Chemistry Commons^™

Nanoparticle Filled Polymeric Systems For Gas Barrier And Flame Retardant Properties, Yingji Wu

Dissertations

Polymer composite gas barrier and fire retardant properties were studied in this investigation. An increase in the gas barrier property was observed by adding silicate nanotubes or clay nanoparticles into polymeric systems. Oxygen permeability, diffusivity, solubility and water vapor permeability were determined for polyimide/silicate nanocomposites with 0 to 9.99% (vol/vol) filler loading. Both oxygen and water vapor permeability for the system gradually decreased when adding increasing amounts of nanofiller up to 4.50% (vol/vol) and increase again after that. The permeability decrease was caused by both the diffusivity and solubility coefficient changes, although diffusivity (the tortuous factor) is the main reason …

Relationships Between Cure Kinetics, Network Architecture, And Fluid Sensitivity In Glassy Epoxies, Katherine Lea Frank

Dissertations

Relationships between chemical structure, cure kinetics, network morphology and free volume have been correlated with fluid ingress for glassy epoxy network blends. Polymers synthesized from diglycidyl ether of bisphenol-A (DGEBA) and diglycidyl ether of bisphenol-F (DGEBF) were blended with varying amounts of triglycidyl-m-aminophenol (TGAP), tetraglycidyl-4,4-diaminodiphenylmethane (TGMP), napthylamine (NA), adamantylamine (AA), and aminopropylisobutyl polyhedral oliogmericsilsesquioxane (AI-POSS) and cured with 3,3’- and 4,4’- diaminodiphenylsulfone (DDS) to control fractional free volume, average hole size and morphology.

Varying curing profiles introduced morphological changes resulting in differences in network architectures. Epoxy with 10% NA had a smaller V_h (71 ų) …

Utilizing Polymer Topology In Peptide-Based Block Copolymers: Unique Aqueous Assembly And Responsive Behavior, Jacob Griffin Ray

Dissertations

This document details work in the area of amphiphilic polypeptide-based block copolymers that are able to self-assemble into well-defined nanostructures in aqueous solution. The main focus of this work is to understand the impacts of polymer topology on self-assembly behavior and response to external stimulus, particularly pH. Poly(L-lysine) and poly(L-glutamic acid) are two pH-responsive, hydrophilic polypeptides that possess the unique property of undergoing α-helix to random coil secondary structure transitions with pH, and this responsiveness can lead to global morphology changes such as changes in aggregate size or even morphology transitions. These polypeptides are synthesized via ring opening polymerization of …

Strategic Electronic Property Control Of Self-Assembling Pyrazine-Acenes, Lacie Brownell

UNLV Theses, Dissertations, Professional Papers, and Capstones

Control of electronic properties in organic semiconductor materials is essential for electro-optical applications such as field-effect transistors, light-emitting diodes, and photovoltaic devices. This work is focused on two systems that highlight different approaches for the manipulation of electronic properties: (I) the development of electron-deficient (n-type) materials by selective lowering of E_LUMO and (II) low energy gap materials by controlling both E_LUMO and E_HOMO

To specifically lower E_LUMO, a pyrazine-acene π-platform was extended using electron-withdrawing moieties. These include: pyridine, pyrazine, and benzothiadiazole (system I). From the base pyrazine-acene, the most significant change in E_LUMO of …

What Can Biochemistry Students Learn About Protein Translation? Using Variation Theory To Explore The Space Of Learning Created By Some Common External Representations, Thomas J. Bussey

UNLV Theses, Dissertations, Professional Papers, and Capstones

Biochemistry education relies heavily on students' ability to visualize abstract cellular and molecular processes, mechanisms, and components. As such, biochemistry educators often turn to external representations to provide tangible, working models from which students' internal representations (mental models) can be constructed, evaluated, and revised. However, prior research has shown that, while potentially beneficial, external representations can also lead to alternative student conceptions.

