Chemistry Commons^™

Development And Applications Of Touch Chemistry Biometrics Analysis Of Latent Fingermarks By Maldi-Ms, Cameron M. Longo

Legacy Theses & Dissertations (2009 - 2024)

Fingerprint evidence has long been a pillar of forensic science and has been used for over a century as a means of identifying an individual. This is accomplished through the comparison of friction ridge patterns, which are inherently unique to each individual, and the practice of visualizing fingerprints and comparing them has become a well-studied field. While these techniques have been optimized and improved over time, they generally rely only on the physical pattern to provide information about the donor, and not the content of the fingerprint material itself. In the modern era, steps have been made to extract from …

Dirhenium Compounds Containing The Diphosphine Ligands Ph2pch2pph2, Ph2pch(Cn)Pph2, Or Ph2pch(Ch3)Pph2: A Comparative Study, Hannah C. Arthur

Undergraduate Honors Theses

When M₂L₁₀ complexes containing two rhenium(III) atoms in a quadruple bond react with an excess of the diphosphine ligand Ph₂PCH₂PPh₂, the bond order decreases, and the rhenium is reduced to rhenium(II). When two diphosphine ligands are bonded to the dirhenium center, they can adopt a trans-trans, trans-cis, or cis-cis configuration. NMR spectra of compounds that adopt the cis-cis arrangement show unusually large downfield shifts for one of the bridgehead methylene hydrogens (P-CH₂-P). To understand the unusual chemical shift, the hydrogens first have to be assigned. The strategy for …

Fabrication And Characterization Of Novel Agnps Functionalized With Chlorothymol (C@Agnps), Lirim Sopaj

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In this study, novel silver nanoparticles (AgNPs) were successfully synthesized and functionalized with an antibacterial agent, namely chlorothymol (denoted C@AgNPs). The resulting colloid (C@AgNPs) was purified by two comparative methods: ultrafiltration and ultracentrifugation. Ultrafiltration proved to be more efficient in purifying and size selecting (10 kD filter) and concentrating the C@AgNPs than ultracentrifugation. The physicochemical properties of the filtered C@AgNPs were then characterized by UV-Vis absorption spectroscopy, inductively coupled plasma optical emission spectroscopy (ICP-OES), Raman spectroscopy, Cytoviva hyperspectral imaging, and Scanning electron microscopy. These measurements confirmed the functionalization of the core AgNPs with chlorothymol and suggest the proposed mechanism of …

Gene Vectors With Fluorescence Tracking Capabilities, Sophia Despina Angelopoulos

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This project focuses on the optimization of benzothiazole-based chromophores to utilize them as fluorescent tags functionalized onto stimuli-responsive, or “smart,” polymers as non-viral gene delivery vectors for gene therapy applications. Blue-fluorescent emissive chromophores will allow tracking capabilities for the transfection pathway of the vector to be monitored as it delivers the DNA payload within intercellular space. The most appropriate chromophore must be covalently bound to a free amine within the vector, which is accomplished through NAS chemistry from fluorophenyl-benzothiazoles (F-BTZ-CBz) derivatives to amidated hyperbranched poly(ethyleneimine)(HPEI-IBAm0.61). HPEI is considered to be a synthetic polycation, which promotes tunable solubility through characteristics of …

Detection Of Benzotriazole And Related Analogues In Surface Samples Collected Near An Ohio Airpark, Clara Leedy

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Benzotriazoles are a class of contaminant of emerging concern which are commonly used as anticorrosive agents in aircraft deicer and anti-icing fluids (ADAFs). The analogues 1H-benzotriazole (BTZ), 4-methyl-1H-benzotrizole (4m-BTZ), and 5-methyl-1H-benzotriazole (5m-BTZ) are commonly found in environmental occurrence together. The two methylated isomers, collectively known as tolytriazole (TTZ), have different toxicity and stability. These contaminants are highly water soluble and resistant to biodegradation, making them persistent through water treatment. Benzotriazoles have been detected worldwide; this investigation focuses on monitoring three sites near a small airpark in Wilmington, Ohio. Two sites that receive runoff from the airpark, Lytle Creek and Indian …

A Spectrophotometric Determination Of Barium Complexation With Methylthymol Blue, Wesley Alexander

