Chemistry Commons^™

Photosensitization And Analytical Study On Reactive Oxygen Intermediates: Self-Sorting Surface Radicals And “On-Off” Sensitizer Function Mechanisms, Sarah J. Belh

Dissertations, Theses, and Capstone Projects

This thesis consists of four chapters which are detailed below. Chapter 1 is an introductory chapter, which lays out the background and purpose of the research.

Chapter 2 describes a study of the mobility of alkoxy radicals on a surface by detection of their recombination product. A novel method called symmetrical product recombination (SRP) utilizes an unsymmetrical peroxide that upon sensitized homolysis recombines to a symmetrical product [R'OOR → R'O•↑ + •OR → ROOR]. This allows for self-sorting of the radical to enhance the recombination path to a symmetrical product, which has been used to deduce surface migratory aptitude. SPR …

Pressure Driven Desalination Membranes: Lyotropic Liquid Crystals Containing Single Walled Carbon, Matteo A. Del Giudice, Samantha Castillo Merigold

Materials Engineering

This project presents a potential alternative desalination technique that utilizes the ion rejection properties of single walled carbon nanotubes dispersed in a lyotropic liquid crystal (LLC) matrix. Previous research has pointed to the polymerizable surfactant methacryloxy ethyl hexadecyl dimethyl ammonium bromide (C16MA) having capabilities of filtering molecular components smaller than a nanometer, when oriented in cylindrical micelles. SWCNTs were dispersed in deionized water by probe sonication and addition of surfactant cetyltrimethylammonium bromide (CTAB) due to SWCNTs’ hydrophobic properties. Membranes were produced containing 55wt% C16MA, 37wt% DI water, 0.1wt% with respect to the monomer (WRM) SWCNTs, 1.9 wt% WRM 2,2-dimethoxy-2-phenylacetophenone (photointiator), …

Computational Modeling Of Water And Proteins In Drug Discovery, Anthony Cruz Balberdy

Dissertations, Theses, and Capstone Projects

This thesis aims to improve how structural and thermodynamic properties of water on protein surfaces can be exploited to aid early stage drug discovery and lead optimization. We first discuss our development of SSTMap, a public domain software suite that maps out the properties of water on biomolecular surfaces. We then show the utility of these maps in describing differences in binding affinities between congeneric pairs of ligands. We then discuss our use of solvation maps in the prospective discovery of novel binders to cytochrome C peroxidase. Finally, we present our creation and validation of a homology model of Interleukin-24 …

Genome-Wide Screening Of Oxidizing Agent Resistance Genes In Escherichia Coli, Hao Chen, Jessica Wilson, Carson Ercanbrack, Hannah Smith, Qinglei Gan, Chenguang Fan

Chemistry & Biochemistry Faculty Publications and Presentations

The use of oxidizing agents is one of the most favorable approaches to kill bacteria in daily life. However, bacteria have been evolving to survive in the presence of different oxidizing agents. In this study, we aimed to obtain a comprehensive list of genes whose expression can make Escherichia coli cells resistant to different oxidizing agents. For this purpose, we utilized the ASKA library and performed a genome-wide screening of ~4200 E. coli genes. Hydrogen peroxide (H₂O₂) and hypochlorite (HOCl) were tested as representative oxidizing agents in this study. To further validate our screening results, we …

A Meta-Analysis Of The Protein Components In Rattlesnake Venom, Anant Deshwal, Phuc Phan, Jyotishka Datta, Ragupathy Kannan, Suresh Kumar Thallapuranam

Chemistry & Biochemistry Faculty Publications and Presentations

The specificity and potency of venom components give them a unique advantage in developing various pharmaceutical drugs. Though venom is a cocktail of proteins, rarely are the synergy and association between various venom components studied. Understanding the relationship between various components of venom is critical in medical research. Using meta-analysis, we observed underlying patterns and associations in the appearance of the toxin families. For Crotalus, Dis has the most associations with the following toxins: PDE; BPP; CRL; CRiSP; LAAO; SVMP P-I and LAAO; SVMP P-III and LAAO. In Sistrurus venom, CTL and NGF have the most associations. These associations …