Considering the breadth of biochemical phenomena, protein translation has been identified as an essential biochemical process and can subsequently be considered a fundamental concept for biochemistry students to learn. External representations of translation range from static diagrams to …

Separation Of Tc From U And Development Of Metallic Tc Waste Forms, Edward Mausolf

UNLV Theses, Dissertations, Professional Papers, and Capstones

The isotope Technetium-99 (⁹⁹Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t_1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO₄]^-, Tc represents long-term concern to the biosphere. Various options have been considered to manage ⁹⁹Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric …

Forensic Signatures Of Chemical Process History In Uranium Oxides, Jonathan Plaue

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation comprehensively explores and develops new tools for nuclear forensic science to facilitate the identification of chemical process history in uranium oxides. Nuclear forensics is an emerging discipline motivated by the need to prevent and combat malevolent acts involving nuclear and radiological materials. This dissertation examined process signatures in uranium oxide powders, precursors, and sintered fuel pellets.

Signatures were investigated on set of powder and pellet exemplars synthesized in the laboratory and a set of real‐world samples with process information obtained from the literature or manufacturer. The examined techniques included morphology as revealed by scanning electron microscopy, near‐infrared reflectance …

Spectroscopic Investigation Of The Interaction Of Fadh In Dna Photolyase With Uv-Damaged Dna, Kyle Luke Williams

Theses, Dissertations and Culminating Projects

Skin cancer is the most prevalent malignancy found in humans, with the diagnosis rate continuing to steadily increase. The primary cause of this disease is overexposure to harmful ultraviolet (UV) radiation from sunlight, which can induce damage to the nitrogenous bases in DNA via dimerization. The most prevalent UV-induced photoproducts in DNA are cyclobutane pyrimidine dimers (CPDs), most commonly between adjacent thymidines.

Organisms have implemented methods by which to repair these CPDs, the primary of which are nucleotide excision repair (NER) and photoreactivation by photolyases. Photolyases are blue-light activated flavoproteins that are more efficient at recognizing and repairing CPDs than …

5,5'-Dichloro-2,2'-Dimethoxybiphenyl, Hans-Joachim Lehmler, Huimin Wu, Sean Parkin

Chemistry Faculty Publications

In the title molecule, C₁₄H₁₂Cl₂O₂, the dihedral angle between the least-square planes of the benzene rings is 62.17 (6)°. Both methoxy groups are slightly out of the plane of the benzene rings to which they are attached, making dihedral angles of 4.22 (18) and 18.82 (16)°.

Polymers For Dna Binding, Sue Yuan Li

Seton Hall University Dissertations and Theses (ETDs)

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Experimenting With Polymer Blend Solar Cells And Active Layer Thickness, Ryan Blumenthal

Physics

Bulk heterojunction organic photovoltaics utilize the electrical characteristics of semi-conductive polymers. These solution processable materials are beneficial because of their low material cost, light weight, and simple fabrication requirements. Our devices employ multiple photoactive polymers, P3HT and PCPDTBT, to absorb photons over a wide spectral range. We optimized various device characteristics including thickness and thermal anneal usage to reach a power conversion efficiency of 3.0% in AM1.5 sunlight. Device performance degrades over time due to atmospheric water and oxygen, prompting us to investigate device packaging to extend cell lifetime for additional testing.

Synthesis Of Porphyrin And Porphyrinoid Structures For Use In Binary Cancer Therapies: Fluorinated Porphyrin-Carborane As A Candidate For Boron Neutron Capture Therapy And Tetrabenzoporphyrin With Polyamine Conjugates As A Candidate For Photodynamic Therapy, Laura A. Clesi

Honors Capstones

No abstract provided.

Synthesis And Characterization Of Chromophores And Semiconducting Polymers Incorporating A 1,4-Fluorenylene Scaffold, Brynna Laughlin

All Dissertations

Research on conjugated chromophores and polymers has been a lucrative and highly active area for over a quarter-century. These pursuits have been driven by the unique properties of conjugated systems that allow their application in myriad fields including photonics (e.g. non-linear optics), and especially optoelectronics (e.g. organic light emitting diodes (OLEDs) and photovoltaic (PV) cells). Despite the years of dedicated research, there is still much work to be done in developing better materials for these types of applications. The full range of available molecular architecture and functionalization that are yet to be explored is still an untapped well of research. …

An Investigation Of The Electronic Coupling In Some Dimeric Ruthenium (Ii) Polypyridine Complexes, Roland Ngebichie Njabon

