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Biological and Chemical Physics Commons

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2010

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Articles 31 - 34 of 34

Full-Text Articles in Biological and Chemical Physics

Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal Jan 2010

Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal

Faculty Publications

The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1-substituted-phenyl-2-propanones and 3-substituted-phenyl-2-butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1-phenyl-2-propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the …


Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, Wayne C. Stolte, Gunnar Ohrwall Jan 2010

Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, Wayne C. Stolte, Gunnar Ohrwall

Chemistry and Biochemistry Faculty Research

We have investigated the photofragmentation properties of the three-membered ring heterocyclic molecule ethylene sulfide or thiirane, C2H4S, by time-of-flight mass spectroscopy. Positive ions have been collected as a function of photon energy around the S K ionization threshold. Branching ratios were derived for all detected ions, which are informative of the decay dynamics and photofragmentation patterns of the core-excited species. We present a new assignment of the spectral features around the S K-edge.


Dielectrophoretic Choking Phenomenon In A Converging-Diverging Microchannel, Ye Ai, Shizhi Qian, Sheng Liu, Sang W. Joo Jan 2010

Dielectrophoretic Choking Phenomenon In A Converging-Diverging Microchannel, Ye Ai, Shizhi Qian, Sheng Liu, Sang W. Joo

Mechanical & Aerospace Engineering Faculty Publications

Experiments show that particles smaller than the throat size of converging-diverging microchannels can sometimes be trapped near the throat. This critical phenomenon is associated with the negative dc dielectrophoresis arising from nonuniform electric fields in the microchannels. A finite-element model, accounting for the particle-fluid-electric field interactions, is employed to investigate the conditions for this dielectrophoretic (DEP) choking in a converging-diverging microchannel for the first time. It is shown quantitatively that the DEP choking occurs for high nonuniformity of electric fields, high ratio of particle size to throat size, and high ratio of particle's zeta potential to that of microchannel. © …


Modeling The Noble Metal/Tio2 (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, Salai Cheettu Ammal, Andreas Heyden Jan 2010

Modeling The Noble Metal/Tio2 (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, Salai Cheettu Ammal, Andreas Heyden

Faculty Publications

The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing …