Chemistry Commons^™

Application Of Carbon Nanoparticles As Dna Detection Probe And Fluorescent Ink, Luckio Frank Owuocha

Graduate Theses/Dissertations

There is a significant interest in developing a sensitive, selective, efficient, and inexpensive method for rapid molecular diagnostic tests. This research aims to develop an inexpensive nucleic acid detection method by using DNA-conjugated carbon nanoparticles that exhibit fluorescence in the visible region. Carbon nanoparticles of this class can be detected without specialized equipment and have great promise toward the development of analytical methods that can be used in resource-limited environments with a lack of access to proper diagnostic and healthcare. We employed EDC-NHS (two-step) and EDC (one-step) coupling techniques to prepare DNA-conjugated carbon nanoparticles. The dot blotting method was adapted …

Doping Effects On Transition-Metal Silicides: Crystal Structures And Physical Properties Of Aluminium Doped Rhenium Silicide, Victoria Decocq

Graduate Theses/Dissertations

Semiconductive transition-metal silicides (e.g., ReSi) express weak thermoelectric properties. These properties can improve through n-type or p-type doping (e.g., Al), resulting in altered crystal structures. Binary rhenium silicide (ReSi_1.75) exhibits promising thermoelectric properties and an intriguing crystal structure. Previous research has shown ReSi_1.75 changes from a commensurate supercell MoSi₂-type structure to an incommensurate superspace group structure, when doped with aluminium to ReAl_0.074Si_1.67. ReSi_1.75 expresses a figure of merit (ZT) of 0.70 at 800°C, which improves to a ZT of 0.95 at 150°C for ReAl_0.02Si_1.75. Because of …

A Simple Predictive Model For Estimating Relative E-Cigarette Toxic Carbonyl Levels, Shawna Vreeke, Xijing Zhu, Robert Strongin

Chemistry Faculty Publications and Presentations

E-cigarette devices are wide ranging, leading to significant differences in levels of toxic carbonyls in their respective aerosols. Power can be a useful method in predicting relative toxin concentrations within the same device, but does not correlate well to inter-device levels. Herein, we have developed a simple mathematical model utilizing parameters of an e-cigarette’s coil and wick in order to predict relative levels of e-liquid solvent degradation. Model 1, which is coil length/(wick surface area*wraps), performed in the moderate-to-substantial range as a predictive tool (R² = 0.69). Twelve devices, spanning a range of coil and wick styles, were analyzed. …

Synthesis, Characterization, And Biological Studies Of Novel Organoantimony(V) Cyanoximates, Kevin Anthony Pinks

Graduate Theses/Dissertations

The requirement of new antimicrobial treatments has become an urgent field recently. Multi-drug resistant (MDR) bacteria are now resistant to common antibiotics. To antagonize such bacteria 8 novel organoantimony(V) cyanoximates were synthesized to be characterized and submitted for biological activity studies. Eight organoantimony(V) cyanoximates were characterized by elemental analysis, thermal analysis, IR-, ¹³C{¹H} NMR, some with UV-visible spectroscopy, and single crystal X-ray analysis. Antimicrobial Disk studies indicated Sb(Ph)₄(ACO) and Sb(Ph)₄(ECO) had significant antimicrobial effect against all three strains: two gram-negative a) Escherichia coli strain S17 and b) Pseudomonas aeruginosa strain PAO1, alongside a …

Characterization Of An Acid Rock Drainage Microbiome And Transcriptome At The Ely Copper Mine Superfund Site, Lesley Ann Giddings, George Chlipala, Kevin Kunstman, Stefan Green, Katherine Morillo, Kieran Bhave, Holly Peterson, Heather Driscoll, Mark Maienschein-Cline

Chemistry: Faculty Publications

The microbial oxidation of metal sulfides plays a major role in the formation of acid rock drainage (ARD). We aimed to broadly characterize the ARD at Ely Brook, which drains the Ely Copper Mine Superfund site in Vermont, USA, using metagenomics and metatranscriptomics to assess the metabolic potential and seasonal ecological roles of microorganisms in water and sediment. Using Centrifuge against the NCBI “nt” database, ~25% of reads in sediment and water samples were classified as acid-tolerant Proteobacteria (61 ± 4%) belonging to the genera Pseudomonas (2.6-3.3%), Bradyrhizobium (1.7-4.1%), and Streptomyces (2.9-5.0%). Numerous genes (12%) were differentially expressed between seasons …

Unbinding Of Testosterone From The Androgen Receptor And Two Bf-3 Site Mutants, Muniruzzaman Chowdhury

Theses and Dissertations

The androgen receptor (AR) can be activated by molecules binding in the steroid binding pocket. It can also be regulated allosterically by cofactors binding to the AF-2 surface site as well as by exogenous small molecules binding to the BF-3 surface site. Recent data indicated that mutations in the BF-3 site changed the amount of the endogenous steroid needed to activate the receptor, indicating that mutations of BF-3 can cause an allosteric effect. Molecular dynamics and steered molecular dynamics simulations were used to study the allosteric effect of the mutations on AR structure and the unbinding pathways of testosterone (TES) …

Nonwovens Of Ceramic Decorated Cellulose Based Fine Fibers For Leaded Water Purification, Alejandro J. Castillo

Theses and Dissertations

Fine fibers of cellulose acetate were Forcespun and used to make nonwoven mats of cellulose. Nonwovens were activated using a solution combustion synthesis which deposited iron nitride onto fibers. Cellulose and cellulose composite mats were tested as adsorbents for lead ion in water. Cellulose showed slightly higher adsorption capacities (mg/g) up to 1300 mg/g lead loading. Adsorption data were further analyzed using several isotherms, of which the Dubinin-Raduskevich gave the best fits.

Synthesis And Characterization Of Bimetallic Gold-Silver (Au-Ag) Nanocatalyst Via Seed Colloid Technique, Berahim Nurafaliana

Student Works (2020-2029)

In the present study, unique catalysts of monometallic gold (Au), silver (Ag) and bimetallic gold-silver (Au-Ag) nanoparticles (NPs) were prepared with different size or diameters by the citrate-thermal reduction and the seed colloidal techniques, respectively. The catalytic nanoparticles were characterized by various advanced analytical techniques such as Ultraviolet-visible spectroscopy (UV-vis), zeta potential, electron dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), High-angle annular dark-field (HAADF) scanning transmission-electron microscopy (STEM) imaging and the energy dispersive spectroscopy (EDS) elemental mapping. The catalytic performance of the nanoparticles were ascertained through the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in …

Synthesis And Characterization Of Self-Cleaning Hydrophobic Organic Coating, Abdul Jaafar Amirul Syafiq

Student Works (2020-2029)

Three self-cleaning coating systems namely Polydimethylsiloxane (PDMS)/Sylgard, PDMS/3-Aminopropyltriethoxysilane (APTES) (tagged as A1) and A1 blended with nano-Calcium Carbonate (CaCO3) have been synthesised on glass substrates via dip-coating and spray-coating techniques. All of the prepared coatings were dried under ambient condition before being subjected to characterisations and testing(s). The effect of various weight percentages of Sylgard resin that are 5wt.% (S1 coating), 10wt.% (S2 coating), 15wt.% (S3 coating), and 20 wt.% (S4 coating) on the hydrophobicity, self-cleaning property, anti-fog performance and mechanical property of PDMS/Sylgard coating have been discussed in the first section of this thesis. The PDMS/Sylgard coated glass substrates …

Synthesis Of Polyaniline Modified With Palm Oil Based Alkyd As Counter Electrode In Solar Cell Application, Ramli Mariam Fadzlina

Student Works (2020-2029)

Presently, shortage of sustainable and environmental friendly energy resources has become an important global concern. Dye-sensitized solar cell (DSSC) has widely been used as a clean energy conversion device that can solve this problem. Platinum (Pt) has commonly been used as counter electrode (CE) in DSSC due to its good redox property. However, Pt is expensive and could be easily corroded in tri-iodide solution. Recently, polyaniline (PAni) has shown promising performance in DSSC, but PAni exhibit poor adhesion on fluorine-doped tin oxide (FTO) substrate. In this study, an environmental friendly CE was developed by modifying PAni using titanium dioxide (TiO2) …

