Physical Sciences and Mathematics | Open Access Articles

Tetrakis(N-Ethyl-9-Oxo-4-Azonia-5-Aza-9h-Fluorene) Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate, Meredith A. Tershany, Andrea M. Goforth, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

The new iodobismuthate compound (C₁₃H₁₁N₂O)₄[Bi₆I₂₂] has been synthesized solvothermally by reacting BiI₃, Zn(NO₃)₂·6H₂O and 4,5-diazafluoren-9-one in a water/ethanol solvent mixture. The asymmetric unit of the compound contains two independent [N-ethyl-4,5-dafo]⁺ cations and one-half of a centrosymmetric [Bi₆I₂₂]^4- anion. The average terminal Bi-I, Bi-₂-I and Bi-₃-I bond lengths in the anion are 2.8923 (2), 3.1403 (2) and 3.3022 (2) Å, respectively.

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Periodic Boundary Condition Induced Breakdown Of The Equipartition Principle And Other Kinetic Effects Of Finite Sample Size In Classical Hard-Sphere Molecular Dynamics Simulation, Randall B. Shirts, Scott R. Burt, Aaron M. Johnson

Faculty Publications

We examine consequences of the non-Boltzmann nature of probability distributions for one-particle kinetic energy, momentum, and velocity for finite systems of classical hard spheres with constant total energy and nonidentical masses. By comparing two cases, reflecting walls (NVE or microcanonical ensemble) and periodic boundaries (NVEPG or molecular dynamics ensemble), we describe three consequences of the center-of-mass constraint in periodic boundary conditions: the equipartition theorem no longer holds for unequal masses, the ratio of the average relative velocity to the average velocity is increased by a factor of [N/(N–1)]^1/2, and the ratio of average collision energy to average kinetic energy is …

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Absorption Properties Of A Porous Organic Crystalline Apohost Formed By A Self-Assembled Bis-Urea Macrocycle, Mahender B. Dewal, Michael W. Lufaso, Andrew D. Hughes, Stevan A. Samuel, Perry J. Pellechia, Linda S. Shimizu

Faculty Publications

We report herein the characterization and binding properties of a microporous crystalline host formed by the self assembly of a bis-urea macrocycle 1. Bis-urea macrocycle 1 has been designed to crystallize into stacked hollow columns. The self-assembly process is guided primarily by hydrogen bonding and aromatic stacking interactions that yield crystals of filled host 1âacetic acid (AcOH). The AcOH guests are bound in the cylindrical cavities of the crystal. The guest AcOH can be removed by heating to form a stable crystalline apohost 1. Apohost 1 displays a type I gas adsorption isotherm with CO₂ that is consistent with …

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Introduction: Self-Organization In Nonequilibrium Chemical Systems, Irving R. Epstein, John A. Pojman, Oliver Steinbock

Faculty Publications

The field of self-organization in nonequilibrium chemical systems comprises the study of dynamical phenomena in chemically reacting systems far from equilibrium. Systematic exploration of this area began with investigations of the temporal behavior of the Belousov-Zhabotinsky oscillating reaction, discovered accidentally in the former Soviet Union in the 1950s. The field soon advanced into chemical waves in excitable media and propagating fronts. With the systematic design of oscillating reactions in the 1980s and the discovery of Turing patterns in the 1990s, the scope of these studies expanded dramatically. The articles in this Focus Issue provide an overview of the development and …

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Tetrakis[2-(2-Pyridyl)Pyridinium] Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate And Bis[Tris(2,2'-Bipyridine)Ruthenium(Ii)] Di-Μ4-Iodo-Octa-Μ2-Iodo-Dodecaiodohexabismuthate, Andrea M. Goforth, Meredith A. Tershansy, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2'-bipyridine and bismuth triiodide as starting materials. Tetrakis[2-(2-pyridyl)pyridinium] tetra-₃-iodo-hexa-₂-iodo-dodecaiodohexabismuthate, (C₁₀H₉N₂)₄[Bi₆I₂₂], crystallizes in the triclinic space group P and is the major reaction product. The asymmetric unit of this compound consists of half a centrosymmetric [Bi₆I₂₂]^4- anion and two independent 2,2'-bipyridinium cations. The minor product of the reaction is bis[tris(2,2'-bipyridine)ruthenium(II)] di-₄-iodo-octa-₂-iodo-dodecaiodohexabismuthate, [Ru(C₁₀H₈N₂)₃] …

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The Effect Of Protein Dielectric Coefficient On The Ionic Selectivity Of A Calcium Channel, Douglas Henderson, Dezso Boda, Monika Valisko, Bob Eisenberg, Wolfgang Nonner, Dirk Gillespie

