Digital Commons Network^™

Design Of Control Release Drug Delivery System (Dds) For Imaging And Therapeutic Applications, Sweta Naik

Theses and Dissertations

The main challenge in disease treatment is no more the discovery of new therapeutic drugs, but to provide targeted delivery of therapeutic drugs to specific sites without incurring systemic toxicity effects. An efficient way of reducing the toxicity is by encapsulating the drug with a biodegradable matrix that can provide controlled release of the drug along with local heating of the drug. Local heating can be obtained by incorporating magnetic iron oxide particles that heat upon exposure to AC electromagnetic fields. The magnetic iron oxide nanoparticles are also gaining much attention as MRI contrast agents. Thus it would be of …

A Modified Surface On Titanium Deposited By A Blasting Process, Caroline O' Sullivan, Peter O'Hare, Greg Byrne, Liam O'Neill, Katie B. Ryan, Abina M. Crean

Publications

Abstract

: Hydroxyapatite (HA) coating of hard tissue implants is widely employed for its biocompatible and osteoconductive properties as well as its improved mechanical properties. Plasma technology is the principal deposition process for coating HA on bioactive metals for this application. However, thermal decomposition of HA can occur during the plasma deposition process, resulting in coating variability in terms of purity, uniformity and crystallinity, which can lead to implant failure caused by aseptic loosening. In this study, CoBlast™, a novel blasting process has been used to successfully modify a titanium (V) substrate with a HA treatment using a dopant/abrasive regime. …

Efficient And Accurate Methods For The Geometry Optimization Of Water Clusters: Application Of Analytic Gradients For The Two-Body:Many-Body Qm:Qm Fragmentation Method To (H2o)N, N = 3-10, Desiree M. Bates, Joshua R. Smith, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

The structures of more than 70 low-lying water clusters ranging in size from (H₂O)₃ to (H₂O)₁₀ have been fully optimized with several different quantum mechanical electronic structure methods, including second-order Møller-Plesset perturbation theory (MP2) in conjunction with correlation consistent triple-ζ basis sets (aug-cc-pVTZ for O and cc-pVTZ for H, abbreviated haTZ). Optimized structures obtained with less demanding computational procedures were compared to the MP2/haTZ ones using both MP2/haTZ single point energies and the root-mean-square (RMS) deviations of unweighted Cartesian coordinates. Based on these criteria, B3LYP/6-31+G(d,2p) substantially outperforms both HF/haTZ and MP2/6-31Gz.ast. B3LYP/6-31+G(d,2p) structures never …

Combinatorial Catalysis Assisted By A Visible Enzymatic Beacon In Real Time: New Synthetically Versatile (Pseudo)Halometalation/Carbocyclizations, Jacob A. Friest, Sylvain Broussy, Woo Jin Chung, David B. Berkowitz

David Berkowitz Publications

Combinatorial approaches to catalysis have made an impact in targeted transformation development, including Ag-mediated carbene insertion,^[1] Sc-pybox-based asymmetric cyclopropanation,^[2] and Rh/Ir-based asymmetric hydrogenation.^[3] Useful design elements have emerged from these studies, e.g. the value of ligand self assembly,^[4] or of the inclusion of peptide-like structural elements^[5],[6],[7] in building ligand arrays. Efficient screening methods are of paramount importance for such efforts. Methods based on fluorescence,^[8] REMPI^,[9] MS,^[10] NMR,^[11] and IR thermography^[12] have appeared. A chromophore may be installed into the substrate^[13] or product^[14] of the reaction under study. Alternatively, …

From Computational Discovery To Experimental Characterization Of A High Hole Mobility Organic Crystal, Anatoliy N. Sokolov, Sule Atahan-Evrenk, Rajib Mondal, Hylke B. Akkerman, Roel S. Sánchez-Carrera, Sergio Granados-Focil, Joshua Schrier, Stefan C.B. Mannsfeld, Arjan P. Zoombelt, Zhenan Bao, Alán Aspuru-Guzik

