Organic Chemistry Commons^™

The Synthesis Of Deuterated Isohumulones For Use As Internal Standards In Lc-Ms Stable Isotope Dilution Assays, Patrick Gleason, Bruce Hamper Dr.

Undergraduate Research Symposium

Humulones are compounds that are prevalent in the hops flowers (Humulus Lupulus) used in beer brewing. These compounds undergo isomerization during the brewing process, and the resulting isohumulones are considered to be the primary contributors to the bitter flavors present in beer. As such, quantifying their presence, and the relative presence of their homologs(n-, co-, ad-), is of great importance in the characterization of beer. In this effort, one of the homologs of humulone (co) was isolated before being subsequently isomerized and deuterated for the purpose of analyzing beer by stable isotope dilution assay mass spectrometry(SIDA-MS). The addition of this …

Nitro-Aromatic Polymers For Conversion-Style Battery Cathodic Materials, Brady P. Samuelson

Honors Thesis

The development of organic electrode materials in rechargeable batteries has seen a resurgence in recent decades. This spike in interest is mostly due to the increased investments in renewable energy sources, grid-scale energy storage, and the rapid transition to electric vehicles. Current lithium battery cathode materials typically use some form of lithium metal oxide (specific capacity: 272 mAh g^-1 which has problems with limited capacity, thermal runaway, and an unreliable supply chain. Our research group’s solution involves investigating new lightweight, organic redox groups combined with a conductive polymer backbone to serve as a possible replacement for the cathode in …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Investigation Of The Analytical Utility Of The Inductively Coupled Plasma Mass Spectrometer (Icp-Ms) For The Quantification Of Proteins Via Lanthanide Labeling, Caitlin Elizabeth Dunlap

Undergraduate Honors Thesis Collection

The discovery and ability to provide an absolute concentration of biomarkers in the body can facilitate early diagnoses of diseases. This information can also be used for more accurate and unique treatments for those patients. While major advances in molecular mass spectrometry allows for a sensitive identification of these biomarkers, they are limited to only four orders of magnitude in their dynamic ranges. Due to this, detection and quantitation of low abundant proteins, which tend to make up these vital biomarkers, is very difficult. On the other hand, ICP-MS offers a wider dynamic range (up to 12 orders of magnitude) …

Design, Synthesis, And Analysis Of Paired Coiled-Coil Peptidic Molecular Building Blocks Used For Linearly Controlled Self-Assembly Of Α-Helical Coiled-Coil Heterodimer Peptide Pairs, Jason Distefano

Chemistry Theses

Molecular building blocks are fundamental to biological synthesis and processes and have been utilized in advanced materials, drugs and drug delivery systems, and biotechnology. Proteins have been used as molecular building blocks for the construction of complex, well-ordered structures. Coiled-coil protein domains are essential subunits used for the oligomerization of protein complexes, gene expression, and structural elements of biological materials. The synthesis and assembly of proteins utilizing coiled-coil motifs are of great scientific interest due to their potential applications in disease treatment, biomechanical motors, nanoscale delivery systems, etc. However, assembling protein complexes with specific morphology is still challenging because …

The Synthesis And Purification Methodology Of An Intermolecular Pyrophosphate Sensor: Applications For The Quantitative Polymerase Chain Reaction, Ethan Gevedon

Honors Projects

The optimized synthesis and purification methodology for an intermolecular pyrophosphate sensor scaffold molecule was performed: high performance liquid chromatography afforded the scaffold in excellent purity and yield. The applications of the sensor assembly in the quantitative polymerase chain reaction were discussed, and preliminary results show that

Fast Photochemical Oxidation And Footprinting Of Proteins Via Trifluoromethyl Radical Chemistry, Elaine Morrow

Honors Theses

Fast photochemical oxidation of proteins (FPOP) is a useful tool in proteomics because of the ability for modifications to occur on the scale of microseconds which reduces the modifications to tertiary and quaternary structure allowing for more accurate labeling of the protein. Labels for FPOP are generated from various radicals in our experiments which include hydroxyl radicals and trifluoromethyl radicals. Hydroxyl radicals are easily generated by using an excimer laser (KrF laser, 248 nm) or a UV flash lamp (as a part of the Fox™ System) by the photolysis of hydrogen peroxide. Trifluoromethyl radicals, however, need hydroxyl radicals to be …

