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961.
The accuracy of the first and second order WKB approximation in describing sub-Coulomb elastic scattering of ions is investigated. Thereby the scattering of non-identical as well as of identical particles is taken into consideration. It is shown that in cases where the behaviour of the scattered ions is not quasi-classical and therefore the first order WKB approximation fails, the second order WKB will be in most cases still a quite good approximation. 相似文献
962.
Taatjes CA Hansen N Osborn DL Kohse-Höinghaus K Cool TA Westmoreland PR 《Physical chemistry chemical physics : PCCP》2008,10(1):20-34
The combination of multiplexed mass spectrometry with photoionization by tunable-synchrotron radiation has proved to be a powerful tool to investigate elementary reaction kinetics and the chemistry of low-pressure flames. In both of these applications, multiple-mass detection and the ease of tunability of synchrotron radiation make it possible to acquire full sets of data as a function of mass, photon energy, and of the physical dimension of the system, e.g. distance from the burner or time after reaction initiation. The data are in essence an indirect image of the chemistry. The data can be quantitatively correlated and integrated along any of several dimensions to compare to traditional measurements such as time or distance profiles of individual chemical species, but it can also be directly interpreted in image form. This perspective offers an overview of flame chemistry and chemical kinetics measurements that combine tunable photoionization with multiple-mass detection, emphasizing the overall insight that can be gained from multidimensional data on these systems. The low-pressure flame apparatus is capable of providing isomer-resolved mass spectra of stable and radical species as a function of position in the flame. The overall chemical structure of the flames can be readily seen from images of the evolving mass spectrum as distance from the burner increases, with isomer-specific information given in images of the photoionization efficiency. Several flames are compared in this manner, with a focus on identification of global differences in fuel-decomposition and soot-formation pathways. Differences in the chemistry of flames of isomeric fuels can be discerned. The application of multiplexed synchrotron photoionization to elementary reaction kinetics permits identification of time-resolved isomeric composition in reacting systems. The power of this technique is illustrated by the separation of direct and dissociative ionization signals in the reaction of C(2)H(5) with O(2); by the resolution of isomeric products in reactions of the ethynyl (C(2)H) radical; and by preliminary observation of branching to methyl + propargyl products in the self-reaction of vinyl radicals. Finally, prospects for future research using multiplexed photoionization mass spectrometry are explored. 相似文献
963.
Zhang Y Illarionov B Bacher A Fischer M Georg GI Ye QZ Vander Velde D Fanwick PE Song Y Cushman M 《The Journal of organic chemistry》2007,72(8):2769-2776
Air oxidation of 1,3,6,8-tetrahydroxy-2,7-naphthyridine afforded 2,5,8,11-tetraaza-5,11-dihydro-4,10-dihydroxyperylene-1,3,6,7,9,12-hexaone. X-ray crystallography of the product revealed that it exists in the meso form in the solid state. The mechanism of product formation most likely involves oxidative phenolic coupling and oxidation. The product proved to be a competitive inhibitor of Schizosaccharomyces pombe lumazine synthase with a Ki of 66+/-13 microM in Tris buffer and 22+/-4 microM in phosphate buffer. This is significantly more potent than the reactant (Ki 350+/-76 microM, competitive inhibition), which had previously been identified as a lumazine synthase inhibitor by high-throughput screening. Ab initio calculations indicate that the meso form is slightly less stable than the enantiomeric form, and that the two forms interconvert rapidly at room temperature. 相似文献
964.