Synthesis And Biological Activities Of Imidazolium Acridines And Their Silver Complexes, H S Sharhan Olla

Student Works (2020-2029)

In the present study, a series of acridine-based imidazolium ligands were synthesized by the Menshutkin reaction and used for the preparation of the silver complexes. The structures were established using NMR and IR spectroscopy as well as high-resolution mass spectrometry. The purity of the ligands was confirmed by CHN elemental analysis, while energy-dispersive X-ray spectroscopy (EDX) was applied for the silver complexes. In view of the luminescent behaviour of acridine, UV-Vis and fluorescence spectra were recorded for ligands and complexes. However, low water solubility constrains potential application as analytical probe. Preliminary in vitro cytotoxicity screenings were performed using an MTT …

Microstructural Evolution And Mechanical Properties Of Ultra-Fine Grained Tubular Components Processed By Severe Plastic Deformation, Mesbah Mohsen

Student Works (2020-2029)

The lightweight alloys have been widely used in various engineering applications such as automotive, aerospace, construction, and biomedical industries due to their low densities, high ductility, formability, and facile machining. However, the emerging trend for materials with high mechanical strength and plasticity hampers the widespread application of these alloys. Over the last two decades, severe plastic deformation (SPD) has been introduced as a promising approach for enhancement of the mechanical performance of the lightweight alloys through microstructural manipulations and grain refinement. However, the SPD techniques have been extensively utilized for the fabrication of non-tubular geometries and the studies on the …

Effect Of Electron Demand On Sensing Behavior Of Carbazolopyridinophanes, Grace Abban

Theses and Dissertations

Hydrazine (HZ), monomethylhydrazine (MMH), and 1,1-dimethylhydrazine (UDMH) are widely used as high energy rocket propellants in bipropellant rocket engines. However, hydrazine and its derivatives are highly flammable and carcinogenic. Currently, hydrazine sensors used for detection are irreversible which makes them costly. Two proposed carbazolopyridinophanes containing intramolecular hydrogen bonds were synthesized to detect hydrazine as real-time reversible sensors. However, their thresholds for detection (100 and 25 ppb for CPand 22OMeCPrespectively) were above the regulatory limit of 10 ppbdue to background fluorescence. It was established that the quenching of carbazole in the presence of the CP system has a direct correlation to …

Freshwater Endmembers Impacting Carbonate Chemistry In The Mississippi Sound, Allison Savoie

Master's Theses

Coastal ecosystems are highly dynamic areas for carbon cycling and are likely to be negatively impacted by increasing ocean acidification. This research focused on dissolved inorganic carbon (DIC) and total alkalinity (TA) in the Mississippi Sound in order to understand the influence of local rivers that supply alkalinity to the area and buffer against ocean acidification. This area receives large fluxes of freshwater from local rivers, in addition to episodic inputs from the Mississippi River through a human-built diversion, the Bonnet Carré Spillway. Sites in the Mississippi Sound were sampled monthly during August 2018 to November 2019 and at weekly …

Directed Evolution Of Macrocyclic Peptides For Inhibition Of Autophagy, Joshua Gray

Dissertations and Theses (Open Access)

In recent decades it has become increasingly clear that induction of autophagy plays an important role in the development of treatment resistance and dormancy in many cancer types. Chloroquine (CQ) and hydroxychloroquine (HCQ), two autophagy inhibitors in clinical trials, suffer from poor pharmacokinetics and high toxicity at therapeutic dosages. This has prompted intense interest in the development of targeted autophagy inhibitors to re-sensitize disease to treatment with minimal impact on normal tissue. We utilized Scanning Unnatural Protease Resistant (SUPR) mRNA display to develop macrocyclic peptides targeting the autophagy protein LC3. The resulting peptides bound LC3A and LC3B—two essential components of …

Connexin-46/50 In A Dynamic Lipid Environment Resolved By Cryoem At 1.9 Å, Jonathan A. Flores, Bassam G. Haddad, Kimberly A. Dolan, Janette Bernadette Myers, Craig C. Yoshioka, Jeremy Yoshioka, Daniel M. Zuckerman, Steve L. Reichow

