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Kinetic studies on the substitution reaction between [Fe(4)S(4)Cl(4)](2-) and Bu(t)NC or Et(2)NCS(2)(-) are reported. The binding of small molecules and ions to Fe-S clusters is a fundamental step in substitution reactions but can be difficult to follow directly because these reactions are rapid and often associated with small spectroscopic changes. A novel kinetic method is reported which allows the time course of molecule and ion binding to Fe-S clusters to be followed by monitoring the lability of the cluster. Using a stopped-flow, sequential-mix apparatus, [Fe(4)S(4)Cl(4)](2-) and L (L = Et(2)NCS(2)(-) or Bu(t)NC) are rapidly mixed, and after a known time (delta) the resulting solution is mixed with a solution of PhS(-). The thiolate substitutes for the chloro ligands on the cluster, in a reaction which is easy to follow because of the large change in the visible absorption spectrum. The rate of this substitution is extremely sensitive to whether L is bound to the cluster or not. By correlation of delta with the rate of the reaction with PhS(-), the time course of the reaction between [Fe(4)S(4)Cl(4)](2-) and L can be mapped out. In studies where L = Bu(t)NC this technique has allowed the detection of an intermediate ([Fe(4)S(4)Cl(4)(CNBu(t))](2-)) which cannot be detected spectrophotometrically. In further studies, the substitution reactions of [Fe(4)S(4)Cl(4)](2-) with PhS(-), Et(2)NCS(2)(-), or Bu(t)NC are all perturbed by the addition of Cl(-). In all cases a common pathway for substitution is evident, but with Et(2)NCS(2)(-) an additional, slower pathway becomes apparent under conditions where the common pathway is completely inhibited by Cl(-). 相似文献
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The first kinetic study of a substrate (CN(-)) binding to the isolated active site (extracted FeMo-cofactor) of nitrogenase is described. The kinetics of the reactions between CN(-) and various derivatives of extracted FeMo-cofactor [FeMoco-L; where L is bound to Mo, and is NMF, Bu(t)NC, or imidazole (ImH)] have been followed using a stopped-flow, sequential-mix method in which the course of the reaction is followed indirectly, by monitoring the change in the rate of the reaction of the cofactor with PhS(-). The kinetic results, together with DFT calculations, indicate that the initial site of CN(-) binding to FeMoco-L is controlled by a combination of the electron-richness of the cluster core and lability of the Mo-L bond. Ultimately, the reactions between FeMoco-L and CN(-) involve displacement of L and binding of CN(-) to Mo. These reactions occur with a variety of rates and rate laws dependent on the nature of L. For FeMoco-NMF, the reaction with CN(-) is complete within the dead-time of the apparatus (ca. 4 ms), while with FeMoco-CNBu(t) the reaction is much slower and exhibits first order dependences on the concentrations of both FeMoco-CNBu(t) and CN(-) (k = 2.5 +/- 0.5 x 10(4) dm(3) mol(-1) s(-1)). The reaction of FeMoco-ImH with CN(-) occurs at a rate which exhibits a first order dependence on FeMoco-ImH but is independent of the concentration of CN(-) (k = 50 +/- 10 s(-1)). The results are interpreted in terms of CN(-) binding directly to the Mo site for FeMoco-NMF and FeMoco-ImH, but with FeMoco-CNBu(t) initial binding at an Fe site is followed by movement of CN(-) to Mo. Complementary DFT calculations are consistent with this interpretation, indicating that, in FeMoco-L, the Mo-L bond is stronger for L = ImH than for L = CNBu(t) and the binding of CN(-) to Mo is stronger than to any Fe atom in the cofactor. 相似文献
5.
H. W. Schffer P. H. Mokler R. W. Dunford C. Kozhuharov A. Krmer A. E. Livingston T. Ludziejewski H. -T. Prinz P. Rymuza L. Sarkadi Z. Stachura Th. Sthlker P. Swiat A. Warczak 《Physics letters. A》1999,260(6):331-494
The photon energy differential shape of the second order matrix element for the two-photon (2E1) decay of the 1s2s1S0 level in He-like gold has been measured. The results are in agreement with a recent fully relativistic calculation. The corresponding 2E1 matrix element deviates from those in lighter He-like systems due to the strong central field in a heavy two-electron ion. 相似文献
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Ahmed SN Anthony AE Beier EW Bellerive A Biller SD Boger J Boulay MG Bowler MG Bowles TJ Brice SJ Bullard TV Chan YD Chen M Chen X Cleveland BT Cox GA Dai X Dalnoki-Veress F Doe PJ Dosanjh RS Doucas G Dragowsky MR Duba CA Duncan FA Dunford M Dunmore JA Earle ED Elliott SR Evans HC Ewan GT Farine J Fergani H Fleurot F Formaggio JA Fowler MM Frame K Fulsom BG Gagnon N Graham K Grant DR Hahn RL Hall JC Hallin AL Hallman ED Hamer AS Handler WB Hargrove CK Harvey PJ Hazama R Heeger KM Heintzelman WJ 《Physical review letters》2004,92(18):181301
The Sudbury Neutrino Observatory has precisely determined the total active (nu(x)) 8B solar neutrino flux without assumptions about the energy dependence of the nu(e) survival probability. The measurements were made with dissolved NaCl in heavy water to enhance the sensitivity and signature for neutral-current interactions. The flux is found to be 5.21 +/- 0.27(stat)+/-0.38(syst) x 10(6) cm(-2) s(-1), in agreement with previous measurements and standard solar models. A global analysis of these and other solar and reactor neutrino results yields Deltam(2)=7.1(+1.2)(-0.6) x 10(-5) eV(2) and theta=32.5(+2.4)(-2.3) degrees. Maximal mixing is rejected at the equivalent of 5.4 standard deviations. 相似文献
8.
Stohlker T Mokler PH Bosch F Dunford RW Franzke F Klepper O Kozhuharov C Ludziejewski T Nolden F Reich H Rymuza P Stachura Z Steck M Swiat P Warczak A 《Physical review letters》2000,85(15):3109-3112
The Lyman- alpha transitions of hydrogenlike uranium associated with electron capture were measured in collisions of stored bare U (92+) ions with gaseous targets at the storage ring ESR. By applying the deceleration technique, the experiment was performed at slow collision energies in order to reduce the uncertainties associated with Doppler corrections. From the measured centroid energies, a ground state Lamb shift of 468 eV+/-13 eV is deduced which gives the most precise test of quantum electrodynamics for a single electron system in the strong field regime. In particular, the technique applied paves the way towards the 1 eV precision regime. 相似文献
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Cumulant functions are introduced to describe the statistical state of a radiation field. These functions are simply related
to the optical coherence functions but have some interesting features. It is shown that if the cumulant functions of all orders
greater than some numberN
0 vanish then they also vanish for all orders greater than 2. Thermal field is the only field having this property. This property
holds whether the field is described by a classical stochastic process or by a quantum density operator. Further the particular
operator ordering used in defining these cumulant functions for the quantized field affects only the second order cumulant
function. To describe the statistical state of a vector field such as partially polarized or unpolarized radiation, one would
need to introduce cumulant tensors. 相似文献