removal effects of the TiO2 particles with different diameters followed the order of 100 nm TiO2 > 5 nm TiO2 > 25 nm TiO2. Component adsorption results showed that the 5 nm TiO2 component adsorption effect was superior to its single adsorption effect, while there was little difference between 100 nm TiO2 component adsorption effect and its single adsorption effect. The results of orthogonal experiments indicated that the influencing factors of the adsorption rate followed the order of pH > the initial concentration of Hg2+ > time > dosage. The optimal experiment scheme was: pH 8.0, a dosage of 100 nm Nano-TiO2 of 2.0 g x L(-1) an initial Hg2+ concentration of 25 mg x L(-1) and adsorption time of 10 min. Under the experimental conditions, the maximum adsorption rate reached 99.9%, at the same time, the equilibrium concentration of Hg(II) was 0.033 mg x L(-1) < 0.05 mg x L(-1), below the current enterprise rules of water pollutants in mercury emissions limits. In addition, the maximum adsorptive capacity was 26.95 mg x g(-1). The adsorption isotherm was in line with the Langmuir isotherm equation, indicating that the Hg(II) uptake by 100 nm Nano-TiO2 was typical monolayer adsorption.


Asunto(s)
Cloruro de Mercurio/química , Nanopartículas del Metal/química , Titanio/química , Contaminantes Químicos del Agua/química , Purificación del Agua , Adsorción , Mercurio/química , Aguas Residuales/química
19.
Acta Biochim Pol ; 62(3): 599-603, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-26351819

RESUMEN

Many studies have reported on the toxicity and related oxidative stress of mercury. Antioxidants play an important role in counteracting metal-induced neurotoxicity under in vivo conditions. In this study, the effect of diallylsulphide (DAS) was evaluated on mercuric chloride induced activities of catalase, superoxide dismutase, glutathione peroxidase and glutathione content in brains of rats. Pretreatment of rats with DAS in the Hg-treated group also inhibited an increase in lipid peroxidation and elevated acetyl cholinesterase and glutathione content. Activities of antioxidant enzymes were also restored concomitantly when compared to the control rats after DAS administration. DAS also caused a decrease in tumor necrosis factor-α level which was higher in HgCl2-treated group. The results indicate that DAS augments antioxidant defense with anti-inflammatory response against HgCl2-induced neurotoxicity. The increased level of antioxidant enzymes enhances the antioxidant potential of the organ to reduce oxidative stress.


Asunto(s)
Compuestos Alílicos/uso terapéutico , Cloruro de Mercurio/química , Mercurio/química , Sulfuros/uso terapéutico , Acetilcolinesterasa/metabolismo , Animales , Antiinflamatorios/química , Antioxidantes/metabolismo , Encéfalo/metabolismo , Catalasa/metabolismo , Glutatión/metabolismo , Glutatión Peroxidasa/metabolismo , Peroxidación de Lípido , Masculino , Neurotoxinas/química , Estrés Oxidativo , Ratas , Ratas Wistar , Superóxido Dismutasa/metabolismo , Factor de Necrosis Tumoral alfa/metabolismo
20.
J Fluoresc ; 25(3): 755-61, 2015 May.
Artículo en Inglés | MEDLINE | ID: mdl-25822190

RESUMEN

N-acryloyl rhodamine B hydrazide, a non-responsive control of a colorimetric Cu(2+) sensor, was used as a turn-on fluorescent sensor for Hg(II) from HgCl2 in the presence of AgNO3. The detection was highly selective and sensitive, and a large number of environmentally and biologically relevant metal ions, such as Na(+), K(+), Ca(2+), Mg(2+), Fe(3+), Cu(2+), Zn(2+), Cr(3+), Pb(2+), Ni(2+), Fe(2+), Mn(2+), Co(2+), Cd(2+), including Hg(II) from the easy dissociated salts, did not show significant interference. The fluorescence of the sensor (10 µM) was enhanced 74 folds by 10 equiv. of Hg(II) from HgCl2 in THF/HAc-NaAc (1/1, v/v, pH = 6) aqueous buffer solution containing 20 equiv. of AgNO3. The maximal fluorescence intensity increased linearly with the concentration of Hg(II) in the range of 0-70 µM. The detection limit of Hg(II) was 0.59 µM. The sensing mechanism was explored by Job's plot experiment, reversible experiment, mass spectrum analysis, spectroscopic analysis, and thin-layer chromatography.


Asunto(s)
Colorantes Fluorescentes/química , Hidrazinas/química , Cloruro de Mercurio/química , Mercurio/análisis , Metales/análisis , Rodaminas/química , Concentración de Iones de Hidrógeno , Límite de Detección , Mercurio/aislamiento & purificación , Metales/aislamiento & purificación , Espectrometría de Fluorescencia/métodos
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