Physical Sciences and Mathematics Commons^™

Piecing It Together: Analysis And Treatment Of A Painted Silk Flag, Katya Zinsli

Art Conservation Master's Projects

Painted flags and banners lie at the intersection of painting and textile conservation. The 37^th New York Volunteer Infantry Regiment’s battle flag from the Civil War presented challenges and advantages of bridging the two disciplines by providing an opportunity for study and experimentation for a graduate student from the Patricia H. and Richard E. Garman Art Conservation Department at SUNY Buffalo State College. This study was conducted to better understand the materials and degradation products present in a painted Civil War flag, which then informed the subsequent treatment of said flag. By characterizing the materials, the severe damage in …

Gas Phase C-H And C-C Bond Activation By Ternary Metal Complexes, Kevin Parker

Graduate Research Theses & Dissertations

The activation of relatively inert C-H bonds has remained a challenge in organic chemistry for over a century. Metal catalysts have been deployed to overcome the labile reactivity of these bonds and through gas-phase studies, detailed mechanisms can be elucidated for this important class of chemistry. The powerful combination of ion-molecule reactions, collisional activation of ions, and density functional theory calculations allows for structural elucidation, intermediate determination, and as shown throughout this work, a complete picture of catalytic processes. Modified linear ion-trap mass spectrometers were used to trap and generate reactive intermediates of the form [(L)(M)(X)]+ (L= auxiliary ligand; M= …

Stoichiometry Question Sets, Myungshim Kang

Open Educational Resources

This is a question pool for general chemistry. This consists of question sets, each of which contains variations of questions for topics, including the mole, molar mass, balancing chemical equations, and quantitative relationships in chemical reactions.

S-Glutathionylation Of Chicken Breast Extract, Isabella Fransisco

Senior Honors Projects

The purpose of this experiment was to analyze chicken breast fractions through affinity chromatography for protein modifications by glutathione disulfide (GSSG). The fractions were incubated with different concentrations of GSSG to determine potential modified proteins. There were proteins modified with GSSG at 33 kDa in fraction I, at 16 kDa, 36 kDa, and 44kDa in fraction II, and at 36 kDa in fraction III for the concentration dependent reactions. In the time dependent reaction for fraction II, there were two major proteins at 65 kDa and 176 kDa that were modified by GSSG. Lastly, we suggest that the major modified …

Cooperative Allosterism In Avidin And Streptavidin Upon Biotin Binding As Observed By Changes In Intrinsic Fluorescence, Alycia Murphy

Senior Honors Projects

Avidin is a homotetrameric protein known for its high binding affinity and specificity for biotin which gives it great functionality in many biotech applications. Prior research on the bacterial analog, streptavidin found cooperative allosterism exhibited in the binding process. This research was aimed at investigating whether this same cooperative allosterism accompanies the binding of biotin to avidin. This work measured intrinsic tryptophan fluorescence as biotin was titrated into avidin. A blueshift in the wavelength of maximum fluorescence as well as quenching of the overall fluorescence intensity, similar to the streptavidin was observed. The saturation point for 335 nm emission (tryptophans …

First Homoleptic Rare Rarth Metal Complexes With Doubly-Reduced Dibenzocyclooctatetraene, James C. Mahoney

Legacy Theses & Dissertations (2009 - 2024)

A set of novel complexes of rare earth elements, M(III) = Y, La, Gd, Tb, and Dy, with the doubly-reduced dibenzo[a,e]cyclooctatetraene (DBCOT) anion has been synthesized and crystallographically characterized for the first time. Preparation of new complexes has been accomplished through the ligand-metathesis reaction of M(III) triiodides with K2(DBCOT) in THF at ambient conditions. Subsequent crystallization via slow solvent evaporation afforded single crystals of good quality. X-ray diffraction technique confirmed that all complexes are isomorphous and conform to the [M(DBCOT)(THF)4][M(DBCOT)2] composition. In their crystal structures, the monoanionic double-decker sandwiches, [M(DBCOT)2], weakly interact with the cationic counterparts, [M(DBCOT)(THF)4]+. In both parts, …