Chemistry

For organic semiconductors to find ubiquitous electronics applications, the development of new materials with high mobility and air stability is critical. Despite the versatility of carbon, exploratory chemical synthesis in the vast chemical space can be hindered by synthetic and characterization difficulties. Here we show that in silico screening of novel derivatives of the dinaphtho[2,3-b:2′2,3′2-f]thieno[3,2-b]thiophene semiconductor with high hole mobility and air stability can lead to the discovery of a new high-performance semiconductor. On the basis of estimates from the Marcus theory of charge transfer rates, we identified a novel compound expected to demonstrate a theoretic twofold improvement in mobility …

Follicular Dendritic Cells, Resting Cd4+ T Cells And Human Immunodeficiency Virus Expression, Changna Wang

Theses and Dissertations

Many events associated with Human Immunodeficiency Virus (HIV) infection/replication occur in and around the germinal centers (GCs) of secondary lymphoid tissues where follicular dendritic cells (FDCs) reside, suggesting that this microenvironment may contribute unique signaling that is important to viral progression. My research focused on characterizing signaling, both positive and negative, contributed by FDCs that affects HIV infection and replication. Specifically, I determined if FDC signals could induce the expression of latent HIV in T cells and if so, to characterize the signaling pathways involved. Moreover, I also examined the ability of FDCs to produce inhibitory signals that might block …

An Integrated Systems Approach To Deconstructing Glycosylation, L. K. Mahal, John F. Rakus, Kanoelani Pilobello, P. Agrawal

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Probing Single-Molecule Enzyme Active-Site Conformational State Intermittent Coherence, Yufan He, Yue Li, Saptarshi Mukherjee, Yan Wu, Honggao Yan, H. Peter Lu

Chemistry Faculty Publications

The relationship between protein conformational dynamics and enzymatic reactions has been a fundamental focus in modern enzymology. Using single-molecule fluorescence resonance energy transfer (FRET) with a combined statistical data analysis approach, we have identified the intermittently appearing coherence of the enzymatic conformational state from the recorded single-molecule intensity-time trajectories of enzyme 6-hydroxymethyl-7,8-dihydropterin pyrophosphokinase (HPPK) in catalytic reaction. The coherent conformational state dynamics suggests that the enzymatic catalysis involves a multistep conformational motion along the coordinates of substrate-enzyme complex formation and product releasing, presenting as an extreme dynamic behavior intrinsically related to the time bunching effect that we have reported previously. …

Energy Transfer From Fluorescent Proteins To Metal Nanoparticles, Suraj Saraswat, Anil Desireddy, Desheng Zheng, Lijun Guo, H. Peter Lu, Terry P. Bigioni, Dragan Isailovic

Chemistry Faculty Publications

Energy transfer plays a significant role in numerous chemical, physical, and biological processes. While the use of fluorescent proteins in Forster resonance energy transfer (FRET) studies of biomolecules is common, energy transfer between fluorescent proteins and inorganic nanoparticles has not been explored in detail. In this study, energy transfer from fluorescent phycobiliproteins to noble metal nanoparticles was analyzed. Solutions of B-phycoerythrin (B-PE) were mixed with colloidal Au and Ag nanoparticles and were characterized by steady-state and time-resolved fluorescence spectroscopy to determine the magnitude and mechanism of the energy transfer. It was found that the protein fluorescence was quenched after the …

High Performance Liquid Chromatography - Mass Spectrometric Analysis Of Bile Acids And Coumarin Derived Sulfonamides, Udaya Bhasker Nasini

Theses and Dissertations

Bile acids are water- soluble steroids and biological emulsions useful in the digestion process of food. The conjugated bile acids play a major role in fat metabolism. Deconjugation of conjugated bile acids by bacterial enzymes produces free bile acids in the colon. The conversion of these primary bile acids takes place in the gut by bacterial flora. It is postulated that a difference in the molecular forms of various bile acids and their concentration profiles exists among various animals, depending upon their food habits and type of bacterial flora. Consequently, it may be possible to distinguish various types of carnivorous …

