Digital Commons Network^™

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 …

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 …

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.

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 …

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 …

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

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 …

Synthetic And Structural Studies Of Novel 1, 10-Phenanthroline Derivatives, Eunjoo Kim

Masters Theses

Asymmetric catalysis can provide a general approach to the preparation of enantiomerically enriched compounds in organic synthesis. Very often these asymmetric catalysts consist of a chiral ligand-metal complex. Because of the growing demand to develop enantioselective reactions in organic chemistry one focus of this area of research is the design and characterization of new chiral ligands for asymmetric synthesis.

The focus of my research is in the design, synthesis, and characterization of novel 1, 10-phenanthroline derivatives that could be used as chiral ligands in enantioselective reactions. Central to these studies have been the effect of substituents on the B-ring of …

Rhizopine Synthesis – Potential Mediators For Nitrogen Fixation In Legume Plants, Venkat Reddy Guduru

Masters Theses

This research project focused on novel and efficient synthetic approaches of inosamine derivatives (rhizopines). The preparation of specific rhizopines would help elucidate the microbial pathway of rhizopine catabolism and degradation, and determine the role of corresponding genes during nitrogen fixation. We have investigated regio - and stereoselective transformations of myo-inositol derivative 28 utilizing an organostannane as key intermediate towards rhizopine 1a. The synthesis involved several protection and deprotection strategies to control competing reactivities of six hydroxyl groups of myo-inositol. Rhizopine 1a was prepared efficiently as a single isomer in 8 steps and 13% yield by controlling reactions …

Effect Of Antioxidants On Cadmium Induced Oxidative Stress And Signal Transduction, Deepti Goel

Masters Theses

A study was done to establish if reactive oxygen species (ROS) participate in the signal transduction pathway through which cadmium induces gene transcription. Cadmium has become a concern in the health care community in the past few years as evidence suggests that cadmium can induce the development of tumors, influence cell signaling and cause damage to organs, tissue, cells and DNA. The mechanism by which cadmium exerts its action on cellular processes or induces toxicity is however unclear although there is evidence to suggest that ROS play a role. Our laboratory is interested in understanding the mechanisms of differentially regulated …

Copper Exchange Studies Between The First And Fourth N-Terminal Metal-Binding Domains Of Wilson Disease Atpase, Jennifer Bunce

Masters Theses

The human copper-transporting ATPase Wilson's disease protein was one of the first proteins shown to be actively involved in cellular copper homeostasis. The protein includes six N-terminal metal binding domains. The individual capabilities of the domains to bind and transfer copper are not yet fully understood. Each metal-binding domain is about 72 amino acid residues long and contains the conserved binding motif GMTCXXC, of which the cysteines are involved in the copper coordination. Studies have shown that the protein binds six copper atoms suggesting the potential involvement of each metal-binding domain. Separate functional roles for the latter domains have been …

The Armstrong Chemical Bond, Armstrong Atlantic State University

Chemical Bond Newsletter (Archived)

No abstract provided.

26Al-Containing Acidic And Basic Sodium Aluminum Phosphate Preparation And Use In Studies Of Oral Aluminum Bioavailability From Foods Utilizing 26Al As An Aluminum Tracer, Robert A. Yokel, Aaron A. Urbas, Robert A. Lodder, John P. Selegue, Rebecca L. Florence

Pharmaceutical Sciences Faculty Publications

We synthesized ²⁶Al-containing acidic and basic (alkaline) sodium aluminum phosphates (SALPs) which are FDA-approved leavening and emulsifying agents, respectively, and used them to determine the oral bioavailability of aluminum incorporated in selected foods. We selected applicable methods from published syntheses (patents) and scaled them down (∼3000- and 850-fold) to prepare ∼300–400 mg of each SALP. The ²⁶Al was incorporated at the beginning of the syntheses to maximize ²⁶Al and ²⁷Al equilibration and incorporate the ²⁶Al in the naturally-occurring Al-containing chemical species of the products. Near infrared spectroscopy (NIR) and X-ray powder diffraction (XRD) were used …

Methods For Fabricating Microarrays Of Motile Bacteria, Sergey Rozhok, Clifton K. -F. Shen, Pey-Lih H. Littler, Zhifang Fan, Chang Liu, Chad A. Mirkin, Richard C. Holz

