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51.
Loferer MJ Webb BM Grant GH Liedl KR 《Journal of the American Chemical Society》2003,125(4):1072-1078
QM/MM methods were used to study the isomerization step from (2R)-methylmalonyl-CoA to succinyl-CoA. A pathway via a "fragmentation-recombination" mechanism is ruled out on energetic grounds. For the other radicalic pathway, involving an addition recombination step, geometries and vibrational contributions have been determined, and a barrier height of 11.70 kcal/mol was found. The effect of adjacent hydrogen-donating groups was found to reduce the energy barrier by 1-2 kcal/mol each and thus to provide a significant catalytic effect for this reaction. By means of molecular dynamics studies, the stereochemistry of the methylmalonyl-CoA mutase catalyzed reaction was examined. It is shown that TYR89 is essential for maintaining stereoselectivity of the abstraction of a hydrogen in the backreaction. The subsequent selective formation of one isomer of methylmalonyl-CoA is probably due to the presence of a bulky side chain. 相似文献
52.
Lithium diisopropylamide reacts with 2-fluoropyridine at low temperature: regioselectivity is excellent and metallation occurs without side reactions such as nucleophilic attack. 2-Fluoro-3-lithiopyridine is formed and with aldehydes it gives the corresponding fluorinated alcohols which are then selectively oxidized. Halogen substitution using amines leads to various 3-oxoalkyl- or 3-aroyl-2-aminopyridines. 相似文献
53.
A series of 2-substituted 4H-3,1-benzoxazinones and 2,3-disubstituted 4-(3H)quinazolinones have been synthesized in mild conditions by the use of triphenyl phosphite and pyridine as cyclising medium. Benzox-azinones are produced either by ring closure of 2-(acylamino)benzoic acids or in the reaction of benzoic acid with anthranilic acids. In the presence of aniline, the reaction leads to quinazolinones. 相似文献
54.
Musangu Mbuyi Michel Evers Guy Tihange Andr Luxen Lon Christiaens 《Tetrahedron letters》1983,24(52):5873-5876
We describe the synthesis of a new heterocyclic system : the 1,3-benzotellurazole, and some of its substituted derivatives. 相似文献
55.
Infant formula powders were analyzed by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) to assess the whey proteins quality, which may be altered by the heat treatment used during the processing conditions. Lactosylation was found to be the major chemical modification occurring in whey proteins. In parallel, a two-dimensional (2-D) gel electrophoresis was performed on the milk sample and the entire protein patterns were analyzed by nano-ESI-MS after cutting the different gel spots and in-gel trypsin digestion. A highly selective and specific tandem MS technique has been developed to characterize and localize up to ten lactosylation sites in beta-lactoglobulin (beta-Lg) and alpha(S2)-casein. alpha-Lactalbumin (alpha-La), with five lactosylated peptides, was found to be an interesting protein marker in the milk powder sample to detect chemical modification induced by the processing/storage conditions. 相似文献
56.
VOXO4 systems have been considered as potential lithium battery electrodes. They mainly present two distinct structural types: the tetragonal “α” type with a two-dimensional framework, and the three-dimensional orthorhombic “β”. DFT calculations were performed on this latter system for several β-LixVOXO4 compounds (x=0, 1; X=P, As, S). They allowed to propose structural models for VOAsO4 and LiVOSO4, not fully crystallographically well described yet. Based on an experimental model of two-phase processes, these calculations led also to a good simulation of electrochemical potential values. A density of states analysis put in evidence the “inductive effect” and the role played by (XO4)n− groups inside the host frameworks on these potentials. 相似文献
57.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
58.
59.
A. E. Asratyan M. Aderholz V. V. Ammosov W. Burkot E. F. Clayton T. Coghen O. Erriquez G. S. Gapienko V. A. Gapienko J. Guy D. Hantke G. T. Jones V. S. Kaftanov U. F. Katz J. Kern V. A. Korotkov S. P. Krutchinin M. A. Kubantsev P. Marage D. B. Miller M. M. Mobayyen D. R. O. Morrison M. Neveu J. Sacton N. Schmitz K. Varvell W. Venus W. Wittek V. G. Zaetz 《Zeitschrift fur Physik C Particles and Fields》1993,58(1):55-60
The diffractive production of charmed strangeD s * and possiblyD s mesons by neutrinos and antineutrinos on nucleons in hydrogen, deuterium and neon targets is observed. The slope parameter of thet distribution is 3.3±0.8 (GeV)?2. The production rate per charged current neutrino interaction with an isoscalar target times the D s + →φτ+ branching fraction is (1.03±0.27)×10?4. 相似文献
60.
Guy Henniart 《Inventiones Mathematicae》1993,113(1):339-350
Résumé SoitF un corps local non archimédien à corps résiduel fini. La conjecture de Langlands locale (prouvée par Laumon, Rapoport et Stuhler quandF est de caractéristique non nulle) associe à une classe d'isomorphisme de représentations irréductibles du groupe de Weil deF une classe d'isomorphisme () de représentations admissibles irréductibles supercuspidales d'un groupe linéaire surF, le groupe GL
n
(F) si est de dimensionn. Nous prouvons dans cet appendice qu'il existe au plus une telle correspondance qui préserve les facteurs de paires et coïncide, en dimension 1, avec l'application donnée par la théorie du corps de classes.
Oblatum 10 XII 1991
Un complément à l'article -elliptic sheaves and the Langlands correspondence par G. Laumon, M. Rapoport et U. Stuhler. 相似文献
Summary LetF be a non-archimedean local field with finite residue field. The local Langlands conjecture (proved by Laumon, Rapoport and Stuhler when the characteristic ofF is positive) associates to an isomorphism class of irreducible representations of the Weil group ofF an isomorphism class () of admissible irreducible supercuspidal representations of some linear group overF, viz. GL n (F) if dim ()=n. In this appendix we prove that there is at most one such correspondence which extends local class field theory in dimension 1, and preserves -factors for pairs.
Oblatum 10 XII 1991
Un complément à l'article -elliptic sheaves and the Langlands correspondence par G. Laumon, M. Rapoport et U. Stuhler. 相似文献