Chemistry Commons^™

Alternative Assay Techniques For Protein Kinase A, Justin Brink

Honors Capstones

Capstone submitted as a graduation requirement for the BSU Honors Program.

Stereoselective Allylation Of Chiral Monoperoxyacetals, Aqeel Ahmed, Patrick Dussault

Patrick Dussault Publications

Neighboring iodo-, alkoxy-, acetoxy- and silyl groups impart useful levels of diastereoselection in the Lewis acid-mediated allylation of monoperoxyacetals. Although monoperoxyacetals are found to be considerably less reactive than corresponding nonperoxidic acetals, similar stereochemical trends are observed in the two series.

Guest-Host Chemistry Of P-Sulfonatocalix[6]Arene And Nizatidine, Galia Debelouchina

Honors Theses

This work investigates the guest-host chemistry in water of p-sulfonatocalix[6]arene and a number of guests related to the amino acids arginine and lysine. Two questions are particularly important: what are the interactions that drive guest-host binding and what is the role of the solvent. The answers to these questions are investigated with isothermal titration calorimetry (lTC), which gives K, ?H, and ?S, and pressure perturbation calorimetry (PPC), which allows the calculation of the thermal coefficient of expansion ? and relating it to a molecule's structure-breaking or structure-making properties. The ITC data suggests that hydrogen bonding and charge-charge interactions are the …

Determination Of The Cyanide Metabolite 2-Aminothiazoline-4-Carboxylic Acid In Urine And Plasma By Gas Chromatography–Mass Spectrometry, Brian A. Logue, Nicholas P. Kirschten, Ilona Petrikovics, Matthew A, Moser, Gary A. Rockwood, Steven I. Baskin

Chemistry and Biochemistry Faculty Publications

The cyanide metabolite 2-aminothiazoline-4-carboxylic acid (ATCA) is a promising biomarker for cyanide exposure because of its stability and the limitations of direct determination of cyanide and more abundant cyanide metabolites. A simple, sensitive, and specific method based on derivatization and subsequent gas chromatography–mass spectrometry (GC–MS) analysis was developed for the identification and quantification of ATCA in synthetic urine and swine plasma. The urine and plasma samples were spiked with an internal standard (ATCA-d2), diluted, and acidified. The resulting solution was subjected to solid phase extraction on a mixed-mode cation exchange column. After elution and evaporation of the solvent, a silylating …

Dispiro-1,2,4-Trioxane Analogues Of A Prototype Dispiro-1,2,4-Trioxolane: Mechanistic Comparators For Artemisinin In The Context Of Reaction Pathways With Iron(Ii), Yuanqing Tang, Yuxiang Dong, Xiaofang Wang, Kamaraj Sriraghavan, James K. Wood, Jonathan L. Vennerstrom

Chemistry Faculty Publications

Single electron reduction of the 1,2,4-trioxane heterocycle of artemisinin (1) forms primary and secondary carbon-centered radicals. The complex structure of 1 does not lend itself to a satisfactory dissection of the electronic and steric effects that influence the formation and subsequent reaction of these carbon-centered free radicals. To help demarcate these effects, we characterized the reactions of achiral dispiro-1,2,4-trioxolane 4 and dispiro-1,2,4-trioxanes 5−7 with ferrous bromide and 4-oxo-TEMPO. Our results suggest a small preference for attack of Fe(II) on the nonketal peroxide oxygen atom of 1. For 4, but not for 5 and 6 …

Determination Of Atrazine And Selected Respective Metabolites Using Strong Cation Exchange Resins, Cierra Cross

Masters Theses & Specialist Projects

A new solid phase extraction procedure (SPE) for the removal of atrazine and three respective metabolites including deisopropylatrazine, desethylatrazine, and didealkylatrazine from aqueous samples is presented. Octadecyl bonded silica (C18) is widely used in analytical preconcentration schemes. While C18 presents a facile method of analyte removal, a new approach is needed to achieve greater trapping for polar analytes. In this study strong cationic exchange (SCX) resins consisting of sulfonated polystyrene are investigated for their extraction capabilities of the selected analytes. By exploiting acid-base and pi-pi interactions the analytes are trapped and therefore extracted from aqueous samples. Salt solutions are used …

