Physical Sciences and Mathematics Commons^™

Nmr Analyses Of Flavored E-Cigarette Liquids Before And After Aerosolization, Paul Joseph Kerber

Dissertations and Theses

Electronic cigarettes (e-cigarettes) are the most commonly used tobacco products among adolescents with ~11 and ~3% of high school and middle school students reporting past 30 day use in 2021 according to the Centers for Disease Control and Prevention (CDC), respectively. Furthermore, greater than ~80% of high school and middle school e-cigarette consumers use flavored e-liquids. Consumers can be exposed to variable toxicant levels upon e-liquid aerosolization, depending on the composition of the e-liquid, type of e-cigarette, e-cigarette settings, and other customizations.

E-liquids are typically composed of a carrier solvent (propylene glycol (PG) and glycerol (GL)), flavorants, and nicotine. PG …

Negative Photoresponse In Ti3C2TX Mxene Monolayers, Nataliia S. Vorobeva, Saman Bagheri, Angel Torres, Alexander Sinitskii

Chemistry Department: Faculty Publications

Two-dimensional transition metal carbides, nitrides, and carbonitrides, collectively known as MXenes, are finding numerous applications in many different areas, including optoelectronics and photonics, but there is limited information about their intrinsic photoresponse. In this study, we investigated the visible and near-infrared range photoresponse of Ti₃C₂T_x, the most popular MXene material to date. The electrical measurements were performed on devices based on individual monolayer Ti₃C₂T_x MXene flakes, which were characterized by a variety of microscopic and spectroscopic methods. For MXene devices with different electrode layouts, the current reproducibly decreased under …

Characterization Of Three-Dimensional Fractional Viscoelastic Models Through Complex Modulus Analysis And Polar Decomposition, Avradip Ghosh, Avinash Kumar Both, Chin Li Cheung

Chemistry Department: Faculty Publications

Soft materials such as gels, elastomers, and biological tissues have diverse applications in nature and technology due to their viscoelastic nature. These soft materials often exhibit complex rheology and display elastic and viscous characteristics when undergoing deformation. In recent years, fractional calculus has emerged as a promising tool to explain the viscoelastic behavior of soft materials. Scalar constants are primarily used to quantify viscoelastic elements such as springs and dashpots. However, in three-dimensional (3D) space, not all materials show the same elastic or viscoelastic properties in all directions, especially under elastic/viscoelastic wave propagation (or anisotropy). Though previously reported studies on …

Design And Synthesis Of Nef:Sfk Interaction Inhibitors For Application In An Immune-Directed Hiv-1 Cure, Antony Lurie

Electronic Thesis and Dissertation Repository

The human immunodeficiency virus type 1 (HIV-1) protein, Nef, binds and activates Src family kinases (SFKs) to reduce cell surface levels of major histocompatibility complex class I (MHC-I), thereby facilitating cytotoxic T lymphocyte (CTL) evasion. Importantly, Nef-mediated CTL evasion compromises the success of immune-directed curative approaches, underscoring Nef:SFK interaction inhibitors as promising adjuvants in an immune-directed cure. Previously, our group identified a dipeptide derivative (H3-1) which inhibits the Nef:SFK interaction and MHC-I downregulation in vitro, but is unstable in vivo. I hypothesized that H3-1’s instability is due to its proteolysis and have generated peptidomimetic analogues of H3-1 which …

Integrating Conformational Dynamics And Perturbation-Based Network Modeling For Mutational Profiling Of Binding And Allostery In The Sars-Cov-2 Spike Variant Complexes With Antibodies: Balancing Local And Global Determinants Of Mutational Escape Mechanisms, Gennady M. Verkhivker, Steve Agajanian, Ryan Kassab, Keerthi Krishnan