Emissions, Shawn Urbanski, Susan O'Neill, Amara L. Holder, Sarah Green, Rick L. Graw

Michigan Tech Publications

This chapter assesses the current state of the science regarding the composition, intensity, and drivers of wildland fire emissions in the USA and Canada. Globally and in the USA wildland fires are a major source of gases and aerosols which have significant air quality impacts and climate interactions. Wildland fire smoke can trigger severe pollution episodes with substantial effects on public health. Fire emissions can degrade air quality at considerable distances downwind, hampering efforts by air regulators to meet air standards. Fires are a major global source of aerosols which affect the climate system by absorbing and scattering radiation and …

Electrochemical Gelation Of Metal Chalcogenide Quantum Dots, Chathuranga Chinthana Hewa Rahinduwage

Wayne State University Dissertations

Quantum dots (QDs) are attractive because of their unique size-dependent optical and electronic properties and high surface area. They are tested in research for diverse applications, including energy conversion, catalysis, and sensing. Assembling QDs into functional solid-state devices while preserving their attractive properties is a challenge. Methods currently under the research are not effective in directly fabricating QDs onto devices, making large area assemblies, maintaining the high surface area by forming 3D porous structures, and conducting electricity for applications such as sensing. QD gels are an example of QD assemblies that consist of a 3D porous interconnected QD network. They …

Phenanthroline-Catalyzed 1,2-Cis Glycosylation: Scope And Mechanism, Jiayi Li

Wayne State University Dissertations

Phenanthroline, a rigid and planar organic compound with two fused pyridine rings, has been used as a powerful ligand for metals and a binding agent for DNA/RNA. We recently discovered that phenanthroline could be used as a nucleophilic catalyst to access high yielding and diastereoselective α-1,2-cis glycosides through the coupling of hydroxyl acceptors with α-glycosyl bromide donors. The utility of the phenanthroline catalysis is expanded to sterically hindered hydroxyl nucleophiles and chemoselective coupling of an alkyl hydroxyl group in the presence of a free C1-hemiacetal functionality. In addition, the phenanthroline-based catalyst has a pronounced effect on site-selective couplings of triol …

Electrochemistry Of Bubbles: Developing New Sensors, Promoting Gas Evolution Reactions, And Extraction Of Rare Earth Elements, Ruchiranga R. Ranaweera

Wayne State University Dissertations

This dissertation presents new analytical, electrocatalysis, and separation strategies that utilize bubble behaviors in different electrochemical systems. The first part of this dissertation focuses on the method development for PFAS preconcentration and detection. First, we present the bubble-nucleation-based electrochemical method for the selective and sensitive detection of surfactants. Our method utilizes the high surface activity of surfactant analytes to affect the electrochemical bubble nucleation and then transduces the change in nucleation condition to an electrochemical signal for determining the surfactant concentration. Using this method, we demonstrate the quantitation of perfluorinated surfactants in water, a group of emerging environmental contaminants, with …

Micro-Rna And Proteomic Profiles Of Plasma-Derived Exosomes From Irradiated Mice Reveal Molecular Changes Preventing Apoptosis In Neonatal Cerebellum, Simonetta Pazzaglia, Barbara Tanno, Ilaria De Stefano, Paola Giardullo, Simona Leonardi, Caterina Merla, Gabriele Babini, Seda Tuncay Cagatay, Ammar Mayah, Munira Kadhim, Fiona Lyng, Christine Von Toerne, Zohaib N. Khan, Prabal Subedi, Soile Tapio, Anna Saran, Mariateresa Mancuso

Articles

Cell communication via exosomes is capable of influencing cell fate in stress situations such as exposure to ionizing radiation. In vitro and in vivo studies have shown that exosomes might play a role in out-of-target radiation effects by carrying molecular signaling mediators of radiation damage, as well as opposite protective functions resulting in resistance to radiotherapy. However, a global understanding of exosomes and their radiation-induced regulation, especially within the context of an intact mammalian organism, has been lacking. In this in vivo study, we demonstrate that, compared to sham-irradiated (SI) mice, a distinct pattern of proteins and miRNAs is found …