Thirupathi N Stricklen PM Liu X Oshel R Guzei I Ellern A Verkade JG 《Inorganic chemistry》2007,46(22):9351-9363
Bicyclic P(CH2NMe)3P was synthesized, and its reactions with MnO2, elemental sulfur, p-toluenesulfonyl azide, BH3.THF, and W(CO)5(THF) were shown to furnish a variety of products in which the PC3 and/or the PN3 phosphorus are oxidized/coordinated. In contrast, reactions of the previously known P(CH2NPh)3P with Mo(0) and Ru(II) precursors were shown to afford products in which only the PC3 phosphorus is coordinated. The contrast in reactivity of P(CH2NR)3P (R = Me, Ph) with the aforementioned reagents is discussed in terms of steric and electronic factors. The new compounds are characterized by analytical and spectroscopic (IR, 1H, 31P, and 13C NMR) methods. The results of crystal and molecular structure X-ray analyses of the previously known compounds P(CH2O)3P and P(CH2NPh)3P and 6 of the 14 new compounds obtained in this investigation are presented. Salient features of these structures and the analysis of the Tolman cone angles calculated from their structural parameters are discussed in terms of the effects of constraint in the bicyclic moieties. Evidence is presented for greater M-P sigma bonding effects on coordination of the PC3 phosphorus of P(CH2NR)3P (R = Me, Ph) than are present in PMe3 analogues of group 6B metal carbonyls. From 1JBP data on the BH3 adducts of P(CH2NMe)3P, it is suggested that the free bases MeC(CH2NMe)3P < P(CH2NMe)3P < (Me2N)3P < P(MeNCH2CH2)3N increase in Lewis basicity at the PN3 phosphorus in the order shown. Substantial differences in 31P chemical shifts in the bicyclic compounds discussed herein relative to their acyclic analogues do not seem to be associated with the relatively small bond angle changes that occur around either the PN3 or the PC3 trivalent phosphorus atoms. 相似文献
965.
Novel Ru2-containing dendritic compounds were prepared from the CuI-catalyzed 1,3-dipolar cycloaddition between Ru2 compounds containing one or two ethynes, Ru2(D(3,5-Cl2Ph)F)4-n(DMBA-4-C2H)n with n=1 and 2, and azidopoly(benzyl ether) dendrons. These new compounds were also characterized with X-ray diffraction and voltammetric techniques. 相似文献
966.
Frances Hammock Peter Luthy Alexander M. Meadows Phillip Whitman 《Proceedings of the American Mathematical Society》2007,135(5):1419-1430
We show partial regularity of bounded positive solutions of some semilinear elliptic equations in domains of . As a consequence, there exists a large variety of nonnegative singular solutions to these equations. These equations have previously been studied from the point of view of free boundary problems, where solutions additionally are stable for a variational problem, which we do not assume.
967.
968.
Wildemann D Schiene-Fischer C Aumüller T Bachmann A Kiefhaber T Lücke C Fischer G 《Journal of the American Chemical Society》2007,129(16):4910-4918
psi[CS-NH]4-RNase S, a site specific modified version of RNase S obtained by thioxylation (O/S exchange) at the Ala4-Ala5- peptide bond, was used to evaluate the impact of protein backbone photoswitching on bioactivity. psi[CS-NH](4)-RNase S was yielded by recombination of the S-protein and the respective chemically synthesized thioxylated S-peptide derivative. Comparison with RNase S revealed similar thermodynamic stability of the complex and an unperturbed enzymatic activity toward cytidine 2',3'-cyclic monophosphate (cCMP). Reversible photoisomerization with a highly increased cis/trans isomer ratio of the thioxopeptide bond of psi[CS-NH](4)-RNase S in the photostationary state occurred under UV irradiation conditions (254 nm). The slow thermal reisomerization (t(1/2) = 180 s) permitted us to determine the enzymatic activity of cis psi[CS-NH](4)-RNase S by measurement of initial rates of cCMP hydrolysis. Despite thermodynamic stability of cis psi[CS-NH](4)-RNase S, its enzymatic activity is completely abolished but recovers after reisomerization. We conclude that the thioxopeptide bond modified polypeptide backbone represents a versatile probe for site-directed photoswitching of proteins. 相似文献
969.
970.
The iron(II) porphyrinogen dication, [LDeltaDeltaFeII]2+, is a multielectron oxidant featuring the metal center in its reduced state and the ligand as the redox reservoir. Oxidations break the ligand's redox-active C-C bonds. Extremely short-lived excited states are consistent with extensive structural reorganization that accompanies charge-transfer excitation of the porphyrinogen. 相似文献