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151.
Charles A. Kingsbury Jon Weinhold Jeremy Winter 《Journal of Physical Organic Chemistry》2007,20(3):161-166
Three reactions were studied in the diastereomers of 1‐(benzenesulfonyl)‐2‐nitro‐1‐phenylpropane ( 1A and 1B ) and briefly in related compounds: elimination of the benzenesulfonyl group, epimerization of one diastereomer to the other, and deuterium/hydrogen exchange at the methine group next to nitro in starting material. The two diastereomers showed quite different reactivity. The high melting diasteromer showed rapid elimination and some exchange. The low melting diastereomer (at approximately a half‐life) showed extensive epimerization, and elimination to the alkene, but little exchange. There is little effect of aromatic substituents on reaction course. The situation is complicated by re‐addition of benzenesulfinate to the alkene. The addition reaction was similar to elimination in agreement with the Principle of Microscopic Reversibility expectations. An electron transfer mechanism for addition is calculated to be comparatively favorable. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
152.
153.
Austin C. Li Jie Ding Xiangyu Jiang Jon Denissen 《Rapid communications in mass spectrometry : RCM》2009,23(18):3003-3012
The relatively high background matrix in in vivo samples typically poses difficulties in drug metabolite identification, and causes repeated analytical runs on unit resolution liquid chromatography/mass spectrometry (LC/MS) systems before the completion of biotransformation characterization. Ballpark parameter settings for the LTQ‐Orbitrap are reported herein that enable complete in vivo metabolite identification within two HPLC/MS injections on the hybrid LTQ‐Orbitrap data collection system. By setting the FT survey full scan at 60K resolution to trigger five dependent LTQ MS2 scans, and proper parameters of Repeat Duration, Exclusion Duration and Repeat Count for the first run (exploratory), the Orbitrap achieved the optimal parallel data acquisition capability and collected maximum number of product ion scans. Biotransformation knowledge based prediction played the key role in exact mass ion extraction and multiple mass defect filtration when the initial data was processed. Meanwhile, product ion extraction and neutral loss extraction of the initial dependent data provided additional bonus in identifying metabolites. With updated parent mass list and the data‐dependent setting to let only the ions on the parent mass list trigger dependent scans, the second run (confirmatory) ensures that all precursor ions of identified metabolites trigger not only dependent product ion scans, but also at or close to the highest concentration of the eluted metabolite peaks. This workflow has been developed for metabolite identification of in vivo or ADME studies, of which the samples typically contain a high level of complex matrix. However, due to the proprietary nature of the in vivo studies, this workflow is presented herein with in vitro buspirone sample incubated with human liver microsomes (HLM). The major HLM‐mediated biotransformation on buspirone was identified as oxidation or hydroxylation since five mono‐ (+16 Da), seven di‐ (+32 Da) and at least three tri‐oxygenated (+48 Da) metabolites were identified. Besides the metabolites 1‐pyrimidinylpiperazine (1‐PP) and hydroxylated 1‐PP that formed by N‐dealkylation, a new metabolite M308 was identified as the result of a second N‐dealkylation of the pyrimidine unit. Two new metabolites containing the 8‐butyl‐8‐azaspiro[4,5]decane‐7,9‐dione partial structure, M240 and M254, were also identified that were formed apparently due to the first N‐dealkylation of the 1‐PP moiety. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
154.
Donald A. Ross Alexander H. Chu Thomas J. Nikolai Jon M. Ryan Donald G. Schaefer Andrew R. Schmidt 《Adsorption》1999,5(4):391-398
Continuous perfusion cell culture, using albumin containing medium, offers the potential advantages of higher recombinant Prourokinase (r-ProUK) yields, higher initial product purity and increased throughput compared to batch culture technology using medium supplemented with fetal bovine serum. We have characterized the production of r-ProUK in medium supplemented with a lipid rich bovine serum albumin (Albumax) in a perfusion system. The results of these studies showed that it was necessary to modify the r-ProUK batch recovery scheme to process r-ProUK from a perfusion system. To accommodate large volumes of perfusate harvested over a ten to fourteen day production cycle, cation exchange and hydrophobic interaction chromatography (HIC) resins were identified that had increased product binding capacity, better flow characteristics and wider pH ranges which allowed caustic cleaning. The mobile phase composition, pH and ionic strength were modified to improve r-ProUK yields from the identified resins, and procedures were developed to eliminate r-ProUK degradation products. Strategies were defined for processing continuous harvest, which contained four to seven times the amount of r-ProUK of batch harvests. 相似文献
155.