Herc5 And The Isgylation Pathway: Critical Modulators Of The Antiviral Immune Response, Nicholas A. Mathieu, Ermela Paparisto, Stephen D. Barr, Donald E. Spratt

Chemistry

Mammalian cells have developed an elaborate network of immunoproteins that serve to identify and combat viral pathogens. Interferon-stimulated gene 15 (ISG15) is a 15.2 kDa tandem ubiquitin-like protein (UBL) that is used by specific E1–E2–E3 ubiquitin cascade enzymes to interfere with the activity of viral proteins. Recent biochemical studies have demonstrated how the E3 ligase HECT and RCC1-containing protein 5 (HERC5) regulates ISG15 signaling in response to hepatitis C (HCV), influenza-A (IAV), human immunodeficiency virus (HIV), SARS-CoV-2 and other viral infections. Taken together, the potent antiviral activity displayed by HERC5 and ISG15 make them promising drug targets for the development …

High Performance Mixed-Matrix Electrospun Membranes For Ammonium Removal From Wastewaters, Shu-Ting Chen, Sumith Ranil Wickramasinghe, Xianghong Qian

Chemical Engineering Faculty Publications and Presentations

Mixed-matrix electrospun membranes were developed to investigate ammonium removal from low ammonium concentration wastewaters for the first time. Particles derived from the inexpensive zeolite 13X were successfully incorporated into polyethersulfone (PES) matrices. The fabricated mixed-matrix electrospun membranes demonstrate high ammonium removal capacity reaching over 55 mg/g_zeolite, more than 2.5 times higher than the previously fabricated mixed-matrix membranes via non-solvent induced phase inversion. Moreover, the membranes fabricated exhibit high permeability and ease of regeneration. Over 90% of total ammonium nitrogen (TAN) can be removed from low TAN wastewaters such as aquaculture wastewaters. In addition to zeolite 13X, other zeolite …

Probe Metal Binding Mode Of Imine Covalent Organic Frameworks: Cycloiridation For (Photo)Catalytic Hydrogen Evolution From Formate, Jiyun Hu, Hamed Mehrabi, Yin-Shan Meng, Maddison Taylor, Jin-Hui Zhan, Qigeng Yan, Mourad Benamara, Robert H. Coridan, Hudson Beyzavi

Chemistry & Biochemistry Faculty Publications and Presentations

Metalation of covalent organic frameworks (COFs) is a critical strategy to functionalize COFs for advanced applications yet largely relies on the pre-installed specific metal docking sites in the network, such as porphyrin, salen, 2,2 '-bipyridine, etc. We show in this study that the imine linkage of simple imine-based COFs, one of the most popular COFs, readily chelate transition metal (Ir in this work) via cyclometalation, which has not been explored before. The iridacycle decorated COF exhibited more than 10-fold efficiency enhancement in (photo)catalytic hydrogen evolution from aqueous formate solution than its molecular counterpart under mild conditions. This work will inspire …

Reconstituting The Cyanobacterial Circadian Clock In Vitro, Pyong Hwa Kim

Dissertations

Cyanobacteria are photosynthetic organisms that are known to be responsible for oxygenating Earth’s early atmosphere. Having evolved to ensure optimal survival in the periodic light/dark cycle on this planet, their genetic codes are packed with various tools, including a sophisticated biological timekeeping system. Among the cyanobacteria is Synechococcus elongatus PCC 7942, the simplest clock-harboring organism with a powerful genetic tool that enabled the identification of its intricate timekeeping mechanism. The three central oscillator proteins—KaiA, KaiB, and KaiC—drive the 24 h cyclic gene expression rhythm of cyanobacteria, and the "ticking" of the oscillator can be reconstituted inside a test tube just …

Isolation And Determination Of The Composition And Structural Components That Comprise Dissolved Organic Matter Using Normal Phase Liquid Chromatography, Jonathan A. Long Jr

