Analytical Chemistry Commons^™

Method Development For A Chemical And Biological Analysis Of Glucocorticoids In Wastewater, Maria Carmen Lozano

Open Access Theses & Dissertations

Glucocorticoids are a class of steroid hormones that can either be produced synthetically or naturally by the adrenal glands. The synthetic glucocorticoids are highly prescribed in the United States for their anti-inflammatory and immunosuppressive properties to treat a variety of ailments and diseases; however, these have been implicated in a number of adverse human conditions such as obesity, metabolic syndrome, immune-suppression, delayed puberty, adrenal insufficiency and Cushing Syndrome, among others. Ongoing research has shown that synthetic and natural hormones are transported to aquatic environments via mammalian excretion or wastewater effluent, and as a result, the release of glucocorticoids into the …

Novel Liquid Chromatography - Fourier Transform Mass Spectrometry (Ms) And Triple Quadrupole Ms Methods For The Determination Of Diarrhetic Shellfish Poisoning (Dsp) Toxins., Bébhine Carey

Theses

Harmful algal blooms (HABs) appear to be on the rise globally, which not only has a negative impact on the shellfish industry but can also cause human and animal intoxications. In order to advance our knowledge of HABs, specific and sensitive analytical methods are required to aid in monitoring shellfish and algal samples for biotoxins, harmful to consumers.

The Spectrophotometric Analysis Of Lead Carbonate Complexation And Carbonate Saturation States In Seawater, Regina Anita Easley

USF Tampa Graduate Theses and Dissertations

The carbon dioxide (CO₂) system is the primary buffer in seawater which controls oceanic pH. Changes in the marine CO₂ system affect a number of processes such as metal speciation, mineral saturation states, auditory responses in fish, and primary productivity rates. Increased atmospheric concentrations of CO₂ from human activities (e.g. burning of fossil fuels, deforestation, and cement production) has led to a global decrease in surface ocean pH termed anthropogenic ocean acidification. One particular concern in response to increased oceanic CO₂ is a substantial decrease in the calcium carbonate (CaCO₃) saturation states, Ω …

The Bench Synthesis Of Silver Nanostructures Of Variable Size And An Introductory Analysis Of Their Optical Properties, Aoife Power, Tony Betts, John Cassidy

Articles

A laboratory practical was designed for use by both undergraduate and second level students to demonstrate the synthesis and characterisation of tuneable silver colloids. It clearly illustrates the novel optical properties of silver nanoparticles compared to the bulk metal. The synthesis is both rapid and repeatable, and can be conducted on the laboratory bench at room temperature.

Treatment Of Reverse Osmosis Brine With Advanced Oxidative Processes For Enhanced Phosphorus Removal, Petrease Patton

Theses and Dissertations (Comprehensive)

Current regulations for sensitive receiving waters are approaching the limit of technology for phosphorus removal and improved methods are required. Existing methods target removal of the orthophosphate form of phosphorus, but to achieve low effluent limits other non-reactive (NRP) forms, such as condensed phosphate and organic phosphorus, must be removed as well. This could be accomplished by developing a quaternary step in wastewater treatment that utilizes reverse osmosis (RO) followed by advanced oxidation processes (AOP) on the produced brine (RO concentrate). The objective during advanced treatment is to convert NRP in the brine to reactive phosphorus for removal by traditional …

Single-Stranded Dna Scanning And Deamination With Single-Molecule Resolution, Padhuk Gamarala Senavirathne

Wayne State University Dissertations

SINGLE-STRANDED DNA SCANNING AND DEAMINATION WITH SINGLE-MOLECULE RESOLUTION

by

GAYAN SENAVIRATHNE

December 2013

Advisor: Dr. David Rueda & Dr.Ashok Bhagwat

Major: Chemistry (Analytical)

Degree: Doctor of Philosophy

APOBEC3G (Apo3G) and Activation-Induced cytidine Deaminase (AID) are the most notable members of APOBEC enzymes, a family of cytidine (C) deaminases with crucial functions in the immune system. In T cells, Apo3G deaminates C in viral cDNA to halt the replication of HIV 1 strains lacking viral infectivity factor (vif). In B cells, AID is required for the diversification of antibodies through initiation of somatic hypermutation (SHM), and class switch recombination (CSR), by …

Chemical Analysis Of Ophthalmic Solutions, Pagagiotis Tavlarakis

Seton Hall University Dissertations and Theses (ETDs)

.

