Chemistry Commons^™

Molecular Level Characterization Of Dissolved Organic Matter Integrating Trapped Ion Mobility Spectrometry And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Dennys Leyva Bombuse

FIU Electronic Theses and Dissertations

Dissolved organic matter (DOM) is an extremely complex mixture of organic molecules ubiquitous in aquatic systems and a critical component of the global carbon cycle. Little is known about DOM structural composition at the molecular level. The work presented in this dissertation summarizes the development of a novel analytical toolbox based on trapped ion mobility spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (TIMS-FT-ICR MS) that has significantly contributed to expand our knowledge of DOM molecular complexity and diversity. The TIMS-FT-ICR MS/MS analysis provided for the first-time lower and upper estimation of the molecular isomeric diversity. The TIMS-FT-ICR MS/MS …

Allosteric Mechanism On Dream Dimerization And Impact On Its Interactions With Divalent Metal Zn2+, Maria D. Santiago Estevez

FIU Electronic Theses and Dissertations

DREAM belongs to the NCS family, and it is involved in several physiological processes mediated by Ca²⁺ association, which produces changes in its oligomerization state. The mechanism of how Ca²⁺ binds to DREAM remains unknown. A kinetic study of the binding of Ca²⁺ to DREAM suggested that DREAM dimerization is a two-step process, the first step( τ₁= 8±0.1ms) is associated with the binding of Ca²⁺ to the monomer, while the second step (τ₂ = 3.6 ±0.4 s ) corresponds to a conformation relaxation that leads to the dimerization. Furthermore, by analyzing the fast …

Assessment Of The Toxicity Of Legacy And Next-Generation Perfluoroalkyl Substances (Pfas) In Early-Life Stages Of Freshwater And Marine Fish, Kiflom Gebreab

FIU Electronic Theses and Dissertations

Per- and polyfluoroalkyl substances (PFASs) are a group of synthetic surfactants that have utilized for several decades in a wide range of industrial and manufacturing applications. Owing to their high chemical stability, PFAS are widespread and persistent in the environment, and have been shown to be bioaccumulative in diverse organisms including plants, wildlife, and humans. Exposure to PFASs has been linked to a range of documented toxic and/or adverse effects in relation to human and animal health. The potential environmental health and ecotoxicity of next-generation PFAS remain unclear. In the present study, toxicity, and bioconcentration potential, of several perfluoroether carboxylic …

Development Of Electrochemical Aptamer-Based Sensors For Sensitive And Specific Detection Of Small-Molecule Targets, Yingzhu Liu

FIU Electronic Theses and Dissertations

Electrochemical aptamer-based (E-AB) sensors have been applied for diverse applications such as forensic science, pharmaceutical diagnostics, food safety, environmental monitoring, and personal medical care due to their rapid, accurate, and specific detection of analytes in complex samples. However, limited sensitivity and a lack of portable devices for point-of-care applications have greatly hindered the maturation of E-AB sensors from proof-of-concept designs to commercial systems. This dissertation describes several novel strategies to improve the sensitivities of E-AB sensors and fabricate portable paper-based devices to remedy these problems. We first detail the development of a novel approach to utilize a defined mixture of …

Exonuclease Digestion Assay For Streamlining Aptamer Characterization, Engineering, And Sensor Development, Juan Canoura

FIU Electronic Theses and Dissertations

Aptamers are DNA or RNA oligonucleotide-based bioreceptors isolated in vitro through the Systematic Evolution of Ligands by Exponential Enrichment. Given the ease with which a selection can be customized, aptamers can be evolved to function in nearly any chemical environment, making them tailormade for their final application. However, the post-SELEX characterization of the 100-1000’s aptamer candidates remains a significant bottleneck as there are no suitable techniques for high-throughput characterization of each candidate’s affinity/specificity. Moreover, the final aptamer must be engineered to possess signal reporting functionality; this is often done via trail-and-error truncation to yield a structure-switching aptamer. This dissertation describes …

