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81.
Samuel K Yin W Stearns RA Tang YS Chaudhary AG Jewell JP Lanza T Lin LS Hagmann WK Evans DC Kumar S 《Journal of mass spectrometry : JMS》2003,38(2):211-221
Metabolic activation of drug candidates to electrophilic reactive metabolites that can covalently modify cellular macromolecules may result in acute and/or idiosyncratic immune system-mediated toxicities in humans. This presents a significant potential liability for the future development of these compounds as safe therapeutic agents. We present here an example of an approach where sites of metabolic activation within a new drug candidate series were rapidly identified using online liquid chromatography/multi-stage mass spectrometry on an ion trap mass spectrometer. This was accomplished by trapping the reactive intermediates formed upon incubation of compounds with rat and human liver microsomes as their corresponding glutathione conjugates and mass spectral characterization of these thiol adducts. Based on the structures of the GSH adducts identified, potential sites and mechanisms of bioactivation within the chemical structure were proposed. These metabolism studies were interfaced with iterative structural modifications of the chemical series in order to block these bioactivation sites within the molecule. This strategy led to a significant reduction in the propensity of the compounds to undergo metabolic activation as evidenced by reductions in the irreversible binding of radioactivity to liver microsomal material upon incubation of tritium-labeled compounds with this in vitro system. With the efficiency and throughput achievable with such an approach, it appears feasible to identify and address the metabolic activation potential of new drug leads during routine metabolite identification studies in an early drug discovery setting. 相似文献
82.
Douglas F. Foster Barry S. Nicholls Anthony K. Smith 《Journal of organometallic chemistry》1982,236(3):395-402
Reactions of Rh6(CO)16 with bis(diphenylphosphino)methane (dppm) gave Rh6(CO)14(dppm), Rh6(CO)12(dppm)2, or Rh6(CO)10(dppm)3, depending upon the reaction conditions. Rh4(CO)10(dppm) may be obtained from the reaction of Rh4(CO)12 with dppm, but this derivative rapidly decomposes in solution to give Rh4(CO)8(dppm)2, Rh6(CO)14(dppm), and Rh6(CO)12(dppm)2. Ir4(CO)10(dppm) and Ir4(CO)8(dppm)2 have also been prepared, and their structures are discussed on the basis of infrared and 31P NMR spectroscopic data. 相似文献
83.
Geng J Ducati C Shephard DS Chhowalla M Johnson BF Robertson J 《Chemical communications (Cambridge, England)》2002,(10):1112-1113
A nanoscale ruthenium/gold bimetallic cluster of clusters has been used as a molecular precursor to produce pure ruthenium nanoparticles (seeds) as catalysts for the growth of carbon nanohorns (CNHs). 相似文献
84.
Intermolecular rhodium-catalyzed [m + n + o] reactions of 1,6-enynes and various pi-components (carbon monoxide, alkynes, 1,3-butadienes, etc.) provide an expeditious approach for the construction of polycyclic fragments that represent important synthons for target-directed synthesis. We present computational and experimental evidence for the existence of a previously undescribed reaction pathway for the rhodium-catalyzed [4 + 2 + 2] reaction involving a 1,6-enyne. This model clearly demonstrates the origin of the excellent diastereoselectivity in this type of reaction and the remarkable tolerance of both (E)- and (Z)-isomers within the 1,6-enyne, which is generally prone to competitive ene-cycloisomerization. 相似文献
85.
Zhang Z Blom DA Gai Z Thompson JR Shen J Dai S 《Journal of the American Chemical Society》2003,125(25):7528-7529
One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes. 相似文献
86.
THREE EXPONENTIAL FLUORESCENCE DECAY OF HORSE LIVER ALCOHOL DEHYDROGENASE REVEALED BY IODIDE QUENCHING 总被引:1,自引:0,他引:1
David R. Demmer † Douglas R. James † Ronald P. Steer Ronald E. Verrall 《Photochemistry and photobiology》1987,45(1):39-48
Abstract— The time resolved fluorescence decay of horse liver alcohol dehydrogenase was measured using a frequency doubled picosecond dye laser and time-correlated single-photon counting detection. A flow-cell technique is described which eliminates the photodegradation artifacts which commonly occur with laser excitation. A procedure is introduced which uses fluorescence quenching to reveal minor fluorescence lifetime components. The decay of the unquenched tryptophanyl fluorescence could be described by a double exponential decay law, but experiments conducted in the presence of iodide ion showed that the fluorescence decay must be more complex than this. A model is presented in which the fluorescence decay consists of three exponential components, only two of which are susceptible to quenching by iodide ion. Several possibilities are presented for the origin of this minor decay component, the most reasonable of which is that it arises from conformational heterogeneity in the solvent-exposed tryptophanyl residue. 相似文献
87.
Jeffrey C. Evans Simon K. Jackson Christopher C. Rowlands Martin D. Barratt 《Tetrahedron》1985,41(22):5191-5194
Under acid conditions aqueous solutions of chloramine-T form nitrogen-centred radicals via loss of the chlorine atom. The nitrogen radicals produced have been studied by ESR spectroscopy using the spintrapping method. Adducts of the spin trap phenyl-t-butyl nitrone are oxidized by chloramine-T in acid media to give a paramagnetic product in which the unpaired electron interacts with two inequivalent nitrogen atoms. The spin trap 5,5-dimethyl-2-pyrrolidine-1 -oxide is oxidized rapidly to 5,5-dimethyl-2-pyrrolidone-1-oxyl by chloramine-T under acid onditions. The water soluble trap α-4-pyridyl-1-oxide-N-t-butyl nitrone forms a stable nitroxide adduct with a nitrogen radical of chloramine-T in acid solution. Identical results were obtained with chloramine-B (sodium salt of N-chlorobenzene sulfonamide), indicating the involvement of the N-chloramine group in radical formation. 相似文献
88.
The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and C are described. Aldol reaction defines the chirality at C-4′and C-5′in two independent routes. Multigram preparation as well as a route amenable to derivatization are highlights of these approaches. 相似文献
89.
Henry DJ Yiapanis G Evans E Yarovsky I 《The journal of physical chemistry. B》2005,109(36):17224-17231
This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.9 groups per nm(2). In each case, the introduction of substituents to the surface of the polyester was calculated to lead to reduced adhesion to graphite. Effects of surface relaxation on adhesion are studied by employing different simulation protocols. The theoretical results suggest one mechanism to reduce adhesion to carbonaceous solids is to increase atomic roughness using strongly hydrophilic or alternatively strongly hydrophobic substituents. 相似文献
90.
Using density functional theory we calculate the density profiles of a binary solvent adsorbed around a pair of big solute particles. All species interact via repulsive Gaussian potentials. The solvent exhibits fluid-fluid phase separation, and for thermodynamic states near to coexistence the big particles can be surrounded by a thick adsorbed "wetting" film of the coexisting solvent phase. On reducing the separation between the two big particles we find there can be a "bridging" transition as the wetting films join to form a fluid bridge. The effective (solvent mediated) potential between the two big particles becomes long ranged and strongly attractive in the bridged configuration. Within our mean-field treatment the bridging transition results in a discontinuity in the solvent mediated force. We demonstrate that accounting for the phenomenon of bridging requires the presence of a nonzero bridge function in the correlations between the solute particles when our model fluid is described within a full mixture theory based upon the Ornstein-Zernike equations. 相似文献