Digital Commons Network^™

Synthesis Of New Platinum-Based Anti-Cancer Drugs, Saud O. Albaroodi Yasser

Masters Theses

Cancer is considered the second leading cause of death after heart attack. Different treatments have been applied to kill cancer cells such as chemotherapy, which is the use of chemicals or drugs in order to treat cancer cells. Platinum-based anti cancer drugs are the backbone of chemotherapy, they play a crucial role in treating various malignant tumor. However, the disadvantages of these drugs are very painful on patients, such as nephrotoxicity and ototoxicity. In the last four decades, thousands of platinum-based anticancer drugs have been synthesized for hope in find a new drug with higher efficacy and less side effects.In …

Forensic Significance Of Teal Colored Cashmere And Black Acrylic Fibers, Nicole M. Martin

Forensic Science Theses

Textile fibers are a valuable type of trace evidence within forensic cases. They have the ability to connect a perpetrator to a victim and or a crime scene. Some types of fibers are more prevalent than others. The purpose of this research was to conduct a target fiber study in order to determine the significance of the selected fibers in a forensic case. Two fibers were selected from two different garments, black acrylic fiber and a teal colored cashmere fiber. Unknown fibers were collected from three local clothing stores and counted. Using light microscopy, all 20,164 fibers were eliminated as …

Three-Dimensional Scaffolds Of Graphene, Carbon Nanotubes And Transition-Metal Oxides For Applications In Electronics, Sensors And Energy Storage, Gilbert N. Mbah

Department of Chemistry: Dissertations, Theses, and Student Research

Electronics, sensors and energy storage devices are the new waves behind economic development, security and communication¹. Engineering small sizes of electronic, sensors and energy storage devices is the hurdle limiting efficient, portable and vast applications of Nano-devices for economic, security and communication advancement². Silicon the major material used in transistors has approached its limit to fabricated Nano-devices³. The discovery of free standing, one atomic layer thick and two-dimensional graphene sheets with high conductivity, inert, high specific surface area, stable and high tensile strength material in 2004 has shown capabilities to replaced silicon in electronics, …

The Intersection Of Nuclear Magnetic Resonance And Quantum Chemistry, Yali Wang

Department of Chemistry: Dissertations, Theses, and Student Research

Nuclear Magnetic resonance and quantum chemistry have been recognized to be strong tools for probing the structure and dynamics of molecules to further solve chemistry and biological problems. Chemical shift measured by NMR experiment and chemical shielding, molecular energy and molecular structure calculated by quantum chemistry provide extensive information.

Exact analytic gradients, are obtained for cavitation, dispersion and repulsion energies and time-dependent density functional theory for the continuum solvation model, which could be used to probe the structure, dynamics and properties of molecules. Copper in Cu_A azurin is recognized to be coordinated by a structure water molecule by comparing …

Hydrothermal Routes To Technetium Cluster Compounds, William M. Kerlin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Transition metals of groups six through nine exhibit unique direct multiple metal-metal bonding cores. Technetium is a group seven transition metal and is the lightest radioelement in the periodic table. Technetium exhibits nine oxidation states (from -I to VII) and an extensive set of mixed oxidation states due to bi- or poly- nuclear complex formation. Technetium has no stable isotopes and thirty four technetium isotopes have been discovered. Two main isotopes are of great importance ⁹⁹Tc and its metastable nuclear isomer ^99mTc. The isotope ^99mTc (T_1/2 = 6.01 hours, γ = 140.5 keV) is used in …

Versatile Synthetic Methods For Photoluminescent Pyrylium Tosylates, Jung Jae Koh