Graduate Theses and Dissertations

A detailed understanding of respiration at the molecular level requires an understanding of the many electron transfer steps involved in the process. These electron transfer processes are extremely fast and are impossible to measure by simple rapid mixing techniques. In order to get around this problem, scientists have used laser flash photolysis. This technique relies on the fact that under proper conditions, a reactant can be generated by a very short laser pulse. Once generated, the course of the reaction can be monitored by various techniques capable of very rapid time response. Many applications of this methodology rely on the …

On Chlorine Salts: Their Detection, Stability And Implications For Water On Mars And Europa, Jennifer Hanley

Graduate Theses and Dissertations

Chlorine salts (e.g. chlorides, chlorates and perchlorates) are an important factor in the stability of water on the surfaces of planetary bodies. Here we have shown that perchlorate and chlorate salts will lower the freezing point of water, allowing it to be liquid down to ~204 K. These salts will also slow down the evaporation rate, extending the lifetime of the liquid water solution. Chlorine salts have been detected on Mars, which has significant implications for the stability of water and hence its habitability. To study their effects on the stability of water on planetary surfaces, we need to first …

New Effects Of Aging And Lattice Intercalation On Surface Properties Of Titanate Nanobelts, Roger Williams

Graduate Theses and Dissertations

Titanate nanobelts (NBs) have structural characteristics beyond that of clays. Due to a negatively charged lattice matrix of edge-shared TiO6-octahedra, the location of intercalated cations within the interlayer space may dictate the charge-conductions. This environment may in turn govern the lattice-framework's stability and surface properties, based upon our preliminary

data.

On that basis, these nanomaterials have been found in our lab to possess superb biological compatibility that is closely related to the types of the intercalated cations. In addition, a prolonged agitation was proven to enable us to manipulate the titanate NBs' length. In a parallel study, a ripening was …

Further Studies On The Allylic Diazene Rearrangement, Maha Laxmi Shrestha

Graduate Theses and Dissertations

Former graduate student Wei Qi and Professor Matt McIntosh have reported diastereoselective reductive 1,3-transpositions of acyclic alpha, beta-unsaturated tosyl hydrazones to afford substrates with a 1,4-syn or 1,4-anti relationship between alkoxy and methyl groups that proceed via an ADR (Qi, W.; McIntosh, M. C. Org. Lett. 2008, 10, 357; Qi, W.; McIntosh, M. C. Tetrahedron 2008, 64, 7021). In these reports, silica gel was employed to accelerate the reduction. We have found that acetic acid gives the same results with high diastereoselectivity in the reaction. We further optimized the reaction by lowering the amount of catecholborane to 3 eq. Effects …

Oxidative Aliphatic Carbon-Carbon Bond Cleavage Reactions, Caleb J. Allpress

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The work presented in this dissertation has focused on the activation and cleavage of chemical bonds between two carbon atoms. The selective oxidative activation of carbon-carbon bonds is important due to potential applications in the utilization of biomass for fuel production, applications in wastewater treatment and bioremediation, and in developing new reactions for organic synthesis of fine chemicals including pharmaceuticals. Ideally these reactions would be carried out with high atom economy at low temperatures and pressures, and using earth-abundant elements as reagents and catalysts. With these points in mind, nature provides an ideal model framework, carrying out its chemistry at …

Structural And Functional Characterization Of The Ldp3 (Vhz) Protein Tyrosine Phosphatase, Vyacheslav I. Kuznetsov

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Protein phosphorylation is as an important regulatory mechanism that controls a large number of physiologically important cellular processes. Proteins are phosphorylated on aliphatic (serine and threonine) as well aromatic (histidine and tyrosine) residues predominantly located on sterically accessible loops. Phosphorylation affects three- dimensional structures of proteins resulting in conformational changes which activate or deactivate enzymatic functions. Because of the ability of protein phosphorylation to modulate a multitude of diverse cellular processes, it became an appealing and promising target for drug therapy.

Attachment of phosphate is accomplished by kinases, whereas the removal of the phosphoryl group is performed by protein phosphatases. …

Enhanced Structural Support Of Metal Sites As Nodes In Metal-Organic Frameworks Compared To Metal Complexes, Sanjit Das

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Crystalline porous materials have gained long-standing interest for their application in gas storage, separation and catalysis. These materials have been useful for domestic, scientific and industrial purposes for many decades. Zeolites are a well known example of such materials.