Hinge-Like Motions In Rna Kink-Turns: The Role Of The Second A-Minor Motif And Nominally Unpaired Bases, Neocles B. Leontis, Filip Rázga, Jaroslav Koča, Jiří Šponer

Chemistry Faculty Publications

Kink-turn (K-turn) motifs are asymmetric internal loops found at conserved positions in diverse RNAs, with sharp bends in phosphodiester backbones producing V-shaped structures. Explicit-solvent molecular dynamics simulations were carried out for three K-turns from 23S rRNA, i. e., Kt-38 located at the base of the A-site. nger, Kt-42 located at the base of the L7/L12 stalk, and Kt-58 located in domain III, and for the K-turn of human U4 snRNA. The simulations reveal hinge-like K-turn motions on the nanosecond timescale. The first conserved A-minor interaction between the K-turn stems is entirely stable in all simulations. The angle between the helical …

Orientation Of Single Crystals Using Linear Approximations To Nmr Transits, Young-Sik Kye, Xingang Zhao, Gerard S. Harbison

Gerard S. Harbison Publications

We have derived analytical expressions for determining the orientation of high-symmetry single crystals from line-crossings in a single rotation plot. We demonstrate the utility of the method using the strontium-87 resonance in strontium nitrate. Employing our new method, which we call orientation of single crystals using linear approximations to NMR transits (OSCULANT), in combination with fourth-order perturbation theory, we obtain a highly accurate value for the quadrupole coupling constant, and an estimate for the chemical shielding anisotropy.

The Synthesis Of Biomimetic Tungsten And Molybdenum Complexes, John Sterling Cole Iii

Honors Theses

The synthesis of novel biomimetic molybdenum and tungsten compounds that are potential model complexes for molybdenum and tungsten oxidase enzymes is being pursued. Model complexes such as these provide a better understanding of the basic chemistry of a metal center in an environment similar to that found in particular enzyme active sites. This understanding provides a good starting point for biologists or biochemists studying those biological systems. The first target complex will incorporate a tetradentate-S4 ligand (L) that features two biphenyl-S2 fragments joined by a propyl linker. The second target complex will incorporate a bidentate ligand (L') with a singly …

Synthesis Of Novel Alkaline Earth Metal Acetylides, Eva Baker

Renée Crown University Honors Thesis Projects - All

Acetylide complexes of the heavy alkaline-earth metals were first introduced by our group. With our group being interested in how the ligand and donor affect the structural chemistry of the resulting complexes, my project was focused on the detailed analysis of past work and the extension towards new ligand and donor sets. The work required the analysis and development of synthetic procedures towards these highly reactive species.

Past synthetic work in our group had established several synthetic routes towards the target compounds including transamination and toluene elimination. Using toluene elimination, I was able to reproduce the synthesis of M(C≡CSiPh_{3 …}

Eluent Component Adsorption Properties And Chromatographic Behavior Of Reversed Phase Adsorbents With Phenyl Functionalities In Reversed Liquid Chromatography, Fred S. Chan

Seton Hall University Dissertations and Theses (ETDs)

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Synthesis, Structural Studies And Desilylation Reactions Of Some N-2-(Trimethylsilyl)Ethyl-N-Nitrosocarbamates, Arpitha Thakkalapally, Vladimir Benin

Chemistry Faculty Publications

The present report describes the preparation and characterization of several N-2-(trimethylsilyl)ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an s-E orientation at the N–N bond. DFT calculations (B3LYP/6-31+G(d)) reproduce accurately the structural features of the title compounds and detailed conformational analysis at the same level of theory addresses the long-standing issue of preferred geometries for three classes of related structures: N-nitrosocarbamates, N-nitrosoureas and N-nitrosoamides. Desilylation studies demonstrate that both the …

