Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, 2010 University of South Carolina - Columbia
Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal
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 substituent ...
Modeling The Noble Metal/Tio2 (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, 2010 University of South Carolina - Columbia
Modeling The Noble Metal/Tio2 (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, Salai Cheettu Ammal, Andreas Heyden
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 ...
Evaluation Of The Potential Of Raman Microspectroscopy For Prediction Of Chemotherapeutic Response To Cisplatin In Lung Adenocarcinoma, 2010 Dublin Institute of Technology
Evaluation Of The Potential Of Raman Microspectroscopy For Prediction Of Chemotherapeutic Response To Cisplatin In Lung Adenocarcinoma, Haq Nawaz, Franck Bonnier, Peter Knief, Orla Howe, Fiona Lyng, Aidan Meade, Hugh Byrne
The study of the interaction of anticancer drugs with mammalian cells in vitro is important to elucidate the mechanisms of action of the drug on its biological targets. In this context, Raman spectroscopy is a potential candidate for high throughput, noninvasive analysis. To explore this potential, the interaction of cis-Diamminedichloroplatinum (II) (Cisplatin) with a human lung adenocarcinoma cell line (A549) was investigated using Raman microspectroscopy. The results were correlated with parallel measurements from the MTT cytotoxicity assay, which yielded an IC50 value of 1.2±0.2 μM. To further confirm the spectral results, Raman spectra were also acquired from ...
Liquid Crystals For Functional Nanomaterials: Electroclinic Artificial Muscle Polymers, Nanorods From Achiral Bent-Core Mesogens, And Thiophenic Photovoltaics, 2010 University of Colorado at Boulder
Liquid Crystals For Functional Nanomaterials: Electroclinic Artificial Muscle Polymers, Nanorods From Achiral Bent-Core Mesogens, And Thiophenic Photovoltaics, Jacqueline Mae Richardson
Chemistry & Biochemistry Graduate Theses & Dissertations (1986-2018)
Three different projects are described, in which target molecules are synthesized based on specific functional goals: electromechanical response, bent-core phase formation, and charge transport behavior. The bulk properties of these materials are then characterized with respect to these goals.
The first project entails the synthesis and characterization of several variations on W317, a calamitic liquid crystal with a strong electroclinic effect. Alpha, omega-diene analogues of this molecule were synthesized and reacted via ADMET into a main-chain polymer, with the goal of creating electromechanical actuators. To improve the bulk strength and macroscopic response of the polymers, attempts were made at cross-linking ...
A Dielectric Affinity Microbiosensor, 2010 University of South Carolina - Columbia
A Dielectric Affinity Microbiosensor, X. Huang, S. Li, J. S. Schultz, Qian Wang, Q. Lin
We present an affinity biosensing approach that exploits changes in dielectric properties of a polymer due to its specific, reversible binding with an analyte. The approach is demonstrated using a microsensor comprising a pair of thin-film capacitive electrodes sandwiching a solution of poly(acrylamide-ran-3-acrylamidophenylboronic acid), a synthetic polymer with specific affinity to glucose. Binding with glucose induces changes in the permittivity of the polymer, which can be measured capacitively for specific glucose detection, as confirmed by experimental results at physiologically relevant concentrations. The dielectric affinity biosensing approach holds the potential for practical applications such as long-term continuous glucose ...
Lattice Expansion In Islands Stabilized By Electron Confinement: Ag On Si(111)-7×7, 2010 Iowa State University
Lattice Expansion In Islands Stabilized By Electron Confinement: Ag On Si(111)-7×7, Barış Ünal, Alex Belianinov, Patricia A. Thiel, Michael C. Tringides
Ag on Si(111)-7×7 was one of the first systems where height selection of metal islands was attributed to electron confinement, i.e., stabilization of selected heights through a quantum size effect (QSE). However, it has been puzzling how the requisite electron standing waves can form, because the Fermi level EF (along the growth  direction) is within the gap for bulk Ag. With detailed experiments over a wide coverage and temperature range, we show that a large increase of 12% is present in the interlayer spacing within the bilayer islands. This can shift EF below ...
Islands And Holes As Measures Of Mass Balance In Growth Of The (√3×√3)R30° Phase Of Ag On Si(111), 2010 Iowa State University
Islands And Holes As Measures Of Mass Balance In Growth Of The (√3×√3)R30° Phase Of Ag On Si(111), Alex Belianinov, Barış Ünal, Ning Lu, Min Ji, Kai-Ming Ho, Cai-Zhuang Wang, Michael C. Tringides, Patricia A. Thiel
It is well known that conversion of Si(111)-(7×7) into the (√3×√3)R30° phase of adsorbed Ag requires a change in the Si density, and causes formation of islands and holes at the surface. By mass balance, the ratio of areas of islands and holes (RIH) should be approximately 1. However, we find that the ratio is significantly higher, depending on preparation conditions. A possible explanation would be that there are different types of (√3×√3)R30° structures. However, neither scanning tunneling microscopy nor density-functional theory (implemented as a genetic algorithm search) supports this explanation. We ...
