Chemistry Commons^™

Nanostructured Ternary Nickel-Based Mixed Anionic (Telluro)-Selenide As A Superior Catalyst For Oxygen Evolution Reaction, Ibrahim Munkaila Abdullahi, Siby Thomas, Alessio Gagliardi, Mohsen Asle Zaeem, Manashi Nath

Chemistry Faculty Research & Creative Works

Developing Protocols for Designing High-Efficiency, Durable, Cost-Effective Electrocatalysts for Oxygen Evolution Reaction (OER) Necessitates Deeper Understanding of Structure–property Correlation as a Function of Composition. Herein, It Has Been Demonstrated that Incorporating Tellurium into Binary Nickel Chalcogenide (NiSe) and Creating a Mixed Anionic Phase Perturbs its Electronic Structure and Significantly Enhances the OER Activity. a Series of Nanostructured Nickel Chalcogenides Comprising a Layer-By-Layer Morphology Along with Mixed Anionic Ternary Phase Are Grown in Situ on Nickel Foam with Varying Morphological Textures using Simple Hydrothermal Synthesis Route. Comprehensive X-Ray Diffraction, X-Ray Photoelectron Spectroscopy, and in Situ Raman Spectroscopy Analysis Confirms the Formation …

Epitaxial Electrodeposition Of Ordered Inorganic Materials, Jay A. Switzer, Avishek Banik

Chemistry Faculty Research & Creative Works

Conspectus The quality of technological materials generally improves as the crystallographic order is increased. This is particularly true in semiconductor materials, as evidenced by the huge impact that bulk single crystals of silicon have had on electronics. Another approach to producing highly ordered materials is the epitaxial growth of crystals on a single-crystal surface that determines their orientation. Epitaxy can be used to produce films and nanostructures of materials with a level of perfection that approaches that of single crystals. It may be used to produce materials that cannot be grown as large single crystals due to either economic or …

Nuclear Magnetic Resonance Study Of Co2 Capture By Fluoroalkylamines: Ammonium Ion Pka Depression Via Fluorine Modification And Thermochemistry Of Carbamylation, Brian Jameson, Kari Knobbe, Rainer Glaser

Chemistry Faculty Research & Creative Works

We are developing energy-efficient and reversible carbon capture and release (CCR) systems that mimic the Lys201 carbamylation reaction in the active site of ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO). The multiequilibria scenario ammonium ion Xa ⇌ amine Xb ⇌ carbamic acid Xc ⇌ carbamate Xd requires the presence of both free amine and CO2 for carbamylation and is affected by the pKa(Xa). Two fluorination strategies aimed at ammonium ion pKa depression and low pH carbamylation were analyzed with (2,2,2-trifluoroethyl) butylamine 2b and 2,2-difluoropropylamine 3b and compared to butylamine 1b. The determination of K1 and ΔG1 of the carbamylation reactions requires the solution of …

Natural Product Co-Metabolism And The Microbiota–Gut–Brain Axis In Age-Related Diseases, Mark Obrenovich, Sandeep Kumar Singh, Yi Li, George Perry, Bushra Siddiqui, Waqas Haq, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

Complementary alternative medicine approaches are growing treatments of diseases to standard medicine practice. Many of these concepts are being adopted into standard practice and orthomolecular medicine. Age-related diseases, in particular neurodegenerative disorders, are particularly difficult to treat and a cure is likely a distant expectation for many of them. Shifting attention from pharmaceuticals to phytoceuticals and "bugs as drugs" represents a paradigm shift and novel approaches to intervention and management of age-related diseases and downstream effects of aging. Although they have their own unique pathologies, a growing body of evidence suggests Alzheimer's disease (AD) and vascular dementia (VaD) share common …

Natural Product Co-Metabolism And The Microbiota–Gut–Brain Axis In Age-Related Diseases, Mark Obrenovich, Sandeep Kumar Singh, Yi Li, George Perry, Bushra Siddiqui, Waqas Haq, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