Preparation, Structural Characterization, And Dynamic Properties Investigation Of Permalloy Antidot Arrays, Scott Whittenburg, Charles J. O'Connor

Chemistry Faculty Publications

Regular nanosized structures are considered to be promising materials for magnetic information storage media with high density of information. Recently attention was paid to static and dynamic magnetic properties arising from dimensional confinement in such nanostructures. Here we present an investigation of permalloy antidot arrays of different thicknesses. Thin permalloy films of thickness ranging from 10 to 500 nm were deposited on anoporous Al2O3 membranes with a pore size of 100 nm. It was found that additional ferromagnetic resonance peaks appear for film thicknesses below 100 nm, while films with larger thicknesses show resonance properties similar to continuous films. A …

Aldol Reactions: E-Enolates And Anti-Selectivity, Matthew Grant Anderson

All Graduate Plan B and other Reports, Spring 1920 to Spring 2023

A common structural motif in complicated natural product molecules is an alkyl group at an alpha position to a carbonyl and an alcohol at the beta position anti to each other. This arrangement occurs in bioactive molecules that are important for medical research such as spongistatin A at the C15-C16 position and in (-)-baconipyrone C at C12-C13. Bioactive molecules such as these generally occur in such a low concentration in the organism in which they originate that deriving them from the natural source for research is not practical so efficient syntheses are sought. Reactions that produce 1,2 syn aldol products …

Microwave Reflectometry As A Novel Diagnostic Method For Detection Of Skin Cancers, Kundan Chand, Pratik Mehta, Daryl G. Beetner, R. Zoughi, William V. Stoecker

Electrical and Computer Engineering Faculty Research & Creative Works

More than one million people are diagnosed with skin cancer each year in the United States and more than ten thousand people die from the disease. Currently, there are some methods for early detection of skin cancers, like visual inspection, but improvements are needed. This paper presents a method involving microwave reflectometry as a diagnostic tool for detection of skin cancers. The results of measurements and simulations for normal and wet skin have been shown to distinguish among skin samples with different properties. Microwave measurements from lesions have also been presented which are used to distinguish between cancerous and benign …

Inside Unlv, Erin O'Donnell, Diane Russell, Carol C. Harter

Inside UNLV

No abstract provided.

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix: Neutronic Evaluation Of Zro2-Mgo Inert Fuels, E. Fridman, S. Kolesnikov, E. Shwageraus, A. Galperin

Fuels Campaign (TRP)

This report presents the results of the Task 4, defined in working program as: evaluation of reactivity feedback coefficients. Three main parameters of the Fertile-Free Fuel (FFF) lattices were evaluated: Moderator Temperature Coefficient (MTC), Fuel Temperature Coefficient due to Doppler Effect (DC), and soluble Boron reactivity worth (BW).

One of the major design challenges associated with utilization of FFF is deterioration of the temperature coefficients and control materials reactivity worth caused by high thermal cross-section of Pu and consequent hardening of the neutron spectrum. The purpose of the investigation reported in this section is to estimate the potential of addition …

Biomolecule Detection Via Target Mediated Nanoparticle Aggregation And Dielectrophoretic Impedance Measurement, Philip J. Costanzo, Enzhu Liang, Timothy E. Patten, Scott D. Collins, Rosemary L. Smith

Chemistry and Biochemistry

A new biosensing system is described that is based on the aggregation of nanoparticles by a target biological molecule and dielectrophoretic impedance measurement of these aggregates. The aggregation process was verified within a microchannel via fluorescence microscopy, demonstrating that this process can be used in a real time sensor application. Positive dielectrophoresis is employed to capture the nanoparticle aggregates at the edge of thin film electrodes, where their presence is detected either by optical imaging via fluorescence microscopy or by measuring the change in electrical impedance between adjacent electrodes. The electrical detection mechanism demonstrates the potential for this method as …