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In this work, a spectrophotometric titration of methylthymol blue (MTB) with barium chloride was performed at pH = 7.5, 9.6, and 12.2 to determine the stoichiometry of complexation between the two as well as formation constants and absorptivity coefficients. Complexes of 1:1, 2:1, and 3:1 Ba:MTB were suggested by the experimental data upon fitting with appropriate models using Beer’s Law. The molar absorptivities of free MTB species at 605 nm were determined to be ����2������4− = 5.0 (± 0.2) x 103 L·mol-1·cm-1, ����������5− = 7.3 (± 0.3) x 103 L·mol-1·cm-1, ��������6− = 1.3 (± 0.2) x 104 L·mol-1·cm-1. At pH …

Estimation Of The Amount Of Active Pharmaceutical Ingredient In Over-The-Counter Available Aspirin Formulations Using Titrimetry, Uv-Visible Spectrophotometry And Raman Spectroscopy, Harismranjeet K. Chahal

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Counterfeit pharmaceuticals are a serious threat to public safety worldwide. Adverse health effects including resistance to treatment and death have resulted from the consumption of such medicines. Aspirin, which is a non-steroidal anti-inflammatory drug, has been counterfeited in the past due to its increasing demand. Rapid and easy analytical methods are needed to detect these counterfeit medicines and put a halt to the growing number of such incidents. In this study, quantitative estimation of active pharmaceutical ingredient (API) content in different over-the-counter available aspirin tablets was done using titrimetry and UV- Visible spectrophotometry. Qualitative analysis was done using Raman spectroscopy. …

Gas-Phase Acid-Base Properties And Conformations Of Oligopeptides Through Mass Spectrometry And Computational Studies, Yuntao Zhang

University of the Pacific Theses and Dissertations

This dissertation presents a comprehensive study of the peptides of interest to deeper understand the gas-phase acid-base properties in relation to their conformations and chirality. In the first part of the study, two pairs of alanine (A)-based isomeric peptides consisting of a basic probe, lysine (Lys) or 2,3-diaminopropionic acid (Dap), were investigated to understand the nature of the enhanced basicity when the basic probe was moved from the N-terminus to the C-terminus. In the second part of the study, alanine-based peptides containing a cysteine (C) as the acidic probe were investigated to understand the chirality effects on the gas-phase acidity …

Peripherally Restricted Opioid Conjugates And Its Use As Pharmacological Probes And Potential Therapeutics, Md Tariqul Haque Tuhin

University of the Pacific Theses and Dissertations

Opioid-induced constipation (OIC) is one of the major adverse effects of opioid analgesics used by millions of patients each year. While progress has been made, there remains a significant unmet medical need in the treatment of OIC. Major gaps remain in our understanding of the role of the gastrointestinal tract and central nervous system (CNS) in precipitating OIC. For the last four decades, numerous investigations to study the sites of action of opioid analgesics have utilized peripherally acting mu-opioid receptor antagonists (PAMORAs), which have been incorrectly believed to have limited penetration across the blood-brain barrier (BBB). Several preclinical and clinical …

The Vagabond Flourine Atom Revisited: Dissociative Photoionization Of Tri- And Pentafluoropropene, Jessica K. De La Cruz

University of the Pacific Theses and Dissertations

Photoelectron Photoion Coincidence (PEPICO) Spectroscopy studies on two unsaturated hydrofluorocarbons (HFCs), also known as hydrofluoroolefines (HFOs), are presented here. Previously, the Sztáray group has studied the dissociation of trans-1,3,3,3-tetrafluoroprop-1-ene (ElixClean), which is a fourth-generation refrigerant and propellant and has lower global warming potential than its precursors. My study is an extension of the ElixClean study as it aims to explore how the different number of fluorine atoms impact the dissociation reactions of these molecules. Both 3,3,3-trifluoropropene (TFP) and cis-1,2,3,3,3- pentafluoropropene (PFP) are also utilized as propellants and refrigerants.Measurements were carried out with remote access to the CRF-PEPICO (combustion reactions followed …

Gc/Ms And Lc/Ms Approaches To Chemical Communication In Plants And Marine Cyanobacteria, Carolyn Keim

University of the Pacific Theses and Dissertations

Natural products are small organic compounds synthesized by living organisms including plants, animals, and microbes. These fall into one of two categories, primary metabolites are required for survival, but secondary metabolites usually play a more accessory role. Extracts from organisms have proven to be useful to humans throughout history. Prior to evidence-based western medicine practices, natural products were the only source of medicine and remain as a treatment source for underdeveloped nations. Today, natural products have either been approved by or have served as the template for many FDA approved drugs. Based on a survey of all FDA approved drugs …

