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141.
142.
Jones AK Lamle SE Pershad HR Vincent KA Albracht SP Armstrong FA 《Journal of the American Chemical Society》2003,125(28):8505-8514
The cycling between active and inactive states of the catalytic center of [NiFe]-hydrogenase from Allochromatium vinosum has been investigated by dynamic electrochemical techniques. Adsorbed on a rotating disk pyrolytic graphite "edge" electrode, the enzyme is highly electroactive: this allows precise manipulations of the complex redox chemistry and facilitates quantitative measurements of the interconversions between active catalytic states and the inactive oxidized form Ni(r) (also called Ni-B or "ready") as functions of pH, H(2) partial pressure, temperature, and electrode potential. Cyclic voltammograms for catalytic H(2) oxidation (current is directly related to turnover rate) are highly asymmetric (except at pH > 8 and high temperature) due to inactivation being much slower than activation. Controlled potential-step experiments show that the rate of oxidative inactivation increases at high pH but is independent of potential, whereas the rate of reductive activation increases as the potential becomes more negative. Indeed, at 45 degrees C, activation takes just a few seconds at -288 mV. The cyclic asymmetry arises because interconversion is a two-stage reaction, as expected if the reduced inactive Ni(r)-S state is an intermediate. The rate of inactivation depends on a chemical process (rearrangement and uptake of a ligand) that is independent of potential, but sensitive to pH, while activation is driven by an electron-transfer process, Ni(III) to Ni(II), that responds directly to the driving force. The potentials at which fast activation occurs under different conditions have been analyzed to yield the potential-pH dependence and the corresponding entropies and enthalpies. The reduced (active) enzyme shows a pK of 7.6; thus, when a one-electron process is assumed, reductive activation at pH < 7 involves a net uptake of one proton (or release of one hydroxide), whereas, at pH > 8, there is no net exchange of protons with solvent. Activation is favored by a large positive entropy, consistent with the release of a ligand and/or relaxation of the structure around the active site. 相似文献
143.
Thomas F.O. Lim Jerry K. Myers Greg. T. Rogers Paul Ronald Jones 《Journal of organometallic chemistry》1977,135(2):249-259
The regioselectivity of the hydroboration of the methylchlorovinylsilanes, ClnMe3?nSiCHCH2 (n= 0 ? 3), has been investigated using BH3←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH3←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts. 相似文献
144.
145.
The effects of adding millimolar quantities of a series of compounds containing the carbonyl function on the conductances of solutions (0.2 mM) of tri-n-butylammonium picrate ino-dichlorobenzene solvent at 25°C have been measured. Values of the complex formation constants K
1
+
for 1:1 cation-ligand complexes are derived from these data. The corresponding values of –G
1
0
at 25°C are (in kcal-mole
–1
): 4-butyrolactone, 4.29; propylene carbonate, 3.87; ethylene carbonate, 3.59; cyclopentanone, 3.42; ethyl acetate, 2.84; and diethyl carbonate, 2.78. These results together with earlier results from this laboratory are discussed in terms of the effects of structure on cation-ligand affinity. 相似文献
146.
LoSecco JM Bionta RM Biewitt G Bratton CB Casper D Chrysicopoulou P Claus R Cortez BG Errede S Foster GW Gajewski W Ganezer KS Goldhaber M Haines TJ Jones TW Kielczewska D Kropp WR Learned JG Lehmann E Park HS Reines F Schultz J Seidel S Shumard E Sinclair D Sobel HW Stone JL Sulak L Svoboda R van der Velde JC Wuest C 《Physical review letters》1985,54(21):2299-2301
147.
148.
R.?Mitchell C.?M.?CarrEmail author M.?Parfitt J.?C.?Vickerman C.?Jones 《Cellulose (London, England)》2005,12(6):629-639
The surface chemical composition of raw unscoured cotton was successfully investigated by the surface analytical techniques
X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The presence of non-cellulosic
material at the fibre surface was established and determined to be a complex mixture of fatty acids, alcohols, alkanes, esters
and glycerides. The effect of scouring and bleaching was to reduce the surface concentration of these materials but even after
aqueous processing some non-cellulosic material residue was still detected at the fibre surface. 相似文献
149.
Bulloch EM Jones MA Parker EJ Osborne AP Stephens E Davies GM Coggins JR Abell C 《Journal of the American Chemical Society》2004,126(32):9912-9913
(6S)-6-Fluoroshikimate has antimicrobial activity. The molecular basis of this effect had not been identified, but there was speculation that (6S)-6-fluoroshikimate is first converted in vivo into 2-fluorochorismate, which then could inhibit 4-amino-4-deoxychorismate synthase (ADCS). 2-Fluorochorismate was prepared from E-fluorophosphoenolpyruvate and erythose-4-phosphate by the sequential reactions of DAHP synthase, dehydroquinate synthase, dehydroquinase, shikimate dehydrogenase, EPSP synthase, and chorismate synthase. Inhibition studies on ADCS showed that it was inhibited rapidly and irreversibly by 2-fluorochorismate. Electrospray mass spectrometry of the inactivated enzyme showed an additional mass of 198 +/- 10 Da. A novel peptide of 1087.6 Da was identified in the HPLC trace for the tryptic digest of 2-fluorochorismate-inactivated ADCS. Sequencing of this peptide by MS/MS showed that the peptide corresponded to residues 272-279 with a modification of 206.1 Da on Lys-274. This observation is particularly exciting in the context of a recent proposal for the catalytic mechanism of ADCS. 相似文献
150.
H. W. Sarkas S. T. Arnold J. H. Hendricks L. H. Kidder C. A. Jones K. H. Bowen 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,26(1):46-50
We present preliminary evidence for catalytic activity by unsupported mixed metal oxide nanocrystalline materials. The results of this study show that a nanophase form of Li-MgO has begun to exhibit catalytic activity by 300 °C. This is at least 200 degrees below the temperature at which conventional Li-MgO catalysts exhibit comparable activity. Furthermore, at higher temperatures, the same nanophase composition shows enhanced activities and somewhat improved hydrocarbon selectivities over conventional Li-MgO catalysts. 相似文献