Chemistry Commons^™

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

Hydrothermal Synthesis Of Frustrated Lanthanide Pyrochlores And Transition Metal Double Perovskites And Germanates, Matthew S. Powell

All Dissertations

Magnetically frustrated materials hold promise of unique behavior allowing for the novel study of quantum phenomena. Such materials are poised to become an integral foundation for technological advancement in the post-Silicon Age. Crystalline materials are given special focus where the rigid lattice allows more detailed study of these quantized effects and frustration behavior. As opposed to polycrystalline powders, large single crystals can be preferentially aligned enabling the study of anisotropic behavior. Two cubic structure types have garnered significant interest due to their 3-D tetrahedral arrangement of symmetry-related metal centers with the potential for magnetic frustration: pyrochlores and perovskites.

The supercritical …

Supramolecular Pi-Donor/Acceptor Arrays Based On Redox-Active Metal-Organic Coordination Assemblies, Paola Benavides

All Dissertations

Coordination-driven self-assembly is an attractive strategy for constructing thermodynamically stable supramolecular coordination complexes, ranging from discrete metallacycles and cages to infinite coordination polymers and metal-organic frameworks for a variety of applications.

Chapter 1 discusses strategies for preparing supramolecular charge-transfer π-donor/acceptor assemblies and their potential applications.

Chapter 2 demonstrates that tricomponent self-assembly method, which was believed to yield 3D-cages, based on tetrapyridyl porphyrin (M’TPP, M’ = Zn or H₂), dicarboxylate ligands (XDC), and caped cis-Pt(II) corners, actually yields 2D-bowties featuring an M’TPP core and two parallel XDC linkers held together by four heteroligated PtII(N,O) corners. The 2D-bowties showed …

Synthesis Of 2-Bromo-6-Alkylaminopyridines, 2,6-Dialkylaminopyridines, And Tren Based Ligands, Stephanie E. Carter

Honors College Theses

Extended metal atom chains (EMAC) are multimetallic complexes that feature a linear metal chain with metal-metal bonds surrounded by stabilizing ligand molecules. When EMACs are formed with paramagnetic metal ions, unique magnetic properties can be derived from direct metal to metal communication. The challenge is that EMAC complexes are challenging to synthesize due to the inherent weakness of most M-M bonds and the specificity of the ligands required to stabilize EMACs. In prior work by the Guillet group, the silyl aminopyridine (SAP) ligands were observed to stabilize very unique triiron complexes, but they were inherently unstable. In other work, scaffolded …

Collisional Excitation Of C2h- By H2: New Interaction Potential And Scattering Calculations, Fabien Dumouchel, Ernesto Quintas-Sánchez, Christian Balança, Richard Dawes, François Lique, Nicole Feautrier

Chemistry Faculty Research & Creative Works

Interstellar Anions Play an Important Role in Astrochemistry as Being Tracers of the Physical and Chemical Conditions in Cold Molecular Clouds and Circumstellar Gas. the Local Thermodynamic Equilibrium is Generally Not Fulfilled in Media Where Anions Are Detected and Radiative and Collisional Data Are Required to Model the Observed Lines. the C2H- Anion Has Not Yet Been Detected in the Interstellar Medium; However, Collisional Data Could Be Used for Non-LTE Models that Would Help in Identifying the Most Intense Lines. for This Purpose, We Have Computed the First 4D Potential Energy Surface (PES) of the C2H--H2 Complex using an Explicitly …

Synthesis And Characterization Of Rhenium 2,2′-Pyridylnaphthyridine Metal Complexes, Benjamin F. Solomon

Honors Theses

Rhenium (Re) is a group 7 heavy 5d transition metal in the same family as manganese (Mn) and technetium (Tc). Re-carbonyl complexes are known to be catalysts for many different kinds of reactions from C-C bond formation to reduction reactions like CO₂ reduction (CO₂RR)^1,2. With this in mind, we have prepared a set of six Re-carbonyl complexes of 2,2′-pyridyl-1,6-naphthyridine (1,6- pynap) and 2,2′-pyridyl-1,8-naphthyridine (1,8-pynap), a redox non-innocent ligand containing a bpy moiety as well as an additional aryl nitrogen binding location at which another metal-ligand bond could form. We have synthesized these complexes as precursors …