Thirdhand Tobacco Smoke: Emerging Evidence And Arguments For A Multidisciplinary Research Agenda, Georg E. Matt, Penelope J. Quintana, Hugo Destaillats, Lara A. Gundel, Mohamad Sleiman, Brett C. Singer, Peyton Jacob, Jonathan P. Winickoff, Prue Talbot, Suzaynn Schick, Yinsheng Wang, Bo Hang, Manuela Martins-Green, James F. Pankow, Melbourne F. Hovell, Neal L. Benowitz, Virender K. Rehan, Jonathan M. Samet

Civil and Environmental Engineering Faculty Publications and Presentations

There is broad consensus regarding the health impact of tobacco use and secondhand smoke exposure, yet considerable ambiguity exists about the nature and consequences of thirdhand smoke (THS). We introduce definitions of THS and THS exposure and review recent findings about constituents, indoor sorption-desorption dynamics, and transformations of THS; distribution and persistence of THS in residential settings; implications for pathways of exposure; potential clinical significance and health effects; and behavioral and policy issues that affect and are affected by THS. Physical and chemical transformations of tobacco smoke pollutants take place over time scales ranging from seconds to months and include …

Properties, Solution State Behavior, And Crystal Structures Of Chelates Of Dotma, Silvio Aime, Mauro Botta, Zoltán Garda, Benjamin E. Kucera, Gyula Tircso, Victor G. Young, Mark Woods

Chemistry Faculty Publications and Presentations

The chemistry of polyamino carboxylates and their use as ligands for Ln(3+) ions is of considerable interest from the point of view of the development of new imaging agents. Of particular interest is the chemistry of the macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and its derivatives. Herein we report that the tetramethylated DOTA derivative, DOTMA, possess several properties that, from an imaging agent development point of view, are more advantageous than those of the parent DOTA. In particular, the Ln(3+) chelates of DOTMA exhibit a marked preference for the monocapped twisted square antiprismatic coordination isomer which imparts more rapid water exchange …

Bismuth Nitrate Pentahydrate-Induced Novel Nitration Of Eugenol, Luis Canales, Debasish Bandyopadhyay, Bimal K. Banik

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

Background: Eugenol, the main constituent of clove oil possesses a number of medicinal activities. To enhance the medicinal property, structural modification is required. On the other hand, bismuth nitrate pentahydrate has been established as an excellent eco-friendly nitrating agent for several classes of organic compounds.

Results: Bismuth nitrate pentahydrate-induced nitration of eugenol has been investigated very thoroughly. Twenty five different conditions have been studied. The microwave-induced solvent-free reaction has been identified as the best condition.

Conclusions: Spectral analyses confirm that 5-nitroeugenol is the sole product in all the cases. No oxidized or isomerized product could be detected.

Complete Determination Of The Pin1 Catalytic Domain Thermodynamic Cycle By Nmr Lineshape Analysis, Alexander I. Greenwood, Monique J. Rogals, Soumya De, Kun Ping Lu, Evgenii L. Kovrigin, Linda K. Nicholson

Chemistry Faculty Research and Publications

The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, k^cis_catand apparent Michaelis constants, K^App_M . By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as …

I. The Synthesis And Coordination Chemistry Of Novel 6Π-Electron Ligands. Ii. Improvement Of Student Writing Skills In Chemistry Lab Reports Through The Use Of Calibrated Peer Review, Wilson Ngambeki William

Chemistry and Chemical Biology ETDs

ABSTRACT I

The goal of this study was to synthesize and characterize a set of coordination complexes containing 6π-cationic ligands. These compounds could be extremely useful as catalysts for the polymerization of olefins that are widely used in the synthetic polymer industry. The original strategy was to synthesize the 6π-cationic ligands using (Ph₂P)₃CH (1) and (Me₂P)₃CH (10) as precursors; however, both precursors 1 and 10 were found to be highly reactive leading to the fragmentation products (Ph₂P)₂CH₂ and (Me₂P)₂CH₂ respectively. In trying …