Synthesis, Structure-Activity And Mechanism Studies Of Poly(Guanylurea)S Against Mycobacteria, Michelle M. Miranda

FIU Electronic Theses and Dissertations

Tuberculosis (TB) continues to be a serious threat worldwide, especially in developing countries. Current first-line treatment for TB infections is a multidrug regimen for 4-9 months; if not taken as prescribed, drug-resistant TB can emerge. Novel drugs with unconventional targets are warranted to lessen the lengthy and four-drug treatment. Antimicrobial polymers mimicking naturally occurring antimicrobial peptides (AMPs) have gained much attention due to their enzymatic stability, tunability, cost-effectiveness, and unique mode of action - directly or indirectly - on bacterial membrane. However, selectivity and toxicity have limited their biological applications. Previously, our group synthesized a novel class of antimicrobial polymers, …

Synthesis Of Phenyl Carbamoylated Guanidine Functionalized Chitosan, Eduardo Hernandez Requejo

FIU Electronic Theses and Dissertations

The lack of solubility of the chitosan in organic solvents hinders its potential for chemical modifications. For this reason, it was hypothesized that the insertion of the phenyl carbamoylated guanidine moiety could lead to increased solubility in DMSO and new potential modifications and uses.

This research involved the synthesis of S-methyl phenyl carbamoylated guanidine (SMPCG) starting from the commercially available S-methyl isothiourea. This was followed by the reaction of the SMPCG with chitosan to yield phenyl carbamoylated guanidine functionalized chitosan (PCGCs) with a degree of substitution of 14%.

The chitosan derivative is fully soluble in DMSO and partially in DMF. …

Modified Guanidine-Containing Polymers For Intracellular Protein Delivery, Alfonso Barrios

FIU Electronic Theses and Dissertations

Protein-based therapeutics have gained significant attention for treating or curing various diseases, especially those untreatable by small molecule-drugs. Despite their widespread success and adoption, the cellular membrane remains a major obstacle for proteins to reach the inner compartments of the cell and have had limited applicability spanning only extracellular targets. Consequently, the efficient intracellular delivery of proteins offers tremendous potential to reach new, unexplored, and otherwise “undruggable” targets. Acknowledging the therapeutic need, research efforts aimed at facilitating the delivery of proteins using polymer-based nanoparticles have emerged.

Guanidine-containing polymers provide a promising platform to address the common hurdles associated with protein …

The Use Of Electrospun Nanofibers With Gold And Silver Nanostars For The Detection Of Fentanyl Using Surface Enhance Raman Spectroscopy, The Modification Of Current Gc-Ms Methods To Increase Separation And Detection Of Synthetic Cathinones In Mixtures, Daniel Rubin

FIU Electronic Theses and Dissertations

Many criminal cases involve the use or sale of illicit substances. The forensic analyst has many different techniques they can use to analyze samples to determine which illicit substance is present. This project aims at developing electrospun nanofibers with nanoparticles to analyze fentanyl by surface enhanced Raman spectroscopy, as well as modifying current GC-MS parameters to enhance separation and analysis of synthetic cathinones. Using the fibers with nanoparticles allowed for the detection of fentanyl standards at 1mg/ml while slowing the oven ramp rate and modifying the hold times led to an increase in separation and better fragmentation patterns for determination. …

Crude Oil Characterization Using Gas Chromatography, Ion Mobility Spectrometry And Mass Spectrometry, Clement A. Olanrewaju

FIU Electronic Theses and Dissertations

The characterization of crude oils at the compositional level remains challenging due to their high chemical complexity and isomeric diversity. The present work expands the analytical separation space of chemical components in crude oils by coupling gas chromatography (GC), trapped ion mobility spectrometry (TIMS), and mass spectrometry (GC-TIMS-MS and TIMS-FT-ICR MS) for the effective separation and identification of isomeric compounds. The coupling of GC and TIMS-MS platform enhanced the peak capacity and showed complementary isomeric separation. The combination of GC-TIMS-MS and GC-EI-MS technique provided a comprehensive characterization of PAHs and similar compounds from crude oils on the basis of retention …

