Chemistry Commons^™

Oriented Surface Immobilization Of Antibodies Using Enzyme-Mediated Site-Specific Biotinylation For Enhanced Antigen-Binding Capacity, Emily Beitello, Kwame Osei, Trent Kobulnicky, Faith Breausche, Jon A. Friesen, Jeremy D. Driskell

Faculty Publications – Chemistry

The effectiveness of surface-immobilized antibodies is often diminished by improper antibody orientation and limited stability, impeding the analytical performance of biosensors. Here, we report a novel enzyme-mediated strategy to biotinylate the Fc region of an anti-horseradish peroxidase (anti-HRP) antibody with site-specificity that enables oriented immobilization on a streptavidin-functionalized surface. Microbial transglutaminase (mTG) catalyzes the covalent coupling between the amine functional group on a biotin analogue (NH₂-PEG₄-biotin) and the side chain of a privileged glutamine residue (Q295) located on the heavy chain Fc region of IgG antibodies. For comparison, an anti-HRP antibody was biotinylated using an amine-reactive …

Synthesis Of Phenaliporphyrin, A Pah-Porphyrin Hybrid, From An Acenaphthene-Fused Cyclopropane Dialdehyde, Sunday Oladapo Jacob, Emily D. Harris, Melissa A. Mathius, Deyaa I. Abusalim, Gregory M. Ferrence, Timothy D. Lash

Faculty Publications – Chemistry

Phenaliporphyrin, a new aromatic benziporphyrin derivative, has been synthesized from an annulated cyclopropane dialdehyde intermediate. Corey-Chaykovsky cyclopropanation of dimethyl acenaphthylene-1,2-dicarboxylate gave a cyclopropane diester, and this was converted to the corresponding bis-Weinreb amide. Reduction with lithium aluminum hydride afforded an unstable dialdehyde and subsequent acid-catalyzed condensation with a tripyrrane dicarboxylic acid, followed by oxidation with aqueous ferric chloride, gave the targeted porphyrinoid system. This involves ring expansion of the acenaphthylene precursor to generate the phenalene unit. Phenaliporphyrin exhibits a porphyrin-like UV–vis spectrum with a Soret band at 443 nm and a relatively intense Q-band at 601 nm. The proton NMR …

Synthesis Of Alkyl Substituted Carbatripyrrins And Their Application To The Preparation Of Carbaporphyrins And Oxacarbaporphyrins, Ian A. Mclauchlan, Bethany K.X. Overbey, Tyler J. Smolczyk, John J. Woods, Timothy D. Lash

Faculty Publications – Chemistry

Unsubstituted carbatripyrrins have previously been shown to be useful intermediates in the synthesis of benzocarbaporphyrins and related core-modified analogues. However, the absence of substituents often resulted in the formation of poorly soluble products. In this study, four examples alkyl substituted carbatripyrrins were constructed by base-catalyzed condensation of dihydrofulvenes with pyrrole aldehydes. Further reaction with a pyrrole dialdehyde in the presence of trifluoroacetic acid afforded a series of carbaporphyrins, while reactions with 2,5-furandicarboxaldehyde generated oxacarbaporphyrins. These results demonstrate that alkyl substituted carbatripyrrins are promising precursors to new carbaporphyrinoid structures.

Synthesis And Characterization Of Free Radical Scavenging Dendrimer Nanogels Via Cross-Linking Reaction-Enabled Flash Nanoprecipitation, Lin Qi, Da Huang, Huari Kou, Anna Chernatynskaya, Nuran Ercal, Hu Yang

Chemistry Faculty Research & Creative Works

This work reports the development and evaluation of dendrimer-based nanogels based on Poly amidoamine (PAMAM) dendrimer generation 5, engineered to act as a carrier with reactive oxygen species (ROS)-scavenging capabilities. We developed a cross-linking reaction-enabled flash nanoprecipitation method in which the cross-linking reaction occurs during the flash nanoprecipitation process to form a cross-linked nanostructure. Using this approach, an N-hydroxy succinimide (NHS)-functionalized ROS-responsive thioketal cross-linker (TK-NHS) was synthesized and utilized to cross-link DAB-core PAMAM dendrimer G5, resulting in the formation of G5-TK nanogels. The resulting nanogels were characterized using dynamic light scattering and transmission electron microscopy, and their cytocompatibility, irritancy, cellular …

