Analytical Chemistry Commons^™

Synthesis And Structures Of New Three-Dimensional Copper Metal-Organic Frameworks, Nitin Kumar Pally

Masters Theses & Specialist Projects

Metal-organic frameworks (MOFs) are crystalline materials with metal ions covalently bonded to organic ligands. The ligands act as spacers often creating a porous structure with very high pore volume and surface area. MOFs are known for their robust structures, high porosity, and different chemical functionalities and are considered for applications in adsorptions, separations, catalysis and gas storage. This work focuses on the synthesis of new MOFs using copper compounds. Different types of carboxylate ligands were used for the synthesis. Two new copper-organic frameworks, [Cu₃(pyz)(btc)] (1), and [(Cu₃(btc))•xH₂O] (2) (btc= benzene-1,3,5-tricarboxylate, pyz= pyrazine) have been …

Synthesis And Characterization Of Manganese Pyridazyl Complexes, Sana Shah

Masters Theses & Specialist Projects

Heterocyclic’s and their fused-ring derivatives have been of interest for their use in electronic materials due to their ease of production, synthetic versatility, and low cost compared to traditional inorganic materials like silicon. Pyridazines have been found to be useful in catalysis gas storage, polymeric sensors and biological mimetics. When a transition-metal is fused into a synthesized pyridazine, unique properties such as conductivity and optics are allowed. In this work, synthesized pyridazine complexes will be analyzed by mass spectroscopy, elemental analysis, nuclear magnetic resonance, imaging, x-ray crystallography, and infrared spectroscopy. We are interested in synthesizing organometallic pyridazines and manganese pyridazyl …

Crevice Corrosion Behavior Of Ni-Cr-Mo-W Alloys In Aggressive Environment, Ajit K. Mishra

Electronic Thesis and Dissertation Repository

Ni-Cr-Mo (W) alloys, having an optimum concentration of Cr. Mo and W, are highly corrosion resistant alloys which do not fail by uniform corrosion in aggressive environments. However, when creviced at high applied potential and high temperatures, these materials can be susceptible to crevice corrosion. This study focuses on a family of seven commercial Ni-Cr-Mo (W) alloys containing various amounts of Cr, Mo and W.

Different electrochemical techniques were used to determine the characteristic potentials and temperature which indicate susceptibility to crevice corrosion, and to investigate the individual and synergistic roles of major and minor alloying elements. The corroded alloys …

Improved Dynamic Headspace Sampling And Detection Using Capillary Microextraction Of Volatiles Coupled To Gas Chromatography Mass Spectrometry, Wen Fan

FIU Electronic Theses and Dissertations

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted …

Rapid Inline Derivatization Of Primary And Secondary Amine Containing Drugs By Capillary Electrophoresis With Laser-Induced Fluorescence, Britt E. Turnquest

FIU Electronic Theses and Dissertations

Despite the ongoing “war on drugs” the seizure rates for phenethylamines and their analogues have been steadily increasing over the years. The illicit manufacture of these compounds has become big business all over the world making it all the more attractive to the inexperienced “cook”. However, as a result, the samples produced are more susceptible to contamination with reactionary byproducts and leftover reagents. These impurities are useful in the analysis of seized drugs as their identities can help to determine the synthetic pathway used to make these drugs and thus, the provenance of these analytes. In the present work two …

Elemental Analysis And Forensic Comparison Of Soils By Laser-Induced Breakdown Spectroscopy (Libs) And Laser Ablation Inductively Coupled Plasma Mass Spectrometry (La-Icp-Ms), Sarah C. Jantzi

FIU Electronic Theses and Dissertations

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS.

Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar …

Method Development For The Analysis Of Smokeless Powders And Organic Gunshot Residue By Ultra Performance Liquid Chromatography With Tandem Mass Spectrometry, Jennifer L. Thomas

FIU Electronic Theses and Dissertations

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure …

Ionic Liquids In Analytical Chemistry: Fundamentals, Advances, And Perspectives, Tien D. Ho, Cheng Zhang, Leandro W. Hantao, Jared L. Anderson

Jared L. Anderson

Since their initial discovery in 1914, ionic liquids (ILs) have been widely studied in multiple chemistry disciplines. Applications of ILs in analytical chemistry have enjoyed much success and contributed to the rapid evolution of the ionic liquid field. ILs are collectively known as organic salts which possess melting points at or below 100 °C. In most cases, ILs are composed of an organic cation and an organic or inorganic anion. It has been estimated there can be up to 1018 possible combinations of ILs, due to the ability to interchange their corresponding cationic/anionic moieties.

Evaluation Of Non-Contact Sampling And Detection Of Explosives Using Receiver Operating Characteristic Curves, Mimy Young

FIU Electronic Theses and Dissertations

The growing need for fast sampling of explosives in high throughput areas has increased the demand for improved technology for the trace detection of illicit compounds. Detection of the volatiles associated with the presence of the illicit compounds offer a different approach for sensitive trace detection of these compounds without increasing the false positive alarm rate. This study evaluated the performance of non-contact sampling and detection systems using statistical analysis through the construction of Receiver Operating Characteristic (ROC) curves in real-world scenarios for the detection of volatiles in the headspace of smokeless powder, used as the model system for generalizing …

The Utilization Of Chiral Ion Mobility Spectrometry For The Detection Of Enantiomeric Mixtures And Thermally Labile Compounds, Howard K. Holness

FIU Electronic Theses and Dissertations

This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by …

An Investigation Of Thin Films Formed On Zinc By Spectroscopic Ellipsometry, Juan Zuo, Ying Chen, Chang-Jian Lin, Andreas Erbe

Journal of Electrochemistry

The formation of natural oxide films on polycrystalline zinc surface, the growth of natural oxide films in different atmospheres, as well as the electrochemical process of metal zinc in alkaline carbonate solution, studied recently by using spectroscopic ellipsometry in our group, are introduced. The objective of this paper is to outline that the optical, electrical properties, the change and growth kinetics of zinc metal oxide film on the surface can be investigated by in-situ and ex-situ ellipsometry, which makes significant sense to evaluate the overall performance of zinc oxide layer.

Applications Of Spectroscopic Ellipsometry In Corrosion Investigation, Ling-Jie Li, Yu-Ling He, Jing-Lei Lei, Sheng Tao Zhang

Journal of Electrochemistry

As a highly-sensitive and non-destructive in situ technique, spectroscopic ellipsometry has been widely applied in corrosion investigation to acquire the dynamic information of the “electrode-medium” interface during corrosion. This paper lays out some representative demonstrations in several established optical models used to interpret data obtained with spectroscopic ellipsometry in corrosion investigation. In addition, the latest trends in development of this technique are analyzed.

Comprehensive Forensic Toxicological Analysis Of Designer Drugs, Madeleine Jean Swortwood

FIU Electronic Theses and Dissertations

New designer drugs are constantly emerging onto the illicit drug market and it is often difficult to validate and maintain comprehensive analytical methods for accurate detection of these compounds. Generally, toxicology laboratories utilize a screening method, such as immunoassay, for the presumptive identification of drugs of abuse. When a positive result occurs, confirmatory methods, such as gas chromatography (GC) or liquid chromatography (LC) coupled with mass spectrometry (MS), are required for more sensitive and specific analyses. In recent years, the need to study the activities of these compounds in screening assays as well as to develop confirmatory techniques to detect …

Optimization Of Polymer Separation By Gradient Polymer Elution Chromatography, Gideon R. Liem, Linda Nien-Hwa Wang

The Summer Undergraduate Research Fellowship (SURF) Symposium

High Performance Liquid Chromatography (HPLC) has been a versatile separation method for polymers for many years. Analysis of different polymers by HPLC is typically done by utilizing the differential solubility of the polymers by mixing a good solvent and an anti-solvent in various compositions. This method is called Gradient Polymer Elution Chromatography (GPEC). While GPEC has been used extensively, it commonly uses a linear gradient to separate components. Linear solvent gradients consume a lot of solvent and take a relatively long time (> 30 minutes) to complete. The goal of this study is to develop a step gradient from a …

