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31.
François Versace Julien Déglon Estelle Lauer Patrice Mangin Christian Staub 《Chromatographia》2013,76(19-20):1281-1293
This article describes a rapid LC–MS/MS target screening method based on an automated extraction of 5 μL dried blood spots (DBS), two 5 min chromatographic runs on orthogonal phase columns (RP and Hilic) and a data dependent acquisition (DDA) of product ions spectra for the reliable identification of the detected compounds. The extraction step was performed in 2 min by using the LC autosampler itself in 96-well plates. This procedure was evaluated using 22 model compounds frequently encountered in forensic investigations, i.e., cocaine, benzodiazepines, amphetamines, opioids, antidepressants and antipsychotics. These investigations showed that even if the extraction step was reduced to a minimum, the extraction recoveries were satisfactory (median value of 40 %) and allowed for the detection of the model compounds in their therapeutic ranges, with the exception of morphine. Moreover, the use of two different chromatographic columns broadened the number of screening targets to those that behaved poorly under RP conditions, such as amphetamines or glucuronides, while keeping chromatographic gradients very short. This procedure was applied to 34 authentic post-mortem cases. It allowed the detection of 89 % of the compounds that were quantified in the routine procedures and the formal identification of 77 % of the compounds using their product ions spectra. These results were considered more than satisfactory compared to routine screening alone (GC–MS and LC-DAD, 55 % compound identification). The method described in this article is therefore a powerful approach for a fast, reliable and efficient target screening of drugs in forensic and clinical investigations. 相似文献
32.
Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host–Guest Complexes Probed by Ion Mobility and Collision‐Induced Dissociation
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Glenn Carroy Charlotte Daxhelet Dr. Vincent Lemaur Dr. Julien De Winter Prof. Edwin De Pauw Prof. Jérôme Cornil Prof. Pascal Gerbaux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4528-4534
Host–guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion‐mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host–guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas‐phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para‐phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision‐induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process. 相似文献
33.
Julien Ramier Estelle Renard Daniel Grande 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1445-1455
Microwave (MW)‐assisted ring‐opening polymerization (ROP) provides a rapid and straightforward method for engineering a wide array of well‐defined poly(3‐hydroxyalkanoate)‐b‐poly(D,L ‐lactide) (PHA‐b‐PLA) diblock copolymers. On MW irradiation, the bulk ROP of D,L ‐lactide (LA) could be efficiently triggered by a series of monohydroxylated PHA‐based macroinitiators previously produced via acid‐catalyzed methanolysis of corresponding native PHAs, thus affording diblock copolyesters with tunable compositions. The dependence of LA polymerization on temperature, macroinitiator structure, irradiation time, and [LA]0/[PHA]0 molar ratio was carefully investigated. It turned out that initiator efficiency values close to 1 associated with conversions ranging from 50 to 85% were obtained only after 5 min at 115 °C. A kinetic investigation of the MW‐assisted ROP of LA gave evidence of its “living”/controlled character under the experimental conditions selected. Structural analyses and thermal properties of biodegradable diblock copolyesters were also performed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
34.
S Sun J Kroll Y Luo L Zhang 《Synlett : accounts and rapid communications in synthetic organic chemistry》2012,2012(1):54-56
A gold-catalyzed regioselective homodimerization of aliphatic terminal alkynes is described. Bulky and less Lewis acidic tBuXPhosAuNTf(2) is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction. 相似文献
35.
Julien Iehl Thi Le Anh Nguyen Stéphane Frein Uwe Hahn Joaquín Barberá Jean-François Nierengarten 《Liquid crystals》2017,44(12-13):1852-1860
ABSTRACTLiquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C60) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, 1H and 13C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C60 functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C60 decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C60 is a unique synthetic platform for the design of fullerodendrimers and dendronised materials. 相似文献
36.
We have studied the effect of interface heterogeneity on fracture, at both local and global scales. The single cantilever beam adhesion test was used to investigate interfacial fracture between polycarbonate plates and an elastic/fragile epoxy adhesive. Two surface treatments were applied to a (given) polycarbonate plate giving zones of strong and weak adhesion parallel to the crack direction. Calculated fracture energies differed from those expected from a simple rule-of-mixtures. A perturbation method, proposed by Rice, was used and results compared with crack fronts observed in situ. The technique was applied successfully but the difference in values of stress intensity factor between the zones was found substantially different from the experimental value. In an attempt to explain discrepancies, specimens with discontinuous crack fronts (adhesive and/or plates severed along the strong/weak adhesion frontier) were tested. Good agreement was found with the rule-of-mixtures predictions raising questions about the role of crack front continuity in load transfer. 相似文献
37.
Dr. Tim Schleif Dr. Jörg Tatchen Julien F. Rowen Frederike Beyer Prof. Dr. Elsa Sanchez-Garcia Prof. Dr. Wolfram Sander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10452-10458
The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b . 相似文献
38.
The research on the electrodes of Li-ion batteries aims to increase the energy density and the power density, improve the calendar and the cycling life, without sacrificing the safety issues. A constant progress through the years has been obtained owing to the surface treatment of the particles, in particular the coating of the particles with a layer that protects the core region from side reactions with the electrolyte, prevents the loss of oxygen, and the dissolution of the metal ions in the electrolyte, or simply improve the conductivity of the powder. The purpose of the present work is to review the different surface modifications that have been tried in the past for the different electrodes that are currently commercialized, or considered as promising, including the three families of positive electrodes (lamellar, spinel, and olivine families) and the three negative electrodes (carbon, Li4Ti5O12, and silicon). The role of the different coats used to improve either the surface conductivity, or the thermal stability, or the structural integrity is discussed. The limits in the efficiency of these different coats are also analyzed along with the understanding of the surface modifications that have been proposed. 相似文献
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