Analytical Chemistry Commons^™

Electrochemical Detection Of Fentanyl Using Screen-Printed Carbon Electrodes With Confirmatory Analysis Of Fentanyl And Its Analogs In Oral Fluid Using Liquid Chromatography-Tandem Mass Spectrometry, Colby E. Ott

Graduate Theses, Dissertations, and Problem Reports (ETD)

Utilizing screen-printed carbon electrodes (SPCEs), a fast, simple, and sensitive approach toward the detection, identification, and quasi-quantitation of fentanyl was achieved both in an electrochemical cell and as a drop on the electrode surface. Electro-oxidation of fentanyl at the electrode was demonstrated using adsorptive stripping square-wave voltammetry between -0.5 V and +1.6 V with 100 mM Tris-HCl buffer at pH 8.5 as supporting electrolyte. Parameter optimization was conducted during method development to include supporting electrolyte and pH, electrochemical technique, pre-treatment and equilibration time, and various surface modifications. The simplest method utilizing an unmodified SPCE was determined to be appropriate for …

Compound-Specific Isotope Analysis Of Amino Acids In Biological Tissues: Applications In Forensic Entomology, Food Authentication And Soft-Biometrics In Humans, Mayara Patricia Viana De Matos

Graduate Theses, Dissertations, and Problem Reports (ETD)

In this work we demonstrate the power of compound-specific isotope analysis (CSIA) to analyze proteinaceous biological materials in three distinct forensic applications, including: 1) linking necrophagous blow flies in different life stages to their primary carrion diet; 2) identifying the harvesting area of oysters for food authentication purposes; and 3) the ability to predict biometric traits about humans from their hair.

In the first application, we measured the amino-acid-level fractionation that occurs at each major life stage of Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) blow flies. Adult blow flies oviposited on raw pork muscle, beef muscle, or chicken liver. Larvae, pupae …

Non-Target Analyses Of Novel Psychoactive Substances; Inherent Variation In Gcms Relative Abundances And Gas Phase Hydrogen Deuterium Exchange Isomer Discrimination, Kristin Michelle Kelly

Graduate Theses, Dissertations, and Problem Reports (ETD)

Novel psychoactive substances (NPSs) are synthetically derived compounds designed to mimic the effects of other illicit drugs. An endless cycle of NPSs continually reach the drug market due to limitations in drug legislation creating two problems: (1) non-availability of standards and (2) multiple isobars indistinguishable even to high resolution mass spectrometry. Gas chromatography-mass spectrometry (GCMS) is the most common instrument used for compound identification in non-targeted seized drug analysis. Compound identification using this technique relies on mass spectra where the percent relative abundances (%RAs) of all m/z values are compared manually or searched against a library database. Lacking standards, laboratories …

Solvation Properites Of Supercritical Carbon Dioxide Using Chirped-Pulse Fourier-Transform Microwave Spectra Of Carbon Dioxide / 1, 1-Difluoroethene (Dfe) Mixtures, Tulana Ariyaratne Subasinghe Arachchige

Masters Theses

Supercritical carbon dioxide (sc-C0₂) is a highly utilized industrial substance identified as an excellent solvent and a surfactant, which is cheaper and less hazardous than other typical solvents. The higher solubility of fluorinated hydrocarbons than their hydrocarbon (HC) analogs is not well understood and the theory behind the microsolvation of sc-C0₂ cannot be fully explained with the existing chemical information. Microwave spectroscopy is a good method of identifying the structural arrangement of clusters made from fluorinated HCs and C0₂. I n this project, microwave scans of the four different mixtures of 1 , 1-difluoroethene (DFE) …

Bottom-Up Lignomics: Towards The Development Of Adduct Electrospray Ionization Mass Spectrometric Methods To Characterize And Sequence Lignin Oligomers, Shardrack O. Asare

Theses and Dissertations--Chemistry

Lignin, the second most abundant naturally occurring polymer found in plant cell wall has the potential of becoming an alternative source for the production of chemical synthons for the pharmaceuticals and other chemical industries. While much gain has been made towards the development of degradation methods to break down lignin, effective analytical methods are still required to rapidly and accurately identify the products of lignin breakdown experiments. The goal of this work was to develop mass spectrometric methods for the characterization of lignin oligomers based on the study of model lignin compounds.