Chemistry Faculty Research and Publications

Motile bacterial cell microarrays were fabricated by attaching Escherichia coli K-12 cells onto predesigned 16-mercaptohexadecanoic acid patterned microarrays, which were covalently functionalized with E. coli antibodies or poly-L-lysine. By utilizing 11-mercaptoundecyl-penta(ethylene glycol) or 11-mercapto-1-undecanol as passivating molecules, nonspecific binding of E. coli was significantly reduced. Microcontact printing and dip-pen nanolithography were used to prepare microarrays for bacterial adhesion, which was studied by optical fluorescence and atomic force microscopy. These data indicate that single motile E. coli can be attached to predesigned line or dot features and binding can occur via the cell body or the flagella of bacteria. Adherent bacteria …

Determining The Optimal Size Of Small Molecule Mixtures For High Throughput Nmr Screening, Kelly A. Mercier, Robert Powers

Robert Powers Publications

High-throughput screening (HTS) using NMR spectroscopy has become a common component of the drug discovery effort and is widely used throughout the pharmaceutical industry. NMR provides additional information about the nature of small molecule-protein interactions compared to traditional HTS methods. In order to achieve comparable efficiency, small molecules are often screened as mixtures in NMR-based assays. Nevertheless, an analysis of the efficiency of mixtures and a corresponding determination of the optimum mixture size (OMS) that minimizes the amount of material and instrumentation time required for an NMR screen has been lacking. A model for calculating OMS based on the application …

Alterations In Uterine And Placental Sodium Pump Abundance May Contribute To The Onset Of Mouse Labor, Carlos Jacob Vance

Theses and Dissertations

Objective: Reductions in sodium pump (SP) abundance can give rise to increases in contractile force in uterine and vascular smooth muscle as well as an increased secretion in secretory cells, including potentially those of the placenta. To determine whether the mouse might serve as a model for human pregnancy in terms of the SP and to determine whether changes in SP abundance anticipate or follow labor, we studied pregnant mice over the final trimester of their pregnancy.

Study Design: C57Bl6 dams (n=46) were bred and studied during their pregnancy. Animals (n=4) were sacrificed at specific gestational time points. Other mice …

Ion Transmission In The First Vacuum Stage Of An Inductively Coupled Plasma Mass Spectrometer, Jeffrey Harris Macedone

Theses and Dissertations

The inductively coupled plasma mass spectrometer (ICP-MS) is the instrument of choice for trace and ultra-trace elemental analysis. However, the ICP-MS suffers from matrix effects. Matrix effects occur when instrument response varies as the composition of the sample matrix is changed. Matrix effects, or non-spectroscopic interferences, limit the accuracy of routine analysis. Identification of the sources of matrix effects provide a basis for reducing or eliminating them. As inaccuracies in the ICP-MS are more severe than those in the ICP atomic emission spectrometer, the problem may be due, at least in part, to the vacuum interface used to couple the …

Semiclassical Nonadiabatic Dynamics With Quantum Trajectories, Vitaly A. Rassolov, Sophya V. Garashchuk

Faculty Publications

Dynamics based on quantum trajectories with approximate quantum potential is generalized to nonadiabatic systems and its semiclassical properties are discussed. The formulation uses the mixed polar-coordinate space representation of a wave function. The polar part describes the overall time evolution of the wave-function components semiclassically using the single-surface approximate quantum potential. The coordinate part represents a complex“population” amplitude, which in case of localized coupling can be solved for quantum mechanically in an efficient manner. In the high-energy regime this is accomplished by using a small basis determined by the coupling between surfaces. An illustration is given for a typical curve-crossing …

Clean, High-Yield Preparation Of S,S- And R,S- Amino Acid Isosteres, Aslam A. Malik, Todd E. Clement, Hasan Palandoken, James Robinson Iii, Joy A. Stringer

Chemistry and Biochemistry

The present invention provides compounds and methods that can be used to convert the intermediate halomethyl ketones (HMKs), e.g., chloromethyl ketones, to the corresponding S,S- and R,S-diastereomers. More particularly, the present invention provides: (1) reduction methods; (2) inversion methods; and (3) methods involving the epoxidation of alkenes. Using the various methods of the present invention, the R,S-epoxide and the intermediary compounds can be prepared reliably, in high yields and in high purity.

