Physical Sciences and Mathematics Commons^™

Fundamental Studies Of The Singlet Oxygenation Of Water Soluble Biological And Environmental Important Molecules, Marcela Jaramillo

FIU Electronic Theses and Dissertations

Singlet oxygen, 1O2, can be easily generated by a sensitizer, solar radiation, and molecular oxygen. 1O2 is very important in a range of biological and environmental systems. The products and mechanisms of the 1O2 reactions are well studied in organic solvents, and despite well-established solvent effects, studies on the reactions of the singlet oxygen in aqueous media are limited. Herein, 1O2 reactions with biologically and environmentally relevant conjugated π systems in aqueous solutions are presented. Water-soluble isomeric 1, 3-hexadienes are simple mechanistic probes for the 1O2 reactions since concerted and non-concerted pathways produce distinct products. The isomerization of sorbic acid …

Organic-Inorganic Halide Perovskite Nanocrystals And Solar Cells, Rui Guo

FIU Electronic Theses and Dissertations

A great challenge facing humanity in the 21^st century is finding inexhaustible and inexpensive energy sources to power the planet. Renewable energies are the best solutions because of their abundance, diversity, and pollution-free emission. Solar energy is the cleanest and most abundant renewable energy source available. In the continuing quest for efficient and low-cost solar cells, perovskite solar cells (PSCs) have emerged as a potential replacement for silicon solar cells. Since 2009, the record efficiencies of PSCs have been skyrocketing from 3.8 % to 25.2 % and are now approaching the theoretical limit. Along with the three-dimensional perovskites used …

Surface Enhanced Raman Spectroscopy (Sers) As A Nanoscale Adsorption Phenomenon: Development Of Tailored Nanomaterials For Applications In Drug Detection, Chiara Deriu

FIU Electronic Theses and Dissertations

Surface Enhanced Raman Spectroscopy (SERS) is an analytical technique in which nanostructured substrates amplify the inherently weak Raman signal of an adsorbed species by several orders of magnitude, enabling the detection of trace compounds, up to the single molecule level. While this may be an exceptional tool for any analytical scientist, SERS is at present relegated to the role of academic sensation, and is underutilized in everyday analytical practice. The SERS community is increasingly attributing this setback to a poor understanding of nanoscale surfaces and their chemical environment; since molecular adsorption at the nanostructured surface enables SERS detection, uncertainty about …

The Development Of A Surface Enhanced Raman Spectroscopy Method For The Detection Of Synthetic Cannabinoids In Urine, Thaddeus Mostowtt

FIU Electronic Theses and Dissertations

The use and abuse of synthetic cannabinoids has increased significantly in recent years due to their easy access and growing popularity. Despite having more known drugs become illegal, new synthetic versions of these drugs are being made that have not yet been recognized or classified as illegal substances. Therefore, standard methods may not be able to detect these drugs.

The most common method of screening detection for drugs of abuse in biological samples is the immunoassay. However, the immunoassay method presents some disadvantages, particularly for newly synthesized compounds. More advanced methods have also been used, such as LC-MS; however, these …

Dipicolinamide Ligands And Analogs For Lanthanides (Ln), Actinides (An) And Mercury (Hg) For Application To Nuclear Fuel Cycle Separations And Waste Management, Ingrid Lehman-Andino

FIU Electronic Theses and Dissertations

Spent nuclear fuel (SNF) – or used nuclear fuel (UNF) – contains long-lived minor actinides such as ²⁴¹Am, ²⁴⁵Cm, and ²³⁷Np, together with fission products that include lanthanides. Minor actinides are responsible for much of the radiotoxicity and heat generation that limits the capacity of geological repositories. Thus, removing minor actinides from UNF can reduce storage time required for decay to natural levels of activity by several orders of magnitude. Actinide(An)/Lanthanide(Ln) separation processes via solvent extraction by selective complexation with organic or aqueous ligands have to overcome difficulties due to similarities in their ionic radii for the …

Use Of Laser Induced Breakdown Spectroscopy For The Detection And Analysis Of Chemical Taggants, Cole Andrew Pajunen

FIU Electronic Theses and Dissertations

Chemical taggants impart a unique imprint on an object so that, if stolen, the ownership or original source of the object can be unambiguously identified. A commercially available tagging system from SmartWater® Technology Ltd. utilizes a polymer-based solution that solidifies upon application and contains a unique combination of up to 27 rare-earth elements as the chemical identification system. Currently, Laser ablation inductively coupled mass spectrometry (LA-ICP-MS) is used as the primary means to determine the presence/absence of these elements. This current study investigates the use of a commercial laser induced breakdown spectroscopy (LIBS) system as an alternative detection method due …

Systematic Comparison Of Pre-Treatment Parameters In Forensic Hair Analysis And Investigating Hair-Drug Interactions, Jennett Chenevert Aijala