Nanoscale “Quantum” Islands On Metal Substrates: Microscopy Studies And Electronic Structure Analyses, 2010 Iowa State University
Nanoscale “Quantum” Islands On Metal Substrates: Microscopy Studies And Electronic Structure Analyses, Yong Han, Barış Ünal, Dapeng Jing, Patricia A. Thiel, James W. Evans
Confinement of electrons can occur in metal islands or in continuous films grown heteroepitaxially upon a substrate of a different metal or on a metallic alloy. Associated quantum size effects (QSE) can produce a significant height-dependence of the surface free energy for nanoscale thicknesses of up to 10–20 layers. This may suffice to induce height selection during film growth. Scanning STM analysis has revealed remarkable flat-topped or mesa-like island and film morphologies in various systems. We discuss in detail observations of QSE and associated film growth behavior for Pb/Cu(111), Ag/Fe(100), and Cu/fcc-Fe/Cu(100 ...
Periodic Step Arrays On The Aperiodic I-Al-Pd-Mn Quasicrystal Surface At High Temperature, 2010 University of California, Davis
Periodic Step Arrays On The Aperiodic I-Al-Pd-Mn Quasicrystal Surface At High Temperature, Y. Sato, Barış Ünal, Thomas A. Lograsso, Patricia A. Thiel, A. K. Schmid, T. Duden, N. C. Bartelt, K. F. Mccarty
We have observed the configuration and motion of surface steps on the aperiodic icosahedral (i-) Al-Pd-Mn quasicrystal using low-energy electron microscopy and scanning tunneling microscopy. As the quasicrystal is cooled from high temperature, bulk vacancies migrate to the surface causing the surface to be etched. Surprisingly, this etching occurs by two types of steps with different heights moving in different directions with different velocities. The steady-state surface morphology is a uniformly spaced rhomboidal step network. This network requires that the layer stacking near the surface deviates from the bulk quasicrystal stacking.
Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, 2010 University of Nevada, Las Vegas
Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, Wayne C. Stolte, Gunnar Ohrwall
Chemistry and Biochemistry Faculty Publications
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.
Crystal Structures Of The Cusa Efflux Pump Suggest Methionine-Mediated Metal Transport, 2010 Iowa State University
Crystal Structures Of The Cusa Efflux Pump Suggest Methionine-Mediated Metal Transport, Feng Long, Chih-Chia Su, Michael T. Zimmermann, Scott E. Boyken, Kanagalaghatta R. Rajashankar, Robert L. Jernigan, Edward W. Yu
Biochemistry, Biophysics and Molecular Biology Publications
Gram-negative bacteria, such as Escherichia coli, frequently utilize tripartite efflux complexes in the resistance-nodulation-cell division (RND) family to expel diverse toxic compounds from the cell.1,2 The efflux system CusCBA is responsible for extruding biocidal Cu(I) and Ag(I) ions.3,4 No prior structural information was available for the heavy-metal efflux (HME) subfamily of the RND efflux pumps. Here we describe the crystal structures of the inner membrane transporter CusA in the absence and presence of bound Cu(I) or Ag(I). These CusA structures provide important new structural information about the HME sub-family of RND efflux ...
Variation Of Growth Morphology With Chemical Composition Of Terraces: Ag On A Twofold Surface Of A Decagonal Al-Cu-Co Quasicrystal, T. Duguet, Barış Ünal, Yong Han, James W. Evans, J. Ledieu, Cynthia J. Jenks, J.-M. Dubois, V. Fournée, Patricia A. Thiel
Growth of Ag thin films on the twofold surface of a decagonal Al-Cu-Co quasicrystal is characterized by scanning tunneling microscopy, at different temperatures, and for coverages ranging from submonolayer to 11 monolayers. From prior work, three types of clean surface terraces are known to exist. By correlation with a bulk structural model, the major difference between them lies in their transition-metal (TM) content, two being aluminum-rich (0 and 15 at. % TM) and one being TM-rich (40–50 at. % TM). The present article focuses on understanding the difference between Ag film morphologies on these terminations, in terms of their chemical content ...
Formation And Coarsening Of Ag(110) Bilayer Islands On Nial(110): Stm Analysis And Atomistic Lattice-Gas Modeling, Yong Han, Barış Ünal, Dapeng Jing, Feili Qin, Cynthia J. Jenks, Da-Jiang Liu, Patricia A. Thiel, James W. Evans
Scanning tunneling microscopy analysis of the initial stages of film growth during deposition of Ag on NiAl(110) reveals facile formation of bilayer Ag(110) islands at temperatures of 130 K and above. Annealing subsequent to deposition at 130 K induces coarsening of the bilayer island distribution. The thermodynamic driving force for bilayer island formation reflects a lower relative surface energy for films of even layer thicknesses. This feature derives from quantum size effects due to electron confinement in the Ag film. The kinetics of island formation and relaxation is controlled by terrace and edge-diffusion barriers, detachment barriers, interlayer diffusion ...