Mathematics, Physics, and Computer Science Faculty Articles and Research

n this study, we combined all-atom MD simulations, the ensemble-based mutational scanning of protein stability and binding, and perturbation-based network profiling of allosteric interactions in the SARS-CoV-2 spike complexes with a panel of cross-reactive and ultra-potent single antibodies (B1-182.1 and A23-58.1) as well as antibody combinations (A19-61.1/B1-182.1 and A19-46.1/B1-182.1). Using this approach, we quantify the local and global effects of mutations in the complexes, identify protein stability centers, characterize binding energy hotspots, and predict the allosteric control points of long-range interactions and communications. Conformational dynamics and distance fluctuation analysis revealed the antibody-specific signatures of protein stability and flexibility of the …

Multiplexed Monitoring Of Neurochemicals Via Electrografting- Enabled Site-Selective Functionalization Of Aptamers On Field-Effect Transistors, Zan Gao, Guangfu Wu, Yang Song, Huijie Li, Yuxuan Zhang, Michael J. Schneider, Yingqi Qiang, Jackson Kaszas, Zhengyan Weng, He Sun, Bryan D. Huey, Rebecca Lai, Yi Zhang

Chemistry Department: Faculty Publications

Neurochemical corelease has received much attention in understanding brain activity and cognition. Despite many attempts, the multiplexed monitoring of coreleased neurochemicals with spatiotemporal precision and minimal crosstalk using existing methods remains challenging. Here, we report a soft neural probe for multiplexed neurochemical monitoring via the electrografting-assisted site-selective functionalization of aptamers on graphene field-effect transistors (G-FETs). The neural probes possess excellent flexibility, ultralight mass (28 mg), and a nearly cellular-scale dimension of 50 μm × 50 μm for each G-FET. As a demonstration, we show that G-FETs with electrochemically grafted molecular linkers (−COOH or −NH2) and specific aptamers can be used …

Quantifying Protein Quality To Understand Protein Homeostasis (Supplemental Data), Hsien-Jung Lavender Lin

ScholarsArchive Data

This data set includes the supplementary data for chpaters 3 and 4 in the dissertation Quantifying Protein Quality to Understand Protein Homeostasis. It includes various excel worksheets that were used to generate the data reported in the dissertation. We make this data available to the public so anyone who wants to reproduce the results has the resources and access to other perspectives that weren't discussed in depth in the dissertation. Chapter 3 used mass-spectrometry to quantify the surface accessibility differences in human serum albumin (HSA)between patients with and without rheumatoid arthritis (RA). We found certain residues are less reactive …

The Total Synthesis Of Glycolipids From Streptococcus Pneumoniae And A Re-Evaluation Of Their Immunological Activity**, Seyed Iraj Sadraei, Greg Yousif, S. Maryamdokht Taimoory, Maryam Kosar, Samaneh Mehri, Raghd Alolabi, Emmanuel Igbokwe, Jason Toma, Mir Munir A. Rahim, John F. Trant

Chemistry and Biochemistry Publications

Invariant natural killer (iNK) T cells, Type I iNKTs, are responsible for the production of pro-inflammatory cytokines which induce a systemic immune response. They are distinctive in possessing an semi-invariant T-cell receptor that recognizes glycolipid antigens presented by CD1d, a protein closely related to the class I major histocompatibility complex, conserved across multiple mammalian species in a class of proteins well-renowned for their high degree of polymorphism. This receptor's first potent identified antigen is the α-galactosylceramide, KRN7000, a synthetic glycosphingolipid closely related to those isolated from bacteria that were found on a Japanese marine sponge. A corresponding terrestrial antigen remained …

Kinetics, Products, And Brown Carbon Formation By Aqueous-Phase Reactions Of Glycolaldehyde With Atmospheric Amines And Ammonium Sulfate (Raw Data), David O. De Haan, Alyssa A. Rodriguez, Michael A. Rafla, Hannah G. Welsh, Elyse A. Pennington, Jason R. Casar, Lelia N. Hawkins, Natalie G. Jimenez, Alexia De Loera, Devoun R. Stewart, Antonio Rojas, Matthew-Khoa Tran, Peng Lin, Alexander Laskin, Paola Formenti, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin

Chemistry and Biochemistry: Faculty Scholarship

The zipped data files are in the following formats: Metadata: Word documents (.docx), Chamber data: Excel spreadsheets (.xlsx) and European Data Format files (.edf), organized by experiment number and instrumentation. “CAPS” files contain cavity attenuated phase shift (CAPS) extinction and scattering data; “SMPS” files contain scanning mobility particle sizing aerosol number and aerosol mass data.