Instantaneous Hydrolysis Of Methyl Paraoxon Nerve Agent Simulant Is Catalyzed By Nontoxic Aminoguanidine Imines, Emmanuel Kingsley Darkwah, Puspa Aryal, Chi Zhang, Charles B. Musgrave, William A. Goddard, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

Exposure to organophosphate-based nerve agents and pesticides poses health and security threats to civilians, soldiers, and first responders. Thus, there is a need to develop effective decontamination agents that are nonhazardous to human health. To address this, we demonstrate that instantaneous hydrolysis of methyl paraoxon (Me-POX), a nerve agent simulant, can be achieved in the presence of aminoguanidine imines at pH 10: ● the pyridine-4-aldehyde aminoguanidine-imine (1) and ● the 2,3-butanedione aminoguanidine-imine (2). The hydrolysis of Me-POX under these conditions is substantially faster than that of the state-of-the-art decontaminating agent, Dekon-139 (2,3-butanedione oxime, potassium salt). Furthermore, Dekon-139 shows adverse effects …

Scalable Fabrication Of High-Payload Dendrimer-Based Nanoparticles For Targeted Atherosclerosis Therapy, Huari Kou, Lin Qi, Da Huang, Jiandong Wu, Honglan Shi, Hu Yang

Chemistry Faculty Research & Creative Works

Nanoparticle-based therapeutics hold promise for the treatment of atherosclerosis, but challenges such as low drug-loading capacity and a lack of scalable, controllable production hinder their clinical translation. Flash nanoprecipitation, a continuous synthesis method, offers a potential solution for scalable and reproducible nanoparticle production. In this study, we employed a custom-designed multi-inlet vortex mixer to perform cross-linking reaction-enabled flash nanoprecipitation, facilitating controlled and scalable synthesis of cross-linked Poly amidoamine (PAMAM) dendrimer nanoparticles. Notably, this approach allows simultaneous nanoparticle cross-linking and drug loading in a single step. The mannose moiety enabled specific targeting of macrophages via mannose receptors, enhancing the localization of …

Pla-Based Bone Tissue Engineering Scaffolds Incorporating Hydroxyapatite And Bioactive Glass Using Digital Light Processing, Engin Gepek, Fateme Fayyazbakhsh, Lev Suliandziga, Vadym Mochalin, Osman Iyibilgin, Yue-Wern Huang, Ming C. Leu

Chemistry Faculty Research & Creative Works

Bone tissue engineering (BTE) aims to repair bone defects using biocompatible materials with tailored geometries and pore structures, providing appropriate mechanical support and control over biodegradation kinetics to promote bone growth. In this study, we utilized digital light processing (DLP) 3D printing to fabricate scaffolds with varying pore sizes using polymer–ceramic slurries composed of polylactic acid (PLA) as the main polymer matrix, incorporated with hydroxyapatite (HA) and bioactive borate glass (BBG) at various ratios. We studied the effect of composition on rheological behavior, printability, mechanical properties, bioactivity, degradation rate, and biocompatibility. While HA increased viscosity and reduced printing accuracy, it …

Unveiling Pseudocapacitance: A Kinetic Treatment Of The Pseudocapacitive Biosensor, Rokas Gerulskis, Egor Baiarashov, Maryam Karimi, Wassim El Housseini, Shelley D. Minteer

Chemistry Faculty Research & Creative Works

A kinetic framework is introduced for a pseudocapacitive potentiometric biosensor. Mathematical derivation and kinetic modeling demonstrate that experimentally observed linearity in analyte-OCP response arises from a dynamic equilibrium between competing redox reactions on a single electrode. This system can be expanded to develop a new generation of biosensors.