UNLV Theses, Dissertations, Professional Papers, and Capstones

Pyrylium salts are an important class of cationic organic molecules that exhibit good absorption, fluorescence, and photo-induced electron transfer properties. They can also function as precursors for synthesis of different heterocyclic organic molecules such as furan, pyridine, pyridinium salt, and betaine dyes. This thesis describes versatile methods of synthesis for a series of 2,4,6-triarylsubstitued pyrylium tosylates with different substituents by using p-toluenesulfonic acid monohydrate instead of conventional acid catalysts including perchloric acid or boron trifluoride diethyl etherate that accompany explosion danger and difficult storage problem, respectively. The chemical structures were established by ¹H and ¹³C NMR spectroscopic techniques …

Ultrafast Charge Carrier Dynamics In Bare And Surface-Modified Semiconductor Nanoparticles, Jameel Abdul-Hadi Hasan

Dissertations

Charge-carrier relaxation dynamics in semiconductor nanoparticles has been in the forefront of research for last three decades both for their fundamental nature as well as for applications in light-harvesting, luminescent labels, light-emitting diodes and nonlinear optics. Significant research has focused on II-VI semiconductors with emphasis on CdS and CdSe that are toxic. On the other hand, ZnO and TiO2 semiconductor nanoparticles are less toxic and have enormous applications in photo-catalysis, water splitting, solar cells and optical sensors. However, the investigations of charge-carrier dynamics in these semiconductor nanomaterials compared to II-VI semiconductor quantum dots are quite limited. The knowledge of charge-carrier …

Phosphinimine Zinc Complexes And Neutral Phosphinimines For Ring Opening Polymerization Of Lactides., Rajesh Thapa

Electronic Theses and Dissertations

Achiral arenesulfonates ligands having a (NNN) or (NNO) side arm have been developed (Chapter 2) and their respective zinc ethyl complexes, NNNZnEt 3.2 and NNOZnEt 3.3, have been synthesized and characterized using spectroscopic methods (Chapter 3). NNNZnEt as well as NNOZnEt complexes are stable under nitrogen atmosphere. In the NNOZnEt 3.3 complex the protons associated with the pendant (dimethylamino)ethyl arm are broad indicating that a fluxional process is operative, most likely dissociation of the (dimethylamino)ethyl arm at 25 °C in CD2Cl2. The fluxional behavior present in the 1H NMR spectrum of 3.2 could be arrested by cooling the CD2Cl2 solution …

Design, Fabrication, And Optimization Of Miniaturized Devices For Bioanalytical Applications, Suresh Kumar

Theses and Dissertations

My dissertation work integrates the techniques of microfabrication, micro/nanofluidics, and bioanalytical chemistry to develop miniaturized devices for healthcare applications. Semiconductor processing techniques including photolithography, physical and chemical vapor deposition, and wet etching are used to build these devices in silicon and polymeric materials. On-chip micro-/nanochannels, pumps, and valves are used to manipulate the flow of fluid in these devices. Analytical techniques such as size-based filtration, solid-phase extraction (SPE), sample enrichment, on-chip labeling, microchip electrophoresis (µCE), and laser induced fluorescence (LIF) are utilized to analyze biomolecules. Such miniaturized devices offer the advantages of rapid analysis, low cost, and lab-on-a-chip scale integration …

Synthesis Of Phenothiazinium Derivatives, Selorm J. Fanah

Electronic Theses and Dissertations

Photodynamic therapy (PDT) employs photosensitizing drugs for treating cancer. Once introduced into the body and localized in tumor cells, these photosensitizers are irradiated with light to produce active singlet oxygen radicals which kill cancer cells. The current drugs used in PDT have low quantum yield and always require a high energy radiation (normally laser). There is always a need for more effective drugs that have a high quantum yield and can be activated by visible light, in order to eliminate side effects caused by laser radiations.