Structural Characterization Of Metal Binding In Metallo-Β-Lactamases Using X-Ray Absorption Spectroscopy, Robert M. Breece

Chemistry and Chemical Biology ETDs

In an effort to probe the structure and mechanism of metallo-β-lactamases, the metal-binding behaviors of several enzymes were studied using EXAFS (Extended X-ray Absorption Fine Structure). Three members of the metallo-β-lactamase subclass B1, BcII from Bacillus cereus, Bla2 from Bacillus anthracis and CcrA from Bacillus fragilis, were compared to examine metal-binding behavior within a subclass. Each system exhibits different metal-binding behavior including cooperative binding (BcII), sequential binding (CcrA), and differential binding between zinc(II) and cobalt(II) forms (Bla2). The metal-binding behavior of subclass B3 of L1 from Stenotrophomonas maltophilia was explored with RFQ (rapid-freeze quenched) EXAFS and site selective metal …

Synthesis And Characterization Of Tanninsulfonic Acid Doped Polyaniline (Tanipani) - Metal Oxide Nanocomposites For Solar Cell Applications, Venu Gopal Bairi

Theses and Dissertations

Nanocomposites of polyaniline have gained much importance due to their improved electronic properties. The presence of metal oxides in the nanocomposites may enhance the photovoltaic effect and increase the efficiency of solar cells. We have synthesized tanninsulfonic acid doped polyaniline (TANI-PANI) composites in view of preparing metal oxide complexed composites due to the presence of o-catechol in tannin. Tanninsulfonic acid doped polyaniline (TANIPANI)-TiO2 or Al2O3 nanocomposites were synthesized by varying the amount of TiO2 from 10% to 70% (with respect to the mass of aniline) and by carrying out the synthesis at -10° C. Covalent bonding of the metal oxide …

Electrochemistry In Neural Stimulation By Biomedical Implants, Zhou David, Greenberg Robert

Journal of Electrochemistry

Advances in biomedical engineering, micro-fabrication technology, and neuroscience have led to many novel and improved biomedical implants for electrical neural stimulation to restore human function and improve the quality of human life. Some examples of such biomedical devices are cochlear implants, visual implants, deep brain stimulators and spinal cord stimulators. One of the key components of biomedical implants is the stimulating electrodes. The electrodes, when in contact with living tissue, form an interface between the electronic device and the biological tissue. This paper reviews electrochemical aspects of neural stimulation implants. A brief introduction on the developments of biomedical implants is …

Study On The Fluorescent Carbon Nanodots With Electrochemical Methods, Bao-Ping Qi, Yan-Min Long, Lei Bao, Cui Liu, Zhi-Ling Zhang, Dai-Wen Pang

Journal of Electrochemistry

Carbon nanodots are a new class of fluorescent nanoparticles with a carbon-based core, which possess wavelength-tunable luminescence, high photostability, resistance to photobleaching, water-solubility, and ease of bioconjugation. Owing to their attractive merits, carbon nanodots like other carbon nanomaterials such as fullerene, carbon nanotubes and graphene, have attracted much attention. In addition, carbon nanodots can be inexpensively produced by electrochemical methods with simple post-processing under mild conditions. Electrochemical approaches have unique advantages in the analysis of surface structures and luminescence mechanism of materials. In this review, recent advances in electrochemical methods used for the synthesis and luminescence mechanism of fluorescent carbon …

Electrochemical Analysis Based On Molecular Recognition Of Nucleic Acids And Its Applications, Dian-Ming Zhou, Jian-Hui Jiang, Guo-Li Shen, Ru-Qin Yu

Journal of Electrochemistry

Nucleic acid as the carrier of genetic information and the functional molecules for molecular biology and bioanalytical chemistry has attracted increasing interest in electrochemical analysis. This review presents a brief outline of some electrochemical analytical assays based on molecular recognition of nucleic acids. Most of these methods are focused on the detection of nucleic acid sequence, genetic mutation and nucleic acids as functional molecules.