Low-Temperature Adsorption Of H2s On Ag(111), 2010 Iowa State University
Low-Temperature Adsorption Of H2s On Ag(111), Selena M. Russell, Da-Jiang Liu, Maki Kawai, Yousoo Kim, Patricia A. Thiel
H2S forms a rich variety of structures on Ag(111) at low temperature and submonolayer coverage. The molecules decorate step edges, exist as isolated entities on terraces, and aggregate into clusters and islands, under various conditions. One type of island exhibits a (×)R25.3° unit cell. Typically, molecules in the clusters and islands are separated by about 0.4 nm, the same as the S–S separation in crystalline H2S. Density functional theory indicates that hydrogen-bonded clusters contain two types of molecules. One is very similar to an isolated adsorbed H2S molecule, with both ...
Adsorbate-Enhanced Transport Of Metals On Metal Surfaces: Oxygen And Sulfur On Coinage Metals, 2010 Iowa State University
Adsorbate-Enhanced Transport Of Metals On Metal Surfaces: Oxygen And Sulfur On Coinage Metals, Patricia A. Thiel, Mingmin Shen, Da-Jiang Liu, James W. Evans
Coarsening (i.e., ripening) of single-atom-high, metal homoepitaxial islands provides a useful window on the mechanism and kinetics of mass transport at metal surfaces. This article focuses on this type of coarsening on the surfaces of coinage metals (Cu, Ag, Au), both clean and with an adsorbed chalcogen (O, S) present. For the clean surfaces, three aspects are summarized: (1) the balance between the two major mechanisms—Ostwald ripening (the most commonly anticipated mechanism) and Smoluchowski ripening—and how that balance depends on island size; (2) the nature of the mass transport agents, which are metal adatoms in almost all ...
Rhombohedrally Distorted Γ-Brasses Cr1−Xfexga, 2010 Iowa State University
Rhombohedrally Distorted Γ-Brasses Cr1−Xfexga, Hyujin Ko, Olivier Gourdon, Delphine Gout, Eun-Deok Mun, Srinivasa Thimmaiah, Gordon J. Miller
A series of rhombohedrally distorted γ-brass structures containing a mixture of magnetically active 3d elements, Cr and Fe, Cr1−xFexGa, is investigated crystallographically. These structures consist of chains of trans-face-sharing Ga-centered transition metal icosahedra. Neutron powder diffraction specifically on Cr0.5Fe0.5Ga, which could be prepared as a single phase material, gave lattice constants (11 K) a = 12.5172(2) Å and c = 7.8325(2) Å and a refined composition of Cr0.502(6)Fe0.498Ga = Cr6.523Fe6.477Ga13 and revealed partial ordering ...
Quantum Trajectory Dynamics In Imaginary Time With The Momentum-Dependent Quantum Potential, 2010 University of South Carolina - Columbia
Quantum Trajectory Dynamics In Imaginary Time With The Momentum-Dependent Quantum Potential, Sophya V. Garashchuk
The quantum trajectory dynamics is extended to the wave function evolution in imaginary time. For a nodelesswave function a simple exponential form leads to the classical-like equations of motion of trajectories, representing the wave function, in the presence of the momentum-dependent quantum potential in addition to the external potential. For a Gaussian wave function this quantum potential is a time-dependent constant, generating zero quantum force yet contributing to the total energy. For anharmonic potentials the momentum-dependent quantum potential is cheaply estimated from the global Least-squares Fit to the trajectory momenta in the Taylor basis. Wave functions with nodes are described ...
Valency Dependence Of Polymorphism And Polyamorphism In Dna-Functionalized Nanoparticles, 2009 Wesleyan University
Valency Dependence Of Polymorphism And Polyamorphism In Dna-Functionalized Nanoparticles, Wei Dai, Chia Wei Hsu, Francesco Sciortino, Francis W. Starr
Nanoparticles (NP) functionalized with single-stranded DNA (ssDNA) offer a route to custom-designed, self- assembled nanomaterials with potentially unusual properties. The bonding selectivity of DNA guarantees one-to-one binding to form double-stranded DNA (dsDNA), and an appropriate base sequence results in head-to-tail binding linking NP into networks. We explore the phase behavior and structure of a model for NP functionalized with between 3 and 6 short ssDNA through simulations of a coarse-grained molecular model, allowing us to examine both the role of the number of attached strands (valency) and their relative orientations. The NP assemble into networks where the number of NP ...