Chemistry Commons^™

Development Of Novel Mass Spectrometric Methods For Reaction Screening, Oligosaccharide Detection, And Nitrosamine Quantitation, Qi Wang

Dissertations

Benefitting from its high detection sensitivity and specificity, mass spectrometry (MS) has become a powerful technique in academia and industry. The aim of this dissertation study is to develop new mass spectrometric methods for organic reaction screening, detection of oligosaccharide/glycan in complex matrices, and nitrosamine absolute quantitation.

First, an electrochemistry/mass spectrometry (EC/MS) platform is built to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes, which leads to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes. Net redox neutral electrosynthesis is quite rare in synthetic organic …

Advanced Cnc/Peg/Pdmaa Semi-Ipn Hydrogel For Drug Delivery Management In Wound Healing, Samia Afrin, Md. Shahruzzaman, Papia Haque, Md. Sazedul Islam, Shafiul Hossain, Taslim Ur Rashid, Tanvir Ahmed, Makoto Takafuji, Mohammed Mizanur Rahman

Department of Chemistry: Faculty Publications

A Semi Interpenetrating Polymer Network (semi-IPN) hydrogel was prepared and loaded with an antibiotic drug, gentamicin, to investigate the wound healing activity of this system. The semi-IPN hydrogel was synthesized by combining natural polymer cellulose nanocrystal (CNC) and synthetic polymer polyethylene glycol (PEG) and poly (N,N0-dimethyl acrylamide) (PDMAA), which was initially added as a monomer dimethyl acrylamide (DMAA). CNC was prepared from locally obtained jute fibers, dispersed in a PEG-NaOH solvent systemand then mixed with monomer DMAA, where polymerization was initiated by an initiator potassium persulphate (KPS) and cross-linked by N,N0-methylenebisacrylamide (NMBA). The size, morphology, biocompatibility, antimicrobial activity, thermal and …

A New Insight Into Fungal Cell Wall Architecture By Functional Genomics And Solid-State Nmr Along With Recent Advancements In Dynamic Nuclear Polarization For Analyzing Biomolecules, Arnab Chakraborty

LSU Master's Theses

This dissertation summarizes the findings related to the way by which supramolecular architecture of fungal cell wall changes with genetic mutation, dispensing genes responsible for biosynthesis of cell wall polysaccharides. This is necessary because without perfect picture of how supramolecular assembly changes with genetic mutation it is hard to assess new anti-fungal targets. Alongside this we have highlighted how recent advancement into Dynamic Nuclear Polarization (DNP) methods improved characterization of biomolecules both in case of labeled and unlabeled samples.

First study utilized Solid-state NMR (SSNMR) which is a non-destructive technique hence enabled us for the first time to deduce how …

Extending The Application Of Polyol-Induced Extraction For The Analysis Of Glucocorticoids And Nsaids In Water Using Uhplc-Ms/Ms, Shipra Patel

Seton Hall University Dissertations and Theses (ETDs)

Polyol induced extraction (PIE) is an extraction technique developed and patented by Sowa Jr., Murphy, and Deshpande at Seton Hall University as a method of removal of water from acetonitrile. PIE is a technique that separates water from a mixture containing an organic liquid and water by adding a polyol to the mixture that leads to phase separation of aqueous and organic phase. The goal of this work was to extend the application of PIE and to demonstrate that PIE can be an alternative method for extraction of glucocorticoids and non-steroidal anti-inflammatory drugs (NSAIDS) which then can be analyzed using …

Using Thermodynamics To Evaluate Stationary Phase Polarity In Gas Chromatography- A New Look, Hetal R. Rana

Seton Hall University Dissertations and Theses (ETDs)

Abstract

Gas chromatography is a separation method in which the components of a sample partition between a gaseous mobile phase (carrier gas) and a solid or liquid stationary phase. The stationary phase is usually a polymer coated or chemically bonded to a solid support on the column wall and its function is to separate different components, based on their relative vapor pressure and their intermolecular interactions with the stationary phase. If the analyte polarity is similar to the stationary phase polarity, then the retention time increases because the intermolecular interactions are stronger and if the polarities are different then the …

Understanding The Effects Of Temperature On Electrostatic Dna Denaturation, Jeffrey Taylor