Fabrication Of Ito Micro-Pore Electrochemical Sensor And The Detection Of Exocytosis, Hui Zhao, Ling Li, Pin-Gang He, Yu-Zhi Fang

Journal of Electrochemistry

Exocytosis is one of the major means for cells to transmit messages. Amperometric detection of exocytosis is an important method in studying communication between cells. In this study a new type of ITO micro-pore electrochemical sensor was fabricated by means of ITO and UV light lithographic mask and was used in the detection of exocytosis with promising results. Compared with the conventional method, the ITO micro-pore sensor can not only replace the carbon fiber electrode, but be combined with fluorescent or chemiluminescent methods in detecting the physiological phenomena of cells.

Surface Diffusion Of Adsorptive Species On Gold Nanoelectrodes, Bao-Fa Su, Wei Wang, Dong-Ping Zhan, Bin Ren, Zhong-Qun Tian

Journal of Electrochemistry

Gold nanoelectrodes were prepared successfully by a programmed laser puller. The Faraday adsorptions of oxygen and iodine, and the underpotential deposition of lead on the gold nanoelectrodes were investigated. The results showed that the active areas of nanoelectrodes were dramatically higher than their appearant geometry areas, which is caused by the surface diffusion of adsorptive species from the nanoscale gold/electrolyte interface to the adjacent gold surface.

Synthesis Of Cyclen Based Receptors And Their Use In Separations Biotechnology., Vivek Kaushik

Theses and Dissertations

A number of purification techniques such as adsorption, centrifugation, chromatography, extraction, distillation, filtration, precipitation etc. to name a few, are commonly used for the purification. However, due to a constant need of purification of even more complex crude mixtures, be it reaction mixtures, various proteins and DNA from cell extracts or medicinal compounds and fragrances from plant extracts, scientists needed to consistently develop new and improved techniques of purification. One such great advancement in the field of chromatography was the development of affinity chromatography. It revolutionized the field of bioseparations technology, and the dream of single stage purification of complex …

Mechanistic Studies On Xanthine Oxidoreductase Enzymes, Abebe Berhane

Chemistry and Chemical Biology ETDs

In humans, the xanthine oxidoreductase enzymes are known to catalyze the final two steps of purine metabolism by converting hypoxanthine successively to xanthine and uric acid. Xanthine oxidoreductase also metabolizes a wide variety of drugs in vivo, and activates a number of antiviral prodrugs of clinical importance. Therefore, understanding the reaction mechanism of this enzyme is of prime importance in furthering our understanding of enzyme-drug interactions. In order to provide a greater understanding on the reaction mechanism, theoretical and enzymatic spectroscopic experimental approaches have been utilized. The theoretical approaches were used to elucidate the electronic structure and geometry of the …

Electrochemical Studies Of The Interaction Between Dna And A Compound Having Anticancer Properties., Antibe Pouliwe

Electronic Theses and Dissertations

Electrochemical method has been used to study the interaction between DNA and the compound N-(3',6'-dihydroxy-3-oxospiro[isobenzofuran-1(3H),9'-[9H]xanthen]-5-yl)-N'-(2-imidazoyl)urea having anticancer properties. A DNA modified nanometer-sized gold electrode was prepared by surface modification of a bare gold electrode using cysteamine. These electrodes have been characterized using electrochemical techniques and were used to study the interaction between DNA and the compound. Our results showed an increase in the adsorption peak current and a negative shift of E_1/2 in the oxidation of ferrocyanide on cysteamine and DNA modified electrodes. For the interaction between the DNA and the compound having anticancer properties, a decrease in peak …

The Nucleotide Exchange Factor Ric-8a Is A Chaperone For The Conformationally Dynamic Nucleotide-Free State Of G Alpha I1, Celestine J. Thomas, Klara Briknarova, Jonathan K. Hilmer, Navid Movahed, Brian Bothner, John P. Sumida, Gregory G. Tall, Stephen R. Sprang

