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21.
Cristina Ripollés José M. Marín Francisco J. López Juan V. Sancho Félix Hernández 《Rapid communications in mass spectrometry : RCM》2009,23(12):1841-1848
A new sensitive and selective method based on on‐line solid‐phase extraction (SPE) coupled to liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS) using a triple quadrupole mass spectrometer has been developed for the determination of epichlorohydrin (ECH) in different types of water samples. ECH is not easily determined directly by ESI‐MS as it is not readily ionized, and it has a low molecular mass and high polarity. Thus, prior derivatization of ECH was necessary, employing 3,5‐difluorobenzylamine as a derivatizing agent with Fe(III) as a catalyst. In order to achieve accurate quantification, correcting for matrix effects, losses in the derivatization process and instrumental deviations, isotope labelled ECH (ECH‐d5) was added as an internal standard (IS) to the water samples. The method was validated based on European SANCO guidelines using drinking and other types of treated water spiked at two concentration levels (0.1 and 1.0 µg/L), the lower level having been established as the limit of quantification (LOQ) of the method. Satisfactory accuracy (recoveries between 70 and 103%), precision (RSD <20%) and linearity (from 0.05 to 50 µg/L, r >0.99) were obtained. The limit of detection (LOD) was set up at 0.03 µg/L. The method was applied to different water samples (drinking water and water samples collected from a municipal treatment water plant). In order to enhance confidence, five selected reaction monitoring (SRM) transitions were acquired, thus obtaining a simultaneous reliable quantification and identification of ECH in water, even at sub‐ppb levels. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
22.
T. Portolés J. V. Sancho F. Hernández A. Newton P. Hancock 《Journal of mass spectrometry : JMS》2010,45(8):926-936
The potential applications of a new atmospheric pressure source for GC‐MS analysis have been investigated in this work. A list of around 100 GC‐amenable pesticides, which includes organochlorine, organophosphorus and organonitrogenated compounds, has been used to evaluate their behavior in the new source. Favoring the major formation of the molecular ion in the source has been the main goal due to the wide‐scope screening possibilities that this fact brings in comparison with the traditional, highly fragmented electron ionization spectra. Thus, the addition of water as modifier has been tested as a way to promote the generation of protonated molecules. Pesticides investigated have been classified into six groups according to their ionization/fragmentation behavior. Four of them are characterized by the abundant formation of the protonated molecule in the atmospheric pressure source, mostly being the base peak of the spectrum. These results show that wide‐scope screening could be easily performed with this source by investigating the presence of the protonated molecule ion, MH+. The developed procedure has been applied to pesticide screening in different food samples (nectarine, orange and spinach) and it has allowed the presence of several pesticides to be confirmed such as chlorpyriphos ethyl, deltamethrin and endosulfan sulfate. The availability of a quadrupole time‐of‐flight instrument made it feasible to perform additional MS/MS experiments for both standards and samples to go further in the confirmation of the identity of the detected compounds. Results shown in this paper have been obtained using a prototype source which exhibits promising features that could be applied to other analytical problems apart from those illustrated in this work. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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24.
Juan Aparicio Juan Carlos Ferrando Ana Meca Julia Sancho 《Annals of Operations Research》2008,158(1):229-241
In this paper we introduce an asymmetric model of continuous electricity auctions with limited production capacity and bounded
supply functions. The strategic bidding is studied with this model by means of an electricity market game. We prove that for
every electricity market game with continuous cost functions a mixed-strategy Nash equilibrium always exists. In particular,
we focus on the behavior of producers in the Spanish electricity market. We consider a very simple form for the Spanish electricity
market: an oligopoly consisting just of independent hydro-electric power production units in a single wet period. We show
that a pure-strategy Nash equilibrium for the Spanish electricity market game always exists. 相似文献
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27.
We study scalar diffusion, both from Eulerian and Lagrangian perspectives, advected by two dimensional flows. Emphasis is devoted to the problem of scalar diffusion under a synthetic turbulent flow. We present numerical and analytical results for the turbulent diffusion coefficient either from the influence of the turbulent synthetic field and a periodic array of eddies. Preliminary results concerning Lagrangian dispersion are also reported. 相似文献
28.