Chemistry Faculty Publications and Presentations

Gap junctions establish direct pathways for cells to transfer metabolic and electrical messages. The local lipid environment is known to affect the structure, stability and intercellular channel activity of gap junctions; however, the molecular basis for these effects remains unknown. Here, we incorporate native connexin-46/50 (Cx46/50) intercellular channels into a dual lipid nanodisc system, mimicking a native cell-to-cell junction. Structural characterization by CryoEM reveals a lipid-induced stabilization to the channel, resulting in a 3D reconstruction at 1.9 Å resolution. Together with all-atom molecular dynamics simulations, it is shown that Cx46/50 in turn imparts long-range stabilization to the dynamic local lipid …

Development Of Plasticized Methylcellulosepotato Starch Blend Based Polymer Electrolytes For Protonic Cell And Supercapacitor Applications, Hamsan Muhamad Hafiz

Student Works (2020-2029)

In the current work, the preparation of the polymer electrolyte (PE) systems consists of methylcellulose-potato starch polymer matrix, ammonium nitrate (NH4NO3) as ionic source and glycerol as plasticizer are done by solution cast technique. X-ray diffraction (XRD) has shown that blend with 60 wt.% methylcellulose and 40 wt.% potato starch possesses the lowest degree of crystallinity. The possible interactions within the PE are verified using Fourier transform infrared (FTIR) spectroscopy. As the concentration of NH4NO3 is at 30 wt.%, the conductivity is optimized up to (4.37 ± 0.16) × 10-5 S cm-1 and then maximized to (1.26 ± 0.1) × …

Enhancement Of Graphene Biocompatibility As A Potential Nano-Carrier For Drug Delivery Applications Using Natural Deep Eutectic Solvent, Zainal Abidin Mohamad Hamdi

Student Works (2020-2029)

Graphene has attracted massive interest in numerous biomedical applications such as anti-cancer therapy, drug delivery, bio-imaging and gene delivery. Therefore, it is important to ensure that graphene is nontoxic, and that its cellular biological behavior is safe and biocompatible. Herein, a new route was used to enhance the biocompatibility of graphene as a nano-carrier for potential drug delivery applications, using different compositions of natural deep eutectic solvents (DESs) as functionalizing agents, owing to their capability to introduce various functional groups and surface modifications. To meet this end, eight different combinations of binary and ternary DESs were synthesized using choline chloride …

Flexible Dye-Sensitized Solar Cells: A Study Of Photoanode And Counter Electrode Materials, Brishty Deb Choudhury

Theses and Dissertations

Compare to flat devices based on rigid substrates, fiber-shaped dye sensitized solar cells hold advantages of smaller size, light weight, facile fabrication, flexibility, and low cost, thus a promising direction for applications such as wearable electronic devices. Due to their unique photovoltaic properties, nanostructured morphologies of TiO2 on flexible substrate have been studied extensively in the recent years for applications in dye sensitized solar cells (DSSCs). Micro-structured electrode materials with high surface area can facilitate rapid charge transport and thus improve the light-to-current conversion efficiency. In the first part of this work the nano-tree morphology of the TiO2 photoanode material …

Antibacterial Coatings Derived From Novel Chemically Responsive Vesicles, Emily B. Mobley

Master's Theses

In order for a drug, or any material used for the purpose of eliciting a change in an organisms’ physical or chemical state, to be effective it must reach the intended target intact and for a sustained rate over time. Drug delivery systems encapsulate a drug to protect it from degradation, prevent side reactions, increase solubility, improve accumulation rates at target sites, and release drugs at a controlled rate. Controlled and sustained release of drugs is achieved by degradation of the carrier triggered by breaking dynamic chemical bonds caused by changes in the chemical environment such as pH or redox …

Li+ Co-Doping Induced Phase Transition As An Efficient Strategy To Enhance Upconversion Of La2zr2o7:Er,Yb Nanoparticles, Santosh K. Gupta, Maya Abdou, Jose P. Zuniga, Partha Sarathi Ghosh, Yuanbing Mao