In this work we synthesized derivatives of phenothiazine and phenothiazinium chromophores from the commercially …

Candida Albicans Hyphal Mannan Is Structurally Distinct From Yeast Mannan, Francis Kwofie

Electronic Theses and Dissertations

C. albicans is a polymorphic fungal pathogen which has the ability to shift from yeast to hyphae. C. albicans cell wall is composed of glucan, chitin, mannoprotein and mannan. It is not possible, using standard extraction methods, to isolate mannan from C. albicans hyphae. To isolate hyphal mannan, we developed a simplified alkali extraction method. Using this method it was determined that hyphal mannan has a much lower molecular weight, a smaller polymer distribution and altered conformation structure when compared to yeast mannan. The hyphal mannan was found to contain little to no acid-labile portion with only α-Man-PO₄ groups …

Computational Modeling Of Rna-Small Molecule And Rna-Protein Interactions, Lu Chen

Dissertations and Theses (Open Access)

The past decade has witnessed an era of RNA biology; despite the considerable discoveries nowadays, challenges still remain when one aims to screen RNA-interacting small molecule or RNA-interacting protein. These challenges imply an immediate need for cost-efficient while predictive computational tools capable of generating insightful hypotheses to discover novel RNA-interacting small molecule or RNA-interacting protein. Thus, we implemented novel computational models in this dissertation to predict RNA-ligand interactions (Chapter 1) and RNA-protein interactions (Chapter 2).

Targeting RNA has not garnered comparable interest as protein, and is restricted by lack of computational tools for structure-based drug design. To test the potential …

Linkage Analysis And Compositional Studies Of Β-Glucan From Saccharomyces Cerevisiae And Compositional Studies Of Mannan From Candida Albicans, Clara Arthur

Electronic Theses and Dissertations

The efficacy of a novel carbohydrate extraction procedure was investigated with methylation analysis and alditol acetate method by Gas Chromatography-Mass Spectrometry. A published extraction procedure for β-glucans was compared to one developed in house. Both procedures gave a dominant glucose peak in the Gas chromatogram indicative of successful β-glucan isolation. Further linkage studies showed four linkage positions for β-glucans isolated with the published method; terminal, 1,3-linkage, 1,6-linkage and 1,3,6-linkage, while β-glucans isolated using the new method showed six linkage positions; terminal, 1,3-linkage, 1,6-linkage, 1,4-linkage, 1,2,3-linkage and 1,3,6-linkage. Diminishing β-glucan linkage peaks in the chromatogram for the published method indicated structure …

Nmr-Based Structural Analysis Of Threonylcarbamoyl-Amp Synthase And Its Substrate Interactions, Kimberly A. Harris, Benjamin G. Bobay, Kathryn L. Sarachan, Alexis F. Sims, Yann Bilbille, Christopher Deutsch, Dirk Iwata-Reuyl, Paul F. Agris

Chemistry Faculty Publications and Presentations

The hypermodified nucleoside N(6)-threonylcarbamoyladenosine (t(6)A37) is present in many distinct tRNA species and has been found in organisms in all domains of life. This post-transcriptional modification enhances translation fidelity by stabilizing the anticodon/codon interaction in the ribosomal decoding site. The biosynthetic pathway of t(6)A37 is complex and not well understood. In bacteria, the following four proteins have been discovered to be both required and sufficient for t(6)A37 modification: TsaC, TsaD, TsaB, and TsaE. Of these, TsaC and TsaD are members of universally conserved protein families. Although TsaC has been shown to catalyze the formation of L-threonylcarbamoyl-AMP, a key intermediate in …

Competitive Halide Binding By Halogen Versus Hydrogen Bonding: Bis-Triazole Pyridinium, Binod Nepal, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The binding of F-, Cl-, Br-, and I- anions by bis‐triazole‐pyridine (BTP) was examined by quantum chemical calculations. There is one H atom on each of the two triazole rings that chelate the halide via H bonds. These H atoms were replaced by halogens Cl, Br, and I, thus substituting H bonds by halogen bonds. I substitution strongly enhances the binding; Br has a smaller effect, and Cl weakens the interaction. The strength of the interaction is sensitive to the overall charge on the BTP, rising as the binding agent becomes singly and then doubly positively charged. The strongest preference …

