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201.
Selected reaction monitoring (SRM) performed on triple quadrupole mass spectrometers has been the reference quantitative technique to analyze small molecules for several decades. It is now emerging in proteomics as the ideal tool to complement shotgun qualitative studies; targeted SRM quantitative analysis offers high selectivity, sensitivity and a wide dynamic range. However, SRM applied to proteomics presents singularities that distinguish it from small molecules analysis. This review is an overview of SRM technology and describes the specificities and the technical aspects of proteomics experiments. Ongoing developments aiming at increasing multiplexing capabilities of SRM are discussed; they dramatically improve its throughput and extend its field of application to directed or supervised discovery experiments. 相似文献
202.
Copping R Mougel V Petit S Den Auwer C Moisy P Mazzanti M 《Chemical communications (Cambridge, England)》2011,47(19):5497-5499
The polymeric complex [(NpO(2)Py(5))(KI(2)Py(2))](n) is prepared from dry "NpO(2)Cl" by anion exchange with potassium iodide in pyridine affording the first convenient starting material for the development of NpO(2)(+) coordination chemistry in anhydrous organic media. 相似文献
203.
Svecova L Cremel S Sirguey C Simonnot MO Sardin M Dossot M Mercier-Bion F 《Journal of colloid and interface science》2008,325(2):363-370
This paper reports a comparative study of three methods for determining the surface charge and acid-base behavior of a TiO(2) rutile material. Electrophoretic mobility measurements were performed using two different batch protocols: (i) a "static" mode that consisted of immersing the rutile powder in aqueous solutions of given pH's and ionic strengths for 10 h, and (ii) a "dynamic" mode that consisted of using an automatic titrator to continuously adjust the solution pH with a contact time of 15 min. The same apparatus (a Nanosizer from Malvern) was used to measure the zeta potential of the particles in both methods. These batch experiments were next compared to the determination of the surface charge of rutile using nonlinear chromatography in column experiments. In that case, the rutile powder was compacted to enable the formation of a proper column bed. Therefore, Raman scattering and X-ray photoelectron spectra were used, as well as other physical information such as specific surface area and morphology of the particles, to verify that the rutile powder and compacted form were identical. The three approaches were then compared and discussed in relation to the acid-base behavior of the rutile material. 相似文献
204.
Mohamed Kharroubi Hamza Assad Sebastien Balme Lakhdar Gacem Cherif Maghni 《Ionics》2016,22(12):2355-2361
A series of zinc phosphate glass doped with cobalt Na2Zn(1???x)CoxP2O7 (x = 0, 1, 2 and 5 mol%) was synthesized. These glasses were characterized by both infrared and large broadband dielectric spectroscopy. Infrared spectra indicate the increase of Zn/Co ratio creates defect in phosphate network due to the depolymeration of phosphate anions. The dc conductivity increases and activation energy decreases with the amount of cobalt ions in the glass network. The impedance measurements reveal that the total conductivity follows Jonscher’s power law. The dielectric constant and dielectric loss increased with the temperature and decreased with the frequency whatever the cobalt proportion. 相似文献
205.
Sebastien Anizan Emmanuelle Bichon Thibault Duval Fabrice Monteau Nora Cesbron Jean‐Philippe Antignac Bruno Le Bizec 《Journal of mass spectrometry : JMS》2012,47(1):131-140
The use of anabolic steroids as growth promoters for meat‐producing animals is banned within the European Union. However, screening for the illegal use of natural steroid hormones still represents a difficult challenge because of the high interindividual and physiological variability of the endogenous concentration levels in animals. In this context, the development of untargeted profiling approaches for identifying new relevant biomarkers of exposure and/or effect has been emerging for a couple of years. The present study deals with an untargeted metabolomics approach on the basis of GC‐MS aiming to reveal potential biomarkers signing a fraudulent administration of 4‐androstenedione (AED), an anabolic androgenic steroid chosen as template. After a sample preparation based on microextraction by packed sorbent, urinary profiles of the free and deglucurono‐conjugates urinary metabolites were acquired by GC‐MS in the full‐scan acquisition mode. Data processing and chemometric procedures highlighted 125 ions, allowing discrimination between samples collected before and after an administration of 4‐AED. After a first evaluation of the signal robustness using additional and independent non‐compliant samples, 17 steroid‐like metabolites were pointed out as relevant candidate biomarkers. All these metabolites were then monitored using a targeted GC‐MS/MS method for an additional assessment of their capacity to be used as biomarkers. Finally, two steroids, namely 5α‐androstane‐3β,17α‐diol and 5α‐androst‐2‐en‐17‐one, were concluded to be compatible with such a definition and which could be finally usable for screening purpose of AED abuse in cattle. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
206.