Tricatalytic Organocatalyst-Enzyme Hybrid Cascade For Improving Complete Oxidation Of Glucose To Carbon Dioxide, Adam Milam, Rokas Gerulskis, Jose Intano, Shelley D. Minteer

Chemistry Faculty Research & Creative Works

Advancing energy harvesting is crucial for the development of wearable and implantable technologies. Given the high concentration of complex fuels, such as glucose, in biological fluids, biofuel cells present a promising avenue for exploration. However, glucose fuel cells that have been published to date typically catalyze only one or two of the maximum 12 oxidation steps for glucose, resulting in low energy density. Although known multienzyme cascades, which are sequential biochemical reactions where multiple enzymes work in tandem to convert a substrate into a final product, have addressed this inefficiency, they come with several trade-offs, such as reduced power density …

Atomistic Mechanisms Of Ti3alc2 Etching: Oxidation, Surface Stability, And Selectivity, Valentina Nesterova, Ana Maria Stratulat, Walter Malone, Vadym Mochalin, Majid Beidaghi, Konstantin Klyukin

Chemistry Faculty Research & Creative Works

Mechanisms governing MAX-phase etching set the properties and stability of resulting MXenes, yet the details of this complex process remain poorly understood. Combining thermodynamic analysis of surface chemistries with ab initio molecular dynamics and enhanced free-energy sampling, we directly model elementary steps at the MAX/etching solution interface. We find that purely thermodynamic analysis overestimates etching selectivity, which is governed by the kinetics of elementary reaction steps. Our calculations reveal that initial exposure to water drives localized, thermodynamically favored edge oxidation that seeds MXene-like terminations into the uppermost layers of Ti₃AlC₂ with oxygen occupying the interlayer space between …

Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols, Raheemat Rafiu, Puspa Aryal, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

The S-trifluoromethylation of thiols is accomplished using a simple and cost-effective organic catalyst (diacetyl) along with a bench-stable and environmentally friendly trifluoro methylating reagent (Langloi's reagent). Under optimized conditions (2.5 equivalents of Langlois reagent, Blue LED irradiation, 48-h reaction time at room temperature), the reaction yielded up to 81% S-trifluoro methylated product. This method's high yields, compatibility with a broad substrate scope (aliphatic, heteroaromatic, and aromatic thiols), and environmentally friendly conditions demonstrate its potential for broader synthetic applications. In contrast to traditional methods that rely on organometallic catalysts and environmentally hazardous reagents, this novel photoredox catalysis method offers a more …

The Road Less Traveled: A Pathway Leading To Research At A Primarily Undergraduate Institution, Timothy D. Lash

Faculty Publications – Chemistry

Scholarly activities in primarily undergraduate institutions involve very different challenges from those in major research universities. In this essay, the author discusses how he initiated a research program involving undergraduates at Illinois State University following a number of missteps and false starts. Although undergraduate researchers have much to learn, and the levels of commitment vary considerably, they can nevertheless often make important contributions.

Assessment Of Analytical Workflows Of Gunshot Residue Evidence And Strategies For Implementation Of Advanced Technology In Crime Laboratories., Leah D. Thomas

Graduate Theses, Dissertations, and Problem Reports (ETD)

The rise in gun violence in the United States has increased the demand on forensic agencies to process evidence promptly and accurately. The exchange of imperceptible traces among objects, suspects, and victims can provide critical insights into the interactions and sequence of events during a crime. Gunshot residue (GSR) is a type of trace evidence that holds significant investigative value in shooting reconstructions. GSR can help identify potential shooters, intermediate targets, and bullet trajectories; however, its analysis is often expensive and time-consuming. Consequently, there is an urgent need for more effective solutions.

Methods for on-site screening can significantly streamline forensic …

Free Energy Approaches To Understanding The Mechanism Of Membrane-Active Peptides, Hannah R. Scott

Graduate Theses, Dissertations, and Problem Reports (ETD)

Cancer is a leading cause of death in the world today. Current methods of treatment fail to distinguish the difference between cancer cells and cells of healthy tissue, leading to off-target effects, often with terminal outcomes. A potential solution to this challenge is to target the cancer cells’ microenvironment. One universal characteristic across all cancer cells is the acidic extracellular environment. The pH-Low Insertion Peptide (pHLIP) is a membrane-active peptide with acid-sensitive function, undergoing folding and insertion into a transmembrane alpha-helix. pHLIP is a promising candidate to be used to deliver anti-cancer agents exclusively to cancer cells. Although the mechanism …

