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241.
Ángel Castillo Emma Gracia-Lor Antoni Francesc Roig-Navarro Juan Vicente Sancho Pablo Rodríguez-González J. Ignacio García Alonso 《Analytica chimica acta》2013
Isotope dilution mass spectrometry (IDMS) based on isotope pattern deconvolution (IPD) has been applied here to MS/MS (QqQ) in order to carry out the quantification and confirmation of organic compounds in complex matrix water samples without the use of a methodological IDMS calibration graph. In this alternative approach, the isotope composition of the spiked sample is measured after fragmentation by SRM and deconvoluted into its constituting components (molar fractions of natural abundance and labeled compound) by multiple linear regression (IPD). The procedure has been evaluated for the determination of the pharmaceutical diclofenac in effluent and influent urban wastewaters and fortified surface waters by UHPLC (ESI) MS/MS using diclofenac-d4 as labeled compound. Calculations were performed acquiring a part and the whole fragment cluster ion, achieving in all cases recoveries within 90–110% and coefficients of variation below 5% for all water samples tested. In addition, potential false negatives arising from the presence of diclofenac-d2 impurities in the labeled compound were avoided when the proposed approach was used instead of the most usual IDMS calibration procedure. The number of SRM transitions measured was minimized to three to make possible the application of this alternative technique in routine multi-residue analysis. 相似文献
242.
Praveen Kumar Antoni Rúbies Francesc Centrich Mercè Granados Nuria Cortés-Francisco Josep Caixach Ramon Companyó 《Analytica chimica acta》2013
Sensitive and unequivocal determination of analytes/contaminants in complex matrices is a challenge in the field of food safety control. In this study, various acquisition modes (Full MS/AIF, Full MS + tMS/MS, Full MS/dd MS/MS and tSIM/ddMS/MS) and parameters of a quadrupole–orbitrap hybrid mass spectrometer (Q Exactive) were studied in detail. One of the main conclusions has been that, reducing the scan range for Full MS (using the quadrupole) and targeted modes give higher signal-to-noise (S/N) ratios and thereby better detection limits for analytes in matrix. The use of Q Exactive in a complex case, for the confirmatory analysis of hormones in animal urine is presented. A targeted SIM data dependent MS/MS (tSIM/ddMS/MS) acquisition method for determination of eight synthetic hormones (trenbolone, 17α ethinylestradiol, zeranol, stanozolol, dienestrol, diethylstilbestrol, hexestrol, taleranol) and a naturally occurring hormone (zearalenone) in animal urine were optimized to have sensitive precursors from targeted SIM mode and trigger MS/MS scans over the entire chromatograph peak. The method was validated according to EC/657/2002. CCα (decision limit) for the analytes ranged between 0.11 μg L−1 and 0.69 μg L−1 and CCβ (detection capability) ranged between 0.29 μg L−1 and 0.90 μg L−1. 相似文献
243.
244.
Jordi Poater Miquel Sol Clara Vias Francesc Teixidor 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(45):12387-12391
A bridge between classical organic polycyclic aromatic hydrocarbons (PAH) and closo borohydride clusters is established by showing that they share a common origin regulated by the number of valence electrons in an electronic confined space. Application of the proposed electronic confined space analogy (ECSA) method to archetypal PAHs leads to the conclusion that the 4n+2 Wade–Mingos rule for three‐dimensional closo boranes is equivalent to the (4n+2)π Hückel rule for two‐dimensional PAHs. More importantly, use of ECSA allows design of new interesting fused closo boranes which can be a source of inspiration for synthetic chemists. 相似文献
245.
Josep Francesc Ventura-Gayete Salvador Garrigues Miguel de la Guardia 《Microchemical Journal》2004,78(1):47-54
The mechanization of attenuated total reflectance measurements (ATR) in Fourier Transform Infrared spectrometry (FTIR) through the use of multicommutation has been evaluated in order to reduce the sample consumption and waste generation also avoiding risks of cells breaking. A new multicommutation ATR-FTIR procedure has been proposed for the determination of sodium alpha-olefin sulfonate (AOS) in liquid detergent formulations. The main advantages of this method are the low consumption of sample (96 ml per 100 determinations) and the analytical throughput (23 h−1 versus 15 h−1 for the manual mode). Results obtained for reference samples containing 7.52% to 9.52% (w/w) of AOS are in the 0.5% (w/w) error range, with a mean precision of 0.3% RSD. Recovery studies evidence the accuracy of the method, with average values around 100%. It was evaluated the possibilities of ATR-FTIR analysis of different types of liquid samples like beer, orange juice, milk and olive oil, showing the great versatility and applications of this approach to improve sample introduction and cell cleaning. 相似文献
246.
IMTL logic was introduced in [12] as a generalization of the infinitely-valued logic of Lukasiewicz, and in [11] it was proved
to be the logic of left-continuous t-norms with an involutive negation and their residua. The structure of such t-norms is
still not known. Nevertheless, Jenei introduced in [20] a new way to obtain rotation-invariant semigroups and, in particular,
IMTL-algebras and left-continuous t-norm with an involutive negation, by means of the disconnected rotation method. In order
to give an algebraic interpretation to this construction, we generalize the concepts of perfect, bipartite and local algebra
used in the classification of MV-algebras to the wider variety of IMTL-algebras and we prove that perfect algebras are exactly
those algebras obtained from a prelinear semihoop by Jenei's disconnected rotation. We also prove that the variety generated
by all perfect IMTL-algebras is the variety of the IMTL-algebras that are bipartite by every maximal filter and we give equational
axiomatizations for it. 相似文献
247.
5-Arylmethylene-3,4-dimethyl-3-pyrrolin-2-ones on treatment withd 1-trifluoroacetic acid (d 1-TFA) undergo deuterium substitution at the carbon atom of the methylene bridge. This electrophilic substitution is related to similar deuteration reactions of verdins (bilatrienes-a,b,c). The results obtained can be interpreted by a free energy relationship, assuming that the field effect, becomes negligible by the influence ofTFA. 相似文献
248.
Armengol Gasull Francesc Mañosas 《Journal of Mathematical Analysis and Applications》2002,269(1):332-351
We study the stability of a type of unbounded polycycles which appear in some planar differential equations. Each of these polycycles has hyperbolic corners, but the product of the hyperbolicity ratios of all its corners does not decide its stability. We obtain an explicit convergent integral whose sign gives the stability of the polycycle. 相似文献
249.
250.
Puig P Tempels FW Somsen GW de Jong GJ Borrull F Aguilar C Calull M 《Electrophoresis》2008,29(6):1339-1346
We present a new system for the sensitive analysis of cephalosporins by CE using both on-line SPE and large-volume sample stacking (LVSS). Sample volumes of 250 muL were loaded onto the SPE microcolumn which was then desorbed with 426 nL of ACN. The SPE elution plug was injected into the CE system via an in-line valve interface filling approximately 60% of the volume of the separation capillary. Subsequently, LVSS was performed by applying a voltage of -5 kV, which resulted in the simultaneous removal of the elution solvent and the preconcentration of the analytes in a narrow zone. This way the amount of analyte loaded into the capillary could be considerably increased without serious loss of CE separation efficiency. LODs for cefoperazone and ceftiofur were in the ng/L range which represents an improvement of a factor of 8450 and 11 450 when compared with direct CE injection. The cephalosporin test compounds presented a good linear response (corrected peak area) between 0.5 and 10 mug/L with correlation coefficients higher than 0.995. The final method is compared with previously reported LVSS-CE and SPE-CE systems for the analysis of cephalosporins. 相似文献