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31.
32.
Laura Rubio María Leticia Oca Luis Sarabia Inmaculada García María Cruz Ortiz 《Journal of Chemometrics》2016,30(2):58-69
Internal standards can be added at different stages of an analytical procedure. When they are added at the beginning of a multiresidue method and their behavior is not exactly the same as that of the analytes, the intended correction for small variations within the analytical process could not be achieved. Because of this, in the present work, the use of d ‐optimal designs together with desirability functions is proposed to state the experimental response under study. The overall desirability function used relates two analytical criteria: to assess a similar chemical behavior of each analyte in relation to its internal standard and to avoid a significant reduction of the absolute peak area of the internal standards. This strategy has been applied to the analysis of the effect of four factors related to the extraction and purification steps of six tranquillizers and a β‐blocker from pig muscle analyzed by liquid chromatography–tandem mass spectrometry. The effect of those factors has been evaluated by means of an ad hoc d ‐optimal design consisting of only 11 experiments. The resulting levels of the four factors that enable to achieve the greatest overall desirability have also been compared with those obtained when either the standardized or absolute peak area has been considered as response. Differences in both the significant factors and their optimum levels have been observed. It is noticeable that the experimental effort necessary to study the effect of the factors has been reduced by more than 50% thanks to the d ‐optimal design. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
33.
34.
Introduction to focus issue: mesoscales in complex networks 总被引:1,自引:0,他引:1
35.
Alfredo Burrieza Inmaculada P. de Guzmán Emilio Muñoz‐Velasco 《Mathematical Logic Quarterly》2010,56(1):89-102
In previous works, we presented a modification of the usual possible world semantics by introducing an independent temporal structure in each world and using accessibility functions to represent the relation among them. Different properties ofthe accessibility functions (being injective, surjective, increasing, etc.) have been considered and axiomatic systems (called functional) which define these properties have been given. Only a few ofthese systems have been proved tobe complete. The aim ofthis paper is to make a progress in the study ofcompleteness for functional systems. For this end, we use indexes as names for temporal flows and give new proofs of completeness. Specifically, we focus our attention on the system which defines injectivity, because the system which defines this property without using indexes was proved to be incomplete in previous works. The only system considered which remains incomplete is the one which defines surjectivity, even ifwe consider a sequence ofnatural extensions ofthe previous one (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
36.
Inmaculada Higueras 《BIT Numerical Mathematics》1994,34(3):361-366
Implicit Runge-Kutta (IRK) methods and projected IRK methods for the solution of semiexplicit index-2 systems of differential algebraic systems (DAEs) have been proposed by several authors. In this paper we prove that if a method satisfiesBA+A
t
B–bb
t
=0, it conserves quadratic invariants of DAEs. 相似文献
37.
Logarithmic norms are often used to estimate stability and perturbation bounds in linear ODEs. Extensions to other classes of problems such as nonlinear dynamics, DAEs and PDEs require careful modifications of the logarithmic norm. With a conceptual focus, we combine the extension to nonlinear ODEs [15] with that of matrix pencils [10] in order to treat nonlinear DAEs with a view to cover certain unbounded operators, i.e. partial differential algebraic equations. Perturbation bounds are obtained from differential inequalities for any given norm by using the relation between Dini derivatives and semi-inner products. Simple discretizations are also considered. 相似文献
38.
Unraveling the Degradation Mechanism of Purine Nucleotides Photosensitized by Pterins: The Role of Charge‐Transfer Steps
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Mariana P. Serrano Dr. Carolina Lorente Dr. Claudio D. Borsarelli Dr. Andrés H. Thomas 《Chemphyschem》2015,16(10):2244-2252
Photosensitized reactions contribute to the development of skin cancer and are used in many applications. Photosensitizers can act through different mechanisms. It is currently accepted that if the photosensitizer generates singlet molecular oxygen (1O2) upon irradiation, the target molecule can undergo oxidation by this reactive oxygen species and the reaction needs dissolved O2 to proceed, therefore the reaction is classified as 1O2‐mediated oxidation (type II mechanism). However, this assumption is not always correct, and as an example, a study on the degradation of 2′‐deoxyguanosine 5′‐monophosphate photosensitized by pterin is presented. A general mechanism is proposed to explain how the degradation of biological targets, such as nucleotides, photosensitized by pterins, naturally occurring 1O2 photosensitizers, takes place through an electron‐transfer‐initiated process (type I mechanism), whereas the contribution of the 1O2‐mediated oxidation is almost negligible. 相似文献
39.
Pau Moneva Lorente Dr. Céline Besnard Prof. Alan F. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(24):8851-8858
Assembly of two ditopic units, a phenanthroline substituted by 4‐ethynyl pyridines at the 2‐and 9‐positions and a dimetallic paddlewheel, gives a linear chain polymer rather than a closed cyclic species, which would appear equally possible. The chain may be decorated by binding a copper‐containing macrocycle around the phenanthroline units to form a polypseudorotaxane. When two phenanthroline ligands are assembled in a first step around copper(I), the paddlewheel acceptor can link them in a second step to form a two‐dimensional interwoven grid that resembles the form of a chain‐link fence. Each copper(I) centre in this structure is chiral, and the crystal shows complete homochirality, implying selection during the assembly process. 相似文献
40.
Böhme K Fernández-No IC Barros-Velázquez J Gallardo JM Cañas B Calo-Mata P 《Electrophoresis》2011,32(21):2951-2965
The rapid identification of food pathogenic and spoilage bacteria is important to ensure food quality and safety. Seafood contaminated with pathogenic bacteria is one of the major causes of food intoxications, and the rapid spoilage of seafood products results in high economic losses. In this study, a collection of the main seafood pathogenic and spoilage Gram-positive bacteria was compiled, including Bacillus spp., Listeria spp., Clostridium spp., Staphylococcus spp. and Carnobacterium spp. The strains, belonging to 20 different species, were obtained from the culture collections and studied by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). A reference library was created, including the spectral fingerprints of 32 reference strains and the extracted peak lists with 10-30 peak masses. Genus-specific as well as species-specific peak masses were assigned and could serve as biomarkers for the rapid bacterial identification. Furthermore, the peak mass lists were clustered with the web-application SPECLUST to show the phyloproteomic relationships among the studied strains. Afterwards, the method was successfully applied to identify six strains isolated from seafood by comparison with the reference library. Additionally, phylogenetic analysis based on the 16S rRNA gene was carried out and contrasted with the proteomic approach. This is the first time MALDI-TOF MS fingerprinting is applied to Gram-positive bacterial identification in seafood, being a fast and accurate technique to ensure seafood quality and safety. 相似文献