The Utilization Of Volatile Organic Compounds And Human Leukocyte Antigen Genes For Ethnic-Specific Differentiation Within Target Populations, Alice Breia Boone

FIU Electronic Theses and Dissertations

Human scent has been previously defined as a complex mixture of volatile organic compounds (VOCs) detected in the headspace above a scent sample. Humans generate odor from several areas of the body including hair, mouth, hand, axillae, and foot. Due to the novelty of human scent research, human scent evidence has been undervalued in the court of law. However, this type of evidence has significant value when physical evidence is not available at crime scenes. To increase the individualization and differentiation power of human scent evidence, this study aimed to further investigate the identification of chemical signatures within axillae of …

An Investigation To Corroborate Volatile And Biological Profiles Of Human Odor For Forensic Subject Identification, Chantrell J.G. Frazier

FIU Electronic Theses and Dissertations

Hands are an integral part in transferring complex microbial communities to and from our surroundings. As a result, hands are significant in provenance investigations as specific microbiota can be deposited on everyday objects through touch interactions. Skin microbiome, including bacteria, fungi, and viruses, are unique to each person, and this ‘uniqueness’ can be exploited and applied to forensic identification. Skin microbiota and volatile organic compounds (VOCs) are closely related due to specific bacteria breaking down non-volatile organic compounds to volatile organic compounds that are characteristically present in human scent. However, analyses of microbiota from touch interactions have proven to be …

Development Of A Microwave-Based Dna Extraction Method To Increase The Success Of Direct And Rapid Pcr Technique, Fabiana Taglia

FIU Electronic Theses and Dissertations

The goal of this project was to develop a fast, microwave-based extraction technique that could be employed for direct and rapid DNA analysis. The hypothesis was that the use of a microwave could increase the yield of DNA by opening the cell membrane, rendering the DNA available without the use of any other chemical treatment, and improving results from very low quantity samples.

At present rapid human DNA analysis is mainly restricted to genotyping saliva and sometimes blood samples. We hypothesized that microwave processing could expand the types of samples assessable to these procedures and increase sensitivity.

There were two …

O-Sulfonamidophenol Ligands And Derivatives For F-Element Sensing, Complexation, And Extraction From Alkaline High-Level Waste, Oluwaseun William Adedoyin

FIU Electronic Theses and Dissertations

The accumulated (>100 Mgal) alkaline high-level waste (HLW), which is a legacy of nuclear weapons manufacturing during the cold war era, is an issue of environmental concern that has presented reprocessing challenges, due to its complex physicochemical properties and the presence of ¹³⁷Cs, ⁹⁰Sr, and long-lived actinides.

This study is focused on o-sulfonamidophenol derivatives bearing electron-rich O- and N- donor sites (when deprotonated in alkaline conditions) for effective complexation, sensing, and extraction of f-elements from highly alkaline solutions. Using Ln(III) as experimental surrogates for An(III), a family of o-sulfonamidophenol ligands (L1H₂ – L4H_{2 …}

Evaluation And Improvement Of Capillary Microextraction Of Volatiles Coupled To Gas Chromatography-Mass Spectrometry For The Analysis Of Ignitable Liquid Residues In Fire Debris, Michelle Nikole Torres

FIU Electronic Theses and Dissertations

A key aspect of fire debris analysis is the ability to extract the remnants of an ignitable liquid from a matrix with a high degree of reliability and sensitivity. Although there are several robust, standardized methods, there is no single technique universally applicable to casework. In this work a novel extraction technique – Capillary Microextraction of Volatiles (CMV) – has been applied, for the first time, for ignitable liquid residue (ILR) extraction. A 20-minute dynamic sampling laboratory protocol from traditional 1 L paint cans was established and optimized based upon ASTM guidelines. The development of new adsorption phases for CMV …