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Lau K 《Physical review D: Particles and fields》1993,47(3):1087-1092
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Jagoda M Warzeska S Pritzkow H Wadepohl H Imhof P Smith JC Krämer R 《Journal of the American Chemical Society》2005,127(43):15061-15070
For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two-metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilization, has been proposed. Inspired by the active site structure of this enzyme, we have designed as a synthetic phosphoryl transfer catalyst the dicopper(II) macrocyclic complex LCu(2). Crystal structures of complexes [(L)Cu(2)(mu-NO(3))(NO(3))](NO(3))(2) (1), [(L)Cu(2)(mu-CO(3))(CH(3)OH)](BF(4))(2) (2), and [(L)Cu(2)(mu-O(2)P(OCH(3))(2))(NO(3))](NO(3))(2) (3) illustrate various possibilities for the interaction of oxoanions with the dicopper(II) site. 1 efficiently promotes the transesterification of dimethyl phosphate (DMP) in CD(3)OD, k(cat) = 2 x 10(-)(4) s(-)(1) at 55 degrees C. 1 is the only available catalyst for the smooth transesterification of highly inert simple dialkyl phosphates. From photometric titrations and the pH dependence of reactivity, we conclude that a complex [(L)Cu(2)(DMP)(OCH(3))](2+) is the reactive species. Steric bulk at the -OR substituents of phosphodiester substrates O(2)P(OR)(2)(-) drastically reduces the reactivity of 1. This is explained with -OR leaving group stabilization by Cu coordination, an interaction which is sensitive to steric crowding at the alpha-C-atom of substituent R. A proposed reaction mechanism related to that of the exonuclease unit of DNA polymerase I is supported by DFT calculations on reaction intermediates. The complex [(L)Cu(3)(mu(3)-OH)(mu-CH(3)O)(2)(CH(3)CN)(2)](ClO(4))(3) (4) incorporates a [Cu(OH)(OCH(3))(2)(CH(3)CN)(2)](-) complex anion, which might be considered as an analogue of the [PO(2)(OCH(3))(2)(OCD(3))](2)(-) transition state (or intermediate) of DMP transesterification catalyzed by LCu(2). 相似文献
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Low-lying vacant molecular orbitals may lead not only to a breakdown of Koopmans' theorem but also to satellite structure in photoelectron spectra. This paper reports examples of the relatively infrequent appearance of shake-up satellites in Hel photoelectron spectra, namely those of N2O4 and CH3NO. An extended version of the HAM/3 program was used to interpret these spectra. 相似文献
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Ash WW Band HR Blume HT Camporesi T Chadwick GB Coombes RW Delfino MC Fernandez E Ford WT Gettner MW Goderre GP Groom DE Heltsley BK Hurst RB Johnson JR Lau KH Lavine TL Leedy RE Lippi I Maruyama T Messner RL Moromisato JH Moss LJ Muller F Nelson HN Peruzzi I Piccolo M Prepost R Qi N Read AL Ritson DM Rosenberg LJ Shambroom WD Sleeman JC Smith JG Venuti JP von Goeler E Verdini P Wald HB Weinstein R Wiser DE Zdarko RW 《Physical review letters》1985,55(20):2118-2121
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Fernandez E Ford WT Qi N Read AL Smith JG Camporesi T De Sangro R Marini A Peruzzi I Piccolo M Ronga F Blume HT Hurst RB Venuti JP Wald HB Weinstein R Band HR Gettner MW Goderre GP Meyer OA Moromisato JH Shambroom WD Sleeman JC von Goeler E Ash WW Chadwick GB Clearwater SH Coombes RW Kaye HS Lau KH Leedy RE Lynch HL Messner RL Moss LJ Muller F Nelson HN Ritson DM Rosenberg LJ Wiser DE Zdarko RW Groom DE Lee H Delfino MC Heltsley BK Johnson JR Lavine TL Maruyama T Prepost R 《Physical review letters》1985,54(15):1620-1623
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Chovan LE Black-Schaefer C Dandliker PJ Lau YY 《Rapid communications in mass spectrometry : RCM》2004,18(24):3105-3112
High-throughput metabolic screening has been requested routinely to keep pace with high-throughput organic synthesis. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) with a fast gradient has become the method of choice for the task due to its sensitivity and selectivity. We have developed an automated system that consists of a robotic system for in vitro incubation and a commercially available software package for automatic MS/MS method development. A short, generic LC gradient and MS conditions that are applicable to most compounds have been developed to minimize the method development time and data analysis. This system has been used to support a number of in vitro screening assays in early drug discovery phase including microsomal stability and protein binding. 相似文献