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101.
Compain S Schlemmer D Levi M Pruvost A Goujard C Grassi J Benech H 《Journal of mass spectrometry : JMS》2005,40(1):9-18
Besides liquid chromatographic (LC)/UV methods adapted to therapeutic drug monitoring, there is still a need for more powerful techniques that can be used for pharmacological research and clinical purposes. We developed an LC method coupled with tandem mass spectrometry (MS/MS) to separate, detect and quantify with high sensitivity the nucleoside analogues used in multitherapies (zidovudine, stavudine, zalcitabine, didanosine, lamivudine and abacavir) in plasma and in the intracellular medium. We worked on two essential issues: (i) the need to use two ionization modes in order to achieve the best sensitivity, which leads to the optimization of the chromatographic separation of drugs detected in the positive ionization mode and drugs detected in the negative ionization mode, and (ii) the need to optimize the extraction step in order to enhance sample recovery. The peripheral blood mononuclear cells were lysed in Tris buffer-MeOH. A clean-up procedure was performed by solid-phase extraction only for plasma samples. The LC separation was carried out on a Zorbax Stable Bond C(18) column followed by MS/MS analysis after electrospray ionization in either the negative or positive mode. The positive ionization mode was applied at the beginning of the run to detect zalcitabine and lamivudine, then the ionization mode was changed to negative for the detection of didanosine, stavudine, internal standard and zidovudine. The calibration range for all the analytes was 0.5-200 ng ml(-1). The recoveries were between 64 and 90%, with coefficients of variation (CVs) lower than 15%. The inaccuracy (bias) was +/-15% with CVs always lower than 12%. The analytes were stable at room temperature and in the extraction solvent for at least 24 h, after storage at -80 degrees C for 3 months, after three freeze-thaw cycles and in the injection solvent after 48 h at 4 degrees C. Together with the measurement of intracellular triphosphorylated metabolites thanks to the powerful plasma and intracellular assay method for intact drugs, it is possible to describe the behaviour of nucleoside analogues against HIV through plasma pharmacokinetics, cell membrane diffusion including drug transport involvement, and also the intracellular metabolism. 相似文献
102.
Dimitri P. Bertsekas David A. Castañon 《Computational Optimization and Applications》1993,2(3):229-259
In this paper we broadly generalize the assignment auction algorithm to solve linear minimum cost network flow problems. We introduce a generic algorithm, which contains as special cases a number of known algorithms, including the -relaxation method, and the auction algorithm for assignment and for transportation problems. The generic algorithm can serve as a broadly useful framework for the development and the complexity analysis of specialized auction algorithms that exploit the structure of particular network problems. Using this framework, we develop and analyze two new algorithms, an algorithm for general minimum cost flow problems, called network auction, and an algorithm for thek node-disjoint shortest path problem. 相似文献
103.
Homogeneous and electrochemical two-electron transfers within the Tl(aq)(3+)/Tl(aq)(+) couple are considered on a common conceptual basis. For the 2 equiv electrochemical reduction of Tl(aq)(3+) to Tl(aq)(+), the intermediate state with a formal reduction potential, E(1) = 1.04 +/- 0.10 V vs the normal hydrogen electrode, was detected, different from the established value of 0.33 V for a Tl(3+)/Tl(2+) couple. Examination of obtained electrochemical (cyclic voltammetry (CV) and rotating disk electrode techniques, along with the CV-curve computer simulation procedure) and literature data indicate that the detected formal potential cannot be the property of electrode-adsorbed species, but rather of the covalently interacting dithallium intermediate [Tl(II)-Tl(II)](4+) located at the outer Helmholtz plane. The analysis of microscopic mechanisms, based on the recent hypothesis of H. Taube and the Marcus-Hush theory extended by Zusman and Beratan, and Koper and Schmickler, revealed that the homogeneous process most probably takes place through the superexchange inner-sphere two-electron-transfer mechanism, via an essentially virtual (undetectable) dithallium intermediate. In contrast, the electrochemical process occurs through a sequential mechanism, via the rate-determining step of Tl(aq)(2+) ion formation immediately followed by activationless formation of the metastable (CV-active) dithallium state. The second electrochemical electron-transfer step is fast, and shows up only in the peak height (but not in the shape) of the observed CV cathodic wave. The anodic wave for a microscopically reverse process of the oxidation of Tl(aq)(+) to Tl(aq)(3+) cannot be observed within the considered potential range due to the blocking of through-space electron transfer by the competitor process of ion transfer to the electrode. 相似文献
104.
105.
Dimitri Mugnai 《NoDEA : Nonlinear Differential Equations and Applications》2012,19(3):299-301
We show the incompleteness of a usually used version of the generalized Ambrosetti?CRabinowitz condition in superlinear problems, also used in the paper cited in the title, and we propose a complete one. 相似文献
106.
107.