Complementary alternative medicine approaches are growing treatments of diseases to standard medicine practice. Many of these concepts are being adopted into standard practice and orthomolecular medicine. Age-related diseases, in particular neurodegenerative disorders, are particularly difficult to treat and a cure is likely a distant expectation for many of them. Shifting attention from pharmaceuticals to phytoceuticals and "bugs as drugs" represents a paradigm shift and novel approaches to intervention and management of age-related diseases and downstream effects of aging. Although they have their own unique pathologies, a growing body of evidence suggests Alzheimer's disease (AD) and vascular dementia (VaD) share common …

Extracellular Poly(Hydroxybutyrate) Bioplastic Production Using Surface Display Techniques, Kevin Beaver, Ashwini Dantanarayana, Willisa Liou, Markus Babst, Shelley D. Minteer

Chemistry Faculty Research & Creative Works

Poly(hydroxybutyrate) is a biocompatible, biodegradable polyester synthesized naturally in a variety of microbial species. A greener alternative to petroleum-based plastics and sought after for biomedical applications, poly(hydroxybutyrate) has failed to break through as a leading material in the plastic industry due to its high cost of production. Specifically, the extraction of this material from within bacterial cells requires lysis of cells, which takes time, uses harsh chemicals, and starts the process again with growing new living cells. Recently, surface display of enzymes on bacterial membranes has become an emerging technique for extracellular biocatalysis. In this work, a fusion protein lpp-ompA-phaC …

Modulatory Effects Of Deacetylated Sialic Acids (A Sugar Residue) In Nk-Mediated Cytotoxicity And Targeted Therapy By Receptor Tyrosine Kinase Inhibitors, Mathias Tawiah Anim

Electronic Theses and Dissertations

The complex nature of the biology of cancer is still an unraveling science, yielding several biomarkers that have served as molecular targets for detection and treatment of the disease. How sugars, glycans, play a role has remained relatively uninvestigated. Sialic acid (Sia), a sugar residue on the surface of cells, has been identified as a hallmark of cancer and its progression. Sialic acid can be highly functionalized, but we became interested in acetylated Sias. This functional group is modulated by Sialate O- acetylesterase (encoded by the gene SIAE) and Sialate O-acetyltransferase (encoded by CASD1), enzymes that play a crucial role …

Design, Synthesis, And Evaluation Of Acetyl Coa Synthetase Inhibitors, Michael Emmett Heene

Graduate Research Theses & Dissertations

Invasive fungal species provide a challenge to the current drug landscape, only partiallymet by approved drugs. The Acetyl Coenzyme Synthetase (ACS) enzymes are an attractive target for antifungal compounds because normal mammalian cells do not rely on ACS for energy metabolism while fungal cells do rely on ACS. This work focuses on the design and synthesis of inhibitors of various fungal ACS enzymes. The first class of inhibitors is based on the 2-aminothiazole scaffold originating from a saturation transfer difference (STD) nuclear magnetic resonance (NMR) study and previous whole-organism assays. Ultimately, the 2-aminothiazole core compounds were found to not be …

The Indivisible System: Modeling The Metal-Pterin-Dithiolene System In Molybdenum And Tungsten Cofactors, Cassandra Gates

Bryn Mawr College Dissertations and Theses

Mo and W enzymes are ubiquitous in living organisms and crucial for sustaining life. Mo and W enzyme variety is diverse, but they contain a highly conserved aspect of functionality in these enzymes, the pyranopterin-dithiolene (PDT) ligand. A total of eight possible electron redox equivalents occurs between the metal center and PDT, making the molybdenum cofactor (Moco) and the tungsten cofactor (Tuco) the most redox rich cofactors in all of biology. This research focuses on the development of new pterin-dithiolene synthetic modeling systems for Moco. The knowledge gained from the characterization of these compounds is applied to the enzymes, furthering …

Rapid Generation Of P(V)-F Bonds Through The Use Of Sulfone Iminium Fluoride Reagents, Lucy P. Miller, James A. Vogel, Shiraz Harel, Jenna M. Krussman, Patrick R. Melvin

Chemistry Faculty Research and Scholarship

Phosphorus–fluorine bonds have become increasingly relevant in the pharmaceutical industry. To continue their exploration, more efficient synthetic methods are needed. Here, we report the application of sulfone iminium fluoride (SIF) reagents to the synthesis of P(V)–F bonds. The SIF reagents promote the deoxyfluorination of phosphinic acids in just 60 s with excellent yields and scope. The same P(V)–F products can also be synthesized from secondary phosphine oxides using an SIF reagent.