Reconstitution Of A Minimal Dna Replicase From Pseudomonas Aeruginosa And Stimulation By Non-Cognate Auxiliary Factors, Thale C. Jarvis, Amber A. Beaudry, James M. Bullard, Nebojsa Janjic, Charles S. Mchenry

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

DNA polymerase III holoenzyme is responsible for chromosomal replication in bacteria. The components and functions of Escherichia coli DNA polymerase III holoenzyme have been studied extensively. Here, we report the reconstitution of replicase activity by essential components of DNA polymerase holoenzyme from the pathogen Pseudomonas aeruginosa. We have expressed and purified the processivity factor (β), single-stranded DNA-binding protein, a complex containing the polymerase (α) and exonuclease (ϵ) subunits, and the essential components of the DnaX complex (τ₃δδ′). Efficient primer elongation requires the presence of αϵ, β, and τ₃δδ′. Pseudomonas aeruginosa αϵ can substitute completely for …

An Investigation Into Palladium-Catalyzed Reduction Of Perchlorate In Water, Eric G. Barney

Theses and Dissertations

In this study, application of a catalytic reactor to facilitate chemical reduction of perchlorate was investigated. Palladium-coated pellets were used as the catalyst, and formic acid was used as the reductant. Reactor performance was evaluated under a variety of operating conditions (influent pH, reductant concentration, residence time). Very little perchlorate reduction was observed under any operating condition. At best, approximately 8% perchlorate reduction was observed. This small reduction efficiency is clearly not sufficient for environmental treatment applications. Perchlorate strongly adsorbed to the catalyst at low pH (3 - 3.3). At higher pH (4 - 10), little adsorption was observed. This …

Optimal Sampling Of A Chemical Hazard Area, Jennifer R. Plourde

Theses and Dissertations

This thesis proposes a methodology for optimally sampling a chemical hazard area subsequent to a chemical weapons attack. The objective is to identify the maximum number of areas that no longer require protective gear for safe operations. We model the area as an undirected graph and employ network analysis techniques to provide a methodological framework for identifying an optimal sampling sequence within a fixed time limit. We propose four models that characterize the secondary vapor concentrations: i) static and deterministic, ii) static and stochastic, iii) dynamic and deterministic, and iv) dynamic and stochastic. Comparisons of the static cases and their …

In-Situ Measurements Of Single-Stranded Dna Hybridization And Cleavage By Quartz Crystal Microbalance, Long-Zhang Zhu, Yu-Xiang Gao, He-Bai Shen, Yong-Tao Yang, Lian-Qun Yuan

Journal of Electrochemistry

The use of quartz crystal microbalance (QCM) for in-situ monitoring the immobilization of single-stranded DNA(oligo-1), marked with mercaptol group at 5′ end, on the surface of gold-filled 7.995 MHz AT-cut quartz crystal by Au-S bond with self-assemble technique is reported. And then the hybridization of ssDNA with the complementary 10-mer ODN(oligo-2) and 8-mer ODN(oligo-3) is described. Moreover, the QCM has been employed to analyze the DNA cleavage by cerium(IV) ions under moderate conditions. The results showed that the QCM, which is capable of sensitive measurement, was able to in-situ investigate immobilization, hybridization and cleavage of ssDNA. And the cerium(IV) ions …

Temperature Dependence Of The Double Layer Capacitance For The Restricted Primitive Model Of An Electrolyte Solution From A Density Functional Approach, Douglas Henderson, J. Reszko-Zygmunt, Stefan Sokolowski, Dezso Boda

Faculty Publications

We apply a different version of the density functional theory, given by Pizio, Patrykiejew, and Sokolowski [J. Chem. Phys. 121, 11957 (2004)], for a nonuniform restricted primitive model of an electrolyte solution to evaluate the temperature dependence of the capacitance of an electric double layer. We show that this theory is capable of reproducing the computer simulation data at a quantitative level. In particular, the reversal of the temperature dependence of the capacitance at low temperatures is predicted. This phenomenon has been difficult to predict from theory. Further, this theory also leads to an accurate description of the double layer …

Preparation Of 2s,3s-N-Isobutyl-N-(2-Hydroxy-3-Amino-4-Phenylbutyl)-P-Nitrobenzenesulfonylamide Hydrochloride And Other Derivatives Of 2-Hydroxy-1,3-Diamines, Aslam A. Malik, Hasan Palandoken, Joy A. Stringer, Roland P. Carlson, John Leach, Thomas G. Archibald, Robert G. Miotke