X-Ray Crystallographic Analysis Of Quinoline N-Oxide And Isoquinoline N-Oxide With Zinc Halides, Nitrates, Perchlorates., Erin N. Groneck

GS4 Student Scholars Symposium

We have worked to analyze the chemistry between aromatic N-oxides, Quinoline N-oxide and Isoquinoline N-oxide, with zinc halides, nitrates, and perchlorates by X-ray crystallography. These structures were formed by reaction of the aromatic N-oxides with an equivalent of the zinc halide, nitrate, or perchlorate. These N-oxides had been chosen due to being the focus of this study. We will present the crystallographic X-ray structures of the synthesized novel complexes of the N-oxides with either a zinc halide, zinc nitrate, and zinc perchlorate.

Comparing And Contrasting Therapeutic Drugs Vs. Lifestyle Changes That Combattype-Ii Diabetes, Alexander Cline Helmuth

Chemistry & Biochemistry Student Projects

In this thesis, I will be presenting various preventive approaches to combat type-II diabetes. The focus of this paper will be comparing and contrasting therapeutic drug targets such as Metformin and Sulfonylureas that are prescribed for type-II diabetic patients versus taking preventative steps such as making lifestyle changes including weight management, physical activity, and having a balanced diet that prevents onset of type-II diabetes or helps patients manage type-II diabetes. From this paper, one will gain insight on how there are multiple approaches to combat type-II diabetes that are not in the form of the pill.

Microfluidic Paper Analytical Devices, Madison Page

Chemistry & Biochemistry Student Projects

Microfluidic paper analytical devices (µPADs) are small, paper-based matrices similar to Lab-on-a-Chip (LOC). They are capable of semi-quantitative analysis, with applications ranging from medical to environmental to food and beverage testing. Important to improving point-of-care devices (POCs), various techniques have been integrated into µPADs to customize analysis and fit different clinical situations.

The Application Of Biological Processes To Increase Energy Potential In Landfills, Ashlyn Eisenhart

Chemistry & Biochemistry Student Projects

There has been a dramatic increase in the amount of waste that we humans have created. This has been due to population growth, an increase in industrial manufacturing, along with urbanization and modernization.⁸ The number of tons of municipal solid waste entering landfills has increased from 82.5 million tons in 1960 to 146.1 million tons in 2018.¹⁷ However, thanks to recycling, composting, and energy recovery from combustion, the percentage of solid waste going to landfills has dramatically decreased, from around 93.6 to about 65.4 percent.¹⁷

Chemistry Of Toothpaste, Kayla Blanche Kirtley

Chemistry & Biochemistry Student Projects

The chemistry of toothpaste is explained, with a description of the chemical components and their mode of action in the role of toothpaste.

Establishing The Relative Composition Of Functionalized Thiols In Mixed Ligand Gold Nanoparticles By 1h-Nmr Spectroscopy, Matthias Carroll

All Master's Theses

Functionalized gold nanoparticles (AuNPs) are of interest for their optical and electrical properties, specifically the surface plasmon resonance phenomenon and potential applications for medicine and nano-circuitry. In this study, the ligand composition of small (~5 nm diameter) thiol functionalized AuNPs with mixed ligand monolayers was investigated to better understand how the molar feed ratio of ligands used during their synthesis influences the composition of ligands on the particle’s surface. The system under study was a combination of two ω-functionalized thiols, mercapto ethoxy ethoxy ethanol (MEEE) and mercapto pentyl trimethyl ammonium chloride (MPTMA). UV/Visible spectrophotometry, dynamic light scattering, and electron …

Application Of Mass Spectrometry For Characterization Of Plant-Based Phenolics And Alkaloids, Masoumeh Dorrani