Combination Of High Ph And An Antioxidant Improves Chemical Stability Of Two-Dimensional Transition-Metal Carbides And Carbonitrides (Mxenes) In Aqueous Colloidal Solutions, Shuohan Huang, Vadym Mochalin

Chemistry Faculty Research & Creative Works

MXenes, a large family of two-dimensional (2D) transition-metal carbides/nitrides, have attracted increased attention in recent years because of their excellent electronic, mechanical, thermal, and optical properties. Studying chemical properties of MXenes is important to prolong the shelf life of their colloids and provide robust performance of MXenes in devices and applications. While the role of MXene reactivity with the environment, including water and components of air, is becoming more recognized, less is known about the role of parameters influencing the reactivity. In this work, we investigate the individual and combined effects of the pH and antioxidant on chemical stability of …

The Interaction And Orientation Of Peptide Kl4 In Model Membranes, Drew Marquardt, Brad Van Oosten, Maksymilian Dziura, Joanna R. Long, Thad A. Harroun

Chemistry and Biochemistry Publications

We report on the orientation and location of synthetic pulmonary surfactant peptide KL4, (KLLLL)4K, in model lipid membranes. The partitioning depths of selectively deuterated leucine residues within KL4 were determined in DPPC:POPG (4:1) and POPC:POPG (4:1) bilayers by oriented neutron diffraction. These measurements were combined with an NMR-generated model of the peptide structure to determine the orientation and partitioning of the peptide at the lipid–water interface. The results demonstrate KL4 adopting an orientation that interacts with a single membrane leaflet. These observations are consistent with past 2H NMR and EPR studies (Antharam et al., 2009; Turner et al., 2014).

Can You Master This? : Initial Attempts At Specifications-Based Grading In Introductory Chemistry, Laura Kopff

Faculty Publications & Research

The Illinois Mathematics and Science Academy (IMSA) requires all incoming students to complete a one-semester introductory chemistry course in their sophomore year – Scientific Inquiries in Chemistry (SI-Chem). This course has historically been taught using a traditional grading/assessment model, however, in the Spring of 2021, a switch was made to a specification-based grading system. One motivating factor in this decision is an institutional shift to an equity-focused grading approach, and an analysis of our historical assessment model indicated areas for improvement.

Our initial foray into specifications grading was during the Spring of 2021 semester, when all of our courses were …

Whole Farm Net Zero: Approaches To Quantification Of Climate Regulation Ecosystem Services At The Whole Farm Scale. Vermont Payment For Ecosystem Services Technical Report #7, Christopher Bonasia, Lindsey Ruhl, Benjamin Timothy Dube, Alissa C. White, Heather M. Darby

UVM Extension Faculty Publications

In this report, approaches to the quantification of climate mitigation ecosystem services at the whole farm scale are reviewed and summarized for easy comparison. Eight quantification tools, and three case studies demonstrating possible tool applications, are summarized to fulfill the requirements of the Technical Services Contract—Task 7. Information from a combination of literature review and expert interviews served to document the inputs, outputs, strengths, weaknesses, opportunities, and threats for each quantification tool. This research was conducted in service to the Vermont Soil Health and Payment for Ecosystem Services (PES) Working Group (VT PES working group). It is our hope that …

A New Class Of Antibiotic That Prevents Drug Tolerance, Persistence, And Resistance By Controlling Emergence Of Phenotypes., Pankaj Dinkar Patil

Dissertations - ALL

The fight against bacterial infections and innovations in antibiotic therapy has never halted throughout human history. However, bacteria have evolved smartly and resistance against practically all conventional antibiotics has been developed. Furthermore, bacteria can form biofilms, which are surface-attached multicellular colonies. Biofilms shield bacteria against antibiotics and makes it harder to entirely eradicate infections . Under antibiotics stress, bacteria evolve into different phenotypes like hyper motile, hyper adherent and hyper virulent which are tolerant and persistent to antibiotic treatment. The use of antibiotic therapy to combat such resilient bacterial phenotypes is extremely tough. As a result, the scientific community is …