Enzymatic Electrochemical Biosensors For Neurotransmitters Detection: Recent Achievements And Trends, Zina Fredj, Baljit Singh Dr., Mohamed Bahri, Peiwu Qin, Mohamad Sawan

Articles

Neurotransmitters (NTs) play a crucial role in regulating the behavioral and physiological functions of the nervous system. Imbalances in the concentrations of NT have been directly linked to various neurological diseases (e.g., Parkinson’s, Huntington’s, and Alzheimer’s disease), in addition to multiple psychotic disorders such as schizophrenia, depression, dementia, and other neurodegenerative disorders. Hence, the rapid and real-time monitoring of the NTs is of utmost importance in comprehending neurological functions and identifying disorders. Among different sensing techniques, electrochemical biosensors have garnered significant interest due to their ability to deliver fast results, compatibility for miniaturization and portability, high sensitivity, and good controllability. …

Isolation And Identification Of Chlorate-Reducing Hafnia Sp. From Milk, William P. Mccarthy, Meghana Srinivas, Martin Danaher, Christine O'Connor, Tom F. O'Callaghan, Douwe Van Sinderen, John Kenny, John T. Tobin

Articles

Chlorate has become a concern in the food and beverage sector, related to chlorine sanitizers in industrial food production and water treatment. It is of particular concern to regulatory bodies due to the negative health effects of chlorate exposure. This study investigated the fate of chlorate in raw milk and isolated bacterial strains of interest responsible for chlorate breakdown. Unpasteurized milk was demonstrated to have a chlorate-reducing capacity, breaking down enriched chlorate to undetectable levels in 11 days. Further enrichment and isolation using conditions specific to chlorate-reducing bacteria successfully isolated three distinct strains of Hafnia paralvei . Chlorate-reducing bacteria were …

Diethoxycarbonyl-Bodipys As Heavy-Atom-Free Photosensitizers For Holographic Recording In Cellulose Acetate Photopolymer, Aimee Sheehan, Tatsiana Mikulchyk, Catherine S.P. De Castro, Safakath Karuthedath, Wejdan Althobaiti, Metodej Dvoracek, Sabad-E Gul, Hugh Byrne, FréDéRic Laquai, Izabela Naydenova, Mikhail Filatov

Articles

A series of new heavy-atom-free photosensitizers based on 2,6-diethoxycarbonyl-BODIPY scaffold was designed and applied for holographic recording in a photopolymerizable material. Photoinduced electron transfer between the BODIPY and meso-aryl subunits, followed by the formation of BODIPY triplet excited states via spin-orbit charge transfer intersystem crossing (SOCT-ISC) was studied by steady-state and ultrafast pump-probe transient optical spectroscopy. Highly efficient photosensitization was observed for dyads bearing pyrene and anthracene substituents, which exhibited singlet oxygen generation quantum yields () of up to 94%. Charge transfer and SOCT-ISC were observed in non-polar solvent (toluene) due to the increased electron accepting ability of the diethoxycarbonyl-BODIPY. …

A Simple Microcalorimetry System To Determine The Adsorption Behaviour Of Acids In Large Adhesive Bond Gaps Using Base-Initiated Solution Polymerisation Of Ethyl-2-Cyanoacrylate, Kevin Raheem, John Cassidy, Tony Betts, Bernard Ryan

Articles

This work presents the use of a simple microcalorimetry cyanoacrylate (CA) polymerisation system for investigating aspects of CA adhesive cure through gap and adsorption of adhesive acid stabiliser by a range of metal and glass substrates. It is well established that strong acid induced inhibition periods (IPs) are almost directly proportional to the acid concentration in weak base initiated polymerisations of alkyl CAs in tetrahydrofuran (THF). Ethyl cyanoacrylate (ECA) polymerisation IP measurements were used to determine the adsorption of methanesulfonic acid (MSA) in THF or ECA solutions by a range of metal, glass and polypropylene (PP) lap shears surfaces. The …

Synthesis Of Fluoxetine, Annaliese Franklin, Erica Nelson

Research Awards

No abstract provided.

