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101.
Time-resolved spectroscopic techniques have been used to prepare and to interrogate transient species that are models for reactive intermediates in cobalt-catalyzed hydroformylation. Flash photolysis of acetylcobalt carbonyl complexes of the type RC(O)Co(CO)3(PR'3) (A; R = CH3, CD3, or C2H5; R' = Ph or nBu) leads to CO photodissociation to give the "unsaturated" intermediate [RC(O)Co(CO)2(PR'3)] (I), which decays by two competitive pathways, alkyl migration to the cobalt to give RCo(CO)3PR'3 (M) and reaction with CO to re-form A. With the perdeuterioacetyl complex (R = CD3, R' = Ph), rate constants both of CO trapping (kco) and of methyl migration (kM) were just slightly smaller than those of the perprotio analogue (kh/kd = 1.04 +/- 0.01 and 1.07 +/- 0.09, respectively). Thus, any stabilization of the "vacant" coordination site of I by agostic interactions with the acetyl methyl group appears to be kinetically insignificant, consistent with the previous conclusion (Inorg. Chem. 2000, 39, 3098-3106) that this site is stabilized by an eta 2-coordinated carbonyl. Changing the phosphine ligand has a greater influence on the kinetics of I. The species generated by the flash photolysis of the trialkyl phosphine complex CH3C(O)Co-(CO)3(P(nBu3)) exhibited a much larger kM than was the case for the PPh3 analogue, although there was little difference in the kco values. Similarly, kM proved to be sensitive to the nature of R as demonstrated by the slower alkyl migration (at 298 K) for the intermediate formed by CO photodissociation from the propionyl complex C2H5C(O)Co(CO)3PPh3 relative to the acetyl analogue. Nonetheless, all these intermediates displayed analogous time-resolved infrared spectra and general kinetics behavior in benzene solution (implying common mechanisms for decay), so it is concluded that all are present as the eta 2-chelated acyl structure under these conditions. 相似文献
102.
A. Baldan Adriaan M. H. van der Veen Daniela Prauß Angelika Recknagel N. Boley Steve Evans Derek Woods 《Accreditation and quality assurance》2001,6(4-5):164-167
Many proficiency tests are operated with a consensus value derived from the participants’ results. Apart from technical issues,
one of the reasons often mentioned is that proficiency tests operated with consensus values would be cheaper than those using
reference values obtained from a priori characterisation measurements. The economy of a proficiency test must of course be balanced by the need of the participants,
and the quality of the comparison in general. The proficiency tests selected in this study had both a reference value and
a consensus value, one of which was used for assessing the performance of the participating laboratories. In this work, both
a technical and an economical assessment of how the comparisons were operated is made. From the evaluation, it follows that
usually the use of consensus values does not necessarily reduce the costs of a proficiency test. However, frequently it may
be observed that the quality of the assessment of the laboratories is better with a reference value.
Received: 11 October 2000 Accepted: 3 January 2001 相似文献
103.
Extracting and concentrating mitochondrial protein complexes from gel strips after blue native PAGE (BN‐PAGE) can be daunting tasks using the traditional methods, such as electroelution, passive diffusion and centrifugal concentration. We present a simplified gel electrophoresis method to concentrate mitochondrial protein complexes with excellent recovery rate. Mitochondrial complex I present in a long gel strip from BN‐PAGE can be easily concentrated into a 0.8 cm gel strip when a second BN‐PAGE is performed with a Y‐shaped gel and the addition of 0.01% n‐dodecyl β‐D ‐maltoside and 0.001% SDS in the cathode buffer. Once completed, the concentrated protein complex in the gel strip is ready for SDS‐PAGE or proteomic studies. 相似文献
104.
105.
Xiaowei Ye Liying Liu Lei Xu Wencheng Wang Mario Affatigato Steve Feller 《Journal of Non》2008,354(12-13):1250-1255
The second-order nonlinearities in thermally poled lead borate glasses were studied. After poling with different electrodes, both bulk and near surface second-order nonlinearities were obtained. The second harmonic generation signal from near surface effect was two orders of magnitude larger than the bulk effect. By simulating the poling process with a multiple carrier model, we concluded that the bulk second-order nonlinearity was caused by the deficiency of Pb2+ in a thick layer after poling, and the near surface second-order nonlinearity was caused by the depletion of H+ in a thin layer when H+ injection from the atmosphere was blocked. 相似文献
106.
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109.
Winfried K. Grassmann Steve Drekic 《Methodology and Computing in Applied Probability》2008,10(1):73-83
A number of authors have recently suggested solving quasi birth-and-death (QBD) processes through the use of eigenvalue-based
methods. These methods take on a special form when there are multiple eigenvalues present. We investigate this problem in
a general setting as well as in the context of a specific preemptive priority queueing model.
相似文献
110.
Matt Grupen Paul Sotirelis Steve Wong John Albrecht Robert Bedford Sarah Maley Tom Nelson Bill Siskaninetz 《Optical and Quantum Electronics》2008,40(5-6):349-354
A unique discretization scheme that couples Maxwell’s full wave vector field equations self-consistently with nonlinear charge and energy transport is presented. The scheme is used to simulate laser modulation achieved in a simple electrically pumped quantum well laser diode by dynamically heating the degenerate quantum charge gases with high frequency radiation. 相似文献