Metal-organic frameworks are a new class of crystalline porous materials. They have many advantages over the more widely known zeolites. Though metal-organic frameworks are relatively new, their basic structure, known as the secondary building unit, very closely resembles the structure of metal complexes. Such metal complexes have been characterized in chemistry for more than a century.

Chemical catalysis is a process …

Rhodium Complexes Of A New Structurally Adaptive Pnn-Pincer Type Ligand, Sarath Wanniarachchi, Jeewantha S. Hewage, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A new PNN-pincer type ligand with pyrazolyl and diphenylphosphine flanking donors on a diarylamido anchor has been prepared. Its bis(tert-butyl isocyanide)rhodium(I) complex exhibits hemilabile behavior in solution, and its solid-state structure verified the elusive κ²P,N coordination mode for this type of ligand. Reactions between (PNN)Rh(CN^tBu)₂ and iodomethane afford both fac- and cis,mer-[(PNN)Rh(CN^tBu)₂(Me)](I), which further showcases the structural versatility of the ligand.

Chitosan-Cellulose Composite Materials: Preparation, Characterization And Application For Removal Of Microcystin, Chieu D. Tran, Simon Duri, Ambra Delneri, Mladen Franko

Chemistry Faculty Research and Publications

We developed a simple and one-step method to prepare biocompatible composites from cellulose (CEL) and chitosan (CS). [BMIm⁺Cl⁻], an ionic liquid (IL), was used as a green solvent to dissolve and prepare the [CEL + CS] composites. Since majority (>88%) of IL used was recovered for reuse by distilling the aqueous washings of [CEL + CS], the method is recyclable. XRD, FTIR, NIR, ¹³C CP-MAS-NMR and SEM were used to monitor the dissolution and to characterize the composites. The composite was found to have combined advantages of their components: superior mechanical strength (from CEL) …

A Comparative Study Of Ce3+/Ce4+ Redox Couple On Pt Electrode In Sulfuric Acid And Methanesulfonic Acid, Zhao-Hua Li, You-Qun Chu, Chun-An Ma

Journal of Electrochemistry

The electrochemical oxidations of Ce³⁺ to Ce⁴⁺ on Pt rotating disk electrode (RDE) in both sulfuric acid and methanesulfonic acid (MSA) solutions were studied by using cyclic voltammetry and linear sweep voltammetry. The complexing behaviors of Ce³⁺/Ce⁴⁺ were preliminarily probed and the exchange current density, diffusion coefficient, as well as reaction rate constant were obtained from Butler-Volmer equation. The activation energies of Ce³⁺ oxidation on Pt electrode in two types of acidic media, obtained from Arrhenius equation, were also compared. The results indicate that Ce³⁺ can be oxidized to Ce4+ much easier in …

An Electrochemical Impedance Spectroscopic Study Of Cuf2/Moo3/C Cathode Composites, Yue-Li Shi, Nan Wu, Ming-Fang Shen, Jia-Qun Dong, Quang-Chao Zhuang, Li Jiang

Journal of Electrochemistry

Composite electrode of CuF₂/MoO₃/C was fabricated through high energy mechanical milling. The properties of CuF₂/MoO₃/C were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), galvanostatic charge-discharge measurements, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the grain sizes of CuF₂ and MoO₃ after milling were 200 ~ 300 nm, and the initial discharge capacity of CuF₂/MoO₃/C was 647 mAh·g^-1 at room temperature and at a current density of 10 mA·g^-1. However, the …

Analysis Of The Material Factors In The Degradation Of Sofc Performance, Ke-Qing Gao, Xiao-Tian Liu, Qing Zhao, Li-Quan Fan, Yue-Ping Xiong

Journal of Electrochemistry

Based on the cell operating conditions, the material factors which influence the cell performance of SOFC including the chemical stability of materials at solid-gas interface in redox atmosphere, the diffusion and reaction between the interface of solid-solid materials, and degradation caused by the external chemical substances brought into the cells at triple phase boundary are mainly analyzed. Given that under the current state of the research it is urgent to explore the material factors on degradation of cell performance to meet demands in SOFC applications.

