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1.
Comb Chem High Throughput Screen ; 24(10): 1593-1602, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-32964820

RESUMO

BACKGROUND: Lead (Pb) remains a common contaminant in the environment in many parts of the world. Pb exposure adversely affects many human organs, including the gonads, via oxidant and inflammatory marker propagation in affected tissues. Moringa oleifera leaf extract (MOE) is a rich source of antioxidants, reported to have robust anti-inflammatory properties. AIMS: This investigation assessed whether MOE could mitigate testicular damage caused by Pb acetate treatment in rats. METHODS: Four experimental groups were used: control animals (saline only), MOE (MOE only), PbAc (Pb acetate injection only), and MOE+PbAc. All treatments were administered for two weeks, after which animals were sacrificed, and tissues and serum were examined. To confirm the potential antioxidant effect of MOE, the total polyphenolic (TP) and flavonoid (TF) concentrations were determined. RESULTS: The obtained results revealed that the TP concentration was 17.4 mg gallic acid equivalents per gram MOE dried weight and the TF concentration was 5.6 mg of quercetin equivalents per gram MOE dried weight. Moreover, MOE partially restored levels of luteinizing hormone (LH) and follicle-stimulating hormone (FSH) and testosterone and significantly attenuated oxidative stress biomarkers, malondialdehyde (MDA) and nitric oxide (NO), compared to levels observed in the PbAc-only group. MOE significantly increased the enzymatic and non-enzymatic antioxidant molecules superoxide dismutase (SOD) and catalase (CAT), glutathione peroxidase (GPx) and glutathione reductase (GR), and glutathione (GSH). Testicular levels of inflammatory cytokines tumor necrosis factor-alpha (TNFα) and interleukin-1beta (IL-1ß) were significantly decreased in MOE+PbAc compared to PbAc. MOE also significantly decreased pro-apoptotic Bax and caspase- 3 mRNA and protein levels and increased anti-apoptotic Bcl-2 mRNA and protein levels. CONCLUSION: MOE extract was associated with significant antioxidant, anti-inflammatory, and anti- apoptotic activity that ameliorated testicular damage induced by Pb acetate. MOE is proposed as a favorable adjuvant to existing treatments for Pb-induced toxicity.


Assuntos
Antioxidantes/farmacologia , Moringa oleifera/química , Extratos Vegetais/farmacologia , Testículo/efeitos dos fármacos , Animais , Antioxidantes/química , Antioxidantes/isolamento & purificação , Masculino , Compostos Organometálicos/análise , Extratos Vegetais/química , Extratos Vegetais/isolamento & purificação , Folhas de Planta/química , Ratos , Ratos Wistar , Testículo/patologia
2.
Se Pu ; 37(1): 21-26, 2019 Jan 08.
Artigo em Chinês | MEDLINE | ID: mdl-30693705

RESUMO

For the determination of organo-tin residues in edible vegetable oil, a method was developed based on gas chromatography-mass spectrometric (GC-MS) with positive chemical ionization (PCI). The edible oil samples were first dissolved by cyclohexane-ethyl acetate (1:1, v/v), and then purified by gel permeation chromatography (GPC). After derivatization by sodium tetraethylborate, the samples were analyzed by GC-MS with PCI source in the single ion monitor (SIM) mode. The seven organo-tin compounds showed good linear relationships in the range of 20-2000 µg/L and the correlation coefficients exceeded 0.99. The limits of quantitation (LOQs) and the average recoveries of the seven organo-tin compounds were 0.3-1.2 µg/kg and 66.2%-103.2%, respectively, and the relative standard deviations were less than 11.5% at three spike levels (0.05, 0.10, and 0.20 mg/kg). The method showed good linearity and high sensitivity and can be used for the determination of organo-tin residues in edible vegetable oil.


Assuntos
Contaminação de Alimentos/análise , Compostos Organometálicos/análise , Resíduos de Praguicidas/análise , Óleos de Plantas/análise , Estanho/análise , Cromatografia em Gel , Cromatografia Gasosa-Espectrometria de Massas , Verduras
3.
Acta Sci Pol Technol Aliment ; 17(3): 219-226, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30269461