A Study Of The Analysis Of Hemp-Derived Oil Products: Development Of A Method For The Analysis Of Phytocannabinoids In Medicinal Products, Erin Johnson

Theses and Dissertations--Pharmacology and Nutritional Sciences

Human interactions with cannabis have a history spanning millennia as a source of fiber, food, and medicine. The plant came across Asia, Europe, and Africa with the movements of people and travelers eventually coming to the Americas with European explorers. In colonizing North America, cannabis fiber was key to the production of canvas and ropes for ships. Although fiber was the driver for cannabis production in the United States, medicinal uses were prevalent and propelled the eventual regulations. The Pure Food and Drug Act of 1906 mandated accurate labeling on drugs such as cannabis followed by the Marihuana Tax Act …

College Of Natural Sciences Newsletter, January 2022, College Of Natural Sciences

College of Natural Sciences Newsletters and Reports

Volume 3, Issue 1

Page 1 Dean's Message
Page 2 Awards & Recognition
Page 3 Outreach in Harrisburg, SD
Page 4 Geography Alumni Named Among 'Highly Cited Researchers', 53rd Annual Geography Convention
Page 5 Geography Convention Speakers, Brookings/SDSU Day
Page 6 Media Coverage of Natural Sciences
Page 7 Open PRAIRIE Data
Page 8 Fall 2021 Dean's List
Page 9 Fall 2021 Dean's List, cont.

Biomedical Applications Of Lanthanide Nanomaterials, For Imaging, Sensing And Therapy, Qize Zhang, Stephen O'Brien, Jan Grimm

Publications and Research

The application of nanomaterials made of rare earth elements within biomedical sciences continues to make significant progress. The rare earth elements, also called the lanthanides, play an essential role in modern life through materials and electronics. As we learn more about their utility, function, and underlying physics, we can contemplate extending their applications to biomedicine. This particularly applies to diagnosis and radiation therapy due to their relatively unique features, such as an ultra-wide Stokes shift in the luminescence, variable magnetism and potentially tunable properties, due to the library of lanthanides available and their multivalent oxidation state chemistry. The ability to …

Synthesis And Modeling Of Manganese Ferrite Nanoparticles For Magnetic Hyperthermia Applications, Margaret E. Thornton

Theses and Dissertations

Biologically targeted magnetic hyperthermia (MH) is a promising cancer therapeutic that is both non-invasive and has the potential to serve as a single-modality cancer treatment. MH operates through the elevation of temperatures between 40-43 °C to induce apoptosis in malignant tumor cells, while the small size of the magnetic nanoparticles preserves the healthy surrounding tissue. At present, MH is limited by low heating efficiency and heterogenous outcomes, and treatment requires direct-injection of the nanoparticles, excluding deep-tissue and metastatic tumors from the therapy. The most popular candidates for MH are the spinel ferrites iron oxide and manganese iron oxide (MFO). These …

Progress Towards Next Generation Modulators Of Ctbp's Oncogenic Effects, Jacqueline L. West

Theses and Dissertations

Human C-terminal binding proteins (CtBP1 and CtBP2) are transcriptional coregulators of multiple genes in the human genome, including tumor suppressor genes (e.g., Bik, PTEN, BRCA1, and E-cadherin) as well as oncogenes (e.g. MDR1 and Tiam1). Both homologues of CtBP are overexpressed in many types of cancer, including breast cancer (92%), ovarian cancer (83%), colorectal cancer (64%), hepatocellular carcinoma (60%), gastric cancer, prostate cancer, and pancreatic adenocarcinoma. Further, expression levels of CtBP correlate with worse prognostic outcomes and more aggressive tumor features because it promotes proliferation, epithelial-mesenchymal transition, and cancer stem cell self-renewal activity.