Ultraviolet-Initiated In-Situ Cross-Linking Of Multifunctional Binder Backbones Enables Robust Lithium-Sulfur Batteries, Sha Li, Xiao Zhan, Gu-Lian Wang, Hui-Qun Wang, Wei-Ming Xiong, Li Zhang

Journal of Electrochemistry

Lithium-sulfur (Li-S) batteries show attractive prospects owing to their high theoretical energy density, but their commercialization still faces such challenges as lithium polysulfides shuttling, severe volume change and considerable polarization. These stubborn issues place higher demands on each component in the battery, such as the development of multifunctional binders with superior mechanical properties. Herein, ethoxylated trimethylolpropane triacrylate was firstly introduced into sulfur cathodes, and in-situ cross-linked by ultraviolet (UV) curing combined with traditional polyvinylidene difluoride binder (i.e., forming a binary binder, denoted as c-ETPTA/PVDF) to construct high-loading and durable Li-S batteries. The covalently cross-linked ETPTA framework not …

Cobalt/Carbon Composites As Sulfur Hosts For High-Performance Lithium-Sulfur Batteries, Yun-Rui Yang, Huan-Huan Dong, Zhi-Qiang Hao, Xiang-Xi He, Zhuo Yang, Lin Li, Shu-Lei Chou

Journal of Electrochemistry

Lithium-sulfur (Li-S) battery is one of the promising energy storage devices because of its high energy density. However, the sulfur cathode suffers from sluggish electrochemical reaction kinetics, slow charge transfer, large volume expansion and severe shuttle effect of lithium polysulfides inevitably resulting in low reversible capacity, poor rate performance and short cycle life, limiting its practical applications. Herein, the recent progress of cobalt/carbon composites, including cobalt nanoparticles and cobalt single atoms, as the sulfur host materials in Li-S batteries is overviewed. In general, cobalt plays the role of electrocatalyst, which inhibits the shuttle effect of lithium polysulfides, accelerates the electrochemical …

Recent Advances Of Functional Electrolyte Additives For Lithium-Sulfur Batteries, Xiu-Qing Zhang, Shuai Tang, Yong-Zhu Fu

Journal of Electrochemistry

Lithium-sulfur (Li-S) batteries have become one of the most promising next-generation battery systems due to their high energy density and low cost. However, the application of Li-S batteries still faces critical challenges, such as the low conductivities of S and Li₂S, shuttle effect of polysulfides and dendrite growth of Li, etc. The optimization of the electrolyte can ameliorate the electrolyte|electrode interphase, conveniently regulating the parasitic reaction and improving the performance of the resultant batteries. The functional additives in electrolytes provide chances to tune the interphase and even the redox mechanism to improve the performance of the batteries. In …

Metals And Alloys As Catalytic Hosts Of Sulfur Cathode For Lithium-Sulfur Batteries, Zhen-Yu Wang, Xue-Ping Gao

Journal of Electrochemistry

Lithium-sulfur batteries are recognized as one of the most promising next-generation energy storage devices, owing to the high theoretical energy density of 2600 Wh·kg^–1. However, their application has been seriously hindered by the sluggish electrochemical reaction kinetics of elemental sulfur and discharged products (Li₂S₂/Li₂S), and the notorious “shuttle effect” of soluble intermediate lithium polysulfide species, leading to poor cycle stability, low sulfur utilization and inferior coulombic efficiency. Introducing catalytic hosts into sulfur cathode is an efficient path to propel the conversion of sulfur-contained species, thus preventing the dissolution and loss of active-sulfur …

Preface To The Special Issue On Lithium-Sulfur Batteries, Jia-Jia Chen, Ren-Jie Chen, Zhong Jin

Journal of Electrochemistry

No abstract provided.

Brown Carbon From Photo-Oxidation Of Glyoxal And So2 In Aqueous Aerosol, David O. De Haan, Lelia N. Hawkins, Praveen D. Wickremasinghe, Alyssa D. Andretta, Juliette R. Dignum, Audrey C. De Haan, Hannah G. Welsh, Elyse A. Pennington, Tianqu Cui, Jason D. Surratt, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin

Chemistry and Biochemistry: Faculty Scholarship

Aqueous-phase dark reactions during the co-oxidation of glyoxal and S(IV) were recently identified as a potential source of brown carbon (BrC). Here, we explore the effects of sunlight and oxidants on aqueous solutions of glyoxal and S(IV), and on aqueous aerosol exposed to glyoxal and SO₂. We find that BrC is able to form in sunlit, bulk-phase, sulfite-containing solutions, albeit more slowly than in the dark. In more atmospherically relevant chamber experiments where suspended aqueous aerosol particles are exposed to gas-phase glyoxal and SO₂, the formation of detectable amounts of BrC requires an OH radical source …