RESUMO

BACKGROUND: A. ursinum is found to contain high levels of some beneficial phenolic and poly phenolic compounds were found to be effective in scavenging DPPH radicals and tyroinase inhibition. The aim of this study was to evaluate the anti-tyrosinase and antioxidant activity of three different extracts from the ultrasound-assisted method and their metal complexes from A. ursinum to discover new candidates for food additives, cosmetic and pharmaceutical products. METHODS: Water, 70% ethanol and absolute ethanol extract of Allium ursinum and their man- ganese and zinc-complexes were characterized by FT-IR and UV-Vis spectra and their antioxidant and anti- tyrosinase activity determined using DPPH radical scavenging and mushroom tyrosinase assay. RESULTS: The antioxidant activity of the water extract was superior to other samples, while the 70% ethanol extract exhibited the highest anti-tyrosinase activity. Metal complex formation of the extracts led to a signifi- cantly lower antioxidant effect. The tyrosinase inhibition strongly related to the metal ion and extraction sol- vent. All the zinc complexes had lower anti-tyrosinase activity than their extracts, while the manganese com- plex of the water and absolute ethanol extracts exhibited higher anti-tyrosinase activity than related extracts. CONCLUSIONS: This study shows that Mn complex of A. ursinum extracts, based on the solvent extraction, could increase tyrosinase inhibition activity and could be a good candidate for intended cosmetic applications and food additives.


Assuntos
Allium/química , Antioxidantes/farmacologia , Complexos de Coordenação/farmacologia , Inibidores Enzimáticos/farmacologia , Manganês , Monofenol Mono-Oxigenase/antagonistas & inibidores , Extratos Vegetais/farmacologia , Agaricales/enzimologia , Antioxidantes/análise , Compostos de Bifenilo/metabolismo , Complexos de Coordenação/análise , Inibidores Enzimáticos/análise , Flavonoides/análise , Flavonoides/farmacologia , Humanos , Compostos Organometálicos/análise , Fenóis/análise , Fenóis/farmacologia , Picratos/metabolismo , Extratos Vegetais/análise , Polifenóis/análise , Polifenóis/farmacologia , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
4.
Biol Trace Elem Res ; 180(2): 355-365, 2017 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-28401398

RESUMO

Baby foods, from the Spanish market and prepared from meat, fish, vegetables, cereals, legumes, and fruits, were analyzed to obtain the concentration of antimony (Sb), arsenic (As), bismuth (Bi), and tellurium (Te) as toxic elements and selenium (Se) as essential element. An analytical procedure was employed based on atomic fluorescence spectroscopy which allowed to obtain accurate data at low levels of concentration. Values of 14 commercial samples, expressed in nanograms per gram fresh weight, ranged for Sb 0.66-6.9, As 4.5-242, Te 1.35-2.94, Bi 2.18-4.79, and Se 5.4-109. Additionally, speciation studies were performed based on data from a non-chromatographic screening method. It was concluded that tellurium and bismuth were mainly present as inorganic forms and selenium as organic form, and antimony and arsenic species depend on the ingredients of each baby food. Risk assessment considerations were made by comparing dietary intake of the aforementioned elements through the consumption of one baby food portion a day and recommended or tolerable guideline values.


Assuntos
Antimônio/análise , Arsênio/análise , Bismuto/análise , Contaminação de Alimentos , Alimentos Infantis/análise , Selênio/análise , Telúrio/análise , Animais , Antimônio/química , Antimônio/toxicidade , Arsênio/química , Arsênio/toxicidade , Arsenicais/efeitos adversos , Arsenicais/análise , Arsenicais/química , Bismuto/química , Bismuto/toxicidade , Exposição Dietética , Poluentes Ambientais/análise , Poluentes Ambientais/química , Poluentes Ambientais/toxicidade , Peixes , Humanos , Lactente , Alimentos Infantis/efeitos adversos , Alimentos Infantis/economia , Alimentos Infantis/normas , Estrutura Molecular , Nível de Efeito Adverso não Observado , Valor Nutritivo , Compostos Organometálicos/análise , Compostos Organometálicos/química , Compostos Organometálicos/toxicidade , Compostos Organosselênicos/análise , Compostos Organosselênicos/química , Medição de Risco , Alimentos Marinhos/efeitos adversos , Alimentos Marinhos/análise , Alimentos Marinhos/economia , Alimentos Marinhos/normas , Selênio/química , Selênio/intoxicação , Espanha , Telúrio/química , Telúrio/toxicidade
5.
J Nucl Med ; 58(3): 432-437, 2017 03.
Artigo em Inglês | MEDLINE | ID: mdl-28082433

