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41.
M. Carmen Sampedro M. Aranzazu Goicolea Nora Unceta Alicia Sánchez‐Ortega Ramón J. Barrio 《Journal of separation science》2009,32(20):3449-3456
A method based on sequential stir bar sorptive extraction followed by automated thermal desorption–GC–MS for the determination of pesticides in underground and superficial water samples has been developed. Retention time locked GC–MS and deconvolution Automated Mass Spectral Deconvolution and Identification System software allows the use of pesticide databases for identification and quantification in routine applications. Quantitation limits and repetitivity using full scan mass spectrometric determination guarantee the applicability of the method, which enables considerable savings to be made in total analysis time, with data processing times of around 2 min/sample. 相似文献
42.
Millán S Sampedro MC Unceta N Goicolea MA Rodríguez E Barrio RJ 《Journal of chromatography. A》2003,995(1-2):135-142
A solid-phase microextraction (SPME) method coupled to high-performance liquid chromatography with diode array detection (HPLC-DAD) for the analysis of six organochlorine fungicides (nuarimol, triadimenol, triadimefon, folpet, vinclozolin and penconazole) in wine was developed. For this purpose, polydimethylsiloxane-divinylbenzene-coated fibers were utilized and all factors affecting throughput, precision, and accuracy of the SPME method were investigated and optimized. These factors include: matrix influence, extraction and desorption time, percentage of ethanol, pH, salt effect and desorption mode. The performed analytical procedure showed detectability ranging from 4 to 27 microg l(-1) and precision from 2.4 to 14.2% (as intra-day relative standard deviation, RSD) and 4.7-25.7% (as inter-day RSD) depending on the fungicide. The results demonstrate the suitability of the SPME-HPLC-DAD method to analyze these organochlorine fungicides in red wine. 相似文献
43.
M. A. Goicolea J. F. Arranz R. J. Barrio Z. Gómez Balugera 《Fresenius' Journal of Analytical Chemistry》1991,339(3):166-168
Summary A new extract-photometric method is proposed for determining trace amounts of Fe3+ based on the formation of a coloured complex with 2-indolehydroxamic acid (2-IHA), that can be extracted into a solution of trioctylmethylammonium chloride solution in toluene. Beer's law was obeyed between 0.06 g/g and 1.25 g/g (minimum error range) of iron in the aqueous phase, with a relative error (p=0.05) of ±0.86%. Molar absortivity at 455 nm was 6500 l mol–1 cm–1. The method was applied to the determination of iron in various samples: commercial pharmaceutical nutritional preparations, wine and standard samples of Portland cement and magnesite. 相似文献
44.
Vladimir Kouznetsov William Rodríguez Elena Stashenko Carmen Ochoa Celeste Vega Miriam Roln David Montero Pereira Jos A. Escario Alicia Gmez Barrio 《Journal of heterocyclic chemistry》2004,41(6):995-999
New N‐aryl substituted 2‐(α‐naphthyl)‐4‐thiazolidinones were prepared by the cyclocondensation of α‐mercaptoacetic acid and corresponding N‐(α‐naphthyliden)anilines. The same starting materials were utilized to obtain a new series of N‐aryl‐N‐[1‐(α‐naphthyl)but‐3‐enyl]amines, which was synthesized through an addition of the Grignard reagent (allylmagnesium bromide) to the double bond C?N of the aldimines. The antichagasic and trichomonacidal in vitro activity, as well as, the antifungal and cytotoxic properties of some of these compounds were evaluated. 相似文献
45.
MA Freitas SR Dillon RC Dougherty AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1622-1625
The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
46.
Sánchez-Ortega A Sampedro MC Unceta N Goicolea MA Barrio RJ 《Journal of chromatography. A》2005,1094(1-2):70-76
The aim of this study was to develop a methodology for the analysis of the insecticide fenitrothion and its two main environmental metabolites, fenitrooxon and 3-methyl-4-nitrophenol. For this purpose, a solid-phase microextraction (SPME) method coupled to high performance liquid chromatography (LC) was optimized. Two on-line detectors, diode array (DAD) and direct current amperometrical (DCAD) were used in order to determine sensitivity and selectivity. The effects of the extraction parameters, including exposure and desorption time, pH, temperature, salt concentration and desorption mode on the extraction efficiency were studied. A satisfactory reproducibility for extractions from samples at 20 ppb-level with RSD < 12.5% (n = 10) was obtained. The calibration graphs were linear in the range of 10-1000 microg l(-1) and detection limits for the target compounds were between 1.2 and 11.8 microg l(-1) depending on which detector was used. The method was applied for determining fenitrothion and both its metabolites in river waters which run through forest areas near to aerial application of the pesticide. 相似文献
47.
Sied MB Diez S Salud J López DO Cusmin P Tamarit JL Barrio M 《The journal of physical chemistry. B》2005,109(34):16284-16289
The two-component system octyloxycyanobiphenyl (8OCB) + decyloxycyanobiphenil (10OCB) has been studied by means of modulated differential scanning calorimetry as well as optical microscopy. The general trends of the phase diagram are similar to the two-component system octylcyanobiphenyl (8CB) + decylcyanobiphenil (10CB), previously published. Evidence for the existence of a TCP have been reported, the molar composition being about 0.33 of 10OCB. Additionally, the smectic mesophase of the 8OCB + 10OCB mixtures has been unmistakably characterized through optical measurements as smectic A for the whole composition range. 相似文献
48.
Esther Rodríguez Zuriñe Gómez de Balugera M. Carmen Sampedro M. Aranzazu Goicolea Ramón J. Barrio 《International journal of environmental analytical chemistry》2013,93(5):433-442
Dimilin 45 ODC (diflubenzuron) was applied in a Mediterranean-climate conifer forest, near Vitoria, Basque Country, Spain. Pine needles were collected at post-treatment 5-day intervals for analysis of the diflubenzuron residues. A liquid chromatography method with on-line diode-array and electrochemical detection was developed for the determination of the pesticide diflubenzuron and its main metabolites: 2,6-diflurobenzamide, 4-chlorophenylurea, 4-chloroacetanilide, 4-chloroaniline and N-methyl-4-chloroaniline in forestry matrices. Aerial application at 56.3 g AI ha?1 resulted in deposition levels of the insecticide of 1080 ng g?1. Within 40-65 days following treatment, 51-73% of the insecticide had been removed from the foliage. During this period, the concentration of diflubenzuron was higher than 295 ng g?1. The only metabolite detected was 2,6-difluorobenzamide and this persisted on foliage until the first rainfalls occurred. An empirical mathematical correlation was found to express the influence of rainfall, solar radiation and temperature on the persistence of the insecticide. 相似文献
49.
Paredis K Ono LK Mostafa S Li L Zhang Z Yang JC Barrio L Frenkel AI Cuenya BR 《Journal of the American Chemical Society》2011,133(17):6728-6735
Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (~1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions. 相似文献
50.
Numerical Algorithms - We consider an accelerated proximal gradient algorithm for the composite optimization with “independent errors” (errors little related with historical... 相似文献