Unlike peptides and oligosaccharides, lignin model compounds that …

Development Of Chromatography And Mass Spectrometry Methods For Enzyme Kinetics And Inhibition In Glycolysis And The Methylerythritol Phosphate (Mep) Pathways, Allison Fabino Carr

Graduate Research Theses & Dissertations

This dissertation focuses on method development for enzymatic activity and inhibition assays for use in screening potential antibacterial compounds. Infection by antibiotic-resistant pathogens in on the rise globally and several enzymes, including the those in the methylerythritol phosphate (MEP) pathway and fructose bisphosphate aldolase, as strong targets for novel pharmaceuticals because they are not present in humans. Several assays exist for the MEP pathway and aldolase, but there is always work to be done to improve sensitivity, increase throughput, and lower cost. This dissertation describes the development of several methods – hydrophilic interaction chromatography (HILIC), liquid chromatography-mass spectrometry (LC-MS), and …

Oleic Acid Vesicles: Formation, Mechanisms Of Reactivity, And Uses In Determination Of Terpene Activity, Laura A. Walther

Theses and Dissertations--Chemistry

This dissertation will focus on the volatile compounds released upon the burning of incense which are numerous and varied. The first part of this dissertation is the gas chromatography-mass spectral (GC-MS) analysis of burning incense collected via solid phase microextraction (SPME) with the aim of developing a library of compounds found in incense as used in the Orthodox church.

The second part of this dissertation has the aim of developing a method for forming oleic acid bilayer vesicle membranes and a fluorescence spectroscopy method by which the reactivities of these vesicles can be analyzed. These reactivities include permeability, fluidity, aggregation, …

Investigation Of Thiol-Containing Biomarkers And Their Role In The Exposome, Tracy Gastineau-Stevens

Theses and Dissertations--Chemistry

Exposomics is an emerging area of study that looks at how the environment around a person or persons affects their overall health. Biomarkers have emerged as useful tools to better understand how the exposome affects a person. In this work, we investigate two potential endogenous biomarkers, homocysteine and glutathione that have been previously implicated in a number of diseases that have been linked to environmental causes. We also investigated an environmental exposure, the fungicide Ziram, which epidemiologically has been linked to diseases. In our investigation, we utilized capillary electrophoresis and capillary electrophoresis-mass spectrometry to develop a method for homocysteine and …

Silicone Wristbands As Passive Samplers For Quantitative Measurement Of Wood Smoke Exposure, Hannah J. Wright

Graduate Student Theses, Dissertations, & Professional Papers

Human exposure to biomass smoke is a health concern worldwide. Although many studies have measured particulate matter in wood smoke as a health concern, exposure to mutagenic and carcinogenic volatile and semivolatile compounds remains understudied. This research introduces a novel method of quantitative measurement of exposure to these compounds using silicone wristbands. The study developed a method to extract analytes of interest from the wristbands and quantify a few volatile organic compounds and polycyclic aromatic hydrocarbons with known ill health effects, and then performed linear regressions between extracted levels and exposure to those analytes using controlled exposure studies. Results indicate …

Evaluating Methods Of Obtaining Male Pheromone From Hymenochirus Sp. Using Analytical Chemistry, Vincent Wing-Kun Leung

University of the Pacific Theses and Dissertations

Male Hymenochirus sp. frogs are known to release pheromone that attracts females of the same species. Four methods for collecting secretions containing pheromone in Hymenochirus sp. were tested: norepinephrine injection, gonadotropin-releasing hormone injection, homogenization of gland tissue, and electrostimulation of the skin over the breeding gland area. The samples collected were analyzed using high-performance liquid chromatography (HPLC) and mass spectrometry. The HPLC chromatograph for the male norepinephrine sample contained a peak at 6.4 min that was not in the female norepinephrine sample HPLC chromatograph. The male norepinephrine sample mass spectrum had a peak of m/z 292.0 not in the female …

