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971.
972.
Somorjai GA Bratlie KM Montano MO Park JY 《The journal of physical chemistry. B》2006,110(40):20014-20022
The mechanism that controls bond breaking at transition metal surfaces has been studied with sum frequency generation (SFG), scanning tunneling microscopy (STM), and catalytic nanodiodes operating under the high-pressure conditions. The combination of these techniques permits us to understand the role of surface defects, surface diffusion, and hot electrons in dynamics of surface catalyzed reactions. Sum frequency generation vibrational spectroscopy and kinetic measurements were performed under 1.5 Torr of cyclohexene hydrogenation/dehydrogenation in the presence and absence of H(2) and over the temperature range 300-500 K on the Pt(100) and Pt(111) surfaces. The structure specificity of the Pt(100) and Pt(111) surfaces is exhibited by the surface species present during reaction. On Pt(100), pi-allyl c-C6H9, cyclohexyl (C6H11), and 1,4-cyclohexadiene are identified adsorbates, while on the Pt(111) surface, pi-allyl c-C6H9, 1,4-cyclohexadiene, and 1,3-cyclohexadiene are present. A scanning tunneling microscope that can be operated at high pressures and temperatures was used to study the Pt(111) surface during the catalytic hydrogenation/dehydrogenation of cyclohexene and its poisoning with CO. It was found that catalytically active surfaces were always disordered, while ordered surface were always catalytically deactivated. Only in the case of the CO poisoning at 350 K was a surface with a mobile adsorbed monolayer not catalytically active. From these results, a CO-dominated mobile overlayer that prevents reactant adsorption was proposed. By using the catalytic nanodiode, we detected the continuous flow of hot electron currents that is induced by the exothermic catalytic reaction. During the platinum-catalyzed oxidation of carbon monoxide, we monitored the flow of hot electrons over several hours using a metal-semiconductor Schottky diode composed of Pt and TiO2. The thickness of the Pt film used as the catalyst was 5 nm, less than the electron mean free path, resulting in the ballistic transport of hot electrons through the metal. The electron flow was detected as a chemicurrent if the excess electron kinetic energy generated by the exothermic reaction was larger than the effective Schottky barrier formed at the metal-semiconductor interface. The measurement of continuous chemicurrent indicated that chemical energy of exothermic catalytic reaction was directly converted into hot electron flux in the catalytic nanodiode. We found the chemicurrent was well-correlated with the turnover rate of CO oxidation separately measured by gas chromatography. 相似文献
973.
[reaction: see text] Unusual palladium-catalyzed arylative fragmentations of acyclic 3-allen-1-ols were observed. Oxidative addition of Pd(0) to aryl halides would form the arylpalladium halides, which added to the central carbon of allenes via carbopalladation to form the pi-allylpalladium intermediates. The pi-allylpalladium intermediates would be reductively eliminated via carbon-carbon cleavage to give the arylated dienes and the alpha-hydroxyalkylpalladium intermediates, which were further reductively eliminated to the corresponding aldehydes. 相似文献
974.
Lee Soon Park Tae Hyung Lee Soo Chang Lee 《Journal of polymer science. Part A, Polymer chemistry》1999,37(14):2311-2317
Copolymerizations of p-dichlorobenzene (DCB)/4-bromophenyl ether (BPE), DCB/4,4′-dibromobiphenyl (DBB), and DBB/BPE pairs with sodium sulfide under high temperature (270–290°C) utilizing N-methyl-2-pyrrolidinone (NMP) as solvent were carried out to give C(DCB/BPE), C(DCB/DBB), and C(DBB/BPE) copolymers, respectively. The reactivity of dihaloaromatic monomers toward thiolate anion in the polycondensation reaction followed the order DBB > DCB > BPE. The reactivity gap between DBB and DCB toward thiolate anion seemed to be smaller than that between BPE and DCB, resulting in both high yield and high molecular weight in the C(DCB/DBB) copolymers compared to C(DCB/BPE) copolymers. The copolymerization of DBB/BPE pair with sodium sulfide, which has larger reactivity gap than the DCB/DBB or DCB/BPE pair, gave mixtures of PBS and PPSE homopolymers especially in the range of 50–80 mol % BPE in the feed. The C(DCB/DBB) and C(DCB/BPE) copolymers, however, exhibited random copolymer character in all comonomer ratios in the feed as evidenced by copolymer composition and DSC data. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2311–2317, 1999 相似文献
975.