Quantum Mechanics-Based Computational Chemistry Has Become A Powerful Partner In The Scientific Research Of Nitrogen-Rich Compounds, Paving The Way For Important Advances In Biochemical, Pharmacological And Other Related Fields, Dobrushe Denburg

Student Theses and Dissertations

The Computational Chemistry of Nitrogen-Rich Compounds; Insight into Pioneering Research

Nitrogen-rich functional groups have long been studied for their diversity; nitrogen can form single, double and triple bonds with itself, and will therefore exist in a very broad range of molecular arrangements. Poly-nitrogen compounds are highly energetic and electron rich, and many compounds display unique properties that allow participation in very specialized chemical reactions. Of import is their ubiquity in biological systems, and throughout the past century and currently, their biological relevance is deeply and widely explored in biochemistry and biomedicine, from their involvement in natural biological processes and complex …

Development Of Bioaffinity Based Assays For Forensic Applications, Juliana Maria Agudelo Cano

Legacy Theses & Dissertations (2009 - 2024)

In the field of forensic science, body fluids are a major contributor of evidence in investigations. However, body fluids are usually used only for their genetic content, overlooking its unique composition of proteins and low-molecular-weight compounds that often serve as biomarkers in clinical diagnostics. This investigation aimed to develop simple, effective, and economical models that can be used to identify different attributes of the originator. The focus of this research was to develop biocatalytic cascades that could analyze body fluids by using UV-Vis spectroscopy. These models could be implemented in forensic settings, as well as in biometric authentications. The central …

Accelerating Molecular Property Calculations With Semiempirical Preconditioning, Zehao Zhou, Shane M. Parker

Faculty Scholarship

Computing ab initio molecular linear response properties, e.g., electronic excitation energies and transition moments, requires the solution of large eigenvalue problems or large systems of equations. These large eigenvalue problems or large systems of equations are commonly solved iteratively using Krylov space algorithms, such as the Davidson algorithm for eigenvalue problems. A critical ingredient in Krylov space algorithms is the preconditioner which is used to generate optimal update vectors in each iteration. We propose to use semiempirical approximations as preconditioners to accelerate the calculation of ab initio properties. The crucial advantage to improving the preconditioner is that the converged result …

Statistical Potentials For Rna-Protein Interactions Optimized By Cma-Es, Takayuki Kimura, Nobuaki Yasuo, Masakazu Sekijima, Brooke Lustig

Faculty Research, Scholarly, and Creative Activity

Characterizing RNA-protein interactions remains an important endeavor, complicated by the difficulty in obtaining the relevant structures. Evaluating model structures via statistical potentials is in principle straight-forward and effective. However, given the relatively small size of the existing learning set of RNA-protein complexes optimization of such potentials continues to be problematic. Notably, interaction-based statistical potentials have problems in addressing large RNA-protein complexes. In this study, we adopted a novel strategy with covariance matrix adaptation (CMA-ES) to calculate statistical potentials, successfully identifying native docking poses.

3d-Printable And Open-Source Modular Smartphone Visible Spectrophotometer, Brandon Winters, Nick Banfield, Cassandra Dixon, Anna Swensen, Dakota Holman, Braxton Fillbrown

Chemistry Faculty Publications

The past four decades have brought significant and increasingly rapid changes to the world of instrument design, fabrication, and availability due to the emergence of 3D printing, open-source code and equipment, and low-cost electronics. These, along with other technological advances represent a nexus in time ripe for the wide-spread production and availability of low-cost sophisticated scientific equipment. To that end, the design of a 3D printable and open-source, modular spectrometer is described. This specific instrument is distinctly different from others that have been reported in recent years in that it was designed outside of the “black box” paradigm of …

Analysis Of Oxycontin Addiction And Recovery From Both A Physical And Psychological Lens, Meagan Munley, Carrie Flickinger

Fall Showcase for Research and Creative Inquiry

We will investigate the physical impacts both short and long term effects of of substance use. In doing so we will frame an argument for the substance's addictive properties as it relates to both its physically addictive and sociological addictive properties. In doing, so a stronger understanding of how an individual can move through the stages of substance use, to abuse, and finally addiction will be reviewed. We will then address current treatment strategies for the substance and how they address or fail to address both the physical and sociological impacts of its use.

