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101.
An experimental design optimization is reported of an analytical procedure used in the simultaneous determination of seven non-steroidal anti-inflammatory drugs (NSAIDs) in bovine milk by gas chromatography with mass spectrometry detection (GC-MS). This analytical procedure involves a solid-phase microextraction (SPME) step and an aqueous derivatization procedure of the NSAIDs to ethyl esters in bovine milk. The following NSAIDs are studied: ibuprofen (IBP), naproxen (NPX), ketoprofen (KPF), diclofenac (DCF), flufenamic acid (FLF), tolfenamic acid (TLF) and meclofenamic acid (MCL). Three kinds of SPME fibers - polyacrylate (PA), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polydimethylsiloxane (PDMS) - are compared to identify the most suitable one for the extraction process, on the basis of two steps: to determine the equilibrium time of each fiber and to select the fiber that provides the best figures-of-merit values calculated with three-way PARAFAC-based calibration models at the equilibrium time. The best results were obtained with the PDMS fiber. Subsequently, 8 experimental factors (related to the derivatization reaction and the SPME) were optimized by means of a D-optimal design that involves only 14 rather than 512 experiments in the complete factorial design. The responses used in the design are the sample mode loadings of the PARAFAC decomposition which are related to the quantity of each NSAID that is extracted in the experiment. Owing to the fact that each analyte is unequivocally identified in the PARAFAC decomposition, a calibration model is not needed for each experimental condition. The procedure fulfils the performance requirements for a confirmatory method established in European Commission Decision 2002/657/EC. 相似文献
102.
Thrombospondin-1 (TSP-1) is a protein involved in angiogenesis and tumor metastasis. In a previous study, a tridecapeptide sequence of TSP-1B [KRFKQDGGWSHWG] was synthesized and its biological activity was determined as well as the activity of three related sequences TSPB-(E), TSPB-(S), and TSPB-(Abu)(6). These peptides were tested for activity on the cell growth of three human carcinoma cells lines and only TSPB-(Abu)(6) increased proliferation of MCF7 and HT-29. The main aim of this study was to perform physicochemical measurements, in a comparative way, to determine if the differences in activity could be related to physicochemical properties. Peptides were characterised by HPLC capacity factors, UV, fluorescence, and CD spectra (either in buffer solution or in the presence of lipid vesicles), surface activity, and aggregation. Moreover, the interaction of these peptides with phospholipids was determined through their penetration in monolayers of DPPC, PG, or PS as well as their miscibility in mixed monolayers. Besides, using liposomes as model membranes, the affinity of these peptides for phosphatidylcholine was measured with vesicles labeled with fluorescent markers (TMA-DPH, laurdan, pyrene). Results show that these molecules are highly hydrophilic and their surface activity is low. Mixed monolayers indicate that there is almost no miscibility. Besides, its presence does not modify noticeably the microviscosity of bilayers. Moreover, UV and fluorescence spectra of peptides were not affected by the presence of lipids in the media but CD spectra recorded in TFE/water (1/1) resulted in small changes for TSPB, TSPB-(E), and TSPB-(S) peptides. On the contrary CD spectra of TSPB-(Abu)(6) derivatives were clearly much more sensitive to the polarity of the environment. According to these data the biological activity of peptide with a cyclic aspartimide moiety at position 6 could be related to a specific conformational change in the peptide chain promoted by a hydrophobic membrane-like environment. 相似文献
103.
Silva C Aranda FJ Ortiz A Martínez V Carvajal M Teruel JA 《Journal of colloid and interface science》2011,358(1):192-201
The effect of sterols composition in a lipid bilayer was investigated on membranes of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and mixtures with the plant sterols β-sitosterol and stigmasterol. Differential scanning calorimetry, 1,6-diphenyl-1,3,5-hexatriene (DPH) fluorescence polarization and infrared spectroscopy studies showed that both sterols changed the packing of the membrane and the hydration of the polar headgroup of the phospholipids, disordering the gel phase and, vice versa, ordering the membrane in the liquid crystalline phase. In all cases some differences among β-sitosterol and stigmasterol could be observed, being β-sitosterol slightly more efficient than stigmasterol in ordering a fluid membrane, bringing the membrane to a more packed liquid ordered phase. Molecular dynamic simulations were carried out to better characterize the distinct behavior of both sterols in a DPPC-membrane. The calculated parameters agreed quite well with the experimental results and a molecular model is proposed to explain differences in the sterols molecules and their effect on the DPPC-bilayer. 相似文献
104.