Theses and Dissertations--Chemistry

Plant-derived compounds have the potential to produce value-added compounds with a variety of applications. For example, the lignin part of the lignocellulosic biomass, produced in large quantities as waste from the paper and pulp industries, is a rich source of phenolics with potential applications in the renewable energy sector, pharmaceutical, and chemical industries. On the other hand, plant alkaloids are the primary source for developing plant-derived therapeutics. Unfortunately, the recalcitrant nature of plant cell walls, low extraction yields of small secondary metabolites, and the lack of effective analytical methods for a rapid and accurate identification of plant-based compounds and plant’s …

Synthesis Of Functionalized Aromatic Heterocyclic Compounds And Its Applications In Organized Self-Assemblies, Emmanuel T. Fasusi

College of Graduate Studies: Theses & Dissertations

1,2,3-triazoles due to their structure, possess good optical properties and are capable of molecular recognition by their supramolecular capabilities of utilizing weak forces of interaction (such as hydrogen bonding, dipole interaction) in establishing a close association with targets. They are easy to synthesize, which opened the opportunity for a wide pharmaceutical application, mostly as pharmacological scaffolds. However, challenges such as poor water solubility, inefficient drug delivery and increased toxicities due to frequent dosing of drugs are commonly faced which reduces the efficacy of the drugs. It is therefore important to have “delivery vehicles” which could help transport the drugs to …

Chromatography-Mass Spectroscopy Analysis Of Native American Pottery For Maple Syrup Residues, Alexis Wirtz

Honors Program Theses

The research conducted regards whether or not Native Americans understood how to create maple syrup before the influence of Europeans. The analytical technique that was used is gas chromatography-mass spectrometry (GC-MS). This technique assisted in understanding what organic residues resided within the pottery and what those organic residues tell us about Native American history. An analysis of organic residues was performed on the following types of pottery: proof of concept pottery, weathered pottery (an analog of the proof of concept), and Native American pottery. The residues used in analysis were obtained through the usage of different solvent systems - Acetone: …

Characterization Of Landfill Leachate For Enhanced Metal Recovery, Hanna Fulford, Amisha Shah, Inez Hua, Nadezhda Zyaykina, Lori Hoagland, Alejandro Rodriguez Sanchez, Umut Bicim

Discovery Undergraduate Interdisciplinary Research Internship

Landfills contain a trove of valuable materials, such as critical, precious, and rare earth metals, that are integral to the United State’s economy and national security. The leachate that filters through landfills picks up these materials, which allows for the possibility of recovery. For this research, samples will be analyzed from landfills throughout the Midwestern United States to provide a baseline on water quality constituents, elements present, and microbial activity. Preliminary data for this study was acquired by analyzing samples of landfill leachate from a landfill in northern Indiana. pH readings indicate that the leachate is slightly basic. It also …

Rapid Method For Consistency And Concentration Reporting Of Cannabidiol Using 1H-Nmr And Computer-Assisted Chemical Software, Michael A. Fernando

University Honors Theses

An integrated computational method was demonstrated with hemp-derived Cannabidiol for an assessment of its purity and concentration. The sample was structurally verified, high purity, and 2.98 mmol/L in dissolved DMSO. The method presented is a general approach to assessing purity and concentration for any small organic molecule in CMC-Assist.

Don't Sell Them Short, There's More To Bacterial Natural Products Than Antibiotics, Alison Clare Domzalski

Dissertations, Theses, and Capstone Projects

Recent genomic studies of microbiomes have revealed an overwhelming number of biosynthetic genes of unknown function. Most of these “cryptic” biosynthetic genes are not expressed in laboratory monocultures of individual microbes. Thus, there remains tremendous untapped potential for natural products discovery. Here we employ mixed microbial culture (MMC) as a simple yet powerful approach to awaken cryptic biosynthetic gene clusters. Our preliminary studies demonstrated that arrays of metabolites could be induced in MMCs upon environmental cues, such as surface adhesion. Using this system, we have screened, identified, and isolated bioactive bacterial metabolites, which were characterized structurally and biologically. Of the …

Immobilized-Enzyme Reactors Integrated Into Analytical Platforms: Recent Advances And Challenges, Bert Wouters Dr, Sinead Currivan, Noor Abdulhussain, T. Hankemeier, Peter J. Schoenmakers