Master's Theses

In this work, the electrostatic denaturation of 18-bp DNA duplexes was investigated via Square Wave Voltammetry (SWV) to determine the extent of melting (∆) and rate of melting (𝝉). Electrostatic denaturation was observed over the temperature range of 20-50 °C, and purely electrostatic melting was defined from 27.5°C. In contrast, electrostatic denaturation for 30 °C was defined as a mixture of thermal melting thiol desorption + electrostatic melting. Electrostatic denaturation is a temperature-dependent process, and the amount of melting of the dsDNA increased with temperature. It was also observed that the ∆ and 𝝉 values increase with temperature further …

Statistical Analyses Of Hemp Cannabinoid Test Results, Rachel J. Stegmeier

Senior Honors Projects, 2020-current

Cannabis sativa L. is a flowering plant used for recreational and industrial purposes that produces a class of compounds called cannabinoids. Industrial hemp is a strain of Cannabis sativa L. that has been propagated to have a low Δ 9 tetrahydrocannabinol (Δ⁹THC) and a high cannabidiol (CBD) content. With recent advancements in legislation, farms are now growing hemp for fiber, CBD production and other hemp derived product purposes but crops risk being destroyed if THC content levels exceed the current maximum legal limit of 0.3%. For the present study hemp samples were dried, ground, extracted with various alcohols, …

Biomaterials: From Scaffold Design To Implant Optimization, Jennifer Marie Armen

Electronic Theses and Dissertations

This work encompasses three individual projects concerning biomaterials and their modifications. Chemically-Induced Cross-Linking of Peptidic Fibrils for Scaffolding Polymeric Particles and Macrophages EAK16-II (EAK) is a self-assembling peptide (SAP) that forms β-sheets and βfibrils through ionic-complementary interactions at physiological ionic strengths. The soft materials can be injected in vivo, creating depots of drugs and cells for rendering pharmacological and biological actions. The scope of the applications of EAK is sought to extend to tissues through which the flow of extracellular fluid tends to be limited. In such anatomical locales the rate and extent of the fibrilization are limited insofar as …

Phosphorus Enriched Modified-Douglas Fir Biochar As A Soil Amendment, Beatrice Arwenyo

Theses and Dissertations

Biochar application as a soil additive is gaining global acceptance. In this era of climate change, biochar use for improved soil productivity is not just a sustainable eco-friendly substitute to synthetic fertilizer, but a noble contributor to the fight against climate change. Although biochar has been accredited with some environmental and agricultural benefits, most studies concentrated on agricultural and biowaste products as feedstocks. This research was designed to explore P-enriched modified-Douglas fir biochar potential as a soil additive. Using corn as a test crop, greenhouse studies were performed on acidic sandy soil, comparing phosphorus enriched modified-Douglas fir biochar efficacy to …

Functionalized Biochar Electrodes For Asymmetric Capacitive Deionization, Hellen Stephanie

Theses and Dissertations

Electrosorption-based capacitive deionization (CDI) has become a viable process for brackish water desalination and defluoridation. In this study, activated Douglas fir biochar is used as a low-cost electrode material with adsorption capacity comparable to activated carbon obtained from biomass precursors. Adding functional groups to the activated biochar enhanced salt removal capacity, providing cation and anion selectivity. The functionalized electrodes were prepared by Nafion, titanium isopropoxide, and p-phenylenediamine treatment, respectively, which introduced sulfonate, titanium dioxide and amine functional groups to the electrode surface. These modification methods are versatile and can be easily performed without sophisticated laboratory environment. Modified biochar electrodes …

Nitro-Aromatic Polymers For Conversion-Style Battery Cathodic Materials, Brady P. Samuelson

Honors Thesis

The development of organic electrode materials in rechargeable batteries has seen a resurgence in recent decades. This spike in interest is mostly due to the increased investments in renewable energy sources, grid-scale energy storage, and the rapid transition to electric vehicles. Current lithium battery cathode materials typically use some form of lithium metal oxide (specific capacity: 272 mAh g^-1 which has problems with limited capacity, thermal runaway, and an unreliable supply chain. Our research group’s solution involves investigating new lightweight, organic redox groups combined with a conductive polymer backbone to serve as a possible replacement for the cathode in …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Real-Time Monitoring Of Paraquat Photodegradation Using Colloidal Gold Surface Enhanced Raman Spectroscopy, Nathan Wilson