Chemistry and Biochemistry Faculty Publications

Heterotrimeric G protein alpha subunits are activated upon exchange of GDP for GTP at the nucleotide binding site of G alpha, catalyzed by guanine nucleotide exchange factors (GEFs). In addition to transmembrane G protein-coupled receptors (GPCRs), which act on G protein heterotrimers, members of the family cytosolic proteins typified by mammalian Ric-8A are GEFs for Gi/q/12/13-class G alpha subunits. Ric-8A binds to G alpha.GDP, resulting in the release of GDP. The Ric-8A complex with nucleotide-free G alpha i1 is stable, but dissociates upon binding of GTP to G alpha i1. To gain insight into the mechanism of Ric-8A-catalyzed GDP release …

Aryl Acetate Phase Transfer Catalysis: Method And Computation Studies, Meisha A. Binkley

Theses and Dissertations

Brief explanation and history of cinchona based Phase Transfer Catalysis (PTC). Studied aryl acetates in PTC, encompassing napthoyl, 6-methoxy napthoyl, phenyl and protected 4-hydroxy phenyl acetates. Investigated means of controlling the selectivity of the PTC reaction by changing the electrophile size, the ether side group size or by addition of inorganic salts. Found that either small or aromatic electophiles increased enantioselectivity more than aliphatic electrophiles, and that increasing the size of ether protecting group also increased selectivity. Positive effects of salt addition included either decreasing reaction time or increasing enantiomeric excess. Applied findings towards the synthesis of S-equol. Computational experiments …

Cell Migration Dynamics After Alteration Of Cell-Cell Contacts In Fibrosarcoma And Glioblastoma Cell Lines, Hassan S. Rizvi, Ronald K. Gary

Undergraduate Research Opportunities Program (UROP)

Cell migration is a vital component of metastasis. In this study, our intent was to study cell migration by alteration of the Wnt/GSK-3 Pathway. Since BeSO4 is a known GSK-3 kinase inhibitor, we hypothesized that this agent would cause cell migration to decrease as a result of β-catenin stabilization. Two human cell lines, HT-1080 (fibrosarcoma) and A172 (glioblastoma), were used to observe migration levels in the presence and absence of BeSO4. Our results show that cell migration is diminished for cells that were pre-treated with BeSO4, in comparison to the untreated (control) cells.

Undergraduate Research Opportunities Program 2011, Nicholle Booker, University Of Nevada, Las Vegas

Undergraduate Research Opportunities Program (UROP)

Undergraduate Research Opportunities Program

On August 9, 2011 the UNLV College of Sciences will celebrate the accomplishments of undergraduate students participating in the Summer 2011 Undergraduate Research Opportunities Program (UROP) and the Research Experience For Undergraduates (REU) Program.

The public is invited to attend, beginning at 10:00 a.m.

Please join us to view student research posters. Student research topics include: biomedicine and human health, Nevada's fragile environment and ecosystems, climate change, stem cell research, microbiology, astrophysics, and many others.

Over 25 UNLV undergraduates and a cohort of 25 undergraduates selected from colleges and universities across the nation will mark the …

The Formation And Stability Of Radical-Molecule And Radical-Radical Complexes And Their Importance In Atmospheric Processes, Jared M. Clark

Theses and Dissertations

This research explores the role that radical-molecule complexes play in the chemistry of Earth's atmosphere. The formation of such complexes can have direct and pronounced effects on the reaction and product outcome of atmospheric chemical reactions. Some attention is also given to the formation of radial-radical pre-reactive complexes in the HO + ClO system. Peroxy radicals (RO2) can form stable complexes with polar compounds such as H2O, NH3, and CH3OH. For the simplest RO2 radical, HO2, complex formation (e.g., HO2-H2O, HO2-NH3, and HO2-722;CH3OH) gives rise to a significant increase in the HO2 self-reaction rate constant. Although this phenomenon has been …