Articles

Immobilized-enzyme reactors (IMERs) are flow-through devices containing enzymes that are physically confined or localized with retention of their catalytic activities. IMERs can be used repeatedly and continuously and have been applied for (bio)polymer degradation, proteomics, biomarker discovery, inhibitor screening, and detection. Online integration of IMERs with analytical instrumentation, such as high-performance liquid chromatography (HPLC) systems, reduces the time needed for multi-step workflows, reduces the need for sample handling, and enables automation. However, online integration can also be challenging, as reaching its full potential requires complex instrumental setups and experienced users. This review aims to provide an assessment of recent advances …

Functionalized Ionic Liquids For Improved Co2 Hydrogenation Catalysts, Amol Nanduji Jaybhaye

Masters Theses & Specialist Projects

Climate change is one of the biggest problems we are facing today, and anthropogenic greenhouse gases contribute significantly to it. Among greenhouse gasses, carbon dioxide emission is increased drastically and affecting majorly for increasing global temperature, and anything we can do to mitigate carbon dioxide emission will be helpful. A carbon dioxide hydrogenation reaction is a promising technique that can convert carbon dioxide into value-added chemicals, but the reaction rate is slow, and for that, we can use catalysts that will accelerate the reaction rate. Platinum-based nanoparticles have sparked research related to energy and environmental catalysts. Catalytic properties are depending …

Microfabrication And Electrochemical Characterization Of A Novel Su-8 Probe With An Array Of Individually Addressable Electrodes Suitable For Redox Cycling Experiments In Ultra-Small Volumes, Mahsa Lotfi Marchoubeh

Graduate Theses and Dissertations

Redox cycling is an electrochemical technique that utilizes closely spaced generator and collector electrodes to cycle reversible redox species between their oxidative states. With advantages in signal amplification, selectivity of species based on their electrochemical reaction mechanism, and limited or no background subtraction, this technique is well suited for selective detection of important electrochemically active molecules such as dopamine at basal or slowly changing levels.

Miniaturized medical devices have become an area of great interest for measurement of chemicals in limited volumes with low concentrations or in sensitive tissues. A probe on a polymeric SU-8 substrate with suitable dimensions and …

The Development Of Novel Carbohydrate-Based Gelators And Their Applications As Advanced Soft Materials, Joedian Morris

Chemistry & Biochemistry Theses & Dissertations

Low molecular weight gelators (LMWGs) are attractive molecules that have been explored extensively due to their practical applications in many disciplines. These small molecules self-assemble forming solid-like gels via three-dimensional cross-linked networks with the solvent as the key component within the matrix. Carbohydrate-based LMWGs are small molecules that can form solid-like gels in water, organic solvents, and aqueous solutions. They have great potential to be utilized in different applications because carbohydrates are biocompatible and can be made from easily accessible and renewable resources. Designing gelators is still a challenge within the field, even though researchers have developed tools to predict …

Assessing Competitive Reaction Rates In The Nitration Of 2-Methylbiphenyl, Biphenyl, And Toluene To Determine Steric Restriction In Resonance-Stabilized Planarization Of The Carbocation Intermediates, Victor A. Hanson, Tristan Wine, Kevin Bartlett, Joshua Padilla, Alessandro Rizzi

Honors Projects

Electrophilic aromatic substitution (EAS) reactions have long been a fundamental addition to sophomore-level organic chemistry classes, allowing students the opportunity to explore the electron donating and withdrawing effects of electrons contained in the substituents of the aromatic reactant. In this paper we present preliminary findings on the nitration of methylated biphenyls using kinetic and regioselective assessments to analyze steric influences on the planarization of 2-methylbiphenyl after EAS nitration. Our preliminary findings show that nitration favors the methylated phenyl ring of 2-methylbiphenyl, indicating that the steric influence of the methyl group restricts planarization of the carbocation intermediate. Furthermore, a competition nitration …

Photosensitization And Analytical Study On Reactive Oxygen Intermediates: Self-Sorting Surface Radicals And “On-Off” Sensitizer Function Mechanisms, Sarah J. Belh

Dissertations, Theses, and Capstone Projects

This thesis consists of four chapters which are detailed below. Chapter 1 is an introductory chapter, which lays out the background and purpose of the research.