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 …

Properties And Behavior Of Tricarbonyl Manganese Scorpionate Complexes, Billy Shone

Master's Theses (2009 -)

Manganese tricarbonyl complexes have widely been studied for their ability to release carbon monoxide (CO) in the presence of light for potential applications in cancer therapy and in catalysis. Most studies focus on the kinetics and quantity of CO release and the overall impact on cell death. Far fewer studies identify the manganese intermediates and final products after decarbonylation. Identification of such products would be critical to improving reactivity and understanding potential (undesirable) side effects in future applications employing these CO releasing molecules (CORMs). Recently, nitrogen confused C-scorpionate ligands were introduced by the Gardinier group where a pyrazolyl ring is …

Photocrosslinking Probes Proximity Of Thymine Modifiers Tethering Excitonically Coupled Dye Aggregates To Dna Holliday Junction, Shibani Basu, Keitel Cervantes-Salguero, Bernard Yurke, William B. Knowlton, Jeunghoon Lee, Olga A. Mass

Chemistry and Biochemistry Faculty Publications and Presentations

A DNA Holliday junction (HJ) has been used as a versatile scaffold to create a variety of covalently templated molecular dye aggregates exhibiting strong excitonic coupling. In these dye-DNA constructs, one way to attach dyes to DNA is to tether them via single long linkers to thymine modifiers incorporated in the core of the HJ. Here, using photoinduced [2 + 2] cycloaddition (photocrosslinking) between thymines, we investigated the relative positions of squaraine-labeled thymine modifiers in the core of the HJ, and whether the proximity of thymine modifiers correlated with the excitonic coupling strength in squaraine dimers. Photocrosslinking between squaraine-labeled thymine …

A Protein-Based Therapeutic Combination For The Treatment Of Hard-To-Heal Wounds, Graham L. Strauss

USF Tampa Graduate Theses and Dissertations

Chronic wounds present many clinical challenges in relation to the successful treatment and closure of the damaged tissue. Most current treatment methods focused on one or two aspects to drive wound closure, while most chronic wounds are multifactorial environments with many of those dependencies relying on the termination of one another to effectively gain tissue construction, closure, and full skin thickness and composition. Natural wound healing processes allude to potential biologics that can impede the chronic breakdown of tissue, while restoring deposition of new tissue, and effectively leading to a healed wound. Proteases secreted by the body’s immune system lay …

Mass Spectrometric Investigation Of Removal/Transformation Of Emerging Contaminants For Safer Potable Wastewater Reuse, Kristin Cochran

Theses and Dissertations

Water scarcity is of increasing global concern as rising demand depletes current sources, so other sources such as potable wastewater reuse are being utilized. Advanced wastewater reuse removes pathogens and many contaminants, but there are concerns about resistant contaminants and the transformation products that are generated during the treatment process. This research focuses on several different contaminant classes, how well they are removed via advanced treatment processes, what transformation products arise from both advanced treatment and chlorination disinfection, and how those treated waters may impact health via toxicity and estrogen activity.

Contaminant classes considered are illicit drugs, pharmaceuticals such as …

Uv- And Visible-Light Photopatterning Of Molecular Gradients Using The Thiol–Yne Click Reaction, Mark Mitmoen, Ofer Kedem

Chemistry Faculty Research and Publications

The rational design of chemical coatings is used to control surface interactions with small molecules, biomolecules, nanoparticles, and liquids as well as optical and other properties. Specifically, micropatterned surface coatings have been used in a wide variety of applications, including biosensing, cell growth assays, multiplexed biomolecule interaction arrays, and responsive surfaces. Here, a maskless photopatterning process is studied, using the photocatalyzed thiol–yne “click” reaction to create both binary and gradient patterns on thiolated surfaces. Nearly defect-free patterns are produced by first coating glass surfaces with mercaptopropylsilatrane, a silanizing agent that forms smoother self-assembled monolayers than the commonly used 3-mercaptopropyltrimethoxysilane. Photopatterning …