Investigation Of Factors Affecting Reverse-Phase High Performance Liquid Chromatography, Rida A. Syed

AUCTUS: The Journal of Undergraduate Research and Creative Scholarship

This study focused on the application of reverse-phase high-performance liquid chromatography (RP-HPLC). RP-HPLC is used for the purification of organic molecules, including pharmaceuticals, natural products, and proteins. We developed a modified version of a United States Pharmacopeia (USP) procedure to separate and purify the chemical components found in Excedrin tablets. The goal was to investigate the relationship between retention time (Tr) and the capacity factor (k') of solutes. By varying the composition of the mobile phase and stationary phase, we experimentally determined the capacity factor of acetaminophen (APAP), caffeine, and aspirin. Our results show that the capacity factor (k') of …

Effect Of Carbon Fiber Reinforcement On Dimensional Variations Of 3d Printed Polyamide-6 Composites: A Simulation Study, Ans Al Rashid, Hamid Ikram, Muammer Koç

Turkish Journal of Chemistry

Due to material design and fabrication flexibility, additive manufacturing (AM) or 3D printing (3DP) processes and polymer composites have paved their way into several industrial sectors. The quality of 3D printed polymer composites is highly dependent on the reinforcement content of polymers and 3DP process parameters. Several experimental studies are performed to optimize the reinforcement contents and process parameters; however, exploring the numerical modeling and simulation techniques is vital to lower the research and development costs. In the study, the numerical simulations for the 3DP process were performed using Digimat® software for carbon fiber-reinforced polyamide-6 (PA6) composites fabricated via the …

Design Of Block Copolymer With Tunable Hydrophobic/Hydrophilic/Fluorophilic Interactions, Tatiane De Fatima Dutra

Theses, Dissertations and Culminating Projects

Block copolymers (BCP) with balanced interactions and their resultant bulk-phase self-assembly have become increasingly important in advancing nanotechnology, separation, and energy applications. However, a few reports have addressed the synthesis challenge and bulk-phase self-assembly of such triblock copolymers. This thesis presents a facile route for preparing triblock copolymer via controlled radical and organocatalytic ring-opening polymerization that allows precise control over the incorporation of individual moieties in resultant polymer, responsible for balanced hydrophilic, hydrophobic/lipophilic, and fluorophilic interactions. Synthesized polymer with suggested self-assembled 2D lamellar nanostructure exhibits high-temperature stability. The long-term goal of this work is to selectively use this polymer class …

A Computational Study Of The Copper-Catalyzed Trifluoromethylation Of Boronic Acids, Kevin Nyhuis

Theses, Dissertations and Culminating Projects

This work is a computational study of a reaction mechanism for the trifluoromethylation of boronic acids. Three steps of the proposed reaction mechanism are studied, •CF₃ addition to a copper catalyst center, base promoted transmetalation between copper and aryl boronic acid, and bond forming reductive elimination in which the CF₃ and aryl substituent form a bond. Limited information is known about this mechanism. This study uses computational methods to attempt to elucidate the mechanism and provide the groundwork for potential improvement. Quantum chemical methods in conjunction with tight-binding based conformational sampling methods are used to investigate the possible …

Investigating The Roles Of Active Site Residues K59, K119 And E168 In M. Tuberculosis Indole-3-Glycerol Phosphate Synthase, Maryum M. Bhatti

Theses, Dissertations and Culminating Projects

Tuberculosis (TB) is a disease that is caused by a bacteria called Mycobacterium tuberculosis and primarily attacks the lungs but can spread to other areas of the body as well. TB can develop resistance to drugs that may be used to cure the disease. Multidrug resistant TB is especially a growing issue as it does not respond to the two most powerful anti-TB drugs, isoniazid and rifampicin. For this reason, finding new ways to target TB are critically needed. One possible way to do this is to target the enzymes in the tryptophan biosynthetic pathway of M. tuberculosis. Studies have …