Design, Synthesis, Characterization And Anti-Cancer Effects Evaluation Of Interchain Cysteine Linked Antibody Drug Conjugates, Ke Li

Doctoral Dissertations

"Antibody drug conjugates (ADCs) are emerging therapeutic products specially designed for the treatment of cancers. Potent cytotoxic agents are linked to antibodies via linkers. Antibody drug conjugates, which take advantage of both antibodies and cytotoxic agents, showed high selectivity towards cancer cells. Cytotoxic agents are delivered to the cancer cells selectively and kill them from inside while leaving low or non-toxicity towards normal cells. Antibody drug conjugates are actually heterogeneous mixtures. The major heterogeneities mainly lie in the drug to antibody ratio (DAR) and drug linking positions, both of which potentially affect the therapeutic index of ADCs. In this research, …

Rapid Analysis Of Magnesium In Infant Formula Powder Using Laser-Induced Breakdown Spectroscopy, Maria Markiewicz-Keszycka, Ming Zhao, Xavier Cama-Moncunill, Toufic El Arnaout, Dana Becker, Colm O'Donnell, P. J. Cullen, Carl Sullivan, Maria Piedad Casado-Gavalda

Articles

Laser-induced breakdown spectroscopy (LIBS) was investigated to determine magnesium (Mg) content in infant formula powder. To predict Mg content in the range established by the Codex Alimentarius, a partial least squares regression (PLSR) model was developed using a calibration data set (n = 30) based on full cross-validation and validated using an independent validation data set (n = 21). The prediction model performance was evaluated using the regression coefficients of determination (Rcv2 = 0.94 and Rp2 = 0.85) with the root mean square errors on cross-validation and prediction (RMSECV = 60 mg kg−1 and RMSEP = 80 mg kg−1). The …

Development And Characterization Of Stationary Phase Gradients For High Performance Liquid Chromatography, Anna Forzano

Theses and Dissertations

Choosing a stationary phase is the first step in developing a liquid chromatography (LC) separation method, where the selectivity is governed by the differential interactions of the analytes with the stationary and mobile phases. Introducing a gradient in stationary phase functionality allows for tuning of analyte retention, translating to a possible improvement in selectivity and an increase in resolution versus that offered by uniform stationary phases.

In this work, C₁₈-silica, phenylbutyl-silica, and phenylbutyl-ammonium opposed continuous stationary phase gradients were fabricated using controlled rate infusion (CRI) on particle packed LC columns. Characterization of the stationary phase was carried out …

2nd Tier Assay For The Detection Of Congenital Adrenal Hyperplasia By Virginia’S Newborn Screening Laboratory: Steroid Profile By Hplc-Ms/Ms, Christopher E. Nixon

Theses and Dissertations

Congenital Adrenal Hyperplasia (CAH) encompasses several disorders related to disruptions in the adrenal steroid production pathway. These disruptions may cause virilization of the external female sex organs, incorrect gender assignment, precocious puberty, and in the most severe form, may cause life-threatening salt wasting and adrenal crisis if not detected and treated early in the newborn period.

17α-Hydroxyprogesterone (17-OHP) is the primary target for immunofluorescence detection of CAH from dried blood spots in newborn screening (NBS). Unfortunately, current immunoassay techniques for the detection of CAH suffer from high false positive rates. The primary factors contributing to false positive determinations can include …

Development Of An In-Field Method For The Detection Of Barium In Various Water Samples Using Differential Pulse Anodic Stripping Voltammetry, Samantha Ridgway, Magdalena Wajrak

Research outputs 2014 to 2021

This work presents a reliable, cost-effective, rapid and in-field voltammetric method for the detection of barium. The optimized method consists of an ultrathin mercury film deposited in situ on a glassy carbon electrode in dilute potassium chloride without deoxygenation, using differential pulse anodic stripping voltammetry (DP-ASV). Application of the method allowed for the quantitative determination of barium concentration in a variety of waters and brake pad dust samples. Comparative analysis of sample results from DP-ASV with inductively coupled plasma mass spectroscopy (ICP-MS) showed a mean percent difference of 1.8%.

