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Hamilton DS Zhang X Ding Z Hubatsch I Mannervik B Houk KN Ganem B Creighton DJ 《Journal of the American Chemical Society》2003,125(49):15049-15058
Human glutathione (GSH) transferase (hGSTP1-1) processes with similar kinetic efficiencies the antitumor agents 2-crotonyloxymethyl-2-cyclohexenone (COMC-6), 2-crotonyloxymethyl-2-cycloheptenone (COMC-7), and 2-crotonyloxymethyl-2-cyclopentenone (COMC-5) to 2-glutathionylmethyl-2-cyclohexenone, 2-glutathionylmethyl-3-glutathionyl-2-cycloheptenone, and 2-glutathionylmethyl-2-cyclopentenone, respectively. This process likely involves initial enzyme-catalyzed Michael addition of GSH to the COMC derivative to give a glutathionylated enol(ate), which undergoes nonstereospecific ketonization, either while bound to the active site or free in solution, to a glutathionylated exocyclic enone. Free in solution, GSH reacts at the exomethylene carbon of the exocyclic enone, displacing the first GSH to give the final product. This mechanism is supported by the observation of multiphasic kinetics in the presence of high concentrations of hGSTP1-1 and the ability to trap kinetically competent exocyclic enones in aqueous acid using COMC-6 and COMC-7 as substrates. That the exocyclic enone is formed by nonstereospecific ketonization of an enol(ate) species is indicated by the observation that COMC-6 (chirally labeled with deuterium at the exomethylene carbon) gives stereorandomly labeled exocyclic enone. The isozymes hGSTP1-1, hGSTA1-1, hGSTA4-4, and hGSTM2-2 catalyze the conversion of COMC-6 to final product with similar efficiencies (K(m) = 0.08-0.34 mM, k(cat) = 1.5-6.1 s(-)(1)); no activity was detected with the rat rGSTT2-2 isozyme. Molecular docking studies indicate that in hGSTP1-1, the hydroxyl group of Tyr108 might serve as a general acid catalyst during substrate turnover. The possible significance of these observations with respect to the metabolism of COMC derivatives in multidrug resistant tumors is discussed. 相似文献
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Dan Donescu Sever Serban Kristiana Gosa Cristian Petcu 《Central European Journal of Chemistry》2005,3(1):10-27
The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl
acrylate) (PEtA) with TiO2 was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved
simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl
acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane
derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl
acetate (VAc). The PVAc-TiO2 hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane
derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly
affected by TiO2 presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of
TiO2 inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network. 相似文献
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Klaus Broschinski Arunachalam Kannan Peter G. Jones Ina Dix Henning Hopf 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):o711-o713
In the title compound, C18H16, the [2.2]paracyclophane geometry is restrained to a considerable extent despite the introduction of the extra C=C bridge; typical paracyclophane features, such as the elongated C—C bridges, are still observed. However, the bridgehead atoms of the C=C bridge are forced into unusually close proximity [2.657 (3) Å], which in turn causes the rings to be rotated to an interplanar angle of 13.7 (2)°. The packing involves hexagonally close‐packed layers of molecules parallel to the xy plane, corresponding to the known `7,11' pattern of paracyclophanes, but without significant short intermolecular contacts. 相似文献
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Peter G. Jones Ina Dix Henning Hopf 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(8):o468-o473
The monosubstituted derivative 4‐ethynyl[2.2]paracyclophane, C18H16, (I), and the four disubstituted isomers, 4,12‐, (II), 4,13‐, (III), 4,15‐, (IV), and 4,16‐diethynyl[2.2]paracyclophane, (V), all C20H16, show the usual distortions of the [2.2]paracyclophane framework. The crystal packing is analyzed in terms of C—H...π interactions, some with H...π as short as 2.47 Å, in which the cyclophane rings and/or the triple‐bond systems may act as acceptors. For compounds (I) and (IV), the known `7,11'‐type cyclophane packing is observed, with a herring‐bone pattern of molecules in a layer structure. 相似文献
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Jaime Portilla Ina Ontiveros Justo Cobo Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(2):172-174
The molecular skeleton of the title compound, C11H9F3N4O2, is almost planar and exhibits a polarized (charge‐separated) electronic structure in the nitroaniline portion. Molecules are linked by N—H...N and C—H...O hydrogen bonds to form a chain in which centrosymmetric R22(6) and R22(16) rings alternate. 相似文献
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Kristiana - Lisette Gosa 《Journal of Dispersion Science and Technology》2013,34(6):577-589
In the poly(vinyl acetate) latexes stabilized by nonyl phenol ethoxylated with 30 moles ethylene oxide, the ratio of the amount of monomer that swells the polymer particles to that of monomer remaining in aqueous phase decreases with the increase of the emulsifier concentration. This behaviour is due to concurrent interactions between monomer - polymer and emulsifier - polymer. At the polymer particle/water interface, the monomer interacts with the adsorbed emulsifier and prevents to swelling process from occuring. 相似文献