FIU Electronic Theses and Dissertations

Forensic toxicological analysis for the purposes of protecting human health and supporting criminal justice activities can be achieved, in part, by means of analysis of human head hair for detection of abused substances. Hair is considered an alternative sample matrix (compared to blood and urine) because of persistent interpretive challenges caused by a lack of standardization in analytical approaches and poor understanding of the biases resulting from physicochemical interactions between major hair components (e.g., melanin) and drugs of abuse. Some of the uncertainty regarding optimal techniques for the pre-treatment of hair specimens results from the unknown nature of the …

Structural Characterization Of Biomolecules Using Tandem Non- Linear And Linear Ion Mobility, Action Spectroscopy, Mass Spectrometry And Molecular Dynamics, Jacob Edward Porter

FIU Electronic Theses and Dissertations

The following thesis comprises the use of novel gas-phase spectroscopic and spectrometric techniques complemented with molecular dynamics for the structural characterization of biomolecules: from small model systems to large proteins. In particular, complementary linear and non-linear ion mobility, mass spectrometry and action spectroscopy has been applied to the separation and characterization of native and kinetic intermediate states of biomolecular ions. This suite of tools, comprising ion mobility in tandem with non-ergodic fragmentation and action spectroscopy, provided unique information on the conformational space, folding and binding dynamics of single stranded DNA, peptides, peptide-cofactor and protein systems. Theoretical modeling provided candidate structures …

Nmr-Based Metabolic Profiles Of Intact Zebrafish Embryos Exposed To Aflatoxin B1 Recapitulates Hepatotoxicity And Supports Possible Neurotoxicity, Zain Zuberi, Muhamed N.H. Eeza, Joerg Matysik, John P. Berry, A. Alia

Department of Chemistry and Biochemistry

Aflatoxin B1 (AFB1) is a widespread contaminant of grains and other agricultural crops and is globally associated with both acute toxicity and carcinogenicity. In the present study, we utilized nuclear magnetic resonance (NMR), and specifically high-resolution magic angle spin (HRMAS) NMR, coupled to the zebrafish (Danio rerio) embryo toxicological model, to characterize metabolic profiles associated with exposure to AFB1. Exposure to AFB1 was associated with dose-dependent acute toxicity (i.e., lethality) and developmental deformities at micromolar (≤ 2 µM) concentrations. Toxicity of AFB1 was stage-dependent and specifically consistent, in this regard, with a role of the liver and phase I enzyme …

Isolation And Characterization Of Potential Neurotoxic Cyanobacterial Metabolites Associated With Intoxication Of Captive Bottlenose Dolphins In The Florida Keys, Christina Lydon

FIU Electronic Theses and Dissertations

Bottlenose dolphins (Tursiops truncatus) living in captivity in the Florida Keys have recently been observed grazing macrophytic algal communities, and particularly, filamentous cyanobacteria, within their enclosures, and subsequently presenting apparent signs of intoxication. Collections of a mixed assemblage of marine filamentous cyanobacteria were morphologically related to the taxonomically complex and toxigenic polyphyletic genus, Lyngbya, sensu lato. Phylogenetic characterization, using 16S rDNA methods, identified an undescribed member of the recently accepted genus Neolyngbya (Oscillatoriales) among Neolyngbya arenicola, and an unknown Oscillatoriacean species within a poorly resolved clade clustering between the genera Limnoraphis and Capilliphycus.

A dual …

Lithological And Geochemical Responses To Abrupt Global And Regional Paleoenvironmental Changes During The Aptian In A Hemipelagic Setting Of The Eastern Iberian Peninsula: A Multi-Proxy Approach, Jander Socorro

FIU Electronic Theses and Dissertations

Intense episodes of environmental perturbations and regionally to globally distributed, oxygen-deprived marine facies characterize the Cretaceous sedimentary record. The Organyà Basin in the Spanish Pyrenees chronicles this period in expanded stratigraphic sequences that enabled high-resolution sampling and detailed analysis of disturbances poorly recorded in more lithologically condensed sections. Here, I present an integrated multi-proxy study aimed at understanding the Basin’s response to changing paleoenvironmental conditions during the early Aptian stage of the Cretaceous.

Results from the El Pui section indicate that large-scale (> 1‰), negative carbon isotope excursions (CIEs) that show no corresponding shifts in local sources of organic matter …

Advanced Oxidation Processes For The Remediation Of Problematic Organophosphorus Compounds And Perfluoroalkyl Substances, A M Abdullah

FIU Electronic Theses and Dissertations

The presence of persistent organic pollutants, including organophosphorus esters (OPEs) and perfluoroalkyl substances (PFASs) in drinking water sources, is a serious threat to the environment and human health. Advanced oxidation processes (AOPs), specifically TiO₂ photocatalysis and sonolysis, were evaluated to degrade these pollutants in water.

The UV/TiO₂ photocatalysis can effectively degrade tris (2-chloroethyl) phosphate (TCEP) to innocuous materials. The degradation follows pseudo-first-order kinetics and consistent with the Langmuir-Hinshelwood model. Intermediate products identified by ³¹P-NMR show sequential oxidation of alkyl chains, ultimately leading to phosphate. Scavenger studies indicate hydroxyl radical (•OH) is the primary species responsible for the …