Kim WS Kim MG Ahn JH Bae BS Park CB 《Langmuir : the ACS journal of surfaces and colloids》2007,23(9):4732-4736
Active protein micropatterns and microarrays made by selective localization are popular candidates for medical diagnostics, such as biosensors, bioMEMS, and basic protein studies. In this paper, we present a simple fabrication process of thick (approximately 20 microm) protein micropatterning using capillary force lithography with bifunctional sol-gel hybrid materials. Because bifunctional sol-gel hybrid material can have both an amine function for linking with protein and a methacryl function for photocuring, proteins such as streptavidin can be immobilized directly on thick bifunctional sol-gel hybrid micropatterns. Another advantage of the bifunctional sol-gel hybrid materials is the high selective stability of the amine group on bifunctional sol-gel hybrid patterns. Because amine function is regularly contained in each siloxane oligomers, immobilizing sites for streptavidin are widely distributed on the surface of thick hybrid micropatterns. The micropatterning processes of active proteins using efficient bifunctional sol-gel hybrid materials will be useful for the development of future bioengineered systems because they can save several processing steps and reduce costs. 相似文献
976.
Sun Pil Park 《Tetrahedron》2010,66(19):3490-3498
A simple method for synthesizing several 6H-pyrrolo[1,2-c][1,2,3]triazole derivatives having a methoxycarbonyl or an acetyl group at C-5 position and 7,8-dihydro-4H-[1,2,3]triazolo[1,5-a]indol-5(6H)-ones via an intramolecular 1,3-dipolar cycloaddition reaction of azido enynes, which were readily obtained from the Morita-Baylis-Hillman acetates of propargyl aldehydes with sodium azide, has been developed. 相似文献
977.
Rubin P Cawlfield C Eisenstein BI Karliner I Kim D Lowrey N Naik P Sedlack C Selen M White EJ Wiss J Shepherd MR Besson D Pedlar TK Cronin-Hennessy D Gao KY Gong DT Hietala J Kubota Y Klein T Lang BW Poling R Scott AW Smith A Dobbs S Metreveli Z Seth KK Tomaradze A Zweber P Ernst J Severini H Dytman SA Love W Mehrabyan S Savinov V Aquines O Li Z Lopez A Mendez H Ramirez J Xin B Huang GS Miller DH Pavlunin V Sanghi B Shipsey IP Adams GS Anderson M Cummings JP Danko I Napolitano J He Q Insler J 《Physical review letters》2006,96(8):081802
Using of data collected with the CLEO-c detector, we report on first observations and measurements of Cabibbo-suppressed decays of D mesons in the following six decay modes: pi+ pi- pi0 pi0, pi+ pi+ pi- pi- pi0, pi+ pi0 pi0, pi+ pi+ pi- pi0, eta pi0, and omega pi+ pi-. Improved branching fraction measurements in eight other multipion decay modes are also presented. The measured D --> pi pi rates allow us to extract the ratio of isospin amplitudes A(DeltaI = (3/2) / A(DeltaI = (1/2)) = 0.420 +/- 0.014(stat) +/- 0.016(syst) and the strong phase shift of delta1 = (86.4 +/- 2.8 +/- 3.3) degrees, which is quite large and now more precisely determined. 相似文献
978.
The decay B(d)-->phi K(S) is a special probe of physics beyond the standard model (SM), since it has no SM tree level contribution. Motivated by recent data suggesting a deviation from the SM for its time-dependent CP asymmetry, we examine supersymmetric explanations. Chirality preserving contributions are generically small, unless gluino is relatively light. Higgs contributions are also too small to explain a large asymmetry. Chirality flipping LR and RL gluino contributions actually can provide sizable effects without conflict with all related results. We discuss how various insertions can be distinguished, and argue the needed sizes of mass insertions are reasonable. 相似文献
979.
980.
Hajjaj F Yoon ZS Yoon MC Park J Satake A Kim D Kobuke Y 《Journal of the American Chemical Society》2006,128(14):4612-4623
Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one. 相似文献