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The Butterfly Dimer [(tBu3SiO)Cr]2 (μ-OSitBu3)2 and Its Oxidative Cleavage to (tBu3SiO)2 Cr(=N-N=CPh2)2 and (tBu3SiO)2 Cr=N(2,6-Ph2-C6H3)

Description: Article discussing research on the butterfly dimer [(ᵗBu₃SiO)Cr]₂(μ-OSiᵗBu₃)₂ and its oxidative cleavage to (ᵗBu₃SiO)₂Cr(=N-N=CPh₂)₂ and (ᵗBu₃SiO)₂Cr=N(2,6-Ph₂-C₆H₃).
Date: January 12, 2006
Creator: Sydora, Orson L.; Kuiper, David S.; Wolczanski, Peter T.; Lobkovsky, Emil B.; Dinescu, Adriana & Cundari, Thomas R., 1964-
Partner: UNT College of Arts and Sciences

Synthesis and Characterization of Methylated PCU Dimers

Description: Conversion of 1-Methylpentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹]undecane- 8,11-dione into the corresponding mono(ethylene ketal) followed by Wolff-Kishner reduction resulted in a mixture of two isomers (i.e., 1- and 7-methyl-8-[2',-(1',3',dioxolano)]pentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹] undecane. Hydrolysis of each isomer in turn resulted in 1- and 7- methyl pentacyclo[5.4.0.0²⋅⁶.0³⋅¹⁰.0⁵⋅⁹ ]undecan-8-ones (i.e.,"methylated PCU-8-ones"), respectively. "Titanium-promoted reductive dimerization of each of the methylated pentacycloundecane (PCU)-8-ones afforded mixtures of "methylated PCU alkene dimers". Individual isomers have been isolated from these mixtures via column chromatography by using silver nitrate impregnated silica gel as adsorbent followed by fractional recrystallizations of individual chromatography fractions. Structures of three isomerically pure methylated PCU alkene dimers (C₂₄H₂₈) have been established unequivocally by application of single crystal X-ray crystallographic methods.
Date: August 1993
Creator: Zope, Anjali U. (Anjali Umesh)
Partner: UNT Libraries

Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one)

Description: Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.
Date: September 11, 2009
Creator: Szigethy, Geza & Raymond, Kenneth N.
Partner: UNT Libraries Government Documents Department

Cassini detection of Enceladus's cold water-group plume ionosphere

Description: This study reports direct detection by the Cassini plasma spectrometer of freshly-produced water-group ions (O{sup +}, OH{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}) and heavier water dimer ions (H{sub x}O{sub 2}{sup +}) very close to Enceladus and where the plasma begins to emerge from the Enceladus plume The data wcre obtained during two close (52 and 25 km) flybys of Enceladus in 2008, and are similar to ion data in cometary comas. The ions are observed in detectors looking in the Cassini ram direction at energies consistent with the Cassini speed, indicating a nearly stagnant plasma flow in the plume. North of Enceladus the plasma slowing commences about 4 to 6 Enceladus radii away, while south of Enccladus signatures ofthe interaction are detected as far as 22 Enceladus radii away.
Date: January 1, 2009
Creator: Tokar, Robert L; Thomsen, Michelle F; Wilson, Robert J; Johnson, R E; Young, D T; Crary, F J et al.
Partner: UNT Libraries Government Documents Department

Crossover from dimer nucleation to adatom exchange during submonolayer epitaxy

Description: The nucleation and growth of islands in the early stages of epitaxial growth is studied with kinetic Monte Carlo Simulations and self-consistent mean field rate equations. Specifically, adatom exchange and irreversible dimer formation are allowed to compete equally as the origin of two-dimensional islands. The island size distribution and number density are found to satisfy a dynamic crossover scaling form. The critical island size evolves from one to zero with increasing temperature, decreasing flux, and increasing coverage.
Date: November 1, 1995
Creator: Bales, G.S.
Partner: UNT Libraries Government Documents Department

Photophysical properties of pyrene, 2,7 diazapyrene and 1,3-bis(β-naphthyl)propane.