The Role Of Sars-Cov-2 Orf8 Protein Arks Motif On Novobiocin Binding, Si Chun Chiu, My T. Nguyen

Celebrating Scholarship and Creativity Day (2018-)

The discovery of the SARS-CoV-2 virus during the COVID-19 pandemic required scientists to develop medical solutions to reduce infectivity, severity of symptoms, and death. Although vaccines and drugs provided urgent assistance, the need to continue developing better drugs is necessary long term, and understanding the structure of the virus and finding potential inhibitors would prove vital to discovering solutions to this worldwide health problem. This experimental project focuses on targeting the unique accessory protein, Open Reading Frame 8 (ORF8) in SARS-CoV-2 through studying its interactions with a repurposable drug, novobiocin. Importantly, ORF8 specializes in helping evade immune system checks by …

Protein Engineering Of A Fluorescent Watermelon Malate Dehydrogenase, William Yu

Celebrating Scholarship and Creativity Day (2018-)

Malate dehydrogenase (MDH) is an enzyme that is prevalent in many metabolic processes, such as the Krebs cycle and the citric acid cycle4. It reversibly forms oxaloacetate and NADH from (S)-malate and NAD+,1. Tryptophan fluorescence would be ideal to monitor conformational changes of MDH, but watermelon glycosomal MDH does not contain any tryptophan amino acids4. The research question being tested here is whether or not it is possible to mutate MDH to contain a tryptophan while still retaining native-like specific activity. This research question has not been addressed as a literature search has shown no research has been done to …

Synthesis And Evaluation Of 1-Substituted Imidazo[4,5-C] Quinoline Tlr7 Agonists With Improved Potency, Emma Grace Deyoung

Undergraduate Honors Theses

TLR7 agonists are small molecules that are useful within cancer immunotherapy due to their ability to stimulate the TLR7 pathway resulting in NFκB activation, and cytokine release.1 Due to the risk of toxicity when delivered systemically, our team has employed a particular type of drug-delivery technology, Antibody Drug Conjugates (ADCs) to deliver these payloads directly to tumor tissue. The initial focus of this work was on E104 (8a), an imidazoquinoline TLR7 agonist, which was synthesized by the Tumey lab.1 However, the agonist was not sufficiently potent for many of the proposed applications of this technology, prompting a need to develop …

Chemically Responsive Hydrogels, Properties, Pharmaceuticals, And Agricultural Applications: A Review, Mohammad Alrbaihat, Qusay Abu-Afifeh, Firas Al-Zeidaneen

Al-Bahir Journal for Engineering and Pure Sciences

A review of the literature on chemically responsive hydrogels about the selection of selectivity based on classification, properties, and application is presented in this article. Chemically responsive hydrogels are a type of hydrogel that undergo changes in their properties in response to specific stimuli. These hydrogels have attracted significant attention due to their potential applications in various fields, including pharmaceuticals and agriculture. Chemically crosslinked hydrogels are synthesized by covalent crosslinking of end-functionalized macromeres. Currently, a great deal of research is being conducted on hydrogel networks, also known as smart networks or hungry networks. This is owing to their potential use …

219 - Developing A Portable System Of Environmental Dna (Edna) Surveillance To Monitor Fish Population Dynamics And Detect Invasive Species In Conesus Lake And The Philippine Seas, Karina Mirza, Micah Ford, Morgan Comstock

GREAT Day Posters

Climate change is an increasing threat to many ecosystems worldwide. Due to global warming, many species are under threat of extinction while others are forced into unusual patterns of migration. In the Philippines, the fish Round Scad is a cheap source of protein in the diet of common citizens. Alarmingly, it is rapidly declining in both population and body size. In this project, we aim to develop a cheap, rapid, and sensitive method of monitoring the population dynamics of this fish in the wild. Recently, a new method called environmental DNA (eDNA) metabarcoding has been developed as a cost-effective way …

195 - Targeting Telomeric And C-Myc G4 Dna As An Anticancer Approach, Alexander Michaels, Sameela Haidari, Courtney Fetzer