Faculty Publications

Calcium-selective ion channels are known to have carboxylate-rich selectivity filters, a common motif that is primarily responsible for their high Ca2+ affinity. Different Ca2+ affinities ranging from micromolar (the L-type Ca channel) to millimolar (the ryanodine receptor channel) are closely related to the different physiological functions of these channels. To understand the physical mechanism for this range of affinities given similar amino acids in their selectivity filters, we use grand canonical Monte Carlo simulations to assess the binding of monovalent and divalent ions in the selectivity filter of a model Ca channel. We use a reduced model where the electrolyte …

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Semiclassical Nonadiabatic Dynamics Based On Quantum Trajectories For The O(3P,1D)+H2 System, Sophya Garashchuk, Vitaly A. Rassolov, George C. Schatz

Faculty Publications

The O(³P,¹D)+H₂→OH+H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions …

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Energy Storage In Cold Non-Elastic Deformation Of Glassy Polymers, E.F. Oleinik, S.N. Rudnev, O.B. Salamatina, S.V. Shenogin, M.I. Kotelyanskii, T.V. Paramzina, S.I. Nazarenko

Faculty Publications

Experimental results on work W(epsilon), heat Q(epsilon) and stored energy U(epsilon) of deformation for glassy polymers such as linear PS, PC, PMMA, Polyimid, amorphous PET, thermotropic aromatic polyesters, Vectra T for example, crosslinked epoxy are presented. All the data was obtained by a deformation calorimetry technique. Loading and unloading of samples were performed at room temperature with strain rate epsilon = 10(-2) - 10(-4) sec(-1) under uniaxial compression up to engineering strains of epsilon(def) = 40-50%. During straining all polymers accumulate an excess of the latent energy U( e). Elastic fraction of the energy is released completely at sample unloading …

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Mechanisms Imposing The Vbeta Bias Of V14a Natural Killer T Cells And Consequences For Microbial Glycolipid Recognition, Paul B. Savage, Dasten G. Wei, Shane A. Curran, Luc Teyton, Albert Bendelac

Faculty Publications

Mouse and human natural killer T (NKT) cells recognize a restricted set of glycosphingolipids presented by CD1d molecules, including self iGb3 and microbial alpha-glycuronosylceramides. The importance of the canonical Valpha 14-Jalpha18 TCR alphachain for antigen recognition by NKT cells is well recognized, but the mechanisms underlying the Vbeta8, Vbeta7, and Vbeta2 bias in mouse have not been explored. To study the influences of thymic selection and the constraints of pairing with Valpha 14-Jalpha 18, we have created a population of mature T cells expressing Valpha 14-Jalpha 18 TCRalpha chain in CD1d-deficient mice and studied its recognition properties in vitro and …

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Peroxyl Radical Clocks, Bill Roschek, Keri A. Tallman, Christopher L. Rector, Jason G. Gillmore, Derek A. Pratt, Carlo Punta, Ned A. Porter

Faculty Publications

A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for reaction with peroxyl radicals (kH-tocopherol = 3.5 × 106 M-1 s-1, kH-linoleate = 62 M-1 s-1). This peroxyl radical clock methodology has been successfully applied to determine inhibition and propagation rate constants ranging from 100 to 107 M-1 s-1.

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Erratum: "Hard Sphere Radial Distribution Function Again", Andrij Trokhymchuk, Douglas Henderson, Ivo Nezbeda, Jan Jirsak

Faculty Publications

Some misprints have been found for parameters given by Eqs. 29 and 30 and the relevant equations in the Appendix.

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The Structure Of Β-Carbonic Anhydrase From The Carboxysomal Shell Reveals A Distinct Subclass With One Active Site For The Price Of Two, Michael R. Sawaya, Gordon C. Cannon, Sabine Heinhorst, Shiho Tanaka, Eric B. Williams, Todd O. Yeates, Cheryl A. Kerfeld

Faculty Publications

CsoSCA (formerly CsoS3) is a bacterial carbonic anhydrase localized in the shell of a cellular microcompartment called the carboxysome, where it converts HCO^-₃ to CO₂ for use in carbon fixation by ribulose-bisphosphate carboxylase/oxygenase (RuBisCO). CsoSCA lacks significant sequence similarity to any of the four known classes of carbonic anhydrase (α, β, γ, or δ), and so it was initially classified as belonging to a new class, ϵ. The crystal structure of CsoSCA from Halothiobacillus neapolitanus reveals that it is actually a representative member of a new subclass of β-carbonic anhydrases, distinguished by a lack of active site …