Understanding The Prevalence Of Γ-Hydroxybutyric Acid In Hair For Clinical And Forensic Applications, Collin J. Kustera

Graduate Theses, Dissertations, and Problem Reports (ETD)

Sexual assault affects over 400,000 Americans annually, including 13% of college students, yet only 2.5% of assailants face incarceration. This disparity stems from significant challenges in evidence collection, particularly in drug-facilitated crimes (DFCs). Victims often delay reporting due to fear, self-blame, or unawareness of the assault which is common in cases involving substances like γ-hydroxybutyric acid (GHB). Current forensic standards rely on blood and urine, which offer detection windows of just 48 and 120 hours, respectively. These short timeframes frequently fail to capture critical toxicological evidence, leaving investigators with only victim testimony, which the judicial system struggles to act upon …

Refinement Of A Thermodynamic Model To Explain The Weathering Patterns Of Ignitable Liquids On Household Substrates At Elevated Temperatures, Chaney Ashlyn Ganninger

Graduate Theses, Dissertations, and Problem Reports (ETD)

ABSTRACT

Refinement of a thermodynamic model to explain the weathering patterns of ignitable liquids on household substrates at elevated temperatures

Chaney A. Ganninger

In 2021, arson caused more than 4,361 deaths in the United States. To aid in the differentiation between arson and accidental or natural causes, investigators often analyze fire debris for the presence of ignitable liquid residues using headspace concentration followed by gas chromatography-mass spectrometry (GC-MS). Classification of ignitable liquids can be confounded by weathering, which is the uneven evaporation of compounds in ignitable liquid residues. The Jackson group, among others, has developed a thermodynamic model to help …

Geochemical Assessment Of Sediment Flux In A Sediment Core From A Tidal Flat In A Tropical Estuary, Olumide Ajulo

Master's Theses or Doctor of Nursing Practice

Sediment flux in estuaries is influenced by both natural processes and anthropogenic activities. Understanding the historical and current trends in sediment flux inputs and geochemical composition are essential for evaluating the estuary’s response to natural and human-induced changes and for developing effective environmental management strategies. The tropical Wouri Estuary in Cameroon receives water and sediment inputs from three main rivers draining urban, industrial, and agricultural areas, as well as different rock terrains. The complex inputs into the estuary can significantly affect sediment flux, consequently impacting the ecosystem. Thereby making an understanding of the temporal variations in sediment inputs in the …

Electrochemically Active Molybdenum Phosphate With Open-Framework Structure, Sutapa Bhattacharya, Milad Aghayi-Anaraki, Nikolay Gerasimchuk, Steven P. Kelley, Amitava Choudhury

Chemistry Faculty Research & Creative Works

Somewhat less investigated, lithium ion containing molybdenum phosphate compounds are synthesized via simple template free hydrothermal method. Single-crystal X-ray diffraction (SCXRD) study reveals that the compounds Li_0.89Mo₂O_1.89F_0.11(PO₄)2(H₂PO₄)·xH₂O (x ≈1) and Li₃Mo₂O₂(PO₄)₃·xH₂O (x ≈1) crystallize in monoclinic C2/m and C2/c space group, respectively. The structures are built of alternate corner-sharing of MoO₆ octahedra and PO₄ tetrahedra forming layers, which are pillared by phosphate groups creating a 3D framework with channels. These …

The Relationship Between Pillar[5]Arene And Pillar[6]Arene In The Synthetic Route To A Water-Soluble Pillar[6]Arene: A Case Of Kinetic And Thermodynamic Products Or Two Distinct, Competing Reactions, Helice A. Gillis

Open Access Dissertations

Pillar[n]arenes, discovered in 2008, have already made their mark as a formidable addition to the field of supramolecular chemistry, largely due to their host-guest chemistry. While the synthesis of pillar[5]arene is well established, the synthesis of pillar[6]arene, with its larger core, has not been so straightforward and mainly accomplished through the use of bulky solvents. Here we present an optimized method for a reproducible, acid-catalyzed synthesis for a brominated pillar[6]arene, starting with a brominated monomer and using chloroform as the templating solvent. Our studies have demonstrated the ratio of brominated pillar[6]arene to brominated pillar[5]arene increases with both decreasing concentration of …