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai-Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

An Expanded Genetic Code In Mammalian Cells With A Functional Quadruplet Codon, Wei Niu, Peter G. Schultz, Jiantao Guo

Department of Chemistry: Faculty Publications

We have utilized in vitro evolution to identify tRNA variants with significantly enhanced activity for the incorporation of unnatural amino acids into proteins in response to a quadruplet codon in both bacterial and mammalian cells. This approach will facilitate the creation of an optimized and standardized system for the genetic incorporation of unnatural amino acids using quadruplet codons, which will allow the biosynthesis of biopolymers that contain multiple unnatural building blocks.

Porous Polymer Coatings As Substrates For The Formation Of High-Fidelity Micropatterns By Quill-Like Pens, Michael Hirtz, Marcus Lyon, Wenqian Feng, Andrea E. Holmes, Harald Fuchs, Pavel A. Levkin

Department of Chemistry: Faculty Publications

We explored the potentials of microarray printing using quill-like microcantilevers onto solid supports that are typically used in microspot printing, including paper, polymeric nitrocellulose and nylon membranes. We compared these membranes with a novel porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) support (HEMA) with narrow pore size distribution in the 150 nm range, which demonstrated advantages in pattern definition, spot homogeneity, and consistent spot delivery of different dyes (phloxine B and bromophenol blue) with diameters of several micrometres. The bromophenol blue arrays on HEMA support were used to detect the presence of bovine serum albumin (BSA). In the presence of BSA, …

Single Transcriptional And Translational Preq1 Riboswitches Adopt Similar Pre-Folded Ensembles That Follow Distinct Folding Pathways Into The Same Ligand-Bound Structure, Krishna C. Suddala, Arlie J. Rinaldi, Jun Feng, Anthony M. Mustoe, Catherine D. Eichhorn, Joseph A. Liberman, Joseph E. Wedekind, Hashim M. Al-Hashimi, Charles L. Brooks Iii, Nils G. Walter

Department of Chemistry: Faculty Publications

Riboswitches are structural elements in the 50 untranslated regions of many bacterial messenger RNAs that regulate gene expression in response to changing metabolite concentrations by inhibition of either transcription or translation initiation. The preQ₁ (7-aminomethyl-7-deazaguanine) riboswitch family comprises some of the smallest metabolite sensing RNAs found in nature. Once ligand-bound, the transcriptional Bacillus subtilis and translational Thermoanaerobacter tengcongensis preQ₁ riboswitch aptamers are structurally similar RNA pseudoknots; yet, prior structural studies have characterized their ligand-free conformations as largely unfolded and folded, respectively. In contrast, through single molecule observation, we now show that, at nearphysiological Mg²⁺ concentration and pH, …

Iodonium Cyclophanes For Secure Arene Functionalization, Stephen Dimagno

Department of Chemistry: Faculty Publications

This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Polymorphism And Polyamorphism In Bilayer Water Confined To Slit Nanopore Under High Pressure, Jaeil Bai, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A distinctive physical property of bulk water is its rich solid-state phase behavior, which includes 15 crystalline (ice I–ice XIV) and at least 3 glassy forms ofwater, namely, low-density amorphous, highdensity amorphous, and very-high-density amorphous (VHDA). Nanoscale confinement adds a new physical variable that can result in a wealth of new quasi-2D phases of ice and amorphous ice. Previous computer simulations have revealed that when water is confined between two flat hydrophobic plates about 7–9 Å apart, numerous bilayer (BL) ices (or polymorphs) can arise [e.g., BL-hexagonal ice (BL-ice I)]. Indeed, growth of the BL-ice I through vapor deposition on …

Sample Preparation Techniques For The Improvement Of Analytical Measurements: Capillary-Channeled Polymer Fibers Employed In Protein Solid Phase Extraction Applications And Characterization Of Active Components In Botanical Dietary Supplements, Carolyn Burdette

All Dissertations

The task of sample preparation encompasses many challenges and demands for analytical techniques. Appropriate preparative steps can be the determining factor between successful measurements and failures. Too little preparation can lead to the inability to detect analytes due to low concentrations, insufficient extraction of analytes, and/or strong matrix effects; exhaustive preparation steps increases analysis times, the potential for analyte losses, and the difficulty to obtain consistent reproducible results. Discussed here are several examples of analytical techniques where sample preparation is critical and can be used to improve existing techniques. Capillary-channeled polymer (C-CP) fibers used for solid phase extraction (SPE) protein …

