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41.
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
42.
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
43.
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
44.
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
45.
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
46.
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
47.
Synchrotron-based in situ time-resolved x-ray diffraction and x-ray absorption spectroscopies were used to study the behavior of nanostructured {Au+AuO(x)}-CeO(2) catalysts under the water-gas shift (WGS) reaction. At temperatures above 250 degrees C, a complete AuO(x)-->Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO(2)(111) single crystal corroborate that cationic Au(delta+) species cannot be the key sites responsible for the WGS activity at high temperatures. The rate determining steps for the WGS seem to occur at the gold-ceria interface, with the active sites involving small gold clusters (<2 nm) and O vacancies. 相似文献
48.
Todorov E Evans M Lee S Rousseau R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(12):2652-2662
The total electronic energies of the six electrons per atom (e per atom) alloys W, TaRe, HfOs, and YIr and the seven electrons per atom alloys Re, WOs, TaIr, HfPt, and YAu have been calculated in the local density approximation of density functional theory. When one considers common alloy structures such as atomically ordered variants of the body-centered cubic, face-centered cubic, or hexagonally closest packed structures and plots the total electronic energy as a function of the unit cell parameter, one finds for both the six and seven electrons per atom series energetic isosbestic points. An energetic isosbestic point corresponds to a critical value of the size parameter for which all members of the 6 or 7 e per atom series of compounds have nearly identical total electronic energy. Just as in spectroscopy, where the existence of such isosbestic points is the hallmark of two compounds present in the mixture, an energy isosbestic point implies there are just two separate energy curves. For both series it is found that the total electronic energy can be viewed as the weighted sum of a purely covalent term and a purely ionic term. Two semi-quantitative models are proposed to account for these two separate energies. In the first model the total energy is viewed as the sum of the elemental structural energy plus an ionic energy based on the Born-Mayer ionic model. In the second model one considers within the confines of mu2-Hückel theory the evolution of the total electronic energy as the Coulombic Hii integrals change in value. 相似文献
49.
Evans PA Sawyer JR Lai KW Huffman JC 《Chemical communications (Cambridge, England)》2005,(31):3971-3973
The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
50.
Siya Ram William Evans Dean S. Wise Leroy B. Townsend John W. Mccall 《Journal of heterocyclic chemistry》1989,26(4):1053-1059
A series of methyl 2-substituted purine 8-carbamates was prepared and evaluated for antifilarial activity. These purines were synthesized as aza congeners of benzimidazole carbamates which have shown significant anthelmintic activity to determine the effect that this modification might have on anthelmintic activity. The compounds were tested against the filarial infection, B. pahangi, in jirds. None of the compounds prepared in this study demonstrated antifilarial activity. 相似文献