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1.
J Agric Food Chem ; 63(18): 4638-45, 2015 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-25905785

RESUMO

The objective of this research was to investigate the development of a reliable fingerprint from elemental and isotopic signatures of Argentinean honey to assess its geographical provenance. Honey, soil, and water from three regions (Córdoba, Buenos Aires, and Entre Ríos) were collected. The multielemental composition was determined by ICP-MS. δ(13)C was measured by isotopic ratio mass spectrometry, whereas the (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. The data were analyzed by chemometrics looking for the association between the elements, stable isotopes, and honey samples from the three studied areas. Honey samples were differentiated by classification trees and discriminant analysis using a combination of eight key variables (Rb, K/Rb, B, U, (87)Sr/(86)Sr, Na, La, and Zn) presenting differences among the studied regions. The application of canonical correlation analysis and generalized procrustes analysis showed 91.5% consensus between soil, water, and honey samples, in addition to clear differences between studied areas. To the authors' knowledge, this is the first report demonstrating the correspondence between soil, water, and honey samples using different statistical methods, showing that elemental and isotopic honey compositions are related to soil and water characteristics of the site of origin.


Assuntos
Mel/análise , Espectrometria de Massas/métodos , Solo/química , Oligoelementos/análise , Água/química , Argentina , Isótopos de Carbono/análise , Análise Discriminante , Geografia
2.
J Agric Food Chem ; 61(16): 3763-73, 2013 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-23531021

RESUMO

The aim of this study was to investigate if elemental and isotopic signatures of Argentinean wheat can be used to develop a reliable fingerprint to assess its geographical provenance. For this pilot study we used wheat cultivated at three different regions (Buenos Aires, Córdoba, and Entre Ríos), together with matching soil and water. Elemental composition was determined by ICP-MS. δ(13)C and δ(15)N were measured by isotopic ratio mass spectrometry, while (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. Wheat samples from three sampling sites were differentiated by the combination of 11 key variables (K/Rb, Ca/Sr, Ba, (87)Sr/(86)Sr, Co, Mo, Zn, Mn, Eu, δ(13)C, and Na), demonstrating differences among the three studied regions. The application of generalized Procrustes analysis showed 99.2% consensus between cultivation soil, irrigation water, and wheat samples, in addition to clear differences between studied areas. Furthermore, canonical correlation analysis showed significant correlation between the elemental and isotopic profiles of wheat and those corresponding to both soil and water (r(2) = 0.97, p < 0.001 and r(2) = 0.96, p < 0.001, respectively). To our knowledge, this is the first report demonstrating the correspondence between soil, water, and wheat samples using different statistical methods, showing that wheat elemental and isotopic compositions are mainly related to soil and irrigation water characteristics of the site of growth.


Assuntos
Isótopos/análise , Solo/química , Triticum/química , Triticum/classificação , Água/química , Argentina , Isótopos de Carbono/análise , Elementos Químicos , Isótopos de Nitrogênio/análise , Isótopos de Estrôncio/análise
3.
Chemosphere ; 69(5): 682-8, 2007 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-17604821

RESUMO

UV/TiO(2) photocatalysis of phenylmercury salts in aqueous solutions has been performed starting from both acetate (C(6)H(5)HgCH(3)CO(2), PMA) and chloride (C(6)H(5)HgCl, PMC) salts, in the presence or the absence of oxygen at acidic pH. Removal of Hg(II) in solution took place with the simultaneous deposit of dark or pale gray solids on the photocatalyst, identified as metallic Hg (when starting from PMA) or mixtures of Hg(0) and Hg(2)Cl(2) (when starting from PMC). Partial mineralization of the organic part of both compounds has also been achieved. Hg(II) removal and mineralization were enhanced in the absence of oxygen. PMA photocatalysis followed a saturation kinetics, going from first order at low concentration to zero order at higher concentrations (>0.5mM). For PMA, reaction was faster at high pH (11) with formation of mixtures of Hg and HgO. Phenol was detected as a product of the reaction in both cases, PMA and PMC, and no formation of dangerous methyl- or ethylmercury species was observed in the first case. A mechanism for the photocatalytic reaction has been proposed. The fact that calomel was found as a deposit when starting from PMC under nitrogen suggests that the mechanism of Hg(II) transformation proceeds through successive one-electron transfer reactions passing by mercurous forms.


Assuntos
Compostos de Fenilmercúrio/química , Titânio/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Catálise , Hidrocarbonetos/análise , Modelos Químicos , Compostos de Fenilmercúrio/efeitos da radiação , Fotoquímica , Sais , Raios Ultravioleta , Poluentes Químicos da Água/efeitos da radiação , Purificação da Água/instrumentação
4.
Anal Bioanal Chem ; 388(2): 499-503, 2007 May.
Artigo em Inglês | MEDLINE | ID: mdl-17345067

RESUMO

A dual-detection technique, consisting of a combination of reversed-phase high-performance liquid chromatography and on-line detection of elemental boron in the column effluents by inductively coupled plasma optical emission spectrometry, was tested for drug analysis. The method was applied to assessing the chemical purity of p-boronophenylalanine (BPA), isotopically enriched in 10B. This compound is employed as a fructose complex solution for biodistribution studies in laboratory and clinical trials of boron neutron capture therapy. Besides the determination of the content of BPA, required for chemical quality controls of solutions of the complex used for infusions, resolution of mixtures of BPA and two usually accompanying residual impurities (phenylalanine and tyrosine) was achieved with UV detection. The limits of detection (in solution) were 1.5 and 0.6 ng ml-1, respectively. In addition, by monitoring a sensitive-element emission wavelength it was possible to jointly observe the elution of boron-containing compounds that may be transparent to UV radiation or to confirm the presence of boron in potential impurities accompanying the drug. Those impurities may arise from the BPA synthesis or may be produced by degradation during the aging of the solutions. Chromatographic peaks corresponding to the amino acids and also to a related inorganic compound were detected in BPA-fructose complex solutions that were stored for different times and under different conditions. An increase in the areas of the peaks attributed to tyrosine and phenylalanine was observed for BPA-fructose solutions stored refrigerated for 1 month to 1 year, suggesting that degradation processes able to reduce the amount of bioavailable BPA could be active.


Assuntos
Compostos de Boro/análise , Boro/química , Cromatografia Líquida de Alta Pressão/métodos , Fenilalanina/análogos & derivados , Espectrofotometria/métodos , Compostos de Boro/química , Soluções Tampão , Estabilidade de Medicamentos , Concentração de Íons de Hidrogênio , Fenilalanina/análise , Fenilalanina/química , Radiossensibilizantes/análise , Radiossensibilizantes/química , Espectrofotometria Ultravioleta , Tirosina/análise
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