LSU New Orleans Theses and Dissertations

A comprehensive understanding of the reactivity associated with organic carbon is critical for recognizing the behavior of newly formed compounds in aquatic environments. In an effort to study the reactivity of complex mixtures, understanding the different processes affiliated with them are key. Understanding the reactivity associated with organic carbon can help to improve chromatographic separation. Using a combination of light and heavy crude oil, a separation procedure was developed to obtain a complete representation of the aromatic subfraction of the crude oil sample. The crude oils were separated into four distinct fractions based on the number of condensed aromatic rings …

Biodiesel Production By Esterification Of Ricinoleic Acid Over A Series Of Synthesized Sulfated Zirconia Catalysts, Elianaso Elimbinzi, Stephen S Nyandoro

Tanzania Journal of Science

A series of sulfated zirconia (SZ) were synthesized and evaluated for catalytic esterification of ricinoleic acid obtained from the castor oil with butanol at 110 °C. The effect of alcohols’ chain length was studied using butanol (C4), propanol (C3), ethanol (C2) and methanol (C1) at 65 °C, and reflux of corresponding alcohol boiling points. The synthesized catalysts were characterized using nitrogen porosimetry, X-ray powder diffraction, thermogravimetric analysis and Diffuse Reflectance Infrared Fourier Transform Spectroscopy. Analysis of ricinoleic conversion was performed using gas chromatography. Sulfuric acid loading improved the surface area of zirconia at a lower dose. The surface areas of …

Analysis And Comparison Of Optical Performance And Collectible Solar Energy Between Multi-Sectioned Compound Parabolic Concentrator (Cpc) And Restricted Exit Angle Cpc, Damasen Ikwaba Paul

Tanzania Journal of Science

This study was conducted to analyse and compare the optical performance and collectible solar radiation energy of two different Compound Parabolic Concentrators (CPCs): multi-sectioned CPC (hereafter called M-CPC) and restricted exit angle CPC (hereafter called R-CPC) so as to ascertain the best CPC for photovoltaics applications. For easy comparison between M-CPC and R-CPC, a standard CPC (hereafter called S-CPC) was also designed. A detailed ray trace simulation analysis was undertaken to compare ray trace diagrams, angular acceptance, optical efficiency and energy flux distribution of the three CPCs. Results indicated that the angular acceptance and optical efficiency of the three CPCs …

Evaluation Of Petroleum Hydrocarbons Contamination In Soils And Groundwater Using Electrical Resistivity And Hydrochemical Methods-Case Study: Ayetoro, Osogbo Southwestern Nigeria, Mutiu A Fakunle, Muhydeen A Ibraheem, Wasiu B Agbaje, Luqman A Abidoye

Tanzania Journal of Science

The presence of Petroleum Hydrocarbons (PHCs) in hand-dug wells has become a concern to the residents of Ayetoro area, Osogbo. Consequently, the detection of PHCs was evaluated using, nine Vertical Electrical Soundings (VES) and 2D electrical resistivity tomography surveys. Soil samples collected were analyzed for porosity and permeability. Hand-dug well water samples were screened for PHCs. VES revealed that second layer had high apparent resistivity of 14415.0 Ωm, indicating presence of PHCs that had penetrated to maximum depth of 19.1 m. The highest resistivity of the control points was 48.0 Ωm, indicating absence of PHCs. The 2D resistivity revealed highest …

Mineralogical And Geochemical Characteristics Of Graphite-Bearing Rocks At Chenjere Area, South-Eastern Tanzania: Implications For The Nature And Quality Of Graphite Mineralization, Charles D Moye, Michael M Msabi

Tanzania Journal of Science

This study focused on the mineralogical and geochemical characteristics of graphite-bearing rocks at Chenjere area by conducting surface geological mapping, geochemical and petrographical analyses with the intention of characterizing the nature of graphite occurrence in these lithological units. This paper presents results of the flake size, grade and mineralization extension of graphite in the graphitic gneiss. Field observations, petrographic investigation and comparison with other studies indicate that graphite occurrence at the Chenjere area is of sedimentary origin which fall under syngenetic type. The petrographic study revealed that nature of metamorphism of rocks in the Chenjere area is of high grade …