Analysis Of Fluoxetine (Prozac) Addiction And Recovery From Both A Physical And Psychological Lens, Kristen Dobek, Hannah Couch

Fall Showcase for Research and Creative Inquiry

We will investigate the physical impacts both short and long term effects of of substance use. In doing so we will frame an argument for the substance's addictive properties as it relates to both its physically addictive and sociological addictive properties. In doing, so a stronger understanding of how an individual can move through the stages of substance use, to abuse, and finally addiction will be reviewed. We will then address current treatment strategies for the substance and how they address or fail to address both the physical and sociological impacts of its use.

So, You Want To Take Zoloft (Sertraline)?: A Biological & Psychological Analysis, Hailey Lux, Mackenzie Harry

Fall Showcase for Research and Creative Inquiry

A lot of individuals around the world suffer with panic disorders, post-traumatic stress disorder (PTSD), obsessive compulsive disorder (OCD). One drug that has been found to significantly decrease these feelings of stress is Sertraline. Sertraline has been proven to increase quality of life among individuals with certain mental health disorders. In addition, it is commonly known as Zoloft and is prescribed to individuals by doctors and psychiatrist. However, we will be talking about how in extreme causes sertraline could become addictive and have withdrawal side effects. Furthermore, during this poster presentation we will be discussing how sertraline is not an …

Physical Chemistry, Ruth E. Stark

Open Educational Resources

This is a provisional syllabus for Physical Chemistry I (Thermodynamics), to be taught using an OER Textmap in Fall, 2021.

Chemistry Card Games - Games For Learning And Enjoying Chemistry, Michelle M. Clark

Sabbatical Projects

Many chemistry students struggle due to a lack of basic math skills. My goal over sabbatical is to develop active learning modules that improve math literacy. I will be collaborating with Dr. Joan Cotter, a renowned math curriculum author whose comprehensive math program utilizes an innovative approach that could benefit chemistry students who have poor math literacy.

Correlation Effects On Intramolecular C-H...Oh And O-H...O Hydrogen Bond Interactions In Azelaic Acid: An Ab Initio Study, Sabina Kalata, Alina Huang, Ruben Parra

DePaul Discoveries

Electron correlation effects on both conventional, O-H…O, and nonconventional, C-H…O, intramolecular hydrogen bonds present in a selected azelaic acid folded conformation were evaluated ab initio using HF and MP2 methodologies. The relative strength of the hydrogen bonds was examined through different indicators derived from geometry, vibrational frequencies, and electron density along the hydrogen bond path. The HF method results in weaker O-H…O and C-H…O hydrogen bonds when compared with the corresponding results using the MP2 method. Additionally, the stability of the folded azelaic conformation is found to depend on the level of theory used. Accordingly, the zero-point corrected energies of …

The Role Of Hydrogen Bonding And Hydrogen Migration In Different Environments, Nassim Beiranvand

Chemistry Theses and Dissertations

Hydrogen bonding is one of the most important topics in chemistry and has been a subject of many studies for years, using both experimental techniques and computational methods. My dissertation focuses on mechanistic studies of various types of intermolecu-lar and intramolecular hydrogen bonding in di˙erent systems based on quantum chemical calculations. In my work, I investigated the interplay of ring puckering and hydrogen bonding in DNA building blocks; hydrogen bonding in natural and unnatural base pairs and the nature of dihydrogen bonding by applying the Ring Puckering Analysis and the Local Vibrational Mode Theory (LVM). An additional aim of my …

From Small Molecules To Infinite Crystals: Probing Noncovalent Interactions Through Vibrational Spectroscopy, Sadisha Nanayakkara

Chemistry Theses and Dissertations

During my four years in the CATCO group supervised by Dr. Kraka, I have been exposed to various topics targeted to address a multitude of chemical problems, broadening our knowledge of modern chemistry research as we know it. In undertaking the age-old problem of understanding the nature of chemical bonding, I could modestly contribute with my work, using in-house tools based on vibrational spectroscopy.