Dynamics Of Metal-Coordinated Coumarin Dyes For Photoswitching Applications, Danielle Jacoby

Open Access Dissertations

Optical transient absorption spectroscopy is a fundamental pump-probe technique that is used to analyze the photophysical and photochemical properties of molecules. Our research group specifically utilizes both a femtosecond and nanosecond set up to probe dynamics of molecules on time scales ranging from 100s of femtoseconds to approximately 50 microseconds. Chapter 2 is a standard operating procedure for the nanosecond transient absorption instrument.

Photoacids are molecules that undergo a change in the acidity of one of their protons when exposed to light. Utilizing this phenomenon, we have designed a series of dyes that, when bound to divalent first row transition …

Development And Characterization Of Polysaccharide-Based Controlled Drug Delivery Platforms, Amanda Pepler

Open Access Dissertations

Drug delivery research focuses on overcoming challenges in patient treatment. Most therapeutics are delivered systemically through oral or intravenous routes. However, these administration methods are often inefficient due to therapeutic hydrophobicity, poor bioavailability, and liver metabolic clearance, necessitating frequent dosing. When treatment plans require frequent dosing, patients experience significant fluctuations in therapeutic concentration in the bloodstream, which can increase adverse side effects. These factors contribute to low patient compliance. Therefore, the core focus of drug delivery research is to develop new administration routes for therapeutics. Drug delivery systems (DDS) that can target therapeutics to a localized region offer advantages over …

Probing Biomolecular Structure And Dynamics Via Infrared Action Spectroscopy, Madeline Schultz

Open Access Dissertations

Biomolecular structure is supported by a network of inter- and intramolecular interactions, which can be inherently complex in the condensed phase. Isolating biomolecules from the condensed phase to vacuum, via electrospray ionization (ESI), can afford precise control over experimental conditions, yielding additional structural insight. However, the loss of solvation inherent to the ESI process can drive structural rearrangement, particularly at charge sites.

Microsolvation reagents can be used to partially mimic the solvation of charged moieties in solution as they are brought into the gas phase through complexation. This serves two primary functions: 1) reducing propensity for structural rearrangement of systems …

Characterization Of Methodological Variability In Compound Specific Isotope Analysis Of Amino Acids (Csia-Aa), Audreyana Brown-Nash

Open Access Dissertations

The use of isotopes in the natural sciences stems from the principle that chemical reactions predictably alter the isotopic composition of a given sample. Recent advances in compound specific isotope analysis of amino acids (CSIA-AA) have paved the way for studies of increasingly complex ecological relationships, including the identification and characterization of organismal physiology, consumer-resource linkages, biogeochemical cycling, and movement ecology. The analytical power of CSIA-AA has caused an exponential increase in the number of application-based studies since its inception in the 1990s. With the technique constantly evolving to accommodate new research goals, it is important to understand how variation …

Investigating The Photophysical Dynamics Of Anthracene And Acridine Derivatives Using Time-Resolved Spectroscopy, Sophia Tiano

Open Access Dissertations

Anthracenes and acridines are among the simplest visible light absorbing heterocyclic and polycyclic aromatic hydrocarbons and as such are extensively used in a variety of applications including photosensitizers and fluorescent sensors. Although the photophysics of some derivatives have been studied in the past, there is still a lot of unknown fundamental information that is vital in order to optimize these molecules for particular applications. Transient absorption spectroscopy was used to study the photophysics of the 9-substituted methyl, hydroxymethyl and formyl derivatives of acridine and anthracene. The growth and decay of the triplet-triplet absorption peak were quantified for each dye in …

Characterization And Leaching Feasibility Studies Of Copper Flue Dust For The Recovery Of Main And Trace Metals, Fardis Nakhaei, Marek Locmelis, Lana Alagha, Michael S. Moats, Carlos Eyzaguirre, Cory Smith