Description: The luminescence properties of Van Der Waals' dimers and clusters of pyrene and diazapyrene have been investigated. Excimers, dimeric species which are associative in an excited electronic state and dissociative in their ground state, have long been established and play an important role in many areas of photochemistry. My work here focuses on the luminescence and absorption properties of ground state dimers/aggregates, which are less understood, and allows further characterization of the ground state and excited state association of these aromatic molecules.
Date: August 2007
Creator: Boateng, Stephen
Partner: UNT Libraries

The effect of pi-stacking, h-bonding, and electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine, thymine-thymine and adenine-thymine dimers

Description: A combined theoretical and experimental study of the ionized dimers of thymine and adenine, TT, AA, and AT, is presented. Adiabatic and vertical ionization energies(IEs) for monomers and dimers as well as thresholds for the appearance of the protonated species are reported and analyzed. Non-covalent interactions stronglyaffect the observed IEs. The magnitude and the nature of the effect is different for different isomers of the dimers. The computations reveal that for TT, the largestchanges in vertical IEs (0.4 eV) occur in asymmetric h-bonded and symmetric pi- stacked isomers, whereas in the lowest-energy symmetric h-bonded dimer the shiftin IEs is much smaller (0.1 eV). The origin of the shift and the character of the ionized states is different in asymmetric h-bonded and symmetric stacked isomers. Inthe former, the initial hole is localized on one of the fragments, and the shift is due to the electrostatic stabilization of the positive charge of the ionized fragment by thedipole moment of the neutral fragment. In the latter, the hole is delocalized, and the change in IE is proportional to the overlap of the fragments' MOs. The shifts in AAare much smaller due to a less effcient overlap and a smaller dipole moment. The ionization of the h-bonded dimers results in barrierless (or nearly barrierless) protontransfer, whereas the pi-stacked dimers relax to structures with the hole stabilized by the delocalization or electrostatic interactions.
Date: September 2, 2009
Creator: Bravaya, Ksenia B.; Kostko, Oleg; Ahmed, Musahid & Krylov, Anna I.
Partner: UNT Libraries Government Documents Department

Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

Description: In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.
Date: May 12, 2008
Creator: Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid & Kostko, Oleg
Partner: UNT Libraries Government Documents Department

DEHYDRATION CONDENSATION IN AQUEOUS SOLUTION

Description: EARLIER investigations have demonstrated that di-cyandiamide (DCDA), the dimer of cyanamide, can successfully promote the dehydration condensation of: (1) glucose and orthophosphate to give glucose-6-phosphate; (2) adenosine and orthophosphate to give adenosine-5'-monophosphate; (3) orthophosphate to give pyrophosphate; (4) alanine to give alanylalanine and alanylalanylalanine. These reactions were carried out in dilute aqueous solutions in the dark. (It was also demonstrated that the combination of ultra-violet light and dicyandiamide could promote the synthesis of dipeptides. This observation has since been confirmed by other investigators.) These experiments were designed to demonstrate one possible means by which such compounds could have been formed on the prebiotic Earth, thus providing materials needed for the origin of living systems. Dicyandiamide itself could have been, present on the primitive Earth as was demonstrated with the ultra-violet irradiation of cyanide solution.
Date: April 1, 1965
Creator: Steinman, Gary; Kenyon, Dean H. & Calvin, Melvin
Partner: UNT Libraries Government Documents Department

Water adsorption on O(2x2)/Ru(0001) from STM experiments andfirst-principles calculations

Description: We present a combined theoretical and experimental study of water adsorption on Ru(0001) pre-covered with 0.25 monolayers (ML) of oxygen forming a (2 x 2) structure. Several structures were analyzed by means of Density Functional Theory calculations for which STM simulations were performed and compared with experimental data. Up to 0.25 monolayers the molecules bind to the exposed Ru atoms of the 2 x 2 unit cell via the lone pair orbitals. The molecular plane is almost parallel to the surface with its H atoms pointing towards the chemisorbed O atoms of the 2 x 2 unit cell forming hydrogen bonds. The existence of these additional hydrogen bonds increases the adsorption energy of the water molecule to approximately 616 meV, which is {approx}220 meV more stable than on the clean Ru(0001) surface with a similar configuration. The binding energy shows only a weak dependence on water coverage, with a shallow minimum for a row structure at 0.125 ML. This is consistent with the STM experiments that show a tendency of the molecules to form linear rows at intermediate coverage. Our calculations also suggest the possible formation of water dimers near 0.25 ML.
Date: October 15, 2007
Creator: Cabrera-Sanfelix, P.; Sanchez-Portal, D.; Mugarza, A.; Shimizu,T.K.; Salmeron, M. & Arnau, A.
Partner: UNT Libraries Government Documents Department