Agro-Waste As Source Of Fine And Industrial Chemicals: Synthesis Of 2-Formyl-6-Hydroxybenzoic Acid And 4-Methoxyisobenzofuran-1,3-Dione From Cashew Nut Shell Liquid, Lydia Kisula, Stephen J.M. Mdachi, Charles De Koning, Quintino A. Mgani

Tanzania Journal of Science

This paper reports on the synthesis of 2-formyl-6-hydroxybenzoic acid (8) and 4-methoxyisobenzofuran-1,3-dione (10) from a renewable natural material Cashew Nut Shell Liquid (CNSL) achieved in five and seven steps, respectively. Anacardic acid was isolated from CNSL, dimethoxylated into (E)-methyl 2-methoxy-6-(pentadec-8-enyl)benzoate which was subsequently hydrogenated into methyl 2-methoxy-6-pentadecylbenzoate. Benzylic bromination of the methoxyester, and dehydrobromination afforded (E)-methyl 2-methoxy-6-(pentadec-1-enyl)benzoate which upon ozonolysis gave methyl 2-formyl-6-methoxybenzoate. Oxidation and dehydration of 8 formed methoxyphthalic anhydride (10). The work reported in this paper has further demonstrated the resourcefulness of cashew nut shell liquid as a renewable natural resource for synthesis of fine and industrial chemicals.

Picolinyl-Assisted Approaches To Stereocontrolled Glycosylation, Jagodige Prithika Yasomanee

Dissertations

Although carbohydrates are the most abundant molecules on Earth, our current knowledge of these fascinating natural compounds is still limited. Some aspects that are already known include the carbohydrate involvement in damaging cellular processes such as bacterial and viral infections, development of tumors, metastasis, septic shock, etc. Consequently the development of effective methods for the synthesis, isolation, analysis, and investigation of complex carbohydrates has become critical in all areas of glycoscience. Among various focus areas, stereocontrolled glycosylation has emerged as a topic of particular importance. Yet, it remains a remarkable challenge to chemists because a new chirality center is formed …

A Structurally-Tunable 3-Hydroxyflavone Motif For Visible Light-Induced Carbon Monoxide-Releasing Molecules (Corms), Stacey N. Anderson, Jason M. Richards, Hector J. Esquer, Abby D. Benninghoff, Atta M. Arif, Lisa M. Berreau

Chemistry and Biochemistry Faculty Publications

Molecules that can be used to deliver a controlled amount of carbon monoxide (CO) have the potential to facilitate investigations into the roles of this gaseous molecule in biology and advance therapeutic treatments. This has led to the development of light-induced CO-releasing molecules (photoCORMs). A goal in this field of research is the development of molecules that exhibit a combination of controlled CO release, favorable biological properties (e.g., low toxicity and trackability in cells), and structural tunability to affect CO release. Herein, we report a new biologically-inspired organic photoCORM motif that exhibits several features that are desirable in a next-generation …

Understanding Mechanistic Details Of Neuroinflammatory Pathways Stimulated By The Alzheimer's Disease Amyloid-Beta Protein, Shana Usery

Dissertations

Alzheimer’s disease (AD) is characterized by neuroinflammation. Senile plaques composed of aggregated amyloid-β protein (Aβ) are found in AD patients’ brains. The Aβ is formed by the proteolytic cleavage of the amyloid precursor protein (APP) resulting in Aβ fragments that are 39-42 amino acids in length. The two most common peptides are Aβ(1-40) and Aβ(1-42), which differ by two amino acids, isoleucine and alanine. Within the brain of AD patients, Aβ monomer self-assembles to form several aggregate morphologies, including oligomers, protofibrils, and fibrils. Activated microglial cells and associated secreted proinflammatory cytokines surround these plaques producing a localized inflammatory environment in …

57th Annual Rocky Mountain Conference On Magnetic Resonance

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 57th annual meeting of the Rocky Mountain Conference on Magnetic Resonance, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Snowbird, Utah, July 26-31, 2015.