Díaz R Ibáñez M Sancho JV Hernández F 《Rapid communications in mass spectrometry : RCM》2011,25(2):355-369
Hybrid quadrupole time-of-flight mass spectrometry (QTOF MS) has gained wide acceptance in many fields of chemistry, for example, proteomics, metabolomics and small molecule analysis. This has been due to the numerous technological advances made to this mass analyser in recent years. In the environmental field, the instrument has proven to be one of the most powerful approaches for the screening of organic pollutants in different matrices due to its high sensitivity in full acquisition mode and mass accuracy measurements. In the work presented here, the optimum experimental conditions for the creation of an empirical TOF MS spectra library have been evaluated. For this model we have used a QTOF Premier mass spectrometer and investigated its functionalities to obtain the best MS data, mainly in terms of mass accuracy, dynamic range and sensitivity. Different parameters that can affect mass accuracy, such as lock mass, ion abundance, spectral resolution, instrument calibration or matrix effect, have also been carefully evaluated using test compounds (mainly pesticides and antibiotics). The role of ultra-high-pressure liquid chromatography (UHPLC), especially when dealing with complex matrices, has also been tested. In addition to the mass accuracy measurements, this analyser allows the simultaneous acquisition of low and high collision energy spectra. This acquisition mode greatly enhances the reliable identification of detected compounds due to the useful (de)protonated molecule and fragment ion accurate mass information obtained when working in this mode. An in-house empirical spectral library was built for approximately 230 organic pollutants making use of QTOF MS in MS(E) mode. All the information reported in this paper is made available to the readers to facilitate screening and identification of relevant organic pollutants by QTOF MS. 相似文献
29.
In the present work, a rapid method with little sample handling has been developed for determination of 23 selected volatile organic compounds in environmental and wastewater samples. The method is based on headspace solid-phase microextraction (SPME) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) determination using triple quadrupole analyzer (QqQ) in electron ionization mode. The best conditions for extraction were optimised with a factorial design taking into account the interaction between different parameters and not only individual effects of variables. In the optimized procedure, 4 mL of water sample were extracted using a 10 mL vial and adding 0.4 g NaCl (final NaCl content of 10%). An SPME extraction with carboxen/polydimethylsiloxane 75 μm fiber for 30 min at 50°C (with 5 min of previous equilibration time) with magnetic stirring was applied. Chromatographic determination was carried out by GC-MS/MS working in Selected Reaction Monitoring (SRM) mode. For most analytes, two MS/MS transitions were acquired, although for a few compounds it was difficult to obtain characteristic abundant fragments. In those cases, a pseudo selected reaction monitoring (pseudo-SRM) with three ions was used instead. The intensity ratio between quantitation (Q) and confirmation (q) signals was used as a confirmatory parameter. The method was validated by means of recovery experiments (n=6) spiking mineral water samples at three concentration levels (0.1, 5 and 50 μg L(-1)). Recoveries between 70% and 120% were generally obtained with relative standard deviations (RSDs) lower than 20%. The developed method was applied to surface water and wastewater from a wastewater treatment plant and from a municipal solid-waste treatment plant. Several compounds, like chloroform, benzene, trichloroethylene, toluene, tetrachloroethylene, dibromochloromethane, xylenes and bromoform were detected and confirmed in all the samples analyzed. 相似文献
30.
Marazzi M Sancho U Castaño O Frutos LM 《Physical chemistry chemical physics : PCCP》2011,13(17):7805-7811
The photochemistry and photophysics of a two-glycine minimal model is studied at the CASPT2//CASSCF level of theory. Different photoinduced processes are discussed, on the basis of the calculated minimum energy paths and the characterization of the electronic state crossings. Two main processes could provide UV-photostability to the hydrogen-bonded peptide system: (i) forward-backward photoinduced electron/proton transfer involving the H in the hydrogen bond, (ii) singlet-singlet energy transfer between two amino acids, providing ultrafast population of the low-energy n,π* state. 相似文献