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

The structural phase transition of materials is one of the most active research areas of solid state and materials chemistry in which atomic rearrangements tune fundamental pysochemical properties during the transition. In most cases, such transition requires high temperature, high pressure, or chemical doping. However, phase transition of complex metal oxides such as La2Zr2O7 has not been studied to enhance the upconversion (UC) and downconversion luminescence of their rare-earth doped nanoparticles (NPs) to meet the demand of their broad applications in solar cells, bioimaging, water purification, etc. In this work, we have successfully co-doped Li+ into La2Zr2O7:Er,Yb NPs to …

Mxenes As Flow Electrodes For Capacitive Deionization Of Wastewater, Naqsh E. Mansoor

Boise State University Theses and Dissertations

The energy-water nexus poses an integrated research challenge, while opening up an opportunity space for the development of energy efficient technologies for water remediation. Capacitive Deionization (CDI) is an upcoming reclamation technology that uses a small applied voltage applied across electrodes to electrophoretically remove dissolved ionic impurities from wastewater streams. Similar to a supercapacitor, the ions are stored in the electric double layer of the electrodes. Reversing the polarity of applied voltage enables recovery of the removed ionic impurities, allowing for recycling and reuse. Simultaneous materials recovery and water reclamation makes CDI energy efficient and resource conservative, with potential to …

Graphite Intercalation Compounds Derived By Green Chemistry As Oxygen Reduction Reaction Catalysts, Jianchao Zhao, Joseph H. Dumont, Ulises Martinez, Javier Macossay-Torres, Kateryna Artyushkova, Plamen Atanassov, Gautam Gupta

Physics & Astronomy Faculty Publications

Precious group metal (PGM) catalysts such as Pt supported on carbon supports are expensive catalysts utilized for the oxygen reduction reaction (ORR) due to their unmatched catalytic activity and durability. As an alternative, PGM-free ORR electrocatalysts that offer respectable catalytic activity are being pursued. Most of the notable PGM-free catalysts are obtained either from a bottom-up approach synthesis utilizing nitrogen-rich polymers as building blocks, or from a top down approach, where nitrogen and metal moieties are incorporated to carbonaceous matrixes. The systematic understanding of the origin of catalytic activity for either case is speculative and currently employed synthesis techniques typically …

Electrochemiluminescence Mechanisms Investigated With Smartphone-Based Sensor Data Modeling, Parameter Estimation And Sensitivity Analysis, Elmer Ccopa Rivera, Rodney Lee Summerscales, Padma P. Tadi Uppala, Hyun J. Kwon

Faculty Publications

The present study introduces a unified framework combining a mechanistic model with a genetic algorithm (GA) for the parameter estimation of electrochemiluminescence (ECL) kinetics of the Ru(bpy)₃²⁺/TPrA system occurring in a smartphone‐based sensor. The framework allows a straightforward solution for simultaneous estimation of multiple parameters which can be, otherwise, time‐consuming and lead to non‐convergence. Model parameters are estimated by achieving a high correlation between the model prediction and the measured ECL intensity from the ECL sensor. The developed model is used to perform a sensitivity analysis (SA), which provides quantitative effects of the model parameters on the …

Testing Flowering Perennial Plants In A Bermudagrass (Cynodon Spp.) Lawn, Paige Elizabeth Boyle, Michelle Wisdom

Horticulture Faculty Publications and Presentations

Most pollinating insects require a season-long succession of floral resources to fulfill life-cycle requirements. Incorporating forbs into turfgrass sites may create a season-long sequence of flowers to support foraging pollinators. However, persistence of forbs in warm-season turfgrasses such as bermudagrass (Cynodon spp.) may be affected by the competitive nature of the turfgrass and routine management practices such as mowing. A 2-year study was conducted to evaluate seven forbs (Bellis perennis L., Lotus corniculatus L., Prunella vulgaris L., Trifolium fragiferum L. ‘Fresa’, Trifolium repens L. ‘Durana’ and ‘Resolute’, Trifolium subterraneum L.) for persistence and ability to produce floral resources …

Innovative Approaches In The Discovery Of Aquatic Mycobacteriophages, Janis H. Doss

Biomedical Sciences Theses & Dissertations

Bacteriophages (phages), viruses that infect bacteria, have many applications in medicine, agriculture, molecular biology, and other fields. As antibiotic resistance becomes an increasing problem, interest in phages has grown. The traditional techniques of phage discovery are successful for some phages, but others require modified procedures to achieve detectable host infection.