In this paper, we study the influence of noise on subgradient methods for convex constrained optimization. The noise may be
due to various sources, and is manifested in inexact computation of the subgradients and function values. Assuming that the
noise is deterministic and bounded, we discuss the convergence properties for two cases: the case where the constraint set
is compact, and the case where this set need not be compact but the objective function has a sharp set of minima (for example
the function is polyhedral). In both cases, using several different stepsize rules, we prove convergence to the optimal value
within some tolerance that is given explicitly in terms of the errors. In the first case, the tolerance is nonzero, but in
the second case, the optimal value can be obtained exactly, provided the size of the error in the subgradient computation
is below some threshold. We then extend these results to objective functions that are the sum of a large number of convex
functions, in which case an incremental subgradient method can be used. 相似文献
108.
Andrew G. Tennyson Dr. Robert J. Ono Todd W. Hudnall Dr. Dimitri M. Khramov Dr. Joyce A. V. Er Justin W. Kamplain Dr. Vincent M. Lynch Dr. Jonathan L. Sessler Prof. Christopher W. Bielawski Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):304-315
Reaction of bromanil with N,N′‐dimesitylformamidine followed by deprotonation with NaN(SiMe3)2 afforded 1,1′,3,3′‐tetramesitylquinobis(imidazolylidene) ( 1 ), a bis(N‐heterocyclic carbene) (NHC) with two NHC moieties connected by a redox active p‐quinone residue, in 72 % yield of isolated compound. Bimetallic complexes of 1 were prepared by coupling to FcN3 ( 2 ) or FcNCS ( 3 ; Fc=ferrocenyl) or coordination to [M(cod)Cl] ( 4 a or 4 b , where M=Rh or Ir, respectively; cod=1,5‐cyclooctadiene). Treatment of 4 a and 4 b with excess CO(g) afforded the corresponding [M(CO)2Cl] complexes 5 a and 5 b , respectively. Analysis of 2 – 5 by NMR spectroscopy and X‐ray diffraction indicated that the electron‐deficient quinone did not significantly affect the inherent spectral properties or coordination chemistry of the flanking imidazolylidene units, as compared to analogous NHCs. Infrared spectroscopy and cyclic voltammetry revealed that decreasing the electron density at MLn afforded an increase in the stretching energy and a decrease in the reduction potential of the quinone, indicative of metal–quinone electronic interaction. Differential pulse voltammetry and chronoamperometry of the metal‐centered oxidations in 2 – 4 revealed two single, one‐electron peaks. Thus, the metal atoms bound to 1 are oxidized at indistinguishable potentials and do not appear electronically coupled. However, the metal–quinone interaction was used to increase the electron density at coordinated metal atoms. Infrared spectroelectrochemistry revealed that the average νCO values for 5 a and 5 b decreased by 14 and 15 cm?1, respectively, upon reduction of the quinone embedded within 1 . These shifts correspond to 10 and 12 cm?1 decreases in the Tolman electronic parameter of this ditopic ligand. 相似文献
109.
Maria Chiara Pietrogrande Dimitri Bacco Mattia Mercuriali 《Analytical and bioanalytical chemistry》2010,396(2):877-885
This paper describes methods for the determination of low-molecular-weight (LMW) dicarboxylic acids in atmospheric aerosols
as important chemical tracers for source apportionment of aerosol organics and for studying atmospheric processes leading
to secondary organic aerosol formation. The two derivatization procedures most widely used in GC analysis of dicarboxylic
acids were compared: esterification using BF3/alcohol reagent and silylation using N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA). The advantages and drawbacks of the two methods are investigated and compared
in terms of (1) precision and accuracy of the results and (2) sensitivity and detection limit of the procedure. The comparative
investigation was performed on standard solutions containing target C3–C9 dicarboxylic acids and on experimental particulate matter (PM) samples. Attention was focused on low-volume sampling devices
that collect small amounts of sample for organic speciation. The results show that, overall, both the techniques appear suitable
for the analysis of LMW dicarboxylic acids in atmospheric aerosols since they provide low detection limits (≤4 ng m−3) and satisfactory reproducibility (RSD% ≤ 15%). Between them, BSTFA should be the reagent of choice under the most limiting
conditions of PM filters collected by low-volume air samplers: It provides determination of all the target C3–C9 dicarboxylic acids with lower detection limits (≤2 ng m−3) and higher reproducibility (RSD% ≤ 10%)
相似文献
110.
Daniel J. Coady Dr. Dimitri M. Khramov Dr. Brent C. Norris Andrew G. Tennyson Dr. Christopher W. Bielawski Prof. 《Angewandte Chemie (International ed. in English)》2009,48(28):5187-5190
A click by any other name : Coupling bis(N‐heterocyclic carbene)s with bis(azide)s afforded a novel class of conjugated polytriazenes. These polymers were rendered electrically conductive upon doping, and fluorene‐containing variants exhibited luminescence. This adaptation of N‐heterocyclic carbene (NHC)/azide coupling chemistry to polymer synthesis reveals the potential of NHCs as building blocks for accessing polymers having useful electronic properties.