Characterization, Dna Binding And Cleavage Activities Of New Prodigiosin And Tambjamine Analogues And Their Cu²⁺ And Zn²⁺ Complexes, Karen Chichetu

Dissertations and Theses

Prodigiosins and tambjamines are natural compounds from bacterial and marine sources belonging to a family containing a common 4-methoxy-2,2'-bipyrrole core. These compounds have received a lot of interest due to their promising biological activities. Studies have suggested DNA as a potential therapeutic target for the natural prodigiosin and tambjamine due to their ability to facilitate oxidative DNA cleavage in the presence of Cu²⁺. Based on this we sought to study the metal binding activity of new prodigiosin and tambjamine analogues. A new prodigiosin analogue was synthesized and complexed with Cu²⁺. This revealed 1:1 complex formation between …

Steps Towards Deciphering The Post-Polyketide Synthase Tailoring Steps In The Phoslactomycin Biosynthesis Pathway, Patience Marimo

Dissertations and Theses

Phoslactomycins (PLMs) are a group of natural products belonging to a polyketides class. These polyketides are synthesized by sequential reaction catalyzed by a collection of enzymes activities called polyketide synthases. A polyketide is a large class of diverse compounds that are characterized by more than two carbonyl groups connected by single intervening carbon atoms. In other words, a polyketide is a polymer whose monomer is a ketide. The PLMs are also known as phosphazomycins or phospholines. These compounds were isolated based on antifungal and antitumor activities. This array of promising biological activities has stimulated research into the field of PLMs …

Poly(N-Isopropylacrylamide) Hydrogels For Storage And Delivery Of Reagents To Paper-Based Analytical Devices, Haydn T. Mitchell, Spencer Schultz, Philip Costanzo, Andres W. Martinez

Chemistry and Biochemistry

The thermally responsive hydrogel N,N'-methylenebisacrylamide-cross-linked poly(N-isopropylacrylamide) (PNIPAM) was developed and evaluated as a reagent storage and delivery system for microfluidic paper-based analytical devices (microPADs). PNIPAM was shown to successfully deliver multiple solutions to microPADs in specific sequences or simultaneously in laminar-flow configuration and was found to be suitable for delivering four classes of reagents to the devices: Small molecules, enzymes, antibodies and DNA. PNIPAM was also able to successfully deliver a series of standard glucose solutions to microPADs equipped to perform a colorimetric glucose assay. The results of these tests were used to produce an external calibration …

Using Peptides To Examine The Interaction Interface Between Aspartate Transcarbamoylase And Dihydroorotase In Pyrimidine Biosynthesis In Aquifex Aeolicus, Nouf Alyami

Master's Theses and Doctoral Dissertations

Aspartate transcarbamoylase (ATCase) and Dihydroorotase (DHOase) catalyze the second and third steps, respectively, in de novo pyrimidine biosynthesis. Both enzymes form an active complex (DAC) in Aquifex aeolicus, where loop A of DHOase interacts with a domain of ATCase. The main objective of this work is to determine the function of specific residues of loop A in DAC interactions and to alter the catalytic activities through disruption of the interface between the two enzymes from A. aeolicus. The ATCase and DHOase domains have been expressed in Escherichia coli and purified using affinity chromatography. The interface of the published …

Microwave-Assisted Synthesis Of Ss-Amino Alcohols, Hinalbahen Sanket Desai

Master's Theses and Doctoral Dissertations

ß-amino alcohols are common substructures in many biologically active compounds and can also be used as catalysts for asymmetric reactions. One common method for forming these moieties is by ring opening of unsymmetrical epoxides using amines via a substitution reaction. However, the majority of these methods requires excess of reagents, inorganic initiators, and/or extended reaction times. We have developed an efficient, regioselective route to synthesize amino alcohols via microwave-assisted aminolysis of several hindered and unhindered epoxides using amine nucleophiles of varying strengths. Microwave reactions can be done without Lewis acids or promoters, even for the most hindered trisubstituted epoxides. In …