Vibrational Spectroscopy For The Detection, Identification, And Differentiation Of Body Fluids And Fingermarks In Forensic Investigations, Samuel Joel Sears

Legacy Theses & Dissertations (2009 - 2024)

This thesis examines the recent literature that has explored the applications of vibrational spectroscopy in forensic science. Specifically, this thesis focuses on how vibrational spectroscopy has improved the detection, identification, and differentiation of body fluid and fingermark evidence in forensic investigations. It is here shown that novel, vibrational spectroscopic techniques have the potential to provide new insights to forensic investigators, and thus revolutionize the field of forensic science. This thesis has been adapted with permission from {Innovative Vibrational Spectroscopy Research for Forensic Application. Alexis Weber, Bailey Hoplight, Rhilynn Ogilvie, Claire Muro, Shelby R. Khandasammy, Luis Pérez-Almodóvar, Samuel Sears, and Igor …

Development Of New Mass Spectrometric Approaches For Biomarker Discovery: Application To Complex Biological Matrices For Tissue Characterization And Disease Diagnosis, Allix Marie Coon

Legacy Theses & Dissertations (2009 - 2024)

In this work, the newly developed technique laser ablation direct analysis in real – time high-resolution imaging mass spectrometry (LADI-MS) and the more established methods direct analysis in real time – high-resolution mass spectrometry (DART-HRMS) and two-dimensional gas chromatography – mass spectrometry (GC×GC-MS), were used to interrogate challenging plant- and human-derived complex matrices that have proven difficult to analyze by conventional methods, in order to extract heretofore inaccessible information that can be applied to the understanding of wood systems biology, ecophysiology, dendrochronology and natural product isolation of biologically relevant compounds (on the plant side), and explore the potential for discovery …

Development Of Ambient Ionization Mass Spectrometry Approaches For The Characterization And Quantification Of Psychoactive Small-Molecule Constituents In Complex Plant Matrices, Megan Isabella Chambers

Legacy Theses & Dissertations (2009 - 2024)

Drug chemistry sections of forensic crime laboratories are tasked with analyzing a variety of unknown materials, a subset of which are derived from plants. In comparison to the analysis of small-molecule drugs, these plant matrices are incredibly complex and present unique challenges. When traditional chromatographic approaches are used to interrogate these materials in forensic investigations, large amounts of time, resources, and funds are directed towards the extensive sample preparation steps required. Exacerbating the issue is that the matrix characteristics often result in instrument downtime to accomplish the maintenance required to address ingredients adhering to columns or clogging syringes, which are …

Dart-Hrms And Chemometric Analysis For Applications In Forensic Entomology, Amy Marie Osborne

Legacy Theses & Dissertations (2009 - 2024)

Forensic entomology, the utilization of insects in the course of legal investigations, is a broad field which encompasses three main branches: medico-legal, stored-product, and urban. This body of research focuses on the first two branches. The first branch, medico-legal forensic entomology, generally applies to death investigations. In death investigations it is imperative to establish the time since death (postmortem interval) and cause of death. Both of these queries can be difficult to assess for remains that are in mid- to late- stages of decay. Carrion insects found on and near the body can assist forensic investigators in this task, as …

Biomimetic Synthesis Of Hitorins A And B And Discovery Of Porous Metallopolymers, Tianran Zhai

Legacy Theses & Dissertations (2009 - 2024)

This work focuses on two research directions: the total synthesis of natural products hitorins A and B and the synthesis of porous metallopolymers/ metallooligomers and study of their properties. Nature has a good understanding and makes good use of cascade reactions to generate complex natural structures. The synthesis of hitorins A and B employed a radical cascade starting from a rare intermolecular alkoxy radical-olefin coupling reaction in our biomimetic synthetic strategy. A radical clock experiment was designed to reveal the mechanism for the key alkoxy radical-olefin coupling cascade. Microporous materials have many applications in diverse areas including gas separation, electronic …