Improved Photodecarboxylation Properties In Zinc Photocages Constructed Using M‐Nitrophenylacetic Acid Variants, Austin K. Shigemoto, Avik Bhattacharjee, Erin E. Hickey, Hallee Jade Boyd, Theresa M. Mccormick, Shawn C. Burdette

Chemistry Faculty Publications and Presentations

The methoxy- and fluoro-derivatives of meta-nitrophenylacetic acid (mNPA) chromophores undergo photodecarboxylation with comparable quantum yields to unsubstituted mNPA, but uncage at red-shifted excitation wavelengths. This observation prompted us to investigate DPAdeCageOMe (2-[bis(pyridin-2-ylmethyl)amino]-2-(4-methoxy-3-nitrophenyl)acetic acid) and DPAdeCageF (2-[bis(pyridin-2-ylmethyl)amino]-2-(4-fluoro-3-nitrophenyl)acetic acid) as Zn2+ photocages. DPAdeCageOMe has a high quantum yield and exhibits other photophysical properties comparable to XDPAdeCage ({bis[(2-pyridyl)methyl]amino}(9-oxo-2-xanthenyl) acetic acid), the best perforiming Zn2+ photocage reported to date. Since the synthesis of DPAdeCageOMe is more straightforward than XDPACage, the new photocage will be a highly competitive tool for biological applications.

Synthesis And Characterization Of Biomimetic Co And Fe Complexes With Trispyrazolylborate Ligands, Praveen Kumar

Dissertations (1934 -)

Numerous reactions of biological and environmental significance are catalyzed by dioxygenases that incorporate both atoms of O2 into the substrate. These enzymes require a transition-metal cofactor for activity, typically a mononuclear nonheme iron center, although dioxygenases with first-row transition metal ions (Mn, Co, Ni) have been discovered. This dissertation focuses on synthetic studies based on mononuclear dioxygenases found in bacterial pathways for the breakdown and assimilation of inert organic compounds, including human-generated pollutants. Such enzymes are essential for bioremediation technologies used to restore contaminated soils and groundwaters. While crystallographic studies have revealed the active-site structures of various types of dioxygenases, …

Guest-Mediated Self-Assembly Of Deprotonated 2-Bromoresorcinarenes, Kwaku Twum, Khai-Nghi Truong, Frank Boateng Osei, Carolina Von Essen, Sanaz Nadimi, John F. Trant, Kari Rissanen, Ngong Kodiah Beyeh

Chemistry and Biochemistry Publications

Doubly and triply deprotonated 2-bromo-C-alkylresorcinarene anions form host–guest complexes with both tetramethylammonium cations and bis-protonated dimethyl piperazine cations. The trianion forms a fully closed dimeric capsule with one endo- and two exo-cavity bis-protonated dimethyl piperazine cations. Interestingly, the dianion crystallized from a mixture of the 2-bromo-C-methylresorcinarene, dimethylethylenediamine, and tetramethylammonium chloride forms a nanotube consisting of only the 2-bromo-C-methylresorcinarene anion and the tetramethylammonioum cation. The nanotube has an exo-functionalized anionic hydrophilic outer surface that interacts with cationic guests and a hydrophobic interior channel. Solution studies support the deprotonation and the formation of these …

The Development Of A Monolithic Spatial Heterodyne Spectrometer For Extreme Environments, Arelis Michelle Colόn

Theses and Dissertations

This work describes improvements to a novel instrument, the monolithic spatial heterodyne Raman spectrometer (mSHRS), which has potential to be utilized in space exploration and deep-ocean marine sensing. In previous work, the spatial heterodyne Raman spectrometer (SHRS) was demonstrated, as a small, high resolution, wide field of view spectrometer, originally developed for space applications where small size and compactness is a key consideration or where a wide field of view is advantageous, such as in remote spectroscopy. The spatial heterodyne spectrometer (SHS) was then later utilized for remote Laser-Induced Breakdown Spectroscopy (LIBS). The high throughput, high spectral resolution, and large …