Molecular Forensic Science Analysis Of Nuclear Materials, Dallas Reilly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Concerns over the proliferation and instances of nuclear material in the environment have increased interest in the expansion of nuclear forensics analysis and attribution programs. A new related field, molecular forensic science (MFS) has helped meet this expansion by applying common scientific analyses to nuclear forensics scenarios. In this work, MFS was applied to three scenarios related to nuclear forensics analysis. In the first, uranium dioxide was synthesized and aged at four sets of static environmental conditions and studied for changes in chemical speciation. The second highlighted the importance of bulk versus particle characterizations by analyzing a heterogeneous industrially prepared …

Progress Toward Red And Near-Infrared (Nir) Emitting Saccharide Sensors, Martha Sibrian-Vazquez, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Red-shifted and near-infrared (NIR)-active rhodamine analogs and their boronic acid derivatives were synthesized and studied. These latter compounds function as fluorogenic NIR active substrates for sugar sensing. The effects of benzannulation and boronic acid functionalization on fluorophore optical and sensing properties are described.

In Situ Pm-Irras Studies Of A Floating Bilayer Lipid Membrane At Au(111) Electrode Surface, Su Zhangfei, Kycia Annia, Jay Leitch J., Lipkowski Jacek

Journal of Electrochemistry

In situ Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) was used to study the structure of a DMPC + cholesterol + GM1 floating bilayer lipid membrane (fBLM) at a Au(111) surface. 1-thio-beta-D-glucose (beta-Tg) was self-assembled onto the Au electrode to increase the overall hydrophilicity of the surface. The fBLM was deposited on the beta-Tg self-assembled monolayer (SAM) using a combination of Langmuir-Blodgett/Langmuir-Schaefer (LB/LS) techniques. The carbohydrate headgroups of the GM1 molecules were physically adsorbed to the beta-Tg SAM forming a water rich cushion between the fBLM and the modified gold substrate. The PM-IRRAS spectra indicate that the DMPC molecules within …

Electrochemical Detection Of Ammonia In Aqueous Solution Using Fluorescamine: A Comparison Of Fluorometric Versus Voltammetric Analysis, Panchompoo Janjira, G. Compton Richard

Journal of Electrochemistry

Fluorescamine is a non-fluorescent reagent widely used for the quantitative determination of primary amines by fluorescence spectroscopy as it reacts readily with primary amines to form a fluorescent product. In this work, a new sensitive voltammetric method for the detection of ammonia in aqueous solution by the reaction with fluorescamine has been developed. First, the electrochemical behaviour of fluorescamine in the absence and presence of ammonia was investigated in 0.1 mol L^-1 borate buffer solution (pH 9.0) by cyclic voltammetry using a glassy carbon (GC) electrode. As for fluorescamine itself, a well-defined irreversible oxidation peak could be observed at …

The Electrochemical Properties Of 1-Pyrenebutyric Acid/Graphene Composites And Their Application In Glucose Biosensors, Min Wang, Jiong Wang, Fengbin Wang, Xinghua Xia

Journal of Electrochemistry

The electrochemical properties of 1-pyrenebutyric acid/graphene composites (PBA/G) obtained by one-step synthesis via π-π stacking was investigated. The electrochemical impedance titration curve shows the surface charge changes as function of solution pH by using ferricyanide/ferrocyanide redox couple as the probe. An apparent pK_a value is estimated as 6.2 according to the impedance titration curve. In addition, a glucose biosensor was constructed by immobilizing glucose oxidase (GOD) on the surface of PBA/G via covalent interaction. This biosensor shows a linear response to glucose within the concentration up to 5 mmol L^-1 with a detection limit of 0.085 mmol L …

A Novel Microfluidic Enrichment Technique For Carbonylated Proteins, Bryant C. Hollins

Doctoral Dissertations

Proteins are the building blocks of cells in living organisms, and are composed of amino acids. The expression of proteins is regulated by the processes of transcription and translation. Proteins undergo post-translational modifications in order to dictate their role physiologically within a cell.

Not all post-translational modifications are beneficial for the protein or the cell. One type of post-translational modification, called carbonylation, irreversibly places a carbonyl group onto an amino acid residue, most commonly proline, lysine, arginine, and threonine. This modification can have severe consequences physiologically, including loss of solubility, loss of function, and protein aggregation.

Carbonylated proteins have commonly …