We develop a kinetic model for the exchange of tritium and deuteriumbetween tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform andheavy water, the measured equilibrium constant is 0.518 at 25–45°C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s at 25°C, 0.72 at 35°C, and 2.0 at 45°C, corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed. 相似文献
156.
Pierre Bonami Lorenz T. Biegler Andrew R. Conn Grard Cornujols Ignacio E. Grossmann Carl D. Laird Jon Lee Andrea Lodi Franois Margot Nicolas Sawaya Andreas Wchter 《Discrete Optimization》2008,5(2):186-204
This paper is motivated by the fact that mixed integer nonlinear programming is an important and difficult area for which there is a need for developing new methods and software for solving large-scale problems. Moreover, both fundamental building blocks, namely mixed integer linear programming and nonlinear programming, have seen considerable and steady progress in recent years. Wishing to exploit expertise in these areas as well as on previous work in mixed integer nonlinear programming, this work represents the first step in an ongoing and ambitious project within an open-source environment. COIN-OR is our chosen environment for the development of the optimization software. A class of hybrid algorithms, of which branch-and-bound and polyhedral outer approximation are the two extreme cases, are proposed and implemented. Computational results that demonstrate the effectiveness of this framework are reported. Both the library of mixed integer nonlinear problems that exhibit convex continuous relaxations, on which the experiments are carried out, and a version of the software used are publicly available. 相似文献
157.
Jon Grantham. 《Mathematics of Computation》2001,70(234):873-891
The proliferation of probable prime tests in recent years has produced a plethora of definitions with the word ``pseudoprime' in them. Examples include pseudoprimes, Euler pseudoprimes, strong pseudoprimes, Lucas pseudoprimes, strong Lucas pseudoprimes, extra strong Lucas pseudoprimes and Perrin pseudoprimes. Though these tests represent a wealth of ideas, they exist as a hodge-podge of definitions rather than as examples of a more general theory. It is the goal of this paper to present a way of viewing many of these tests as special cases of a general principle, as well as to re-formulate them in the context of finite fields.
One aim of the reformulation is to enable the creation of stronger tests; another is to aid in proving results about large classes of pseudoprimes.
158.
L. L. Kiang G. C. Kiang P. K. Teng G. C. Jon T. H. Yuan Y. M. Hsu 《Zeitschrift für Physik A Hadrons and Nuclei》1989,333(1):19-28
The excited states of154Gd populated by theβ-decay of154Eu (T 1/2=8.5y) have been studied. With a HPGe-NaI (T1) Compton suppression spectrometer and a HPGe-NaI(T1) coincidence circuitυ-ray singles spectra, coincidence spectra and theγ-γ directional correlational functions have been obtained. The deduced mixing ratios of multipolarities are presented. The energy levels and the relativeB(E2) values of the variousγ-transitions in154Gd nucleus have been calculated both in the IBA model and it's extended version with boson surface delta interaction (BSDI). 相似文献
159.
M. Manickam Alun Smith Maura Belloni Elwyn J. Shelley Peter R. Ashton Neil Spencer Jon A. Preece 《Liquid crystals》2002,29(4):497-504
The synthesis and characterization of four C 60 Bingel cyclopropanation adducts incorporating bis-biphenylene (three adducts) and bis-triphenylene (one adduct) moieties are described. The thermal analysis (POM and DSC) of these materials reveals that they are not liquid crystalline. However, two of the precursor bis-biphenylene malonate esters possess monotropic mesophases. Furthermore, each of the corresponding C 60 adducts is miscible in the melts of the precursor malonate ester, and at low dopings, retains the liquid crystalline monotropic mesophases of the precursor. 相似文献
160.