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Although copper smelter dust (CSD) is classified as hazardous waste, it also serves as a valuable secondary resource, offering potential for the recovery of critical elements. In this study, CSD samples were collected from the waste heat boiler (WHB) and electrostatic precipitator (ESP) units connected to the flash smelting furnace at a copper smelter. The representative samples were extensively characterized by particle size, and chemical and mineralogical analyses. Following sample characterization, leaching experiments were performed to evaluate the potential extraction of Cu, Fe, As, Zn, Pb, In, Ga, and Ge from the flue dusts. Distilled water, H2SO4, and HCl were …

Valorizing Municipal Solid Waste For Sustainable Aviation Fuel And Polyhydroxyalkanoate Bioplastics: Pyrolysis And Microbial Pathways, Emon Das

Theses and Dissertations--Biosystems and Agricultural Engineering

The escalating global burden of municipal solid waste (MSW), projected to reach 3.88 billion tons annually by 2050, calls for innovative valorization strategies to mitigate environmental impacts and promote a circular bioeconomy. This thesis investigates the conversion of MSW into two high-value products: sustainable aviation fuel (SAF) and polyhydroxyalkanoate (PHA) bioplastics. Chapter one presents comprehensive physicochemical characterization and pyrolysis-GC/MS analysis of MSW feedstocks. The physicochemical results reveal that densification enhances handling and storage properties, while pyrolysis-GC/MS analysis indicates that plastic-rich MSW streams produce bio-oils with favorable hydrocarbon profiles suitable for SAF production, potentially contributing to decarbonization efforts in the aviation …

Surface Modifications Of Titanium Alloys For Biomedical Applications, Justynne Fabian

Doctoral

Hip implant failure remains a critical concern in healthcare, primarily driven by poor bone integration and bacterial infection. These issues contribute to a rising number of revision surgeries, posing significant challenges that must be addressed, particularly in light of an ageing global population. Titanium surface anodisation emerges as a promising solution for biomedical applications, offering a cost-effective, controllable, and efficient process. The anodisation technique results in the formation of titanium dioxide nanotubes (TiO2 NTs) on the metal surface. These nanostructures offer several advantages, including enhanced mechanical properties, and potential for surface modification through the incorporation of antibacterial and osteoinductive properties. …

The Chemical Nature Of Colors, Bryant Corbin, Bryant Corbin

Longwood Senior Thesis Proposal

No abstract provided.

High Throughput, Solid Sample Analysis With Cone-Based Mass Spectrometric Ionization Sources, Emily J. Wiggins

Theses and Dissertations

The widespread presence of environmental and consumer-product contaminants (e.g. trace metals, opium alkaloids) has underscored the need for rapid, reliable, and high-throughput analytical techniques that are capable of handling complex solid samples. While traditional mass spectrometric (MS) methods tend to have high sensitivity and accuracy, they often require labor-intensive and time-consuming sample preparation steps that limit throughput and field applicability. This thesis investigates the use of 3D-Printed Cone Spray Ionization-Mass Spectrometry (3D-PCSI-MS) as an ambient ionization technique for the direct screening of contaminants from solid matrices, eliminating the need for traditional sample preparation and allowing for real-time analysis.

In …

Asymmetric Synthesis Of The Hiv Protease Inhibitor Tmc-126 And An Anti-Malarial Agent Via A Titanium Tetrachloride Mediated Asymmetric Glycolate Aldol Addition Reaction. Redefining The Curtius Rearrangement Reaction Via Dehomologation Of Carboxylic Acids Bearing Alpha-Leaving Groups, Kweku Amaning Affram

Theses and Dissertations

Acquired Immune Deficiency Syndrome (AIDS) and malaria are two devastating infectious diseases caused by HIV and Plasmodium parasites. AIDS is caused by HIV-1 and HIV-2, transmitted through sexual contact, blood transfusions, needle sharing, and perinatal routes. Malaria, caused by plasmodium parasites through mosquito bites. Today, millions of people around the world have been infected with HIV and malaria and much research has been done to treat it. However, despite advancements in therapeutic options, these diseases remain a significant global health threat, particularly in developing countries due to the emergence of drug-resistant strains for both HIV and malaria complicating eradication efforts. …