Collective sliding states for colloidal molecular crystals

Description: We study the driving of colloidal molecular crystals over periodic substrates such as those created with optical traps. The n-merization that occurs in the colloidal molecular crystal states produces a remarkably rich variety of distinct dynamical behaviors, including polarization effects within the pinned phase and the formation of both ordered and disordered sliding phases. Using computer simulations, we map the dynamic phase diagrams as a function of substrate strength for dimers and trimers on a triangular substrate, and correlate features on the phase diagram with transport signatures.
Date: January 1, 2008
Creator: Reichhardt, Charles & Reichhardt, Cynthia
Partner: UNT Libraries Government Documents Department

Intramolecular condensation reactions of {alpha}, {omega}- bis(triethoxy-silyl)alkanes. Formation of cyclic disilsesquioxanes

Description: Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane (1) and 1,4-bis(triethoxysilyl)butane (2) were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed withe the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to perserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.
Date: August 1, 1996
Creator: Loy, D.A.; Carpenter, J.P.; Myers, S.A.; Assink, R.A.; Small, J.H.; Greaves, J. et al.
Partner: UNT Libraries Government Documents Department

Diamond films grown from fullerene precursors

Description: Fullerene precursors have been shown to result in the growth of diamond films from argon microwave plasmas. In contradistinction to most diamond films grown using conventional methane-hydrogen mixtures, the fullerene-generated films are nanocrystalline and smooth on the nanometer scale. They have recently been shown to have friction coefficients approaching the values of natural diamond. It is clearly important to understand the development of surface morphology during film growth from fullerene precursors and to elucidate the factors leading to surface roughness when hydrogen is present in the chemical vapor deposition (CVD) gas mixtures. To achieve these goals, we are measuring surface reflectivity of diamond films growing on silicon substrates over a wide range of plasma processing conditions. A model for the interpretation of the laser interferometric data has been developed, which allows one to determine film growth rate, rms surface roughness, and bulk losses due to scattering and absorption. The rms roughness values determined by reflectivity are in good agreement with atomic force microscope (AFM) measurements. A number of techniques, including high-resolution transmission electron microscopy (HRTEM) and near-edge x-ray absorption find structure (NEXAFS) measurements, have been used to characterize the films. A mechanism for diamond-film growth involving the C{sub 2} molecule as a growth species will be presented. The mechanism is based on (1) the observation that the optical emission spectra of the fullerene- containing plasmas are dominated by the Swan bands of C{sub 2} and (2) the ability of C{sub 2} to insert directly into C-H and C-C bonds with low activation barriers, as shown by recent theoretical calculations of reactions of C{sub 2} with carbon clusters.
Date: July 1, 1995
Creator: Gruen, D.M.; Zuiker, C.D. & Krauss, A.R.
Partner: UNT Libraries Government Documents Department

Molecular dynamics simulations and thermochemistry of reactive ion etching of silicon by chlorine, chlorine dimer, bromine, and bromine dimer cations

Description: Simulations of Cl plasma etch of Si surfaces with MD techniques agree reasonably well with the available experimental information on yields and surface morphologies. This information has been supplied to a Monte Carlo etch profile resulting in substantial agreement with comparable inputs provided through controlled experiments. To the extent that more recent measurements of etch rates are more reliable than older ones, preliminary MD simulations using bond-order corrections to the atomic interactions between neighboring Si atoms on the surface improves agreement with experiment through an increase in etch rate and improved agreement with XPS measurements of surface stoichiometry. Thermochemical and geometric analysis of small Si-Br molecules is consistent with the current notions of the effects of including brominated species in etchant gases.
Date: May 8, 1998
Creator: Valone, S.M.; Hanson, D.E. & Kress, J.D.
Partner: UNT Libraries Government Documents Department