Synergistic Effects Of Halide Ions And Acacia Senegal Gum On The Corrosion Inhibition Of Mild Steel In Sulfuric Acid Solution, Jovine Emmanuel, Joseph Buchweishaija

Tanzania Journal of Science

The synergistic effects of halide ions, Br– and I– and Acacia senegal gum exudates on the corrosion inhibition of mild steel in 0.5 M sulfuric acid solution has been investigated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy techniques. Results showed that Acacia senegal gum exudate moderately reduces the corrosion rate of mild steel. The inhibition efficiencies on mild steel electrodes increased with increase in gum exudate concentrations up to 300 ppm, corresponding to the inhibition efficiency of about 43% and its inhibition efficiency increased up to 81.6% with addition of halide ions due to synergistic effects. The enhancement effect …

A Theoretical Study Of Synchronous Proton Transfer In (Hf)N, (H2O) N, And (Hcl) N Where N = 3, 4, 5, Johnny Yang

Honors Theses

For (HF)_n, (H₂O)_n, and (HCl)_n (n = 3 − 5), we have rigorously characterized the structures for the minima and transition states for synchronous proton transfer (SPT) with the CCSD(T) method and aug-cc-pVTZ basis set. The electronic barrier heights (∆E^†) associated with these transition states have also been computed with the explicitly correlated CCSD(T)-F12 method and the aug-cc-pVQZ-F12 basis set (abbreviated aQZ-F12). (HCl)_n (n = 3 − 5) SPT transition states have not been previously identified to the best of our knowledge, and they have been found …

The Emerging Applications Of Sulfur (Vi) Fluorides In Catalysis, Nicholas Ball, Cayo Lee, Jonathan E. Elisabeth, Nathan C. Friede, Glenn M. Sammis

Pomona Faculty Publications and Research

The past decade has witnessed remarkable growth of catalytic transformations in organic sulfur(VI) fluoride chemistry. This Perspective concentrates exclusively on foundational examples that utilize catalytic strategies to synthesize and react S(VI) fluorides. Key mechanistic studies that aim to provide insight toward future catalytic systems are emphasized.

Effects Of Amino Acid Side-Chain Length And Chemical Structure On Anionic Polyglutamic And Polyaspartic Acid Cellulose-Based Polyelectrolyte Brushes., Dmitry Tolmachev, George Mamistvalov, Natalia Lukasheva, Sergey Larin, Mikko Karttunen

Chemistry Publications

We used atomistic molecular dynamics (MD) simulations to study polyelectrolyte brushes based on anionic α,L-glutamic acid and α,L-aspartic acid grafted on cellulose in the presence of divalent CaCl₂ salt at different concentrations. The motivation is to search for ways to control properties such as sorption capacity and the structural response of the brush to multivalent salts. For this detailed understanding of the role of side-chain length, the chemical structure and their interplay are required. It was found that in the case of glutamic acid oligomers, the longer side chains facilitate attractive interactions with the cellulose surface, which forces the …

Extraction And Analysis Of Eugenol From Cloves, James V. Defrancesco

Chemistry: Faculty Publications and Other Works

This paper describes a laboratory procedure for the extraction and identification of eugenol from cloves (Syzygium aromaticum L.). The purpose is to instruct students in the isolation and identification of a medicinally relevant compound from a plant via simple solvent extraction. The analytical tools employed to identify eugenol and other naturally occurring chemical components in the cloves extract include color tests, thin layer chromatography (TLC), infrared spectrophotometry (IR), and gas chromatography coupled to mass spectrometry (GC-MS). In addition to eugenol, the cloves extract contains acetyl eugenol which can be distinguished from eugenol by several test methods. Triethylamine is used as …

Bruton's Tyrosine Kinase Targeting In Multiple Myeloma., Max Von Suskil, Kazi Nasrin Sultana, Weam Othman Elbezanti, Omar S Al-Odat, Robert Chitren, Amit K Tiwari, Kishore B Challagundla, Sandeep Kumar Srivastava, Subash C. Jonnalagadda, Tulin Budak-Alpdogan, Manoj K Pandey

