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131.
Cristoni S Basso E Gerthoux P Mocarelli P Gonella E Brambilla M Crotti S Bernardi LR 《Rapid communications in mass spectrometry : RCM》2007,21(15):2515-2523
Surface-activated chemical ionization (SACI) was employed for the analysis of cocaine and its metabolite, benzoylecgonine, extracted from hair. Following decontamination and acid hydrolysis procedures on the hair sample, the sample solution was diluted (1:10) and directly analyzed by liquid chromatography/surface-activated chemical ionization multiple collisional stage single reaction monitoring mass spectrometry (LC/SACI-MS(3)-SRM) without solid-phase extraction (SPE) pre-purification and concentration procedures. To increase the selectivity of the method, MS(3) was chosen instead of the less selective MS/MS. This data was compared with that achieved using gas chromatography/mass spectrometry (GC/MS), the reference method used by the Italian Government Institute of Health protocol. The limits of detection (LODs) were 0.003 ng/(mg hair) for cocaine and 0.02 ng/(mg hair) for benzoylecgonine and the limits of quantitation (LOQs) were 0.01 ng/(mg hair) for cocaine and 0.04 ng/(mg hair) for benzoylecgonine. The squared correlation coefficient (R(2)) of the calibration curve was 0.9887-0.9980 for cocaine and 0.9987-0.9997 for benzoylecgonine. The percent accuracy error was 2-5% for both cocaine and benzoylecgonine using the LC/SACI-MS(3)-SRM approach, whereas it was higher for benzoylecgonine (20-25%) using the LC/SACI-MS/MS-SRM approach compared with the GC/MS data due to hair matrix contamination. In both cases, high precision was achieved (1-3% precision error), which confirmed the stability of the developed methods. 相似文献
132.
Elisa Frederico Seneme Daiane Carla dos Santos Evelyn Marcela Rodrigues Silva Yollanda Edwirges Moreira Franco Giovanna Barbarini Longato 《Molecules (Basel, Switzerland)》2021,26(19)
Natural products have been used by humanity for many centuries to treat various illnesses and with the advancement of technology, it became possible to isolate the substances responsible for the beneficial effects of these products, as well as to understand their mechanisms. In this context, myristicin, a substance of natural origin, has shown several promising activities in a large number of in vitro and in vivo studies carried out. This molecule is found in plants such as nutmeg, parsley, carrots, peppers, and several species endemic to the Asian continent. The purpose of this review article is to discuss data published in the last 10 years at Pubmed, Lilacs and Scielo databases, reporting beneficial effects, toxicity and promising data of myristicin for its future use in medicine. From 94 articles found in the literature, 68 were included. Exclusion criteria took into account articles whose tested extracts did not have myristicin as one of the major compounds. 相似文献
133.
Antonio Cervilla Francisco Prez‐Pla Antonio Ribera Elisa Llopis Antonio Domenech 《国际化学动力学杂志》2001,33(3):212-224
The heterogeneous reduction of nitrobenzene by thiophenol catalyzed by the dianionic bis(2‐sulfanyl‐2,2‐diphenylethanoxycarbonyl) dioxomolybdate(VI) complex, [MoVIO2(O2CC(S)(C6H5)2)2]2−, intercalated into a Zn(II)–Al(III) layered double hydroxide host [Zn3−xAlx(OH)6]x+, has been investigated under anaerobic conditions. Aniline was found to be the only product formed through a reaction consuming six moles of thiophenol for each mol of aniline produced. The kinetics of the system have been analyzed in detail. In excess of thiophenol, all reactions follow first‐order kinetics (ln([PhNO2]/[PhNO2]0) = −kappt) with the apparent rate constant kapp being a complex function of both initial nitrobenzene and thiophenol concentrations, as well as linearly dependent on the amount of solid catalyst used. A mechanism for this catalytic reaction consistent with the kinetic experiments as well as the observed properties of the intercalated molybdenum complex has thiophenol inducing the initial coupled proton–electron transfer steps to form an intercalated MoIV species, which is oxidized back to the parent MoVI complex by nitrobenzene via a two‐electron oxygen atom transfer reaction that yields nitrosobenzene. This mechanism is widespread in enzymatic catalysis and in model chemical reactions. The intermediate nitrosobenzene thus formed is reduced directly by excess thiophenol to aniline. The values of rate coefficients indicate that reduction of nitrobenzene proceeds much faster than proton‐assisted oxidation of thiophenol. This may account for the observation that the presence of protonic amberlite IR‐120(H) increases considerably the rate of the overall reaction catalyzed. Activation parameters in excess of the protonic resin and PhSH were ΔH≠ = 80 kJ mol−1 and ΔS≠ = −70 J mol−1 K−1. The large negative activation entropy is consistent with an associative transition state. The present system is characterized by a well‐defined catalytic cycle with multiple‐turnovers reductions of nitrobenzene to aniline without appreciable deactivation. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 212–224, 2001 相似文献
134.