Post-Synthetic Modification Of Metal-Organic Frameworks And Demonstration Of Their Characteristics For Chemistry Education, Audrey Barbara Crom

Legacy Theses & Dissertations (2009 - 2024)

Metal–organic frameworks (MOFs) have risen in popularity in recent decades due to their applications in gas storage, separations, and catalysis. The vast potential of these materials is a result of the inherent characteristics and properties afforded by the composition and combination of ligand and metal clusters used to construct MOFs. In this dissertation, we explore the properties and capabilities of these frameworks from a variety of perspectives. First, we demonstrate the characteristics of MOFs in experiments designed to be suitable for integration in an educational environment. Inorganic chemistry derives many of its concepts from multiple facets of chemistry, which makes …

Length Of Course-Based Undergraduate Research Experiences (Cure) Impacts Student Learning And Attitudinal Outcomes: A Study Of The Malate Dehydrogenase Cures Community (Mcc), Sue Ellen Dechenne-Peters, John F. Rakus, Amy D. Parente, Tamara L. Mans, Rebecca Eddy, Nicole Galport, Courtney Joletar, Joeseph J. Provost, J. Ellis Bell, Jessica K. Bell

Chemistry and Biochemistry: Faculty Scholarship

Course-based undergraduate research experiences (CUREs) are laboratory courses that integrate broadly relevant problems, discovery, use of the scientific process, collaboration, and iteration to provide more students with research experiences than is possible in individually mentored faculty laboratories. Members of the national Malate dehydrogenase CUREs Community (MCC) investigated the differences in student impacts between traditional laboratory courses (control), a short module CURE within traditional laboratory courses (mCURE), and CUREs lasting the entire course (cCURE). The sample included approximately 1,500 students taught by 22 faculty at 19 institutions. We investigated course structures for elements of a CURE and student outcomes including student …

Peptide Conjugates With Polyaromatic Hydrocarbons Can Benefit The Activity Of Catalytic Rnas, Kevin J. Sweeney, Tommy Le, Micaella Z. Jorge, Joan G. Schellinger, Luke J. Leman, Ulrich F. Müller

Chemistry and Biochemistry: Faculty Scholarship

Early stages of life likely employed catalytic RNAs (ribozymes) in many functions that are today filled by proteins. However, the earliest life forms must have emerged from heterogenous chemical mixtures, which included amino acids, short peptides, and many other compounds. Here we explored whether the presence of short peptides can help the emergence of catalytic RNAs. To do this, we conducted an in vitro selection for catalytic RNAs from randomized sequence in the presence of ten different peptides with a prebiotically plausible length of eight amino acids. This in vitro selection generated dozens of ribozymes, one of them with ∼900-fold …

Cytotoxicity Profiling And Apoptotic Potential Of Carboxylic Acids-Based Deep Eutectic Solvents On Mammalian Cell Lines, Mavis Korankye

Electronic Theses and Dissertations

In the past few years, there has been a notable surge in demand for high-purity medicines due to the prevalence of chronic diseases such as cancer, hypertension, diabetes, cardiovascular diseases, and neurological disorders. Considerable efforts have been dedicated to discovering new solvents that are environmentally friendly and cost-effective that are well-suited for industrial applications. Deep eutectic solvents have gained recognition as a highly promising alternative to organic solvents and ionic liquids due to their easily sourced raw materials, simple and cheap preparation methods, high tunability, low volatility, low toxicity, and biodegradability. The industrial utilization of deep eutectic solvents (DESs) is …

Reducing Disposable Plastic Waste From Protein Quantitative Assays, Justin Buiter

All Capstone Projects

Protein concentration quantification is important for many areas of biology and biochemistry. This quantification happens in large quantities in laboratories and needs to be done accurately and quickly. The Bradford assay is one of the most common ways of accomplishing this task (1). This assay relies on the binding of the protein and the Coomassie Blue G250 dye. The anionic blue form binds to the protein and has a maximum at 595 nm. This allows for accurate quantification by reading how much of the sample absorbs at 595 nm (2).

In 2014, it was estimated that 5.5 million tons of …