RESUMO

Radiolabeling of the prostate-specific membrane antigen (PSMA) inhibitor Glu-NH-CO-NH-Lys(Ahx) using the 68Ga chelator HBED-CC (PSMAHBED) allows imaging of prostate cancer lesions because of high expression of PSMA in prostate carcinoma cells and in bone metastases and lymph nodes related to the disease. The aim of this work was to optimize labeling of 68Ga-PSMAHBED using the efficient cation-exchange postprocessing of 68Ga as well as the development of a thin-layer chromatography (TLC)-based quality control system. Methods: Labeling was optimized for online ethanol-postprocessed 68Ga eluate investigating various parameters, such as buffer molarity (0.1-1 M), temperature (25°C-90°C), tracer amount (0.11-0.74 nmol), and labeling time. In addition, purification of the crude product was tested. For radio-TLC quality control, various mobile phases were analyzed using silica gel 60 plates and the results were validated using high-performance liquid chromatography. The most superior mobile phases were also applied on instant thin-layer chromatography (ITLC) silica gel plates. Results: Using optimized conditions, labeling yields of more than 95% were obtained within 10 min when ethanol-based postprocessing was applied using PSMAHBED amounts as low as 0.1 nmol. A higher precursor concentration (0.7 nmol) further increased labeling and quantitative yields to more than 98% within 5 min. In clinical routine, patient batches (>200 applications) with radiochemical purity greater than 98% and specific activities of 326 ± 20 MBq/nmol are obtained reproducibly. When TLC quality control was performed on silica gel 60 plates, 4 mobile phases with suitable separation properties and complementary Rf values were identified. Two systems showed equivalent separation on ITLC silica gel plates, with ITLC analysis finished within 5 min, in contrast to 20 min for the TLC system. Labeling of PSMAHBED was optimized for cation-exchange postprocessing methods, ensuring almost quantitative labeling and high nuclide purity of final 68Ga-PSMAHBED, making subsequent purification steps unnecessary. Conclusion: The new radio-TLC method allows quality control in a short time using a fast, reliable, low-cost method with little equipment complexity. Using this approach, the synthesis is easily adopted by automated synthesis modules.


Assuntos
Antígenos de Superfície/química , Contaminação de Medicamentos/prevenção & controle , Radioisótopos de Gálio/química , Glutamato Carboxipeptidase II/química , Marcação por Isótopo/métodos , Compostos Organometálicos/síntese química , Compostos Radiofarmacêuticos/síntese química , Ácido Edético/análogos & derivados , Isótopos de Gálio , Radioisótopos de Gálio/análise , Radioisótopos de Gálio/normas , Alemanha , Glutamato Carboxipeptidase II/normas , Marcação por Isótopo/normas , Oligopeptídeos , Compostos Organometálicos/análise , Compostos Organometálicos/normas , Controle de Qualidade , Geradores de Radionuclídeos/normas , Compostos Radiofarmacêuticos/análise , Compostos Radiofarmacêuticos/normas
6.
Environ Toxicol ; 32(3): 813-822, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27170105

RESUMO

The objective of this study was to evaluate markers of oxidative stress in the brains of rats exposed to lead acetate (Pb(C2 H3 O2 )2 ), either associated or not associated with ferrous sulfate (FeSO4 ). A total of 36 weaning rats (Rattus norvegicus) were divided into 6 groups of six animals and exposed to lead acetate for six weeks. In the control group (control), the animals received deionized water. The Pb260 and Pb260 + Fe received 260 µM lead acetate, and the Pb1050 and Pb1050 + Fe received 1050 µM lead acetate. The Pb260 + Fe and Pb1050 + Fe were supplemented with 20 mg of ferrous sulfate/Kg body weight every 2 days. Group Fe received deionized water and ferrous sulfate. The rat brains were collected to analyze the enzymatic activity of catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPx), and the concentration of reduced glutathione (GSH), lipid peroxidation (TBARS), and total antioxidant substance (TAS) (DPPH• technique). The activity of SOD and GPx in the experimental groups decreased compared to the control, together with the concentration of GSH (p < 0.05). For CAT analysis, SOD tended to increase in concentration in the experimental groups without a concomitant exposure to FeSO4 , whereas GPx showed a slight tendency to increase in activity compared to the control. For TAS-DPPH• , there was a decrease in the experimental groups (p < 0.05). According to the results, SOD, GPx, and GSH were affected by lead acetate and exposure to ferrous sulfate changed this dynamic. However, further studies are needed to verify whether ferrous sulfate acts as a protectant against the toxic effects of lead. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 813-822, 2017.