Masters Theses & Specialist Projects

Monitoring chemical reactions in aqueous solution is a challenge because most instrumental techniques either are not suited for the rapid timescales, are not sensitive enough to detect products at low concentrations, or do not have sufficient structure-to-spectrum relationships. Raman spectroscopy is a promising method to monitor reactions, as it is fast, dependent on chemical structure, and has little interference from water. However, Raman scattering is generally very weak. Surface-enhanced Raman spectroscopy (SERS) improves the signal strength of Raman spectroscopy by using a metal surface plasmon, or oscillation of the surface’s electrons, to allow for highly selective and sensitive detection and …

Towards The Determination Of Estrone And 17Β-Estradiol In Dairy Cattle Waste Using Solid Phase And Stir Bar Sorptive Extractions With Liquid Chromatography-Mass Spectrometry And Gas Chromatography-Mass Spectrometry, Pallavi Ragi

Masters Theses & Specialist Projects

Steroidal hormones are naturally produced as a part of many physiological processes and are excreted in the urine and feces of animals and humans. Farm animals in concentrated animal feeding operations (CAFOs) are routinely implanted with synthetic and natural hormones to enhance growth and production, contributing significantly to environmental steroid hormone contamination. Every year around 49 tons of estrogens are generated by livestock waste in the United States alone. Due to rainfall and runoff, these steroid hormones reach the environment when animal waste is applied as manure. Studies show that estrogens and other steroidal hormones present in the surface waters …

Nitrogen Doping Of Electrochemically Activate Carbon Screen-Printed Electrodes, Ethan Galloway

Undergraduate Honors Theses

Screen printed electrodes (SPEs), which are prepared by patterning conductive inks or pastes onto an insulating support (e.g., plastic film), are widely employed as sensing and biosensing platforms due to their ease of fabrication and relatively low cost. This is especially applicable to electrodes of this nature prepared with carbon-based inks (SPCEs). To date, the most successful and significant commercial application of SPEs has been as test strips for glucose meters. Despite the maturity of this technology, SPE research remains very active as improvements in sensitivity and selectivity, which often involve modifying the electrode surface, hold the key to advancing …

Liquid Chromatography With Tandem Mass Spectrometry Method Development For The Determination Of Β–Defensins In Bovine Milk, Symone T. Whalin

Masters Theses & Specialist Projects

Bovine mastitis, caused by a wide array of pathogens, results in a substantial economic loss for the dairy cattle livestock industry. β-defensins are a part of the bovine’s innate immune system and act as the first line of defense against mastitis. Only foundational research has been done on β-defensins’ ability to treat and prevent mastitis. There have been no analytical methods reported in the literature for analyzing β-defensins in bovine milk. This research aims to create an analytical approach to determine β-defensins in bovine milk. It is challenging to determine an analyte in a complex sample matrix, and milk is …

Investigation Of The Analytical Utility Of The Inductively Coupled Plasma Mass Spectrometer (Icp-Ms) For The Quantification Of Proteins Via Lanthanide Labeling, Caitlin Elizabeth Dunlap

Undergraduate Honors Thesis Collection

The discovery and ability to provide an absolute concentration of biomarkers in the body can facilitate early diagnoses of diseases. This information can also be used for more accurate and unique treatments for those patients. While major advances in molecular mass spectrometry allows for a sensitive identification of these biomarkers, they are limited to only four orders of magnitude in their dynamic ranges. Due to this, detection and quantitation of low abundant proteins, which tend to make up these vital biomarkers, is very difficult. On the other hand, ICP-MS offers a wider dynamic range (up to 12 orders of magnitude) …

Screening Of Near-Ir Surface-Enhanced Raman Scattering (Sers) Dyes Using Quick Freezing-Induced Aunp Aggregates (Qfiaas)., Carleigh A. Cimmerer

Forensic Science Master's Projects

Near-IR (NIR) surface-enhanced Raman scattering (SERS) is an emerging bioimaging technique that can be a safe alternative with a resolution better than current bioimaging techniques, such as MRI, CT, and PET. These can be hazardous with long-term exposure due to powerful magnetic fields or ionizing radiation. The success of NIR SERS bioimaging lies partially in the selection of highly sensitive NIR Raman reporters, which is essential to achieve highly resolved bioimaging of the body system. NIR Raman dyes must satisfy three important conditions: strong absorption in the NIR region, strong binding to the surfaces of gold nanoparticles (AuNPs), and excellent …