Search For Global Minimum Geometries For Medium Sized Germanium Clusters: Ge12–Ge20, Satya S. Bulusu, S. Yoo, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We have performed an unbiased search for the global minimum geometries of small-to-medium sized germanium clusters Ge_n (12≤n≤18) as well as a biased search (using seeding method) for Ge_n (17≤n≤20). We employed the basin-hopping algorithm coupled with the plane-wave pseudopotential density functional calculations. For each size, we started the unbiased search with using several structurally very different initial clusters, or we started the biased search with three different seeds. Irrespective of the initial structures of clusters we found that the obtained lowest-energy clusters of the size n=12–16 and 18 are the same. Among …

Bimetallic Pt-Ag And Pd-Ag Nanoparticles, Frank D. Blum, Akira Tokuhiro, Massimo F. Bertino, Carmen M. Doudna

Chemistry Faculty Research & Creative Works

We report studies of bimetallic nanoparticles with 15%-16% atomic crystal parameters size mismatch. The degree of alloying was probed in a 2-nm Pt core (smallest attainable core size) of Pt-Ag nanoparticles (completely immiscible in bulk) and 20-nm-diameter Pd-Ag nanowires (completely miscible in bulk). Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical (nanowire) morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report January-March 2005, Spencer M. Steinberg

Separations Campaign (TRP)

We have continued experiments on the reaction of iodate with sphagnum peat moss. We have established that iodate added to a suspension of peat moss undergoes reduction and to a significant extent is incorporated in to the peat moss. We have confirmed the incorporation of iodine into the peat matrix using pyrolysis GC/MS. In addition, we have performed a scaled up pyrolysis using the preparative GC system that was described in a previous report. This instrument consisted of a packed column gas chromatograph (SRI 8010) with a TCD detector and injector valve equipped with a thermal desorber. Pyrolysis experiments were …

An Introduction To The Use Of Fillers And Nanocomposites In Fire Retardancy, Charles A. Wilkie

Chemistry Faculty Research and Publications

No abstract provided.

Fire Retardancy Of Polystyrene - Hectorite Nanocomposites, Dongyan Wang, Bok Nam Jang, Shengpei Su, Jinguo Zhang, Xiaoxia Zheng, Grace Chigwada, David D. Jiang, Charles A. Wilkie

Chemistry Faculty Research and Publications

No abstract provided.

The Elastic Constants And Related Properties Of Β-Hmx Determined By Brillouin Scattering, Lewis L. Stevens, Craig J. Eckhardt

Craig J. Eckhardt Publications

By scattering from a variety of acoustic phonons, a complete stiffness tensor has been determined for crystalline β-HMX. The results are compared with recent experimental and theoretical determinations of the elastic constants and bulk modulus. Reasons for disagreement are discussed in terms of experimental limitations and anharmonic effects. The observed ordering of stiffness constants, C₁₁ (18.4 GPa), C₂₂ (14.4 GPa), and C₃₃ (12.4 GPa), is qualitatively associated with physical phenomena including cleavage planes, patterns in crystal growth, and molecular packing. This interpretation is further corroborated by the linear compressibilities plotted in three crystallographic planes. The Voigt–Reuss–Hill bulk …

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2-3 Forensics Project Gives Students Real Life Experience in Analytical Chemistry; 2005 Chemistry and Biochemistry Graduates

Page 4-5 Treasure Hunting at the South Pole

Page 6 Floyd Melrose Retires After 40 Years with Department

Page 7 Alumni News; Scholarship and Award Winners

Page 8 Department News; Recent Faculty Publications

11-(2,2-Dimethylpropyl)-12-{2-[12-(2,2-Dimethylpropyl)- 9,10-Dihydro-9,10-Ethenoanthracen-11-Yl]- Ethyl}-9,10-Dihydro-9,10-Ethenoanthracene, Joseph P. Herres, Mark A. Forman, Kraig A. Wheeler, Glenn P.A. Yap

Faculty Research and Creative Activity

Reaction of tert-butyllithium with 11,12-dimethylene-9,10- dihydro-9,10-ethanoanthracene and 4,5-diiodopentacyclo- [4.3.0.02,4.03,8.05,7]nonane gives three products, one of which crystallizes from petroleum ether as the title compound, C44H46, (I). Molecules of (I) are positioned on inversion centers (Z0 = 0.5) in the space group P21/n and lack any discernible intermolecular interactions.