135.
Ilse Manet Luca Francini Stefano Masiero Silvia Pieraccini GianPiero Spada Giovanni Gottarelli 《Helvetica chimica acta》2001,84(7):2096-2107
The self‐assembly of guanosine (G) derivatives in the presence of alkali‐metal ions gives octameric or polymeric aggregates composed of stacked G quartets. This process is studied for some lipophilic G derivatives by means of ESI‐MS. The ESI‐MS results are discussed in the light of complementary information obtained from NMR and SANS (small‐angle neutron scattering) studies. ESI‐MS gives an excellent picture of the self‐assembly process and gives new information on the effect of different cations and anions on the dimensions of the assembled species, information that could not have been obtained with SANS and NMR alone. 相似文献
136.
137.
The intermolecular reaction and its role in determining the partial compatibility between diethylsuccinate containing linear low-density polyethylene or ethylene propylene copolymer and poly-ϵ-caprolactam (PA6) has been investigated in the melt using a Brabender mixer. The reaction product has been submitted to selective solvent extraction with formic acid and n-heptane; the characterization of the two extracted fractions and the insoluble residue has demonstrated the formation of a polyolefin–nylon (PO–PA6) grafted copolymer. The formation of grafted copolymer has an evident effect on the compatibilization of the two original polymers, indeed the differential scanning calorimetry analysis shows a remarkable decrease of temperature and enthalpy of PA6 crystallization. Moreover scanning electron microscopy micrographs show clear evidence of size reduction of PA6 domains associated with improved interface interactions. © 1998 John Wiley & Sons, Ltd. 相似文献
138.
The unit of time of the International System of Units (SI), the “atomic second” was defined through a constant of physics in 1967. It is derived from the frequency of the hyperfine transition of the atom of cesium 133. From the astronomical definition of the second until today, the accuracy of the realization of the second has improved by eight orders of magnitude, with a rate that has increased since the development of the cesium frequency standards, to reach parts in 1016 for the best clocks today. In 2018, when the new SI was adopted, the time metrology community proved that a new generation of frequency standards operating in optical wavelengths has uncertainties at the level of 10–18, and challenge the implementation of high accurate frequency and time comparison techniques to decide on a revision of the definition of the second. Herein, the progress in the definition and realization of the second from astronomy until today is reviewed, an inventory of the present resources is assembled and a brief view for the future given. 相似文献
139.
Rodrigues LM Sivasubramanian A Pinto EM Oliveira-Campos AM Seijas JA Vázquez-Tato MP 《Magnetic resonance in chemistry : MRC》2009,47(1):84-86
A series of 21 substituted pyrazolo[3,4-d]pyrimidines-4-amines were studied by (1)H and (13)C NMR. The application of two-dimensional techniques, HMQC and HMBC, allowed the complete assignment of the spectra for all the compounds. 相似文献
140.
Barbara Chiavarino Dr. Maria Elisa Crestoni Prof. Simonetta Fornarini Prof. Francesco Lanucara Dr. Joel Lemaire Dr. Philippe Maître Prof. Debora Scuderi Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(33):8185-8195
Anion–π interactions between a π‐acidic aromatic system and an anion are gaining increasing recognition in chemistry and biology. Herein, the binding features of an electron‐deficient aromatic system (1,3,5‐trinitrobenzene (TNB)) and selected anions (OH?, Br?, and I?) are examined in the gas phase by using the combined information derived from collision‐induced dissociation experiments at variable energy, infrared multiple‐photon dissociation spectroscopy, and quantum chemical calculations. We provide spectroscopic evidence for two different structural motifs of anion–arene complexes depending on the nature of the anion. The TNB–OR? complexes (R=H, or alkyl groups which were studied earlier) adopt an anionic σ‐complex structure whereby RO? attacks the aromatic ring with covalent bond formation, and develops a tetrahedral ring carbon bound to H and OR. The halide complexes rather conform to a structure in which the TNB moiety is hardly altered, and the halogen is placed on an unsubstituted carbon atom over the periphery of the ring at a C–X distance that is appreciably longer than a typical covalent bond length. The ensuing structural motif, previously characterized in the solid state and named weak σ interaction, is now confirmed by an IR spectroscopic assay in the gas phase, in which the sampled species are unperturbed by crystal packing or solvation effects. 相似文献