Novel Synthetic Strategies Toward Polyolefin-Grafted Nanoparticles, Richard Tran Ly

Theses and Dissertations

Surface functionalization of nanoparticles has proven to be a powerful and versatile strategy in the development of various materials with advanced properties. Polymer brush composition can range from complex copolymers to more simplistic polyolefin, and by functionalizing nanoparticle surfaces, mobility of distinct particles can then be tuned and, therefore, control over dispersion in a polymer matrix can be achieved. Presented in this dissertation are new synthetic strategies for the preparation of polymer nanocomposites.

The first chapter covers a novel synthetic strategy for ethylene/propylene-like copolymers grafted to silica nanoparticles. This approach utilizes Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization to promote living …

Materials Discovery By Flux Crystal Growth: Synthesis, Structure Determination, Magnetic, And Optical Properties Of Complex Oxides, Oxychlorides, And Oxyfluorides, Darren Andrew Carone

Theses and Dissertations

Exploratory crystal growth has proven to be a successful technique in the synthesis of new compounds with desired properties. This method is very versatile and has various iterations, but results described herein were obtained through flux growth at high temperatures utilizing mixed alkali halide salts. The tunability of these reactions with respect to reactant ratios, reaction temperature, heating/cooling rates, metal precursors, and choice of flux allow for the exploration of phase spaces between a combination of elements and observation of significantly different products and/or structure types from minor tweaks.

Most of the research presented in this dissertation describes results that …

Taking Action: Managing Inclusive Excellence In Academia, Lesley Ann Giddings, Christine Salomon

Chemistry: Faculty Publications

No abstract provided.

Large Area Projection Sintering Of Semicrystalline Polymers And Part Analysis Of The Printed Specimens, Taranjot Kaur

USF Tampa Graduate Theses and Dissertations

As the requirements posed to products have increased in recent years. The trend towards individualized serial products steps up the need for respective manufacturing techniques to be more and more flexible. Conventional techniques of serial production, such as injection molding, are unable to fully meet the requirements of this trend. Additive manufacturing techniques generate components directly from a CAD data set while requiring no specific mold, producing minimal waste, and reaching satisfactory geometric accuracy. This is how, as opposed to conventional techniques, they comply with these increased demands to processing technology. Over the last two decades, the research community has …

Evaluation Of The Energetic Factors In Crystalline Pharmaceuticals Using Solid-State Density Functional Theory And Low-Frequency Vibrational Spectroscopy, Margaret P. Davis

Dissertations - ALL

Due to the importance of maintaining stable and effective pharmaceutical solid doses, it is critical to study the variety of solid forms that active pharmaceutical ingredients can adopt including polymorphs, hydrates, and cocrystals. In this work, low-frequency vibrational spectroscopies and rigorous quantum mechanical simulations are combined to provide a new technique for characterizing and investigating pharmaceutically relevant polymorphs, hydrates, and cocrystals as well as a series of model cocrystals. Low-frequency spectra in the sub-200 cm-1 range provide not only unique and characteristic spectra for all of the systems explored here but, along with X-ray structural parameters, they offer a way …

Pyridyl Bis-Urea Macrocycles As Supramolecular Synthons And The Design And Synthesis Of Small Molecule Pharmaceuticals Targeting Ly6k, Devan D. Buchanan

Theses and Dissertations

Assembled pyridyl bis-urea macrocycles have been utilized as 1D supramolecular synthons to construct hierarchical assemblies. These macrocycles have both urea and pyridyl functional groups and can form non-covalent interactions with hydrogen or halogen bond donors through symmetric, ditopic acceptor motifs. Bis-urea macrocycles offer interesting capabilities as synthons to organize donors into well-defined crystal structures. In part, this is due to the urea motifs’ propensity to assemble through hydrogen bonding. New, asymmetric pyridyl macrocycles were synthesized, crystallized, and experimentally probed to determine how symmetry affects their assembly and utility as supramolecular synthons.

The Uphadhyay group identified small molecules, including NSC11150, …