Assuntos
Antioxidantes/metabolismo , Encéfalo/efeitos dos fármacos , Compostos Ferrosos/farmacologia , Compostos Organometálicos/toxicidade , Estresse Oxidativo/efeitos dos fármacos , Animais , Antioxidantes/química , Peso Corporal/efeitos dos fármacos , Encéfalo/metabolismo , Catalase/metabolismo , Glutationa/metabolismo , Glutationa Peroxidase/metabolismo , Peroxidação de Lipídeos/efeitos dos fármacos , Masculino , Compostos Organometálicos/análise , Compostos Organometálicos/sangue , Ratos , Ratos Wistar , Superóxido Dismutase/metabolismo
7.
Talanta ; 152: 482-8, 2016 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-26992545

RESUMO

Due to insufficient information, the aim of study was to concern on the optimization of extraction procedure of selected metal complexes with flavonoids from chia seeds. Evaluation of the amount of elements in compound, not only their total concentration content, is highly important due to the fact, that only a part from total content of metal is absorbed by human body. At the beginning the total amount of elements in chia seeds was established as 14.51±0.42 µg g(-1) for copper, 57.44±1.23 µg g(-1) for manganese, 81.12±1.89 µg g(-1) for zinc and 0.35±0.13 µg g(-1) for cobalt. After the most suitable solvent was established, effects of several parameters on the efficiency of metal extraction were studied. Solvent concentration, solid-solvent ratio, extraction method, extraction time and temperature have been investigated as independent variables. The optimal extraction conditions included vortexing during 20 min in 50°C, using an ionic liquid (1-butyl-3-methylimidazolium bromide) as an extractant, with solid-solvent ratio of 1:20. The determination of total and extractable amount of metals in chia seeds was carried out by standalone ICP MS. In addition, a complementary analysis of extracted metal complexes was performed using SEC-ICP MS method. It was confirmed that the ionic liquid is able to extract different copper complexes in comparison with commonly used solvents. The study indicated that extraction by using an ionic liquid has been successfully applied for determination of metals and metal complexes in chia seeds.


Assuntos
Fracionamento Químico/métodos , Líquidos Iônicos/química , Compostos Organometálicos/isolamento & purificação , Salvia/química , Sementes/química , Cobre/análise , Flavonoides/química , Imidazóis/química , Espectrometria de Massas , Compostos Organometálicos/análise , Solventes/química , Temperatura , Fatores de Tempo
8.
NMR Biomed ; 28(10): 1257-66, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26286889

RESUMO

(+/-)3,4-methylenedioxymethamphetamine (MDMA, "ecstasy") is an abused psychostimulant that produces strong monoaminergic stimulation and whole-body hyperthermia. MDMA-induced thermogenesis involves activation of uncoupling proteins (UCPs), primarily a type specific to skeletal muscle (UCP-3) and absent from the brain, although other UCP types are expressed in the brain (e.g. thalamus) and might contribute to thermogenesis. Since neuroimaging of brain temperature could provide insights into MDMA action, we measured spatial distributions of systemically administered MDMA-induced temperature changes and dynamics in rat cortex and subcortex using a novel magnetic resonance method, Biosensor Imaging of Redundant Deviation in Shifts (BIRDS), with an exogenous temperature-sensitive probe (thulium ion and macrocyclic chelate 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetramethyl-1,4,7,10-tetraacetate (DOTMA(4-))). The MDMA-induced temperature rise was greater in the cortex than in the subcortex (1.6 ± 0.4 °C versus 1.3 ± 0.4 °C) and occurred more rapidly (2.0 ± 0.2 °C/h versus 1.5 ± 0.2 °C/h). MDMA-induced temperature changes and dynamics in the cortex and body were correlated, although the body temperature exceeded the cortex temperature before and after MDMA. Temperature, neuronal activity, and blood flow (CBF) were measured simultaneously in the cortex and subcortex (i.e. thalamus) to investigate possible differences of MDMA-induced warming across brain regions. MDMA-induced warming correlated with increases in neuronal activity and blood flow in the cortex, suggesting that the normal neurovascular response to increased neural activity was maintained. In contrast to the cortex, a biphasic relationship was seen in the subcortex (i.e. thalamus), with a decline in CBF as temperature and neural activity rose, transitioning to a rise in CBF for temperature above 37 °C, suggesting that MDMA affected CBF and neurovascular coupling differently in subcortical regions. Considering that MDMA effects on CBF and heat dissipation (as well as potential heat generation) may vary regionally, neuroprotection may require different cooling strategies.