Chapter 2 describes a study of the mobility of alkoxy radicals on a surface by detection of their recombination product. A novel method called symmetrical product recombination (SRP) utilizes an unsymmetrical peroxide that upon sensitized homolysis recombines to a symmetrical product [R'OOR → R'O•↑ + •OR → ROOR]. This allows for self-sorting of the radical to enhance the recombination path to a symmetrical product, which has been used to deduce surface migratory aptitude. SPR …

The Reactivity Of Metal Phosphites: Oxidative Rate Analysis, Jamie Kitchens

Symposium of Student Scholars

Phosphorous compounds are involved in many of the biomolecular processes deemed fundamental for life. DNA, ATP, and phospholipids are a few of the molecules where phosphates can be found in the body. Phosphates are geochemically characterized by their low solubility and poor reactivity. This has led to the investigation of reaction mechanisms that could lead to the formation of the phosphorous compounds found in organisms. The oxidation of phosphite into phosphate could be how phosphates were introduced to life, due to phosphites being more soluble and more reactive than phosphates. We will present the synthesis and oxidation reactivity of four …

Advancing The Preclinical Development Of Secondary Metabolites From Cacospongia Mycofijiensis For The Treatment Of Cancer, Joseph Morris

Natural Sciences and Mathematics | Biological Sciences Master's Theses

The marine sponge Cacospongia mycofijiensis from the Indo-Pacific has proven to be a source of structurally diverse secondary metabolites that are biologically active against a variety of distinct targets. Current interest in the secondary metabolites of C. mycofijiensis largely stems from a) their potent and preferential cytotoxicity for cancer cell lines versus normal cells, making many of them promising leads as cancer therapeutics and b) the novel mechanisms of action responsible for their impressive cytotoxicity. However, limited compound availability has resulted in a paucity of studies aimed at advancing the preclinical development of these secondary metabolites from C. mycofijiensis for …

Cu-Promoted C-H Bond Hydroxylation Inspired By Cu-Dependent Metalloenzymes, Rachel Trammell

Chemistry Theses and Dissertations

From 2003 to 2015, Schӧnecker and Baran proposed a dinuclear Cu/O₂ species in their mechanistic proposal for the hydroxylation of sp³ C-H bonds within their systems (proposed based on yields). Inspired from the site selectivity of this methodology and poor analysis of the mechanism, the first project was inspired to re-examine the sp³ C-H bond hydroxylation by Schrӧnecker and Baran and perform an intensive investigation into understanding how Cu/O₂ interact which led us to propose a new mechanism based on the evidence collected (i.e., LCu^II-hydroperoxide species that undergoes homolytic O-O bond cleavage). From there …

Effects Of Halogen Bonding On 13c Nmr Shifts Of Various Tolan Species, Anthony Lybrand

Honors Theses

Halogen bonding is slowly becoming a more and more useful part of the world of chemistry and is beginning to be incorporated into various aspects of the chemical industry. This study’s purpose is to determine whether or not halogen bonding can cause any effect in the 13C NMR shifts. The specific purpose of this study is to determine whether these chemical shifts change when a Lewis Base is added to the dissolved sample. In order to do this, the tolan species (4-iodotolan and 4-chlorotolan) had to be synthesized. Once synthesized, the tolan species were analyzed via NMR. NMR data indicated …

The Power Of Sulfur: A Study Of An Isothiocyanate Chiral Derivatizing Agent, Thioamide Based Chiral Solvating Agents, And The Geometry Of Sulfonamides, Emily B. Crull

Dissertations

This three-part dissertation is connected by the thread of utilizing sulfur-based functional groups, hence the power of sulfur. The first project was the development of a pentafluorobenzene based isothiocyanate chiral derivatizing agent (CDA), a class of compounds that differentiate enantiomers through covalent bond formation. This project, which was addressed using a combination of synthetic and computational methods and NMR analysis, gave rise to an CDA that was highly selective for amines and computationally predictable. Branching off of that, the second project demonstrated the use of two thioamide chiral solvating agents (CSAs), which had never been reported as a core functional …