College of Science & Mathematics Departmental Research

Multiple myeloma (MM), a clonal plasma cell disorder, disrupts the bones' hematopoiesis and microenvironment homeostasis and ability to mediate an immune response against malignant clones. Despite prominent survival improvement with newer treatment modalities since the 2000s, MM is still considered a non-curable disease. Patients experience disease recurrence episodes with clonal evolution, and with each relapse disease comes back with a more aggressive phenotype. Bruton's Tyrosine Kinase (BTK) has been a major target for B cell clonal disorders and its role in clonal plasma cell disorders is under active investigation. BTK is a cytosolic kinase which plays a major role in …

Structural Dependence Of The Thermal Stability Of Aminium Salts With Dicarboxylic Acids, Samantha Annunziata

Honors Theses

This proposed research project will investigate the thermal decomposition profiles and mechanisms of aminium dicarboxylates, the salts from the neutralization reactions between amines and dicarboxylic acids. Information on this research is currently missing from literature and will contribute to our knowledge on ambient amines and their transformation in the atmosphere.

Amines can be found in various forms in the environment. They are differentiated by the functional groups that replace one or more of the hydrogens from ammonia (NH3). One amine that will be studied is methylamine. Methylamine is the simplest amine: It has a methyl group (- CH3) that is …

Computational Modelling Of Drugs For Alzheimer’S Disease (Ad) And Applications On Artifical Neural Network Systems (Nets), Nouf Masarweh

Theses and Dissertations

Alzheimer’s disease (AD) is an irreversible and progressive disease that affects neurons and their connections in parts of the brain specifically the hippocampus and entorhinal cortex. The purpose of this research is to modify current medications used for the treatment of Alzheimer’s Disease utilizing computational modelling. The medications chosen to be modified are the most common drugs used in AD patients to treat mild to severe symptoms. The modifications are concluded to increase the half maximal inhibitory concentration (IC50) value which is the concentration needed for the drug to inhibit a specific biological function. Drug design throughout this research has …

Binding Affinity Of Flavins To The Dehydrogenase Domain Of Spnox, Quinesha Williams

Master of Science in Chemical Sciences Theses

NADPH oxidases (NOX’s) are enzymes that catalyze the production of superoxide through single electron transfer. This superoxide production leads to the production of other reactive oxygen species (ROS). ROS affect many metabolic processes throughout the body that can cause several different diseases, making this an ideal target for drug discovery. The general structure of NOX contains a transmembrane (TM) domain and a dehydrogenase (DH) domain connected by a linker. The DH domain contains binding sites for FAD and NADPH/NADH that both participate in the electron transfer necessary for producing superoxide. Structural information of NOX’s is still relatively new to the …

Carbonate Paleothermometry In Fayetteville Green Lake, New York, Micah Wiesner

Theses - ALL

Lacustrine carbonates are important paleoclimate archives, but unknowns in the seasonal timing and depth of precipitation obscure the interpretation of temperatures associated with them. The clumped isotope paleothermometer records the formation temperature T(D47) of carbonates. This study examines a set of lacustrine carbonates formed in the water column, in addition to carbonate from a sediment core, to better understand the depth and seasonality of carbonate formation in a lacustrine setting. We test that, regardless of season and formation temperature, lacustrine carbonates form in isotopic equilibrium with respect to D47 and d18O fractionation. Further, we account for the effect of our …

Effects Of Air Pollution, Temperature And Moisture Content On Copper And Silver Corrosions And The Reliability Of Data Center Equipment, Rui Zhang

Dissertations - ALL

The effects of moisture content, temperature, and pollutant mixture on atmospheric corrosion of copper and silver were investigated by exposing test specimens to different environmental conditions, followed by surface characterization using the coulometric reduction, Scanning Electron Microscopy, and Energy Dispersive Spectrometry (SEM/EDS). Printed circuit board test cards (PCBs) with bare copper were also used to investigate the effects of voltage bias on the PCBs on the corrosion rate. The test specimens were exposed to mixed flowing gases (MFG) environment with eight different combinations of the following five pollutants at the fixed concentration levels: 60 ppb O3, 80 ppb NO2, 40 …