Assuntos
Temperatura Corporal , Encéfalo/efeitos dos fármacos , Febre/fisiopatologia , Espectroscopia de Ressonância Magnética , N-Metil-3,4-Metilenodioxianfetamina/toxicidade , Acoplamento Neurovascular/efeitos dos fármacos , Anestesia Geral , Animais , Encéfalo/irrigação sanguínea , Córtex Cerebral/irrigação sanguínea , Córtex Cerebral/efeitos dos fármacos , Febre/induzido quimicamente , Masculino , Compostos Organometálicos/análise , Compostos Organometálicos/farmacocinética , Estresse Oxidativo , Ratos , Ratos Sprague-Dawley , Tálamo/irrigação sanguínea , Tálamo/efeitos dos fármacos
9.
ACS Appl Mater Interfaces ; 7(8): 4589-94, 2015 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-25658750

RESUMO

Uranyl (UO2(2+)) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2(2+)) with a detection limit of 1.86 µM. In the absence of UO2(2+), the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2(2+), this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2(2+) was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2(2+) and consequently prompt the recycling of UO2(2+) from seawater.


Assuntos
Materiais Biomiméticos/metabolismo , Colorimetria , Água do Mar/química , Urânio/análise , Animais , Materiais Biomiméticos/química , Bovinos , Ouro/química , Íons/química , Nanopartículas Metálicas/química , Metais/química , Compostos Organometálicos/análise , Peroxidase/metabolismo , Soroalbumina Bovina/química , Soroalbumina Bovina/metabolismo
10.
Talanta ; 113: 14-8, 2013 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-23708617

RESUMO

A method was developed for the quantification of Zn-, Cu- and Mn-glycinates in supplemented feed samples. The coupling of capillary electrophoresis (CE) with ICP MS detection after purification of the extract by ultrafiltration was shown to be efficient for the quantitative recovery of glycinates. The method developed was then applied to evaluate the bioaccessibility of glycinates using a sequential enzymolysis approach. The data obtained indicated a strong bioaccessibility of each element (79-94%). A new complex was also found to be formed during the digestion process. Bioavailability was then evaluated by analyzing plasma samples of horses supplemented with glycinates-rich feed. Intact glycinates could not be detected in plasma samples but a Cu-containing molecule was found more abundant after CuGly treatment.


Assuntos
Glicina/análogos & derivados , Cavalos/sangue , Manganês/farmacocinética , Compostos Organometálicos/farmacocinética , Ração Animal/análise , Animais , Disponibilidade Biológica , Glicina/análise , Glicina/farmacocinética , Manganês/análise , Compostos Organometálicos/análise
11.
Inorg Chem ; 50(21): 11242-51, 2011 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-21985054

RESUMO

An extensive series of heterometal-iron-sulfur single cubane-type clusters with core oxidation levels [MFe(3)S(3)Q](3+,2+) (M = Mo, W; Q = S, Se) has been prepared by means of a new method of cluster self-assembly. The procedure utilizes the assembly system [((t)Bu(3)tach)M(VI)S(3)]/FeCl(2)/Na(2)Q/NaSR in acetonitrile/THF and affords product clusters in 30-50% yield. The trisulfido precursor acts as a template, binding Fe(II) under reducing conditions and supplying the MS(3) unit of the product. The system leads to specific incorporation of a µ(3)-chalcogenide from an external source (Na(2)Q) and affords the products [((t)Bu(3)tach)MFe(3)S(3)QL(3)](0/1-) (L = Cl(-), RS(-)), among which are the first MFe(3)S(3)Se clusters prepared. Some 16 clusters have been prepared, 13 of which have been characterized by X-ray structure determinations including the incomplete cubane [((t)Bu(3)tach)MoFe(2)S(3)Cl(2)(µ(2)-SPh)], a possible trapped intermediate in the assembly process. Comparisons of structural and electronic features of clusters differing only in atom Q at one cubane vertex are provided. In comparative pairs of complexes differing only in Q, placement of one selenide atom in the core increases core volumes by about 2% over the Q = S case, sets the order Q = Se > S in Fe-Q bond lengths and Q = S > Se in Fe-Q-Fe bond angles, causes small positive shifts in redox potentials, and has an essentially nil effect on (57)Fe isomer shifts. Iron mean oxidation states and charge distributions are assigned to most clusters from isomer shifts. ((t)Bu(3)tach = 1,3,5-tert-butyl-1,3,5-triazacyclohexane).


