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981.
Sérandour AL Ledreux A Morin B Derick S Augier E Lanceleur R Hamlaoui S Moukha S Furger C Biré R Krys S Fessard V Troussellier M Bernard C 《Analytical and bioanalytical chemistry》2012,403(7):1983-1993
Human poisoning due to consumption of seafood contaminated with phycotoxins is a worldwide problem, and routine monitoring programs have been implemented in various countries to protect human consumers. Following successive episodes of unexplained shellfish toxicity since 2005 in the Arcachon Bay on the French Atlantic coast, a national research program was set up to investigate these atypical toxic events. Part of this program was devoted to fit-for-purpose cell-based assays (CBA) as complementary tools to collect toxicity data on atypical positive-mouse bioassay shellfish extracts. A collaborative study involving five laboratories was conducted. The responses of human hepatic (HepG2), human intestinal (Caco2), and mouse neuronal (Neuro2a) cell lines exposed to three known lipophilic phycotoxins-okadaic acid (OA), azaspiracid-1 (AZA1), and pectenotoxin-2 (PTX2)-were investigated. A screening strategy composed of standard operating procedures and a decision tree for dose-response modeling and assay validation were designed after a round of "trial-and-error" process. For each toxin, the shape of the concentration-response curves and the IC(50) values were determined on the three cell lines. Whereas OA induced a similar response irrespective of the cell line (complete sigmoid), PTX2 was shown to be less toxic. AZA1 induced cytotoxicity only on HepG2 and Neuro2a, but not on Caco2. Intra- and inter-laboratory coefficients of variation of cell responses were large, with mean values ranging from 35 to 54 % and from 37 to 48 %, respectively. Investigating the responses of the selected cell lines to well-known toxins is the first step supporting the use of CBA among the panel of methods for characterizing atypical shellfish toxicity. Considering these successful results, the CBA strategy will be further applied to extracts of negative, spiked, and naturally contaminated shellfish tissues. 相似文献
982.
Versace F Uppugunduri CR Krajinovic M Théorêt Y Gumy-Pause F Mangin P Staub C Ansari M 《Analytical and bioanalytical chemistry》2012,404(6-7):1831-1838
The role of busulfan (Bu) metabolites in the adverse events seen during hematopoietic stem cell transplantation and in drug interactions is not explored. Lack of availability of established analytical methods limits our understanding in this area. The present work describes a novel gas chromatography-tandem mass spectrometric assay for the analysis of sulfolane (Su) in plasma of patients receiving high-dose Bu. Su and Bu were extracted from a single 100 μL plasma sample by liquid-liquid extraction. Bu was separately derivatized with 2,3,5,6-tetrafluorothiophenolfluorinated agent. Mass spectrometric detection of the analytes was performed in the selected reaction monitoring mode on a triple quadrupole instrument after electronic impact ionization. Bu and Su were analyzed with separate chromatographic programs, lasting 5?min each. The assay for Su was found to be linear in the concentration range of 20-400?ng/mL. The method has satisfactory sensitivity (lower limit of quantification, 20?ng/mL) and precision (relative standard deviation less than 15?%) for all the concentrations tested with a good trueness (100?±?5?%). This method was applied to measure Su from pediatric patients with samples collected 4?h after dose 1 (n?=?46), before dose 7 (n?=?56), and after dose 9 (n?=?54) infusions of Bu. Su (mean?±?SD) was detectable in plasma of patients 4?h after dose 1, and higher levels were observed after dose 9 (249.9?±?123.4?ng/mL). This method may be used in clinical studies investigating the role of Su on adverse events and drug interactions associated with Bu therapy. 相似文献
983.
T Courant VG Roullin C Cadiou M Callewaert MC Andry C Portefaix C Hoeffel MC de Goltstein M Port S Laurent LV Elst R Muller M Molinari F Chuburu 《Angewandte Chemie (International ed. in English)》2012,51(36):9119-9122
Do not tumble dry: Gadolinium-DOTA encapsulated into polysaccharide nanoparticles (GdDOTA?NPs) exhibited high relaxivity (r(1) =101.7?s(-1) mM(-1) per Gd(3+) ion at 37?°C and 20?MHz). This high relaxation rate is due to efficient Gd loading, reduced tumbling of the Gd complex, and the hydrogel nature of the nanoparticles. The efficacy of the nanoparticles as a T(1) /T(2) dual-mode contrast agent was studied in C6 cells. 相似文献
984.
Möller I Thomas A Wingender A Machnik M Schänzer W Thevis M 《European journal of mass spectrometry (Chichester, England)》2012,18(4):407-412
Erythropoietin (EPO) and its recombinant analogues are suspected to be illicitly administered to horses for performance enhancing purposes and, consequently, prohibited in equine sports. Recently, a new erythropoiesis-stimulating agent, peginesatide (Omontys, formerly referred to as Hematide), belonging to the upcoming class of EPO-mimetic peptides, received approval for the treatment of anaemia in humans with chronic kidney disease on dialysis. As the pegylated dimeric peptide of approximately 45 kDa without sequence homology to EPO is not detectable by conventional EPO detection assays, specific methods are bound to be established for horse sports drug testing. Thus, by fortifying equine serum with peginesatide, an approach consisting of a proteolytic digestion with subtilisin after protein precipitation was developed, eventually targeting a proteotypic and xenobiotic pentapeptide which is easily accessible to liquid chromatography- tandem mass spectrometry analysis. The method was validated for qualitative purposes and demonstrated to be specific, precise (relative standard deviations below 14%), sensitive (limit of detection 10 ng mL(-1)) and linear. Being simple, cost-effective and readily transferable to other doping control laboratories, a mass spectrometric assay for the detection of therapeutic concentrations of peginesatide in equine serum is, in terms of preventive doping research, applicable to routine analysis shortly after approval of the drug. 相似文献
985.