Molecular Characterization Of Free Tropospheric Organic Aerosol And The Development Of Computational Tools For Molecular Formula Assignment, Simeon Schum

Dissertations, Master's Theses and Master's Reports

Organic aerosol affects human health and climate. These effects are largely determined by the composition of the organic aerosol, which is a complex mixture of species. Understanding the complexity of organic aerosol is critical to determining its effect on human health and climate. In this study, long range transported organic aerosol collected at the Pico Mountain Observatory was analyzed using ultrahigh resolution mass spectrometry. Organic aerosol transported in the free troposphere had an overall lower extent of oxidation than aerosol transported in the boundary layer. It was hypothesized that the lower oxidation was related to a more viscous phase state …

Near-Infrared Fluorescent Probes For Sensitive Determination Of Lysosomal & Mitochondrial Ph In Live Cells, Wafa Mazi

Dissertations, Master's Theses and Master's Reports

Varied intracellular pH levels are critical for various physiological processes such as enzymatic activity, cell proliferation and apoptosis, ion transport, and muscle contraction. Cellular compartments, like lysosomes, must retain an acidic environment (pH ~ 4.5) to activate hydrolytic enzymes necessary for the breakdown of large biomolecules. Another cellular organelle, the mitochondria, provides the cell with energy and must retain an alkalis environment (pH ~ 8.0) for proper function. Substantial lysosomal and mitochondrial pH deviation is associated with cellular dysfunction and disease. Therefore, the precise detection of lysosomal and mitochondrial pH is essential to provide a better understanding of cellular physiological …

Increased Utility Of Ph Sensitive Indicators As High Concentration Co2 Detectors Through The Use Of Polyelectrolyte Complexes As Stabilizing Media, Camden James Johnson

All Master's Theses

Development of plastic materials which produce visible color change when exposed to different environments has recently attracted attention for many biomedical applications.^1,2Many biomedical devices are packaged under high concentrations of carbon dioxide (CO₂) which can lower the pH of the packaging environment. This is similar to the CO₂ chemistry responsible for ocean acidification.³ Dye molecules that are sensitive to environmental changes in pH (known as pH indicators) can be encapsulated in plastics and produce a visible color change when a medical device is removed from the sterile CO₂ environment. Plastics made from large …

Effect Of Iron On The Oxidative Capacity Of Carbonaceous Nanoparticles, Daniel Chavez

All Master's Theses

Inhalation of ambient particulate matter (PM_2.5) emitted during combustion of fuels has negative impacts on human health. Triggered in part by the generation of reactive oxygen species (ROS) that lead to oxidative stress, significant gaps exist in the understanding of the detailed chemistry of these detrimental effects. Trace metals and carbonaceous material of the nanometer-sized particles contained in PM_2.5 have been implicated as key players in causing these effects. Here, the role of Fe is investigated with carbonaceous nanoparticles (CNP) while mimicking simple cellular conditions. By adding environmentally representative and controlled concentrations of Fe(II) or Fe(III) to …

The Pilot Application Of Electrochemical Impedance Spectroscopy On Dynamic Proton Exchange Membrane Fuel Cell, Jian-Wei Guo, Jian-Long Wang

Journal of Electrochemistry

By analyzing Electrochemical Impedance Spectroscopy (EIS) in applications of dynamic proton exchange membrane fuel cell (PEMFC), bottlenecks which restrict EIS tool development have been pointed out in this paper. Though the high-frequency resistance in EIS is largely accepted as cell inner-resistance, this can only be applied for cell with low current. The low-frequency resistance is difficult to be realized due to its relation with mass transfer. Furthermore, the improved Randles equivalent circuits are built up preliminarily, thus, penetrating into studies for mass transfer reaction, cell operation/degeneration, and high temperature fuel cell. Inspiringly, EIS is becoming an analyzing tool for stack …