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141.
The mechanism of decomposition of dialkylamino diazeniumdiolate salts, R(2)N[NONO](-)M(+), to form nitric oxide, NO, was explored using theoretical methods. B3LYP/6-311+G(d) density functional theory calculations gave the optimized geometries, and energetics were further evaluated with the high accuracy CBS-QB3 method, when feasible. Relative pK(a) values were estimated using the PCM model for aqueous solvation. The terminal oxygen is the most basic site, followed closely by the internal oxygen. Protonation of these sites does not lead to decomposition. However, protonation of the weakly basic amino nitrogen leads to very rapid decomposition and NO generation. 相似文献
142.
Selenium-catalyzed halolactonization: nucleophilic activation of electrophilic halogenating reagents
Diphenyl diselenide catalyzes the halolactonization of unsaturated acids with N-halosuccinimides under mild conditions. The diselenide not only accelerates the reactions, but in some cases affords regiocontrol in favor of gamma-lactone products. Experiments show that the regioselectivity in favor of gamma-lactones is a result of kinetic rather than thermodynamic control. 相似文献
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Nagarajan K Joshi HK Chaudhury PK Pal K Cooney JJ Enemark JH Sarkar S 《Inorganic chemistry》2004,43(15):4532-4533
Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions. 相似文献
145.
We show that the position of a fluorescent nanoparticle can be measured in three dimensions with subnanometer precision and 100-ms temporal resolution by use of standard epifluorescence video imaging in off-focus mode. The particle can be tracked without feedback in a volume of at least 40 microm x 60 microm x 3 microm. With the technique presented, the structure-mobility relationship of 216-nm latex particle in a porous polymer network was studied in three dimensions. 相似文献
146.
The coupling of rhodium carbenoids from vinyl diazoacetates with 2-thio-3-alkyl indoles was found to generate C(3) quaternary substituted indolines via a thionium ylide-initiated [3,3]-sigmatropic rearrangement. 相似文献
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Schoonover JR Dattelbaum DM Osborn JC Bridgewater JS Kenney JW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(2):309-319
The effects of hydrostatic pressure upon (1) a segmented poly (ester urethane), (2) a hydrolytically degraded sample of the same polymer, and (3) models for the polyurethane and polyester segments in this polymer have been studied by Fourier transform infrared spectroscopy using high-pressure diamond anvil cells (DACs). The pressure responses of the vibrational frequencies of specific functional groups of the poly (ester urethane) in the 0-100-kbar range are compared with data for individual segment models and the partially degraded sample. The results indicated that the polymer is highly stable in this pressure regime, with no measurable degradation or phase changes. Differences in the pressure dependency of specific infrared bands between the poly (ester urethane) sample and the partially degraded sample are slight and consistent with changes in hydrogen-bonding interactions and shorter chain lengths in the degraded sample. 相似文献
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