GREAT Day Posters

G-quadruplex (G4) DNA are non-canonical higher order DNA structures formed from guanine rich sequences, made up of stacked G-tetrads stabilized by non-Watson-Crick (Hoogsteen) base pairing and K⁺ ions. Early interests in G4 DNA were spurred on by the revelation that G4 was formed in telomeric DNA sequences at the end of our chromosomes. This was particularly promising given that G4 structures formed in telomeric DNA were also found to inhibit an enzyme known as telomerase, which is overexpressed (>90%) in cancer cells. Cancer cells require telomerase activity for survival and "immortality", therefore stabilization of telomeric G4 can inhibit …

Probing The Effect Of Nitrogen And Boron Doping On Structures, Properties, And Stability Of C20 Clusters, Ramsay Revennaugh, Martina Kaledin

Symposium of Student Scholars

Fullerenes are carbon molecules arranged in a closed hollow shell to form spherical-like structures. These clusters exist in various sizes, C_n, with the smallest being C₂₀. C₂₀, often when doped with other elements, has shown promise in creating new materials as a catalyst and as energy storage material. Here, we look at the existence of C₂₀ doped with nitrogen or boron atoms using density functional theory (DFT). C₂₀ is doped with one to three boron or nitrogen atoms, respectively, including the five different C₁₈N₂ / C₁₈B_{2 …}

Ab Initio Calculations Of Vibrational Spectra Of Model Peptides, Katheryn Foust, Martina Kaledin

Symposium of Student Scholars

The function of biological molecules is closely related to their spatial structure and conformational dynamics. Therefore, understanding the structure and functions of small peptides contributes to gaining insight into the behavior of more complex systems. The peptide bond (-CO-NH-) is among the very important binding patterns in biochemistry. It links amino acids together, specifies rigidity to the protein backbone, and includes the two essential docking sites for hydrogen-bond-mediated protein folding and protein aggregation, namely, the C=O acceptor and the N-H donor parts. Therefore, the C=O (amide-I) and N-H (amide-A) vibrations provide sensitive and widely used probes into the structure of …

Toward The Design, Synthesis, And Characterization Of Abiotic Coiled-Coil Peptides Via Solid-Phase Copper-Catalyzed Azide-Alkyne Cycloaddition (Sp-Cuaac) Click Reaction For The Preparation Of Controlled Self-Assembly Molecular Building Block, Liaquat Ali

Chemistry Theses

The production of cutting-edge materials, the development of novel medications, drug delivery systems, technological advancements, and biosynthesizing all depend on molecular building blocks. Proteins are required for the creation of intricate, well-organized structures, and coiled-coil protein domains are vital subunits for the oligomerization of protein complexes, gene expression, and the structural components of biological materials. The numerous interactions between a wide variety of amino acids make it difficult to assemble protein complexes with a particular shape. In the current study, we successfully designed and synthesized four different 32-residue peptides, each of which had two modified amino azide residues. These peptides …

Methods For Increasing The Electron Richness Of Iron Tricarbonyl Diimine Complexes, Francesca Lombardi, Joseph Maher, Sean Peloquin

Chemistry & Biochemistry Student Scholarship

Francesca Lombardi ’24, Major: Chemistry

Joseph Maher ’25, Major: Chemistry

Sean Peloquin ’26, Major: Biochemistry

Faculty Mentor: Dr. Maria Carroll, Chemistry and Biochemistry

The goal of our research is to synthesize new iron complexes that can reduce carbon dioxide. Increasing the electron richness of iron tricarbonyl diimine complexes, which have been synthesized previously in the Carroll research group, will increase the likelihood of a reaction with carbon dioxide occurring. We have taken two approaches to changing the electron density in the complexes. First, we reacted the complex Fe((CF3)2ArDABMe)(CO)¬3 with the reducing agent potassium on graphite, in order to reduce either …

Actualistic Testing Of The Influence Of Groundwater Chemistry On Degradation Of Collagen I In Bone, Paul V. Ullmann, Kristyn K. Voegele, Kenneth Lacovara

School of Earth & Environment Faculty Scholarship

Recent experiments have heightened our understanding of reactions which can stabilize biomolecules during early diagenesis, yet little remains known about how groundwater chemistry can aid or hinder molecular preservation within a bone through geologic time. To elucidate this issue, we conducted actualistic experiments of bone decay employing varied fluid compositions to simulate a suite of groundwaters. Modern domestic chicken (Gallus gallus) femora were placed in a matrix of compositionally- and texturally-mature, fluvially-deposited sand. To simulate groundwater flow, deionized water or solutions enriched in calcium carbonate, phosphate, or iron were percolated through separate trials for a period of 90 days. After …