Aerosol Properties And Chemical Apportionment Of Aerosol Optical Depth At Locations Off The U.S. East Coast In July And August 2001, Brian I. Magi, Peter V. Hobbs, Thomas W. Kirchstetter, Tihomir Novakov, Dean A. Hegg, Song Gao, Jens Redemann, Beat Schmid

Chemistry and Physics Faculty Articles

Airborne in situ measurements of vertical profiles of the aerosol light scattering coefficient, light absorption coefficient, and single scattering albedo (ω₀) are presented for locations off the East Coast of the United States in July–August 2001. The profiles were obtained in relatively clean air, dominated by airflows that had passed over Canada and the Atlantic Ocean. Comparisons of aerosol optical depths (AODs) at 550 nm derived from airborne in situ and sun-photometer measurements agree, on average, to within 0.034 ± 0.021. A frequency distribution of ω₀ measured in the atmospheric boundary layer off the coast yields …

Double-Stranded Rna-Dependent Protein Kinase (Pkr) Is Downregulated By Phorbol Ester, Yan Zhou, Barbara I. Chase, Mark Whitmore, Bryan R.G. Williams, Aimin Zhou

Chemistry Faculty Publications

The double-stranded RNA-dependent protein kinase (PKR) is one of the key mediators of interferon (IFN) action against certain viruses. PKR also plays an important role in signal transduction and immunomodulation. Understanding the regulation of PKR activity is important for the use of PKR as a tool to discover and develop novel therapeutics for viral infections, cancer and immune dysfunction. We found that phorbol 12-myristate 13-acetate (PMA), a potent activator of protein kinase C (PKC), decreased the level of autophosphorylated PKR in a dose- and time-dependent manner in IFN-treated mouse fibroblast cells. Polyinosinic–polycytidylic acid (poly I:C) treatment enhanced the activity of …

How To Choose One-Dimensional Basis Functions So That A Very Efficient Multidimensional Basis May Be Extracted From A Direct Product Of The One-Dimensional Functions: Energy Levels Of Coupled Systems With As Many As 16 Coordinates, Richard Dawes, Tucker Carrington Jr.

Chemistry Faculty Research & Creative Works

In this paper we propose a scheme for choosing basis functions for quantum dynamics calculations. Direct product bases are frequently used. The number of direct product functions required to converge a spectrum, compute a rate constant, etc., is so large that direct product calculations are impossible for molecules or reacting systems with more than four atoms. It is common to extract a smaller working basis from a huge direct product basis by removing some of the product functions. We advocate a build and prune strategy of this type. the one-dimensional (1D) functions from which we build the direct product basis …

Strongly Decoupled Europium And Iron Vibrational Modes In Filled Skutterudites, Gary J. Long, Raphäel P. Hermann, Fernande Grandjean, Ercan E. Alp, Wolfgang Sturhahn, Charles E. Johnson, Dennis E. Brown, Olaf Leupold, Rudolf Rüffer

Chemistry Faculty Research & Creative Works

The europium partial vibrational density of states (DOS) in EuFe₄Sb₁₂ and the iron partial vibrational DOS in both EuFe₄Sb₁₂ and Ce⁵⁷Fe₄Sb₁₂ have been obtained by nuclear inelastic scattering. The results reveal the strong independence of the iron and rare-earth vibrational modes. The cage filling europium only participates significantly to the low-energy local vibrational modes. The force constants have been obtained from the measured probability of nuclear absorption. The energies of the peaks in the europium and iron DOS are in excellent agreement with the calculated DOS in LaFe_{4 …}