Mycobacterium is a diverse bacterial genus characterized by a unique cell wall containing mycolic acids, which aids in survival and pathogenesis. The aims of the present research were to isolate mycobacteriophages, use bioinformatics techniques to analyze mycobacterial prophages, and combine genetic analysis with multi-well plate host range studies to identify …

Computationally-Guided Investigation Of Dual Amine/Pi Lewis Acid Catalysts For Direct Additions Of Aldehydes And Ketones To Unactivated Alkenes And Alkynes, Eric Greve, Jacob D. Porter, Chris Dockendorff

Chemistry Faculty Research and Publications

Dual amine/pi Lewis acid catalyst systems have been reported for intramolecular direct additions of aldehydes/ketones to unactivated alkynes and occasionally alkenes, but related intermolecular reactions are rare and not presently of significant synthetic utility, likely due to undesired coordination of enamine intermediates to the metal catalyst. We reasoned that bulky metal ligands and bulky amine catalysts could minimize catalyst poisoning and could facilitate certain examples of direct intermolecular additions of aldehydes/ketones to alkenes/alkynes. Density Functional Theory (DFT) calculations were performed that suggested that pyridine-2,6-bis(oxazoline) (PyBOX)-Pt(II) catalysts for alkene/alkyne activation could be combined with MacMillan's imidazolidinone organocatalyst for aldehyde/ketone activation to …

How Oxygen-Binding Affects Structural Evolution Of Even-Sized Gold Anion Clusters (Size Range 20 To 34), David Brunken-Deibert

Department of Chemistry: Dissertations, Theses, and Student Research

We report a joint anion photoelectron spectroscopy (PES) and theoretical study to investigate the effect of O₂-binding on the mid-sized even-numbered gold clusters, Au_n− (n = 20−34), a special size region of bare gold clusters that entail rich forms of structural evolution and transformation. Specifically, within this size range, bare Au₂₀₋ is a highly-symmetric pyramidal cluster, bare Au_21-25− are flat-planar or hollow-tubular clusters, bare Au₂₆₋ is the smallest core-shell gold cluster, while bare Au₃₄₋ is a magic-number/fluxional core-shell cluster with the high-symmetry tetrahedral Au₄ core. In light of the strong …

Chemistry And Biochemistry Authored Faculty Publications: Snapshot Of The Ranking Of Journals In Which They Published Based On Data From Journal Citation Reports (Jcr), Lutishoor Salisbury, Yang Tian, Jeremy Smith

University Libraries Faculty Publications and Presentations

This report presents a snapshot of the research output of the Chemistry and Biochemistry Department at the University of Arkansas for the period 2015-2019. The contents of the report were generated using Web of Science Core Collection databases and the Journal Citation Report only. It highlights the journals in which the researchers published and the ranking of those journals.

Effect Of Vortex-Induced Physical Stress On Fluorescent Properties Of Dye-Containing Poly(Ethylene Glycol)-Block-Poly(Lactic Acid) Micelles, Tyler L. Odom, Jacob R. Blankenship, Giselle Campos, Devin C. Mart, Wenyan Liu, Risheng Wang, Keiichi Yoshimatsu

Chemistry Faculty Research & Creative Works

The effect of vortex-induced mechanical stresses on the fluorescent properties of dye-containing poly(ethylene glycol)-block-poly(lactic acid) (PEG-b-PLA) block copolymer micelles has been investigated. PEG-b-PLA block copolymer micelles containing fluorescent dyes, 3,3′-dioctadecyloxacarbocyanine perchlorate (DiO) and/or 1,1′-dioctadecyl-3,3,3′,3′-tetramethylindocarbocyanine perchlorate (DiI), are prepared by a simple one-step procedure that involves the self-assembly of block copolymers and spontaneous incorporation of hydrophobic dyes into the core of the micelles. Upon vortexing, the micelle dispersion samples showed a decrease in fluorescence intensity in a rotational speed- and time-dependent manner. The results demonstrated that the vortexing can alter the fluorescent properties of the dye-containing PEG-b-PLA block copolymer micelle dispersion …