Assuntos
Química Bioinorgânica/métodos , Ferro/química , Molibdênio/química , Compostos Organometálicos/síntese química , Tungstênio/química , Compostos Aza/química , Proteínas de Bactérias/química , Biomimética , Cristalografia por Raios X , Modelos Moleculares , Conformação Molecular , Nitrogenase/química , Compostos Organometálicos/análise , Oxirredução , Selênio/química , Enxofre/química
12.
J Chromatogr A ; 1218(30): 4934-43, 2011 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-21474140

RESUMO

Hydrophilic interaction chromatography (HILIC) has emerged as a very useful separation method for polar analytes, including non-covalent metal species. Several types of stationary phases are available for HILIC applications, differing mainly in their chemical functionalities that supply additional interaction modes and alternative selectivities for the separation of special analytes. With regard to the separation of metal species only few of these stationary phases have been applied to date, and it is not completely clear what are their differences with respect to the chromatographic separation of metal species, but also with respect to species stability during chromatography. Here, a comparison of different column types for the HILIC separation of iron citrate and copper histidine species is presented and the results are discussed with respect to retention mechanisms and chromatographic stability of these metal species. It is shown that different stationary phases display very different separation patterns. In particular, three types of HILIC columns enable successful separation of iron citrates and copper histidine at pH 5.5, namely a crosslinked diol phase, a zwitterionic phase, and an amide phase. Two groups of iron-citrates are separated on all three columns, consisting of a species of 3:3 stoichiometry and another one of mainly 3:4 stoichiometry (plus 1:2 and 2:2 species). For copper-histidine only one stable species is found based on the 1:2 stoichiometry. Detection and unambiguous identification of the different species is possible by employing electrospray mass spectrometry in the negative ionization mode. Species found in standard solutions are consistent with species found in spiked plant samples. Also in unspiked solutions iron citrate of 3:4 stoichiometry (plus 1:2 and 2:2) is detectable, but no species of 3:3 stoichiometry. Significant differences of related species patterns are found in real plant samples.


Assuntos
Cromatografia Líquida/instrumentação , Citratos/isolamento & purificação , Histidina/análogos & derivados , Ferro/isolamento & purificação , Compostos Organometálicos/isolamento & purificação , Extratos Vegetais/química , Cromatografia Líquida/métodos , Citratos/análise , Histidina/análise , Histidina/isolamento & purificação , Hordeum/química , Interações Hidrofóbicas e Hidrofílicas , Ferro/análise , Compostos Organometálicos/análise , Folhas de Planta/química
13.
J Mol Model ; 15(6): 759-64, 2009 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-19277729

RESUMO

The presence of doubly charged ions in mass spectra is detected only occasionally because their clusters are observed more rarely than singly charged ones. The patterns connected with doubly charged ions are located in the spectrum below M/2. The narrow shapes of such patterns as well as overlapping with other bands generate significant problems in their interpretation. The method described here is based on modelling of the isotopomeric form of single- and double-charged mass ion clusters. The present work attempts to explain the generation of the double charge disotopomeric patterns of high- as well as low-resolution spectra. Predicting the high-resolution mass cluster is simpler than calculations of the low-resolution cluster. The high-resolution cluster may represent the initial form of low-resolution pattern formation.


Assuntos
Análise por Conglomerados , Íons/química , Espectrometria de Massas/métodos , Algoritmos , Íons/análise , Íons/classificação , Modelos Químicos , Estrutura Molecular , Compostos Organometálicos/análise , Compostos Organometálicos/química , Reprodutibilidade dos Testes , Selênio/análise , Selênio/química
14.
J Mol Model ; 15(6): 747-58, 2009 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-19319580

RESUMO

The interpretation of mass spectra (ms) of molecules containing poly-isotopic elements (e.g. Ge, Se, W, Os, Sn, Te, Zn, Yb) can be difficult due to the occurrence of fragments resulting from isotopomeric composition. MS-clusters located in the range lower than or equal to M/2 are very difficult to interpret. In this area many perturbations may be observed. The coincidence of different fragmentation pathways, the existence of multiply charged ions, background levels, etc. can all contribute to this problem. The present paper reports the application of multi-isotopomeric analysis methods for low-resolution ms. We present a solution that may be useful for detection of the symmetrical decomposition of a molecule and for elucidation of cluster ion genesis. The complex character of the cluster does not perturb determination of the contents of the investigated pattern. In such cases the dominated component is applied in subsequent computations.