Dunk PW Kaiser NK Mulet-Gas M Rodríguez-Fortea A Poblet JM Shinohara H Hendrickson CL Marshall AG Kroto HW 《Journal of the American Chemical Society》2012,134(22):9380-9389
The smallest fullerene to form in condensing carbon vapor has received considerable interest since the discovery of Buckminsterfullerene, C(60). Smaller fullerenes remain a largely unexplored class of all-carbon molecules that are predicted to exhibit fascinating properties due to the large degree of curvature and resulting highly pyramidalized carbon atoms in their structures. However, that curvature also renders the smallest fullerenes highly reactive, making them difficult to detect experimentally. Gas-phase attempts to investigate the smallest fullerene by stabilization through cage encapsulation of a metal have been hindered by the complexity of mass spectra that result from vaporization experiments which include non-fullerene clusters, empty cages, and metallofullerenes. We use high-resolution FT-ICR mass spectrometry to overcome that problem and investigate formation of the smallest fullerene by use of a pulsed laser vaporization cluster source. Here, we report that the C(28) fullerene stabilized by encapsulation with an appropriate metal forms directly from carbon vapor as the smallest fullerene under our conditions. Its stabilization is investigated, and we show that M@C(28) is formed by a bottom-up growth mechanism and is a precursor to larger metallofullerenes. In fact, it appears that the encapsulating metal species may catalyze or nucleate endohedral fullerene formation. 相似文献
986.
Oxidized abasic sites such as 2-deoxyribonolactone (L) are produced in DNA by a variety of oxidizing agents, including potent cytotoxic antitumor natural products. 2-Deoxyribonolactone is labile under alkaline conditions, but its half-life in free DNA at pH 7.5 is approximately 1 week. Independent generation of L at defined positions within nucleosomes reveals that the histone proteins catalyze strand scission and increase the rate between 11- and ~43-fold. Mechanistic studies indicate that DNA-protein cross-links are not intermediates en route to strand scission and that C2 deprotonation is the rate-determining step. The use of mutant histone H4 proteins demonstrates that the lysine-rich tail that is often post-translationally modified in cells contributes to the cleavage of L but is not the sole source of the enhanced cleavage rates. Consideration of DNA repair in cells suggests that L formation in nucleosomal DNA as part of bistranded lesions by antitumor antibiotics results in de facto double strand breaks, the most deleterious form of DNA damage. 相似文献
987.
Costentin C Drouet S Robert M Savéant JM 《Journal of the American Chemical Society》2012,134(27):11235-11242
The search for efficient catalysts to face modern energy challenges requires evaluation and comparison through reliable methods. Catalytic current efficiencies may be the combination of many factors besides the intrinsic chemical properties of the catalyst. Defining turnover number and turnover frequency (TOF) as reflecting these intrinsic chemical properties, it is shown that catalysts are not characterized by their TOF and their overpotential (η) as separate parameters but rather that the parameters are linked together by a definite relationship. The log TOF-η relationship can often be linearized, giving rise to a Tafel law, which allows the characterization of the catalyst by the value of the TOF at zero overpotential (TOF(0)). Foot-of-the-wave analysis of the cyclic voltammetric catalytic responses allows the determination of the TOF, log TOF-η relationship, and TOF(0), regardless of the side-phenomena that interfere at high current densities, preventing the expected catalytic current plateau from being reached. Strategies for optimized preparative-scale electrolyses may then be devised on these bases. The validity of this methodology is established on theoretical grounds and checked experimentally with examples taken from the catalytic reduction of CO(2) by iron(0) porphyrins. 相似文献
988.
Fromentin C Sanders P Nau F Anton M Fromentin G Tomé D Thibault JN Gaudichon C 《Rapid communications in mass spectrometry : RCM》2012,26(1):43-48
The aim of this study was to produce intrinsically and uniformly doubly (15)N-(13)C-labeled proteins. These proteins can be used as intrinsic tracers of dietary amino acids, both α-amino groups and carbon skeletons, during postprandial metabolic utilization. Two (Rhodes) laying hens were fed for 16 days with a standard poultry diet supplemented with 0, 0.2% or 0.4% of a mixture of 20 doubly (15)N-(13)C-labeled AAs. A third hen was given a non-enriched diet, as the control. The eggs laid were collected over 24 days, from 3 days before to 4 days after supplementation. The (15)N and (13)C enrichments in proteins from white and yolk were measured by EA-IRMS and GC-C-IRMS for enrichment in individual amino acids. After 10 days of supplementation, the (15)N enrichment reached an isotopic plateau at 1500 to 3000 ‰, depending on the supplementation level, in both white and yolk while the (13)C enrichment was 220 to 650 ‰ in white and was 100 to 250 ‰ in yolk. The (15)N enrichment was similar among the amino acids, except for the aromatic ones in which the enrichment was lower. The δ(13)C values were variable among amino acids in both white and yolk, ranging from 77 ‰ for tyrosine to 555 ‰ for proline with the 0.2 % supplementation level. In conclusion, the incorporation of 0.2 % labeled amino acids in the hen diet allowed us to achieve sufficient enrichment for metabolic studies. However, due to the non-homogeneity of the (13)C labeling, adequate (13)C enrichment of individual amino acids must be considered depending on the investigated metabolic pathway. 相似文献
989.
990.