First part of my dissertation is focused on inventing new methods and tools to efficiently investigate chemical bonding, followed by the study of some non-covalent interactions, imperative in catalysis and solid-state chemistry. This includes analysis of …

Quantum Chemical Investigation Of Novel Noncovalent Interactions Utilizing Vibrational Spectroscopy, Seth Francis Yannacone

Chemistry Theses and Dissertations

Theoretical/computational methods have been utilized to investigate a diverse array of questions currently at the forefront of modern chemistry research. The focus of this work is Local Vibrational Mode (LVM) Theory, originally formulated by Konkoli and Cremer, and under continuous development by the CaTcO research group. Derived from LVM theory, local stretching force constants (ka) represent physically meaningful measurements of chem- ical bond strength. Decomposition of normal vibrational modes into LVM contributions, also called characterization of normal modes (CNM), is another powerful manifestation of LVM theory; most notably when applied to the analysis of theoretical/experimental IR/Ra- man spectra. Recent developments …

Identification Of Chemical Structures And Substructures Via Deep Q-Learning And Supervised Learning Of Ftir Spectra, Joshua D. Ellis

Graduate Theses/Dissertations

Fourier-transform infrared (FTIR) spectra of organic compounds can be used to compare and identify compounds. A mid-FTIR spectrum gives absorbance values of a compound over the 400-4000 cm^-1 range. Spectral matching is the process of comparing the spectral signature of two or more compounds and returning a value for the similarity of the compounds based on how closely their spectra match. This process is commonly used to identify an unknown compound by searching for its spectrum’s closes match in a database of known spectra. A major limitation of this process is that it can only be used to identify …

Structure And Reactivity Of The First Row Transition Metals Bearing Redox-Active Ligands And Tunable H-Bonding Interactions, Khashayar Rajabimoghadam

Chemistry Theses and Dissertations

Metalloenzymes, as natural catalysts, can break a reaction with high activation energy to multiple small reactions with lower activation energies; in these small reactions, multiple bonds form and dissociate rapidly, some metalloenzymes use redox-active ligands in their active site to provide the needed electrons for these multiple small reactions. Additionally, in the secondary coordination sphere in the vicinity of the metalloenzymes, the hydrogen bonding interactions facilitate the transfer and interaction of the substrates and the stabilization of the active intermediates. These unique features in metalloenzymes inspired chemists to design molecular models that can partially mimic the structure and reactivity of …

Ahr Expression On Rorc-Expressing Immune Cells Is Essential For I3c-Mediated Protection Against Colitis, Michal C. Williams

Senior Theses

Colitis is an inflammatory bowel disorder (IBD) whose etiology is attributed to modification in the luminal microbiota and dysregulation in the immune response. Indole is a signaling molecule which is naturally produced by gut luminal microbiota. Indole-3- carbinol (I3C) is a compound commonly found in vegetables and a ligand for the aryl hydrocarbon receptor (AhR). Previous studies have detected decreased expression and activation on the AhR receptor in colitis patients, thought to possibly alter gut microbiota metabolism, subsequently promoting colitis. 1 AhR, expressed in a variety of immune and epithelial cells, contributes to gut homeostasis by affecting vital mediators such …

Emergent Photophysics In Diketopyrrolopyrrole Superstructures, Andrew Levine

Dissertations, Theses, and Capstone Projects

Organic semiconductors have received substantial attention as active components in optoelectronic devices because of their processability and customizable electronic properties. Tailoring the organic active layer in these devices to exhibit desirable optoelectronic properties requires understanding the complex and often subtle structure-property relationships governing their photophysical response to light. Both structural organization and frontier molecular orbitals (FMO) play pivotal roles in energy relaxation processes, and complex interplay between organization and orbital energies are difficult to anticipate based upon the molecular structure of the components alone, especially in systems comprised of multiple components. In pursuit of design rules, there is a need …

Lipoates As Building Blocks Of Macromolecules, Mojdeh Raeisi

Chemistry Theses and Dissertations

Since the discovery of Lipoic acid in the early 1950s, there have been several studies to further investigate properties and applications of this interesting, naturally occurring compound. In 1956, the dynamic nature of disulfide bonds in Lipoic acid was reported, which can exist through conversions of monomeric disulfide, polymeric disulfide, and reduced form (dithiol) from one to another under proper conditions. This dynamic nature and reducibility of disulfide bonds via thiol-disulfide exchange, opened doors to the use of Lipoic acid in drug delivery systems, especially for delivery to cancer cells that suffer from overexpression of glutathione – a thiol-bearing tripeptide …