Assuntos
Análise por Conglomerados , Íons/química , Espectrometria de Massas/métodos , Algoritmos , Simulação por Computador , Íons/análise , Íons/classificação , Modelos Químicos , Estrutura Molecular , Compostos Organometálicos/análise , Compostos Organometálicos/química , Selênio/análise , Selênio/química , Zircônio/análise , Zircônio/química
15.
Talanta ; 77(1): 304-13, 2008 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-18804638

RESUMO

This study aims to identify the essential antioxidant compounds present in parsley (Petroselinum sativum) and celery (Apium graveolens) leaves belonging to the Umbelliferae (Apiaceae) family, and in stinging nettle (Urtica dioica) belonging to Urticaceae family, to measure the total antioxidant capacity (TAC) of these compounds with CUPRAC (cupric ion reducing antioxidant capacity) and ABTS spectrophotometric methods, and to correlate the TAC with high performance liquid chromatography (HPLC) findings. The CUPRAC spectrophotometric method of TAC assay using copper(II)-neocuproine (2,9-dimethyl-1,10-phenanthroline) as the chromogenic oxidant was developed in our laboratories. The individual antioxidant constituents of plant extracts were identified and quantified by HPLC on a C18 column using a modified mobile phase of gradient elution comprised of MeOH-0.2% o-phosphoric acid and UV detection for polyphenols at 280 nm. The TAC values of HPLC-quantified antioxidant constituents were found, and compared for the first time with those found by CUPRAC. The TAC of HPLC-quantified compounds accounted for a relatively high percentage of the observed CUPRAC capacities of plant extracts, namely 81% of nettle, 60-77% of parsley (in different hydrolyzates of extract and solid sample), and 41-57% of celery leaves (in different hydrolyzates). The CUPRAC total capacities of the 70% MeOH extracts of studied plants (in the units of mmol trolox g(-1)plant) were in the order: celery leaves>nettle>parsley. The TAC calculated with the aid of HPLC-spectrophotometry did not compensate for 100% of the CUPRAC total capacities, because all flavonoid glycosides subjected to hydrolysis were either not detectable with HPLC, or not converted to the corresponding aglycons (i.e., easily detectable and quantifiable with HPLC) during the hydrolysis step.


Assuntos
Antioxidantes/análise , Antioxidantes/química , Apium/química , Compostos Organometálicos/análise , Compostos Organometálicos/química , Petroselinum/química , Urtica dioica/química , Calibragem , Cromatografia Líquida de Alta Pressão , Flavonoides/química , Íons/química , Estrutura Molecular , Folhas de Planta/química , Solventes
16.
J Med Chem ; 51(16): 5035-42, 2008 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-18680271

RESUMO

NMR-based drug screening methods provide the most reliable characterization of binding propensities of ligands to their target proteins. They are, however, one of the least effective methods in terms of the amount of protein required and the time needed for acquiring an NMR experiment. We show here that the introduction of tryptophan to proteins permits rapid screening by monitoring a simple 1D proton NMR signal of the NH side chain ((N)H(epsilon)) of the tryptophan. The method could also provide quantitative characterization of the antagonist-protein and antagonist-protein-protein interactions in the form of KDs and fractions of the released proteins from their mutual binding. We illustrate the method with the lead compounds that block the Mdm2-p53 interaction and by studying inhibitors that bind to cyclin-dependent kinase 2 (CDK2).


Assuntos
Avaliação Pré-Clínica de Medicamentos/métodos , Chumbo/análise , Ressonância Magnética Nuclear Biomolecular/métodos , Compostos Organometálicos/análise , Proteínas/química , Triptofano/genética , Quinase 2 Dependente de Ciclina/química , Quinase 2 Dependente de Ciclina/genética , Humanos , Ligantes , Modelos Moleculares , Mutação Puntual , Mapeamento de Interação de Proteínas/métodos , Proteínas/genética , Proteínas Proto-Oncogênicas c-mdm2/química , Proteínas Proto-Oncogênicas c-mdm2/genética , Relação Estrutura-Atividade , Triptofano/química , Proteína Supressora de Tumor p53/química
18.
Anal Bioanal Chem ; 390(7): 1781-7, 2008 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-18305928