Electrochemical Activities Of Oxygen-Doped Carbon Surface For V(Iv)/V(V) Redox Couple, Huan Zhang, Lin-Lin Qin, Yi-Ning Shi, Ming-Sen Zheng, Quan-Feng Dong, Zhao-Wu Tian

Journal of Electrochemistry

Graphite plate electrodes were treated with oxygen plasma and doped with oxygen as well as oxygen functional groups. With the treatment, the activities of graphite plate electrodes toward VO²⁺/VO₂⁺ redox reactions were improved. FT-IR and EDS analysis results indicated that oxygen functional groups were introduced to the surface of graphite plates after oxygen plasma treatment. In this paper, the graphite plate treated for 20 min showed the highest activity. The average charge efficiency reached 91%, suggesting an increase of 19%, compared with that of the untreated graphite plate under a current density of 8 mA·cm^{-2 …}

Hydrothermal Synthesis Of Pure Li4Ti5O12 And Its Electrochemical Performance, Wen-Jun Xie, Yu-Shi He, Hong Wang, Xiao-Zhen Liao, Zi-Feng Ma

Journal of Electrochemistry

Spinel Li₄Ti₅O₁₂ was prepared by hydrothermal method using commercial anatase (TiO₂) and lithium hydroxide (LiOH) as raw materials. The effects of the LiOH concentration of lithium hydroxide, hydrothermal reaction time and calcination temperature on the structure and electrochemical performance of Li₄Ti₅O₁₂ were investigated. The formation process of Li₄Ti₅O₁₂ was also proposed. The micro-structure and morphology wereas characterized by XRD, SEM, TEM techniques, and the electrochemical performance was analyzed by galvanostatic charge-discharge test. The results show that the pure phase spinel Li₄Ti …

Current Statuses And Prospects Of Bioeletrochemical Instruments, Ren Hu, Chun-Hui Piao, Chang-Jian Lin, Dong-Ping Zhan, Bin Ren, Amatore Christian, Zhong-Qun Tian

Journal of Electrochemistry

Charge transfer is one of the essential life processes. In the past decades, the electrochemical methods have been developed to study life science in a unique physicochemical view and have exhibited abundant and precious information beyond conventional biological techniques. As bioelectrochemical research areas evolved from the fundamental studies of biomolecules’ electrochemical behaviours in non-living conditions to the living cells in intro and in vivo, and further to the single molecule in living systems, the role of instruments becomes more and more crucial. The performances of instruments such as sensitivity, resolution (time, spatial and eneygy resolutions) and controllability are more demanding …

Preparation And Catalytic Properties Of Feco Alloy Nanocatalyst, Ming-Xuan Li, Jie-Lian Ou, Sheng-Pei Chen, Peng Wang, Bin-Bin Xu, Shi-Gang Sun

Journal of Electrochemistry

The FeCo alloy nanoparticles were electrodeposited on glassy carbon electrode by chronoamperometry and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the shapes of FeCo nanoparticles were cubes with an average size of 65 nm. The atom ratio of Fe and Co is 1:1. As indicated from the pattern of selected area electron diffraction (SAED), the FeCo cubic nanoparticles were single crystal which belonged to body-centered cubic with an interval of 0.201 nm referring to the (110) facets of FeCo alloy. The FeCo cubic nanoparticles exhibited the enhanced electrocatalytic …

Fabrication And Localized Surface Plasmon Resonance Of Ultrathin Nanoporous Gold Films, Shi Feng, Shu Chen, Qing Yang, Juan Xiang

Journal of Electrochemistry

Ultrathin nanoporous gold films (NPGF) with a thickness of approximately 50 nm were fabricated via electrochemical dealloy method. The morphology of NPGF was evaluated with a parameter of surface roughness. SEM results demonstrate that the fabrication of NPGF with different roughness factors can be achieved by controlling the circles of cyclic voltammetry. UV-Vis spectra indicate that the localized surface plasmon resonance (LSPR) of NPGF is affected by the roughness of NPGF. With the optimal roughness factor, NPGF displays a linear relationship between the ethanediol concentration and the absorbance intensity at λ = 450 nm. The LSPR effect of NPGF presents …