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Structure And Vibrational Spectra Of Mononitrated Benzo [A] Pyrenes., Kefa Karimu Onchoke, Christopher M. Hadad, Prabir K. Dutta

Faculty Publications

The molecules benzo[a]pyrene (BaP) and 1-, 3-, and 6-nitrobenzo[a]pyrene (1-NBaP, 3-NBaP, 6-NBaP) are currently of significant interest due to their presence in respirable combustion exhaust particulates and their mutagenic and carcinogenic properties. Structure−function correlations as well as spectroscopic signatures for trace analysis are necessary for these benzo[a]pyrene derivatives. In this paper, detailed infrared and Raman spectroscopic data of BaP and its three mononitrated isomers are provided for the first time. By utilizing density functional theory (DFT, B3LYP method with 6-311+G** basis set), the molecular geometries and the vibrational spectra are calculated. Good agreement is …

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Full-Text Articles in Physical Sciences and Mathematics

Tetrakis(N-Ethyl-9-Oxo-4-Azonia-5-Aza-9h-Fluorene) Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate, Meredith A. Tershany, Andrea M. Goforth, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

Periodic Boundary Condition Induced Breakdown Of The Equipartition Principle And Other Kinetic Effects Of Finite Sample Size In Classical Hard-Sphere Molecular Dynamics Simulation, Randall B. Shirts, Scott R. Burt, Aaron M. Johnson

Faculty Publications

Absorption Properties Of A Porous Organic Crystalline Apohost Formed By A Self-Assembled Bis-Urea Macrocycle, Mahender B. Dewal, Michael W. Lufaso, Andrew D. Hughes, Stevan A. Samuel, Perry J. Pellechia, Linda S. Shimizu

Faculty Publications

Introduction: Self-Organization In Nonequilibrium Chemical Systems, Irving R. Epstein, John A. Pojman, Oliver Steinbock

Faculty Publications

Tetrakis[2-(2-Pyridyl)Pyridinium] Tetra-Μ3-Iodo-Hexa-Μ2-Iodo-Dodecaiodohexabismuthate And Bis[Tris(2,2'-Bipyridine)Ruthenium(Ii)] Di-Μ4-Iodo-Octa-Μ2-Iodo-Dodecaiodohexabismuthate, Andrea M. Goforth, Meredith A. Tershansy, Mark D. Smith, Leroy Peterson Jr., Hans-Conrad Zur Loye

Faculty Publications

The Effect Of Protein Dielectric Coefficient On The Ionic Selectivity Of A Calcium Channel, Douglas Henderson, Dezso Boda, Monika Valisko, Bob Eisenberg, Wolfgang Nonner, Dirk Gillespie

Faculty Publications

Semiclassical Nonadiabatic Dynamics Based On Quantum Trajectories For The O(3P,1D)+H2 System, Sophya Garashchuk, Vitaly A. Rassolov, George C. Schatz

Faculty Publications

Energy Storage In Cold Non-Elastic Deformation Of Glassy Polymers, E.F. Oleinik, S.N. Rudnev, O.B. Salamatina, S.V. Shenogin, M.I. Kotelyanskii, T.V. Paramzina, S.I. Nazarenko

Faculty Publications

Mechanisms Imposing The Vbeta Bias Of V14a Natural Killer T Cells And Consequences For Microbial Glycolipid Recognition, Paul B. Savage, Dasten G. Wei, Shane A. Curran, Luc Teyton, Albert Bendelac

Faculty Publications

Peroxyl Radical Clocks, Bill Roschek, Keri A. Tallman, Christopher L. Rector, Jason G. Gillmore, Derek A. Pratt, Carlo Punta, Ned A. Porter

Faculty Publications

Erratum: "Hard Sphere Radial Distribution Function Again", Andrij Trokhymchuk, Douglas Henderson, Ivo Nezbeda, Jan Jirsak

Faculty Publications

The Structure Of Β-Carbonic Anhydrase From The Carboxysomal Shell Reveals A Distinct Subclass With One Active Site For The Price Of Two, Michael R. Sawaya, Gordon C. Cannon, Sabine Heinhorst, Shiho Tanaka, Eric B. Williams, Todd O. Yeates, Cheryl A. Kerfeld

Faculty Publications

Structure And Vibrational Spectra Of Mononitrated Benzo [A] Pyrenes., Kefa Karimu Onchoke, Christopher M. Hadad, Prabir K. Dutta

Faculty Publications