RESUMO

The applicability of spectrochemical analysis of minute amounts of powder samples was investigated using an ultraviolet Nd-YAG laser (355 nm) and low-pressure ambient air. A large variety of chemical powder samples of different composition were employed in the experiment. These included a mixture of copper(II) sulfate pentahydrate, zinc sulfide, and chromium(III) sulfate n-hydrate powders, baby powder, cosmetic powders, gold films, zinc supplement tablet, and muds and soils from different areas. The powder samples were prepared by pulverizing the original samples to an average size of around 30 microm in order to trap them in the tiny micro holes created on the surface of the quartz subtarget. It was demonstrated that in all cases studied, good quality spectra were obtained with low background, free from undesirable contamination by the subtarget elements and featuring ppm sensitivity. A further measurement revealed a linear calibration curve with zero intercept. These results clearly show the potential application of this technique for practical qualitative and quantitative spectrochemical analysis of powder samples in various fields of study and investigation.


Assuntos
Lasers de Estado Sólido , Pós/análise , Análise Espectral/métodos , Ar , Ouro/análise , Compostos Organometálicos/análise , Tamanho da Partícula , Pressão , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Solo/análise , Análise Espectral/instrumentação , Sulfetos/análise , Compostos de Zinco/análise
19.
Anal Chem ; 80(3): 775-82, 2008 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-18181583

RESUMO

Anion-exchange chromatography was utilized for speciation of arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA(V)), monomethylarsonic acid (MMA(V)), monomethylarsonous acid (MMA(III)), and the new As species monomethylthioarsonic acid (MMTA), using inductively coupled plasma mass spectrometric (ICPMS) detection. MMA(III) and MMTA were identified for the first time in freeze-dried carrot samples that were collected over 25 years ago as part of a joint U.S. EPA, U.S. FDA, and USDA study on trace elements in agricultural crops. The discovery of MMA(III) and MMTA in terrestrial foods necessitated the analytical characterization of synthetic standards of both species, which were used for standard addition in carrot extracts. The negative ion mode, high-resolution electrospray mass spectrometry (HR-ESI-MS) data produced molecular ions of m/z 122.9418 and 154.9152 for MMA(III) and MMTA, respectively. However, ESI-MS was not sensitive enough to directly identify MMA(III) and MMTA in the carrot extracts. Therefore, to further substantiate the identification of MMA(III) and MMTA, two additional separations using an Ion-120 column were developed using the more sensitive ICPMS detection. The first separation used 20 mM tetramethylammonium hydroxide at pH 12.2 with MMA(III) eluting in less than 7 min. In the second separation, MMTA eluted at 11.2 min by utilizing 40 mM ammonium carbonate at pH 9.0. Oxidation of MMA(III) and MMTA to MMA(V) with hydrogen peroxide was observed for standards and carrot extracts alike. Several samples of carrots collected from local markets in 2006 were also analyzed and found to contain low levels of inorganic arsenic species.


Assuntos
Intoxicação por Arsênico , Arsenicais/análise , Daucus carota/química , Poluentes Ambientais/análise , Compostos Organometálicos/análise , Arsenicais/metabolismo , Poluentes Ambientais/química , Poluentes Ambientais/metabolismo , Concentração de Íons de Hidrogênio , Compostos Organometálicos/metabolismo , Extratos Vegetais/química , Compostos de Amônio Quaternário/química , Espectrometria de Massas por Ionização por Electrospray/métodos , Fatores de Tempo
20.
Chemosphere ; 70(2): 237-47, 2007 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-17709130

RESUMO

This work studied interactions of uranium with pure organic compounds, such as glutathione, and more complex mixtures, such as humic acid and aqueous plant extracts. High performance liquid chromatography with UV absorption interfaced to inductively coupled plasma mass spectrometry sequential detection was used to detect organouranium complexes in a variety of soils and plant materials, indicating that nearly 100% of the uranium extracted from certain plant tissues was bound to organic ligands. In addition, soil sorption experiments indicated that humic acid generally decreased uranium sorption to soils and promoted subsequent desorption of uranium because of uranium partitioning to the organic phase. These experiments demonstrate that organic compounds influence the mobility and chemistry of uranium in the environment.


Assuntos
Monitoramento Ambiental/métodos , Substâncias Húmicas/análise , Compostos Organometálicos/análise , Desenvolvimento Vegetal , Poluentes do Solo/análise , Urânio/análise , Adsorção , Cromatografia Líquida de Alta Pressão , Glutationa/química , Plantas/química , Solubilidade , Espectrofotometria Atômica
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