Spectroscopic Measurements Of Meibum Compositional, Structural, And Functional Relationships To Elucidate The Role Of Meibum In Dry Eye., Anthony Chigozie Ewurum

Electronic Theses and Dissertations

The major aim of my dissertation was to investigate the etiology of dry eye disease which affects about 7 million people in the United States, causing symptoms that can lead to visual disturbance. Correlation between dry eye and an abnormal lipid layer of the tear film has been found. Tear film lipids originate mostly from the meibomian glands. Cholesteryl ester (CE) and Wax ester (WE) lipids make up most of the human meibum lipidome and the CE/WE ratio has been shown to decrease in patients with meibomian gland dysfunction. Model studies using synthetic CE and WE, although providing some insight, …

Lipid Rafts, Exosomal Vesicles And Anti-Giardial Therapies, Brian Ivan Grajeda

Open Access Theses & Dissertations

Giardia lamblia, a protozoan parasite, is a major cause of waterborne infection, worldwide. While the trophozoite form of this parasite induces pathological symptoms in the gut, the cyst forms transmit the infection via contaminated water. Since Giardia is a non-invasive parasite, the actual mechanism by which it causes infection remains elusive. We have previously reported that Giardia assembles cholesterol and GM1 glycolipid-enriched lipid rafts (LRs) that participate in encystation and cyst production. To further delineate the role of LRs in pathogenesis, we isolated LRs from Giardia and subjected them to proteomic analysis. Various cellular proteins including the virulent proteins—e.g., giardins, …

Design, Synthesis, And Analysis Of Paired Coiled-Coil Peptidic Molecular Building Blocks Used For Linearly Controlled Self-Assembly Of Α-Helical Coiled-Coil Heterodimer Peptide Pairs, Jason Distefano

Chemistry Theses

Molecular building blocks are fundamental to biological synthesis and processes and have been utilized in advanced materials, drugs and drug delivery systems, and biotechnology. Proteins have been used as molecular building blocks for the construction of complex, well-ordered structures. Coiled-coil protein domains are essential subunits used for the oligomerization of protein complexes, gene expression, and structural elements of biological materials. The synthesis and assembly of proteins utilizing coiled-coil motifs are of great scientific interest due to their potential applications in disease treatment, biomechanical motors, nanoscale delivery systems, etc. However, assembling protein complexes with specific morphology is still challenging because …

Investigating Ionic Current Rectification As A Means Of Controllable Drug Delivery Using Silica Nanoparticles And Nano Porous Membranes, Katie L. Nolan

Honors College Theses

This project investigates a novel ionic current rectification (ICR) phenomenon created by the opening and closing of nanopores by charged silica nanoparticles (SNPs) under electrophoretic flow. This voltage-controlled opening and closing of the pores can be exploited to allow delivery of nicotine through the pores at programmable intervals. The ICR phenomenon was thoroughly investigated by varying pH, buffer concentration, SNP concentration, and applied voltage range. The mechanism was also verified by testing with a 2-, 3-, and 5-electrode system. Potential cake layer formation was demonstrated in a longer ICR test, and the implications of this on the drug delivery mechanism …

The Synthesis And Purification Methodology Of An Intermolecular Pyrophosphate Sensor: Applications For The Quantitative Polymerase Chain Reaction, Ethan Gevedon

Honors Projects

The optimized synthesis and purification methodology for an intermolecular pyrophosphate sensor scaffold molecule was performed: high performance liquid chromatography afforded the scaffold in excellent purity and yield. The applications of the sensor assembly in the quantitative polymerase chain reaction were discussed, and preliminary results show that

Collision-Induced Dissociation And Ion Mobility Mass Spectrometry Of Au30(S-Tbu)18 Nanoclusters, Christopher Hood

Honors Theses

Collision Induced Dissociation (CID) and Ion Mobility Mass Spectrometry (IM-MS) are methods used to understand the structural arrangement and stability of large molecules. In this study, the gold nanocluster Au₃₀(S-tBu)₁₈ was dissociated at varying Trap collision energies, and drift time vs mass spectrometry data was plotted to determine the order of cluster fragmentation. Comparing Au₃₀(S-tBu)₁₈ data to that of Au₂₅(SCH₂CH₂Ph)₁₈, the only current nanocluster published with IM-MS data, two distinctly different dissociation patterns were seen. Unlike the linear CID fragmentation of Au …