Multiphoton ionization of ions, neutrals, and clusters. Progress report

Description: Scientific results are summarized from a three year research program on multiphoton ionization in aromatic molecules, clusters, and their ions. As originally proposed, the studies elucidated a new cluster ionization mechanism, characterized properties of long range intermolecular interactions, and investigated electronic transitions of aromatic cations cooled in a supersonic beam. The studies indicate that the new cluster ionization mechanism is highly efficient and dominates conventional 1 + 1 resonant ionization. In the case of the dimer of the large aromatic molecule fluorene, the results suggest that excimer formation competes with a direct ionization process. Highly selective excitonic spectra have been identified for several cluster species.
Date: June 28, 1991
Creator: Wessel, J.
Partner: UNT Libraries Government Documents Department

Ion dip spectroscopy of cold molecules and ions. Progress report and renewal proposal

Description: A research program is underway with the objective of developing techniques of high resolution multiphoton spectroscopy for selective, ultrasensitive molecular detection. Methods under study include various forms of ion dip spectroscopy and new methods of ion fragmentation spectroscopy. The studies are providing a new understanding of the fundamental spectroscopy and photophysics of large molecular ions. Dimer and cluster ions of polynuclear aromatics and related species are also being investigated, with potential detection applications.
Date: August 13, 1987
Creator: Wessel, J.
Partner: UNT Libraries Government Documents Department

Final technical brief / DOE grant DE-FG03-96 ER 62219. Computational study of electron tunneling in proteins

Description: Electron transfer (ET) processes in proteins are characterized by the motion of a single electron between centers of localization (such as the chlorophyll dimer in photosynthetic reaction centers). An electronic donor state D is created by the injection of an electron or by photo-excitation, after which the system makes a radiationless transition to an acceptor state A., resulting in the effective transfer of an electron over several angstroms. The experimental and theoretical understanding of the rate of this process has been the focus of much attention in physics, chemistry and biology.
Date: March 3, 1999
Creator: Regan, Jeffrey J.
Partner: UNT Libraries Government Documents Department

Resonance ionization spectroscopy of molecules, clusters, and ions. Annual technical progress report

Description: High resolution photoionization and fluorescence excitation spectra of dimers of the aromatic molecule fluorene (C{sub 13}H{sub 12}){sub 2} reveal complex excitonic interactions. Comparison of results for isotopically pure and isotopically mixed dimers provide the information necessary to analyze the spectra in terms of intermolecular motion on two perturbed adiabatic potential surfaces. The intermolecular force field on the lower surface is characterized by a perturbed quartic potential, whereas the upper surface is characterized by a displaced quadratic potential. The results provide the first detailed experimental description of strong coupling between an intermolecular coordinate and the excitonic state of a molecular dimer.
Date: July 14, 1993
Creator: Wessel, J.
Partner: UNT Libraries Government Documents Department

Importance of protamine phosphorylation to histone displacement in spermatids: can the disruption of this process be used for male contraception

Description: Protamine is a small protein that packages DNA in the sperm of most vertebrates. Shortly after its synthesis, the serine and threonine residues in each protamine are phosphorylated and the modified proteins are deposited onto DNA, displacing the histones and other chromatin proteins. We have hypothesized that the phosphorylation of protamine 1 induces protamine dimerization and these dimers are required for efficient histone displacement. Histone displacement by protamines in late-step spermatids appears to be essential for the production of fertile sperm in man and other mammals, and the disruption of this process could provide a new approach for male contraception. As a first step towards testing this theory, we have initiated a set of in vitro experiments to determine whether of not protamine phosphorylation is essential for histone displacement. Thee results of these experiments, although incomplete, confirm that unphosphorylated protamine cannot effectively displace histone from DNA. Polyarginine molecules twice the size of a protamine molecule and salmine dimer were found to be more effective. These results are consistent with the theory that the disruption of protamine phosphorylation may prove to be a useful new approach for male contraception if it can be shown to facilitate or induce protamine dimerization.
Date: June 1, 1995
Creator: Balhorn, R.; Hud, N.V.; Corzett, M. & Mazrimas, J.
Partner: UNT Libraries Government Documents Department