Surface Characterization Of Mixed-Mode Adsorbents Using Bet C-Constant Energy Scale, Dinah C. Lee

Seton Hall University Dissertations and Theses (ETDs)

Mixed-mode chromatography is a chromatographic method in which solutes interact with stationary phase through more than one interaction mode or mechanism. It is because of these multiple complex interactions, which makes it difficult to predict chromatographic behavior of analytes on Mixed-mode columns. In order to fully understand the retention mechanisms on Mixed-mode columns, the packing material properties must be well characterized since each characteristic may contribute to the overall chromatographic performance of the column. Many non-chromatographic and chromatographic techniques are available to characterize and compare Mixed-mode columns in terms of their interaction abilities, retentivity, surface chemistry, chemical properties and geometry. …

School Of Stem Poster Session, Keith Schimmel

Scholar Week 2016 - present

Location: Reed 2^nd floor Tech Center and lobby

This poster session will include displays of work from the School of STEM - Engineering Senior Design and Freshman Design Projects along with Undergraduate Research.

Senior Design Projects

(1) Holland - Shear-Die [Nathan Marks, Nolan Paape, Seth Beyer]

(2) Aginno - Solar-Powered Fish Pond Aeration System [Hoai Do, Bella Lopez, Kendyl Clark, Megan Schroeder]

(3) Peddinghaus - Tube Conveyor [Carson Caldwell, Alisha Wright, Michael Rollberg, Rebecca Witvoet]

(4) American Institute of Chemical Engineers (AIChE) Student Design Problem [Marissa Anderson, Brady Chambers, Cam Steele]

(5) Kankakee Elks Country Club and Golf …

A Highly Charged Topic: Intrinsically Disordered Proteins And Protein Pka Values, Carter J. Wilson

Electronic Thesis and Dissertation Repository

Intrinsically disordered proteins (IDPs) are known not only for their roles in disease but also for their conformational flexibility, which makes them elusive for experimentation. We consider the role played by theory and simulation in resolving important questions pertaining to IDP structure and dynamics, as well as the nature of the charged residues (e.g., glutamate, lysine, etc.) that enrich them. Specifically, we investigated how the deep learning trained AlphaFold2 (AF2) predictor estimates disorder content, revealing both strong performance in relation to conventional approaches and an important relationship between the AF2 confidence metric and IDP dynamics. We also assessed how modern …

Characterization Of Shinella 6-Hydroxy-(L)-Nicotine Oxidase (6hlno-Se), Kaitrin Funckes

Honors Theses

6-hydroxy-(L)-nicotine oxidase, isolated from the organism Shinella sp. HZN7 (6HLNO-SE), is an enzyme that during the catabolism of nicotine catalyzes the oxidation of (S)-6-hydroxynicotine to 6-hydroxypseudeooxynicotine. This enzyme is a member of the monoamine oxidase (MAO) structural family of flavoproteins, which contain a highly conserved FAD-binding domain. Within the binding domain is a conserved lysine residue that can be traced throughout evolutionary history in this family. 6HLNO isolated from Arthrobacter nicotinovorans serves as a model enzyme for the one isolated from Shinella as both catalyze the same reaction in this biochemical pathway and much has been studied about the Arthrobacter …

Synthesis And Characterization Of Some Disubstituted Cyclopentadienyl Rhenium Complexes As Potential Candidates In Semiconductive Materials, Chloe Vernon

Liberty University Research Week

Undergraduate

Three Minute Thesis

Thp-1 Monocytes As A Model For The Characterization Of Potential Agents For Hypersensitization Observed In Ags?, Colin Baker

Liberty University Research Week

Undergraduate

Three Minute Thesis

Incorporation Of Thiophenes And Benzothiophenes Into Novel Pi-Extended Dibenzophosphole Systems, Joshua Kim, Conner Schell

Campus Research Day

Dibenzophospholes are molecules with extended pi conjugation. This project aims to incorporate thiophenes and benzothiophenes into dibenzophosphole systems by using 2-bromothiophene, 2-bromobenzothiophene, and 3-bromobenzothiophene as starting materials. An ethyne intermediate is created via the Sonagashira reaction, which is further reacted to form the novel dibenzophosphole system. The ultimate goal is to fuse the newly incorporated functional groups, creating an even greater degree of conjugation.