Mini-Ises Identifies Promising Carbafructopyranose-Based Salens For Asymmetric Catalysis: Tuning Ligand Shape Via The Anomeric Effect, Kannan R. Karukurichi, Xiang Fei, Robert A. Swyka, Sylvain Broussy, Weijun Shen, Sangeeta Dey, Sandip K. Roy, David B. Berkowitz

David Berkowitz Publications

This study introduces new methods of screening for and tuning chiral space and in so doing identifies a promising set of chiral ligands for asymmetric synthesis. The carbafructopyranosyl-1,2-diamine(s) and salens constructed therefrom are particularly compelling. It is shown that by removing the native anomeric effect in this ligand family, one can tune chiral ligand shape and improve chiral bias. This concept is demonstrated by a combination of (i) x-ray crystallographic structure determination, (ii) assessment of catalytic performance, and (iii) consideration of the anomeric effect and its underlying dipolar basis. The title ligands were identified by a new mini version of …

The Quantum Efficiency Of Cdse Semiconducting Nanocrystals, Charles Bledsoe

Undergraduate Theses

CdSe molecules are semiconducting nanocrystals that absorb visible light and emit broad wavelengths of light in response. They utilize electromagnetic radiation not only for emitting broad wavelengths of visible light, but for fluorescence, conducting electricity, and vibrational relaxation. The Thermal Lensing technique (TL) can be used to study the lifetimes of the excited state transitions and the various nonradiative processes molecules can undergo in order to better understand the excited state dynamics of semiconducting nanocrystals, and in turn, better understand how these molecules may be applied in solar cells, lasers, and fluorescence labeling. Using known methods, four samples of CdSe …

Antioxidant Mechanisms Of Glutathione Against Metal-Mediated Oxidative Dna Damage, Elias Eteshola

Graduate Theses - Chemistry and Biochemistry

Oxidative damage of DNA strands has been strongly linked with the development of diseases such as certain cancers, cystic fibrosis and Parkinson’s, as well as aging. In intercellular reactions involving hydrogen peroxide endogenous metals have been shown to increase the generation of site-specific base modifications through their formation of reactive oxygen species (ROS). The damage markers measured via HPLC are the 8-hydroxy-2’-deoxyguanosine (8-OHdG) and the dA-N1 oxide markers. The current study deals with the reduced form of the sulfur antioxidant glutathione (GSH) and elucidating its ameliorating effects against ROS formation. Comparative studies with the known radical-scavenging sulfur antioxidant dimethyl sulfoxide …

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

Chemistry & Biochemistry Newsletter: 2002-2015

Inside

Page 2 Prototype Detects Cyanide Poisoning in 70 Seconds
Page 3 Department TAs Receive CETL Awards; Li Li Ji is Lardy Distinguished Lecturer
Page 4 Fulbright Scholar Uses Soil Components to Trap Pollutants; 2015 Graduates
Page 5 ASBMB Accredits CBC’s Biochemistry Major; Recent Faculty Publications
Page 6 Reaching Out to the Community
Page 7 Faculty and Student News; Alumni News
Page 8 Raynie Becomes an LCGC Editor; Retired Department Head Featured

A Ph Switchable Responsive Surface For The Trapping And Release Of A Hydrophobic Substance, Ali Esmail Karim

Masters Theses & Specialist Projects

Solid phase extraction is one of the most widely used techniques to trap and release compounds in a solution. A hydrophobic substance will stick efficiently to a hydrophobic surface (the “like dissolves like” principle). With an introduced response (i.e. pH change), a responsive surface can change from hydrophobic to hydrophilic, weakening the hydrophobic substance’s attraction and thus facilitate in an easy removal. A surface has been prepared having a terminal anthranilic acid (AA) moiety on silica gel particles, microscope slides, and TLC plates in three steps. First, a vinyl group was attached to the surface. Then, this vinyl group was …