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61.
62.
The method of time-ordered cumulants is used to investigate the behavior of heat pulses in a one-dimensional medium in which the thermal conductivity is random. A partial differential equation is obtained for the average temperature profile; it is the heat equation modified by the addition of a fourth-order spatial derivative. A solution is obtained by asymptotic series. The first two spatial moments of the average temperature profile are evaluated and are shown to tend to those of a Gaussian whent is large. Finally, an equation is obtained for the covariance function.Alfred P. Sloan Fellow. 相似文献
63.
Köhler T Seidel D Lynch V Arp FO Ou Z Kadish KM Sessler JL 《Journal of the American Chemical Society》2003,125(23):6872-6873
Oxidative coupling of a tetraalkylbipyrrole under FeIII-mediated coupling conditions in the presence of HCl results in a mixture of cyclo[6]- and cyclo[7]pyrroles, as well as the known cyclo[8]pyrrole. This "matched set" of heteroannulenes was analyzed by spectroscopic, electrochemical, and X-ray diffraction methods. 相似文献
64.
Michael FE Duncan AP Sweeney ZK Bergman RG 《Journal of the American Chemical Society》2003,125(24):7184-7185
The zirconium-mediated stereoinversion of allenes has been investigated by studying the stereochemical behavior of metallacycles derived from [2 + 2] cycloaddition of enantioenriched allenes with chiral and achiral imidozirconocene complexes. Relative rates of metallacycle racemization were measured by circular dichroism, and intermediates in the selective stereoinversion of diphenylallene with a chiral imidozirconium complex were observed by NMR spectroscopy. Metallacycles derived from dialkylallenes are proposed to racemize via reversible beta-hydride elimination. Stereoinversion of diarylallene-derived metallacycles proceeds much more slowly and is thought to proceed through an eta4-azatrimethylenemethane transition state. 相似文献
65.
Evans DA Michael FE Tedrow JS Campos KR 《Journal of the American Chemical Society》2003,125(12):3534-3543
Chiral mixed phosphorus/sulfur ligands 1-3 have been shown to be effective in enantioselective Rh-catalyzed dehydroamino acid hydrogenation and ketone hydrosilylation reactions (eqs 1, 2). After assaying the influence of the substituents at sulfur, the substituents on the ligand backbone, the relative stereochemistry within the ligand backbone, and the substituents at phosphorus, ligands 2c (R = 3,5-dimethylphenyl) and 3 were found to be optimal in the Rh-catalyzed hydrogenation of a variety of alpha-acylaminoacrylates in high enantioselectivity (89-97% ee). A similar optimization of the catalyst for the Rh-catalyzed hydrosilylation of ketones showed that ligand 3 afforded the highest enantioselectivities for a wide variety of aryl alkyl and dialkyl ketones (up to 99% ee). A model for asymmetric induction in the hydrogenation reaction is discussed in the context of existing models, based on the absolute stereochemistry of the products and the X-ray crystal structures of catalyst precursors and intermediates. 相似文献
66.
Highly phosphorescent bis-cyclometalated iridium complexes: synthesis, photophysical characterization, and use in organic light emitting diodes. 总被引:21,自引:0,他引:21
S Lamansky P Djurovich D Murphy F Abdel-Razzaq H E Lee C Adachi P E Burrows S R Forrest M E Thompson 《Journal of the American Chemical Society》2001,123(18):4304-4312
The synthesis and photophysical study of a family of cyclometalated iridium(III) complexes are reported. The iridium complexes have two cyclometalated (C(**)N) ligands and a single monoanionic, bidentate ancillary ligand (LX), i.e., C(**)N2Ir(LX). The C(**)N ligands can be any of a wide variety of organometallic ligands. The LX ligands used for this study were all beta-diketonates, with the major emphasis placed on acetylacetonate (acac) complexes. The majority of the C(**)N2Ir(acac) complexes phosphoresce with high quantum efficiencies (solution quantum yields, 0.1-0.6), and microsecond lifetimes (e.g., 1-14 micros). The strongly allowed phosphorescence in these complexes is the result of significant spin-orbit coupling of the Ir center. The lowest energy (emissive) excited state in these C(**)N2Ir(acac) complexes is a mixture of (3)MLCT and (3)(pi-pi) states. By choosing the appropriate C(**)N ligand, C(**)N2Ir(acac) complexes can be prepared which emit in any color from green to red. Simple, systematic changes in the C(**)N ligands, which lead to bathochromic shifts of the free ligands, lead to similar bathochromic shifts in the Ir complexes of the same ligands, consistent with "C(**)N2Ir"-centered emission. Three of the C(**)N2Ir(acac) complexes were used as dopants for organic light emitting diodes (OLEDs). The three Ir complexes, i.e., bis(2-phenylpyridinato-N,C2')iridium(acetylacetonate) [ppy2Ir(acac)], bis(2-phenyl benzothiozolato-N,C2')iridium(acetylacetonate) [bt2Ir(acac)], and bis(2-(2'-benzothienyl)pyridinato-N,C3')iridium(acetylacetonate) [btp2Ir(acac)], were doped into the emissive region of multilayer, vapor-deposited OLEDs. The ppy2Ir(acac)-, bt2Ir(acac)-, and btp2Ir(acac)-based OLEDs give green, yellow, and red electroluminescence, respectively, with very similar current-voltage characteristics. The OLEDs give high external quantum efficiencies, ranging from 6 to 12.3%, with the ppy2Ir(acac) giving the highest efficiency (12.3%, 38 lm/W, >50 Cd/A). The btp2Ir(acac)-based device gives saturated red emission with a quantum efficiency of 6.5% and a luminance efficiency of 2.2 lm/W. These C(**)N2Ir(acac)-doped OLEDs show some of the highest efficiencies reported for organic light emitting diodes. The high efficiencies result from efficient trapping and radiative relaxation of the singlet and triplet excitons formed in the electroluminescent process. 相似文献
67.
MA Freitas SR Dillon RC Dougherty AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1622-1625
The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
68.
J. H. Teichroeb P. Z. McVeigh J. A. Forrest 《The European physical journal. E, Soft matter》2009,30(2):157-164
We have studied p H-dependent conformational transitions of Bovine Serum Albumin adsorbed onto different sizes of gold nanospheres. For larger
spheres (D > 10 nm) there is evidence for a path-dependent extended state near p H 4, over a very small p H range. For smaller nanospheres (5nm and 10nm) the evidence for such a transition is either much weaker or completely suppressed.
We suggest that the absence of the transition on small spheres is due to the fact that the protein adsorbed on such small
spheres has already lost at least some of its tertiary structure. The results have important implications for the functionality
of proteins adsorbed onto nanospheres or surfaces with nm scale roughness. 相似文献
69.
Eric Y.Jiang Forrest J. Weesener 《光散射学报》2005,17(3):315-317
pacc:0765Thispaperdemonstratesthreevibrational spectroscopictechniquesandtheirapplicationsin characterizationofspatiallyheterogamousmateri als,namelystep-scanphasemodulationFTIR photoacousticspectroscopy(S2MPAS),visible(confocal)Ramanmicroscopy(CRM)andF… 相似文献
70.
Forrest J. Agee 《Hyperfine Interactions》2002,143(1-4):1-6
Induced gamma emission with the potential for substantial energy gain is an exciting area of research. This paper reviews
related work done internationally, including some that has potential for a gamma-ray laser.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献