A computational study of the kinetics of isomerization and elimination reactions of organophosphorus and organosulfur reactions is presented with a view to characterizing the predictive capabilities of widely applied techniques for processes that pertain to the destruction of chemical warfare agents. A set of 22 reactions has been studied, and the results have been compared to experimentally derived data. The BMK functional and the MG3S basis set have been used to compute minimum energy paths. Corrections have been added from CBS-QB3, CASSCF, and CASMP2 calculations. Thermal rate constants at experimental temperatures have been calculated with canonical variational transition state theory and small-curvature tunneling theory. The quality of these results may depend on recrossing of the variational transition state, the amount of radical or diradical character found in the minimum energy paths, or the accuracy of barrier heights. 相似文献
105.
Novais Luciano Maqueira Juan Manuel Ortiz Ángel Bruque Sebastián 《Central European Journal of Operations Research》2021,29(4):1185-1218
Central European Journal of Operations Research - Hypothesis contrast using statistical models with Structural Equations is a technique widely used in Supply Chain Management research. However,... 相似文献
106.
We study a first-order identification problem in a Banach space. We discuss the nondegenerate and mainly the degenerate case. As a first step, suitable hypotheses on the involved closed linear operators are made in order to obtain unique solvability after reduction to a nondegenerate case; the general case is then handled with the help of new results on convolutions. Some applications to partial differential equations motivate this abstract approach.Communicated by I. GalliganiWork partially supported by MIUR (Ministero dell’ Istruzione, dell’ Università e dalla Ricerca), Project PRIN 2004011204 “Analisi Matematica nei Problemi Inversi,” and by the University of Bologna Funds for Selected Research Topics. 相似文献
107.
Organotin compounds are widely distributed toxicants. They are membrane‐active molecules with broad biological toxicity. We have studied the interaction of tributyltin and triphenyltin with phosphatidylserine model membranes using differential scanning calorimetry, infrared spectroscopy and X‐ray diffraction techniques. Organotin compounds produced a broadening of the gel to the liquid‐crystalline phase transition of the phospholipid and a shifting of the phase transition temperature to lower values. Infrared spectroscopy experiments showed that tributyltin exerted a fluidizing effect on the apolar part of the bilayer, and that both tributyl‐ and triphenyltin interact with the interfacial region of the bilayer, making the carbonyl groups less accessible to water. As seen by X‐ray diffraction experiments, organotin compounds were unable to change the bilayer macroscopic organization of the phospholipid, but they were able to reduce the long‐range order of the multibilayer system and to disorder the packing of the phospholipid molecules. The observed interaction between organotin compounds and phosphatidylserine membranes promotes physical perturbations that could affect membrane function and may mediate some of their toxic effects. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
108.
Javier Ulises Ortiz MayoMartial Thomas Carole SaintoméPascale Clivio 《Tetrahedron》2003,59(37):7377-7383
The synthesis of a building block containing the photobiologically relevant cis-syn thymine cyclobutane photoproduct and its incorporation into oligonucleotides by the phosphoramidite-based solid-phase synthesis is reported. Compared to previous syntheses, this route is extremely short and allows such modified oligonucleotides to be easily available for biological studies. 相似文献
109.
Deanna Marcano Jeannette De Mndez Ana C. Ortiz Mirna Salinas 《Magnetic resonance in chemistry : MRC》1984,22(11):736-738
The 13C chemical shift data of several D-homoandrostanes with heteroatoms (N,O) in the 17a-position are reported. Heteroatom effects on the shieldings of the carbons of rings C and D are discussed. 相似文献
110.
C.Alvarez Ibarra J.A. Cereceda P. Ortiz A. Vicente M.L. Quiroga 《Tetrahedron letters》1985,26(2):243-246
We report the synthesis of 5-aryl-2-ethoxycarbonyl-4-methylthio-2,3-dihydrooxazoles from a cyclocondensation reaction betweeen dimethyl N-ethoxycarbonylmethyliminodithiocarbonate and aromatic aldehydes. 相似文献