Chemistry and Biochemistry

The present invention provides a new process for the preparation of 2S,3S-N-isobutyl-N-(2-hydroxy-3-amino-4phenylbutyl)- p-nitrobenzenesulfonylamide hydrochloride, wherein this compound is prepared directly from the chloromethylalcohol. Importantly, the process of the present invention results in higher yields of 2S,3S-N-isobutyl-N-(2hydroxy -3 -amino -4-phenylbutyl) -pnitrobenzenesulfonylamide hydrochloride without sacrificing its purity. The processes of the present invention can be used to prepare not only the 2S,3S-derivative, but also the 2R,3S-, 2S,2R- and the 2R,3R-derivatives.

Developing A Genetic System For Functional Manipulations Of Fum1, A Polyketide Synthase Gene For The Biosynthesis Of Fumonisins In Fusarium Verticillioides, Fengan Yu, Xiangcheng Zhu, Liangcheng Du

Liangcheng Du Publications

Fumonisins are mycotoxins produced by Fusarium verticillioides, a filamentous fungus that is a widespread pathogen of corn. The biosynthesis of fumonisins is catalyzed by an iterative modular polyketide synthase (PKS). The study of the biosynthetic mechanism for these reduced fungal polyketides has been challenging due to the difficulties in detecting the intermediates with a linear carbon chain and manipulating the 7-domain PKS gene from the filamentous fungus. Here, we described the development of a genetic system for functionally manipulating the methyltransferase domain of FUM1 that is responsible for the assembly of a dimethylated 18-carbon chain. Using a two-stage screening strategy, …

Cystic Renal Neoplasia Following Conditional Inactivation Of Apc In Mouse Renal Tubular Epithelium, Chao Nan Qian, Jared Knol, Peter Igarashi, Fangming Lin

University Faculty Publications and Creative Works

Alterations in Wnt/β-catenin signaling have been linked to abnormal kidney development and tumorigenesis. To gain more insights into the effects of these alterations, we created mice carrying a conditional deletion of the Apc tumor suppressor gene specifically in the renal epithelium. As expected, the loss of Apc leads to increased levels of β-catenin protein in renal epithelium. Most of these mice die shortly after birth, and multiple kidney cysts were found upon histological examination. Only rarely did these animals survive to adulthood. Analysis of these adults revealed severely cystic kidneys associated with the presence of renal adenomas. Our results confirm …

Basic Region Of Residues 228-231 Of Protein Kinase Ck1Α Is Involved In Its Interaction With Axin: Binding To Axin Does Not Affect The Kinase Activity, Pablo Sobrado, Ana Jedlicki, Victor H. Bustos, Catherine C. Allende, Jorge E. Allende

Chemistry Faculty Research & Creative Works

Protein kinase CK1, also known as casein kinase 1, participates in the phosphorylation of β-catenin, which regulates the functioning of the Wnt signaling cascade involved in embryogenesis and carcinogenesis. β-catenin phosphorylation occurs in a multiprotein complex assembled on the scaffold protein axin. The interaction of CK1α from Dani rerio with mouse-axin has been studied using a pull-down assay that uses fragments of axin fused to glutathione S transferase, which is bound to glutathione sepharose beads. The results indicate that the three lysines present in the basic region of residues 228-231 of CK1α are necessary for the binding of CK1 to …

Atomic Force Microscopy Investigation Of Virus Aggregation And Assembly At Chemical Templates Formed By Scanned Probe Nanolithography, Chin Li Cheung, S. -W. Chung, J. J. De Yoreo, A. Chatterji, T. Lin, J. E. Johnson

Barry Chin Li Cheung Publications

Aggregation and assembly of macromolecules are important processes in a number of scientific fields including structural biology, medicine, and materials science. For example, growth of well-ordered two-dimensional (2-D) arrays and bulk crystals remains the rate-limiting step in macromolecular structure determination. Uncontrolled aggregation of proteins is the source of a number of devastating pathologies such as Creutzfeldt-Jakob syndrome. Moreover, the demonstrated ability of engineered viruses and proteins to act as templates for growth of inorganic nanostructures is driving a need for methods to deterministically pattern their assembly at surfaces in order to fabricate hierarchical materials and devices.