Monte Carlo simulations were performed to investigate the mechanisms of glass dissolution as equilibrium conditions are approached in both static and flow-through conditions. The glasses studied are borosilicate glasses in the compositional range (80 ? x)% SiO2 (10 + x / 2)% B2O3 (10 + x / 2)% Na2O, where 5 < x < 30%. In static conditions, dissolution/condensation reactions lead to the formation, for all compositions studied, of a blocking layer composed of polymerized Si sites with principally 4 connections to nearest Si sites. This layer forms atop the altered glass layer and shows similar composition and density for all glass compositions considered. In flow-through conditions, three main dissolution regimes are observed: at high flow rates, the dissolving glass exhibits a thin alteration layer and congruent dissolution; at low flow rates, a blocking layer is formed as in static conditions but the simulations show that water can occasionally break through the blocking layer causing the corrosion process to resume; and, at intermediate flow rates, the glasses dissolve incongruently with an increasingly deepening altered layer. The simulation results suggest that, in geological disposal environments, small perturbations or slow flows could be enough to prevent the formation of a permanent blocking layer. Finally, a comparison between predictions of the linear rate law and the Monte Carlo simulation results indicates that, in flow-through conditions, the linear rate law is applicable at high flow rates and deviations from the linear rate law occur under low flow rates (e.g., at near-saturated conditions with respect to amorphous silica). This effect is associated with the complex dynamics of Si dissolution/condensation processes at the glass–water interface. 相似文献
207.
An acousto-optic programmable dispersive filter pulse shaper has been designed using KDP material for operation in the 200-500 nm wavelength range. With an acousto-optic interaction length of 72 mm, a spectral resolution of 0.15 nm has been measured to be consistent with theoretical predictions. Theory and experiments indicate that diffraction efficiencies up to 50% are expected in practical experimental conditions. 相似文献
208.
Wander MC Kerisit S Rosso KM Schoonen MA 《The journal of physical chemistry. A》2006,110(31):9691-9701
Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment. 相似文献
209.
We study the relationship between minimality and unique ergodicity for adic transformations. We show that three is the smallest
alphabet size for a unimodular “adic counterexample”, an adic transformation which is minimal but not uniquely ergodic. We
construct a specific family of counterexamples built from (3 × 3) nonnegative integer matrix sequences, while showing that
no such (2 × 2) sequence is possible. We also consider (2 × 2) counterexamples without the unimodular restriction, describing
two families of such maps.
Though primitivity of the matrix sequence associated to the transformation implies minimality, the converse is false, as shown
by a further example: an adic transformation with (2 × 2) stationary nonprimitive matrix, which is both minimal and uniquely
ergodic. 相似文献
210.
David M. Haddleton Alex M. Heming Adam P. Jarvis Afzal Khan Andrew Marsh Sebastien Perrier Stefan A.F. Bon Stuart G. Jackson Ryan Edmonds Elizabeth Kelly Dax Kukulj Carl Waterson 《Macromolecular Symposia》2000,157(1):201-208
The use of copper(I) Schiff base complex catalysed atom transfer polymerisation of methacrylates is described. The use of a range of functional and multi‐functional initiators enables the synthesis of a range of functional and star polymers to be prepared under undemanding synthetic conditions. End capping with silyl enol ethers allows for ω‐functional polymers. The combination of novel initiators, functional monomers and end capping allows an unprecedented array of macromolecular structures to be produced with limited need for protecting group chemistry. 相似文献