Computational Algorithms For Predicting Membrane Protein Assembly From Angstrom To Micron Scale, Nandhini Rajagopal

Dissertations - ALL

Biological barriers in the human body are one of the most crucial interfaces perfected through evolution for diverse and unique functions. Of the wide range of barriers, the paracellular protein interfaces of epithelial and endothelial cells called tight junctions with high molecular specificities are vital for homeostasis and to maintain proper health. While the breakdown of these barriers is associated with serious pathological consequences, their intact presence also poses a challenge to effective delivery of therapeutic drugs. Complimenting a rigorous combination of in vitro and in vivo approaches to establishing the fundamental biological construct, in addition to elucidating pathological implications …

Carbonate Paleothermometry In Fayetteville Green Lake, New York, Micah Wiesner

Theses - ALL

Lacustrine carbonates are important paleoclimate archives, but unknowns in the seasonal timing and depth of precipitation obscure the interpretation of temperatures associated with them. The clumped isotope paleothermometer records the formation temperature T(D47) of carbonates. This study examines a set of lacustrine carbonates formed in the water column, in addition to carbonate from a sediment core, to better understand the depth and seasonality of carbonate formation in a lacustrine setting. We test that, regardless of season and formation temperature, lacustrine carbonates form in isotopic equilibrium with respect to D47 and d18O fractionation. Further, we account for the effect of our …

Effects Of Air Pollution, Temperature And Moisture Content On Copper And Silver Corrosions And The Reliability Of Data Center Equipment, Rui Zhang

Dissertations - ALL

The effects of moisture content, temperature, and pollutant mixture on atmospheric corrosion of copper and silver were investigated by exposing test specimens to different environmental conditions, followed by surface characterization using the coulometric reduction, Scanning Electron Microscopy, and Energy Dispersive Spectrometry (SEM/EDS). Printed circuit board test cards (PCBs) with bare copper were also used to investigate the effects of voltage bias on the PCBs on the corrosion rate. The test specimens were exposed to mixed flowing gases (MFG) environment with eight different combinations of the following five pollutants at the fixed concentration levels: 60 ppb O3, 80 ppb NO2, 40 …

Exploring The Mechanism Of The Electrostatic Denaturation Of Double-Stranded Dna, Gayatri Raghu

Master's Theses

Electrostatic melting is an electrochemical tool that can be used to analyze the stability of DNA, allowing for the detection of various mutations in double-stranded DNA (dsDNA). Here, we explore the influence of electrostatic double layer formation on the unzipping of dsDNA to better comprehend the mechanism of this process. Previous studies by our lab show that the melting curve produced can distinguish between fully complementary 34-bp strands and a version of the same sequence in which one base pair has been replaced with a mismatch pair or detect and characterize the crosslinking of the dsDNA by anticancer drug cisplatin. …

The Regiochemistry And Relative Reaction Rates Of Methylbiphenyl Isomers In Electrophilic Aromatic Substitution Reaction (Eas) Nitrations Suggest A Non-Planar Geometry For 2-Methylbiphenyl While 3- And 4-Methylbiphenyl Remain Planar, Tristan Pj Wine

Honors Projects

Electrophilic aromatic substitution (EAS) reactions have long been a fundamental addition to sophomore-level organic chemistry classes, allowing students the opportunity to explore the electron donating and withdrawing effects of electrons contained in the substituents of the aromatic reactant. In this paper we present preliminary findings on the nitration of methylated biphenyls using kinetic and regioselective assessments to analyze steric influences on the planarization of 2-methylbiphenyl after EAS nitration. Our preliminary findings show that nitration favors the methylated phenyl ring of 2-methylbiphenyl, indicating that the steric influence of the methyl group restricts planarization of the carbocation intermediate. Furthermore, a competition nitration …