Electrochemical Reduction Of Aqueous Uranium, Jonathan M. Scaggs

Boise State University Theses and Dissertations

The electrochemical reduction of uranium in acidic aqueous environments with the express purpose of generating U(III) consistently is critically evaluated. Generating U(III) in an aqueous environment is difficult and extremely unstable and has historically been difficult to achieve and isolate for further investigation. The electrochemical cell, electrodes, supporting electrolytes, and pH’s are all reviewed and evaluated for the purpose of optimizing the systemic requirements to electrochemically generate U(III). Several new types of electrochemical cells to include two new spectroelectrochemical for UV-Vis and FT-Raman investigation were designed and tested for the purpose of analyzed the redox species of aqueous uranium generated …

Conversion Of Iodide To Hypoiodous Acid And Iodine In Aqueous Microdroplets Exposed To Ozone, Elizabeth A. Pillar, Marcelo I. Guzman, Jose M. Rodriguez

Chemistry Faculty Publications

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O₃) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O₃ and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O₃ at variable iodide (I^–) concentration (0.010–100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates …

Construction And Demonstration Of A Tandem Mass Spectrometer Based Instrument For Cold Ion Spectroscopy, James Gerhardt Redwine

Open Access Dissertations

A new instrument incorporating ion trap based tandem mass spectrometry and cold ion UV and UV-IR double resonance spectroscopy has been developed at Purdue University for the study of gas phase, biologically relevant ions. The instrument incorporates multiple quadrupole linear ion trap mass analyzers to prepare and isolate the precursor ions as well as to analyze the resultant photofragments. A 22-pole ion trap cooled to 5 K via a closed cycle helium cryostat is used to cool the ions for spectroscopic interrogation. Results show the vibrational and rotational temperature of a wide assortment of ions to be 12±2 K.

The …

Instrumentation, Applications And Fundamentals Of Plasma Ionization Of Organic Molecules From Surfaces, Joshua Scott Wiley

Open Access Dissertations

Various aspects of the interaction of low-temperature plasma (LTP) ambient ionization with organic molecules and surfaces are discussed. As an application, LTP-MS has been used for the analysis of pesticides directly from fruits and vegetables revealing low parts per billion limits of detection (LODs). Due to low power and gas requirements, a battery-operated and handheld LTP probe was developed for the point-and-shoot MS analyses. Handheld LTP was compared with large-scale LTP on a benchtop and miniature MS revealing similar LODs for both. Long-distance ion transport up to one meter was also demonstrated with flexible tubing for non-proximate sample interrogation. Fundamentals …

Development Of Quantitative Ft- Ir Methods For Analyzing The Cure Kinetics Of Epoxy Resins, Sang Ha Son

Open Access Dissertations

Epoxy thermosets are important engineering materials with applications in coating, adhesives, packaging and as structural components in a variety of advanced engineering products. The ultimate performance of polymer critically depends upon the details of the cure chemistry used to produce the thermoset. In order to better understand and monitor the cure chemistry, quantitative analysis of the FT-IR response has been developed for describing the epoxy-amine curing reaction as well as monitoring the hydrogen bonding that occurs in these systems The FT-IR analysis includes (i) quantitative deconvolution of complex peaks into individual spectral contributions, (ii) peak identification via DFT analysis and …

Development Of Isotags For Nmr Based Metabolite Profiling And Applications, Fariba Tayyari

Open Access Dissertations

NMR spectroscopy is a powerful analytical tool for both qualitative and quantitative metabolite profiling analysis. However, accurate quantitative analysis of biological systems especially using one dimensional NMR has been challenging due to signal overlap. In contrast, the enhanced resolution and sensitivity offered by chemoselective isotope tags have enabled new and enhanced methods for detecting hundreds of quantifiable metabolites in biofluids using NMR spectroscopy or mass spectrometry. In this thesis we show improved sensitivity and resolution of NMR experiments imparted by 15N and 13C isotope tagging which enables the accurate analysis of plasma metabolites. To date, isotope tagging has been used …