Fast Photochemical Oxidation And Footprinting Of Proteins Via Trifluoromethyl Radical Chemistry, Elaine Morrow

Honors Theses

Fast photochemical oxidation of proteins (FPOP) is a useful tool in proteomics because of the ability for modifications to occur on the scale of microseconds which reduces the modifications to tertiary and quaternary structure allowing for more accurate labeling of the protein. Labels for FPOP are generated from various radicals in our experiments which include hydroxyl radicals and trifluoromethyl radicals. Hydroxyl radicals are easily generated by using an excimer laser (KrF laser, 248 nm) or a UV flash lamp (as a part of the Fox™ System) by the photolysis of hydrogen peroxide. Trifluoromethyl radicals, however, need hydroxyl radicals to be …

X-Ray Crystallographic Analysis Of Quinoline N-Oxide And Isoquinoline N-Oxide With Zinc Halides, Nitrates, Perchlorates., Erin N. Groneck

GS4 Student Scholars Symposium

We have worked to analyze the chemistry between aromatic N-oxides, Quinoline N-oxide and Isoquinoline N-oxide, with zinc halides, nitrates, and perchlorates by X-ray crystallography. These structures were formed by reaction of the aromatic N-oxides with an equivalent of the zinc halide, nitrate, or perchlorate. These N-oxides had been chosen due to being the focus of this study. We will present the crystallographic X-ray structures of the synthesized novel complexes of the N-oxides with either a zinc halide, zinc nitrate, and zinc perchlorate.

Temporal Changes And Possible Sources Of Dissolved Calcium Levels In Stream, River, And Lake Waters In Western Kentucky, Kelsie Meystedt

Scholars Week

ABSTRACT

Zebra Mussels (Dreissena polymorpha) are an exotic and invasive mollusk that spread extensively over various rivers and lakes in the United States. These mussels are known for being notorious in their “biofouling” capabilities, costing the U.S. government billions of dollars in removal operations. Recently, zebra mussel colonies were found in Kentucky Lake possibly due to human activities increasing the salinity of today’s freshwater resources. The increase in salinity from human activities may have adversely affected the ecosystems and water supplies. The Specific aim of this study was to determine the temporal trend of dissolved calcium in Kentucky Lake …

Comparing And Contrasting Therapeutic Drugs Vs. Lifestyle Changes That Combattype-Ii Diabetes, Alexander Cline Helmuth

Chemistry & Biochemistry Student Projects

In this thesis, I will be presenting various preventive approaches to combat type-II diabetes. The focus of this paper will be comparing and contrasting therapeutic drug targets such as Metformin and Sulfonylureas that are prescribed for type-II diabetic patients versus taking preventative steps such as making lifestyle changes including weight management, physical activity, and having a balanced diet that prevents onset of type-II diabetes or helps patients manage type-II diabetes. From this paper, one will gain insight on how there are multiple approaches to combat type-II diabetes that are not in the form of the pill.

Microfluidic Paper Analytical Devices, Madison Page

Chemistry & Biochemistry Student Projects

Microfluidic paper analytical devices (µPADs) are small, paper-based matrices similar to Lab-on-a-Chip (LOC). They are capable of semi-quantitative analysis, with applications ranging from medical to environmental to food and beverage testing. Important to improving point-of-care devices (POCs), various techniques have been integrated into µPADs to customize analysis and fit different clinical situations.

The Application Of Biological Processes To Increase Energy Potential In Landfills, Ashlyn Eisenhart

Chemistry & Biochemistry Student Projects

There has been a dramatic increase in the amount of waste that we humans have created. This has been due to population growth, an increase in industrial manufacturing, along with urbanization and modernization.⁸ The number of tons of municipal solid waste entering landfills has increased from 82.5 million tons in 1960 to 146.1 million tons in 2018.¹⁷ However, thanks to recycling, composting, and energy recovery from combustion, the percentage of solid waste going to landfills has dramatically decreased, from around 93.6 to about 65.4 percent.¹⁷