Our laboratory has identified a lead inhibitor …

Molten Salt Technologies For Advanced Nuclear Fuel Cycles And Molten Salt Reactors, Dimitris Killinger

Theses and Dissertations

This dissertation provides five topics—an assessment of different monitoring and analytical techniques often cited in the literature for molten salt systems and designs for nuclear engineering applications. First, we explored commonly used materials for quasi-reference electrodes in molten chloride salts. Second, the limitations of the electrochemical analysis known as cyclic voltammetry due to the concentration of uranium(III) present were being investigated. Third, we provided an experimental assessment on the development of a spectroelectrochemical cell for interrogating various spectroelectrochemical techniques, namely chronoabsorptometry and chronofluorometry, and their limitations due to the presence of uranium(III) ions. Fourth, a study on the corrosion resistance …

Behavioral Screening And Chiral Bioanalysis Of Emerging Stimulant-Type Drugs In Rats, Tyson R. Baird

Theses and Dissertations

The epidemic of drug use in the United States and elsewhere in the world has resulted in tragic loss of life and substantial economic costs. Novel psychoactive substances (NPS) are one of the contributors to this problem, and the lack of information about many of these drugs compounds their risk. This dissertation proposes a strategy to use intracranial self-stimulation (ICSS) as a behavioral screening tool to assess emerging drugs of abuse for their abuse potential in order to generate a proactive threat assessment. A series of stimulant-type drugs including methcathinone, α-pyrrolidinohexanophenone (α-PHP), cocaine, and the phenyltropane analogs of cocaine WIN35428 …

Asymmetric Cuh-Catalyzed Reductive Coupling Of Alleneamides With Carbonyl Electrophiles And The Mechanistic Investigation Into The Suzuki-Miyaura Cross-Couplings Of Electron-Deficient Systems, Samantha L. Gargaro

Theses and Dissertations

Most natural products and other biologically active small molecules contain multiple stereogenic heteroatoms throughout their carbon scaffold. As a result, methods to install these multi-heteroatom functionalities efficiently are highly desirable. Reductive coupling reactions have been studied extensively, and reductive allylation has been a key method for generating chiral secondary and tertiary allylic alcohols. This work focuses on utilizing naturally abundant and inexpensive Cu for the asymmetric reductive coupling of alleneamides with carbonyl electrophiles to access highly functionalized multi-heteroatom scaffolds that are difficult to produce via traditional methods. Described herein are methods for these asymmetric reductive coupling reactions. Chapter 1 describes …

Analysis Of Blue Fountain Pen Ink By Uv-Vis Spectroscopy, Atr-Ftir Spectroscopy, And Thin Layer Chromatography Enhanced With Rgb Spot Evaluation To Construct A Database For Comparison And Identification., Elliot D. Quinteros

Dissertations and Theses

Pen ink can be a crucial piece of physical evidence in the area of Forensic Science. For example, evidence such as notes, letters, printed documents, checks, currency, ransom notes, and books may contain ink. Analysis of ink is typically done for identification or differentiation purposes. To improve existing methods, it was proposed to create a database with many samples and experimental information. The methods used and evaluated were thin-layer chromatography (TLC) enhanced with RGB spot evaluation, UV-Vis spectroscopy, and ATR-FTIR spectroscopy. All three methods were used to analyze 89 fountain pen ink samples. All three methods were able to discriminate …

Analyzing The Free Energy Of Ions Sampling A Voltage Gated Sodium Ion Channel, Isabel Varghese

Honors Theses

Voltage gated sodium ion channels are implicated in cardiac diseases, seizures, etc., and they play a role in maintaining ionic homeostasis in cells. Computational studies use prokaryotic model because they are simpler but function similarly to human voltage gated sodium ion channels. This study uses molecular dynamics (MD) to study three specific questions regarding voltage gated sodium ion channels of Magnetococcus marinus. The first question in this study is how the free energy of sodium diffusion compares to that of calcium ion diffusion. We were not able to find any physically significant information due to poor sampling and a lack …

Characterization Of Functionalized Carbon Nanotubes And Polystyrene/Cnt Composites Prepared With Microwave-Induced Polymerization, Allen Hulette

Electronic Theses and Dissertations

The use of carbon nanotubes in polymer composites can increase the mechanical properties of the resulting product. Carbon nanotubes are known to have chemical interactions that make them attracted to one another and fall out of solution. To reduce this agglomeration and disperse the mechanical properties throughout the composite, functional groups are covalently added to the carbon nanotubes. Another known property of carbon nanotubes is their ability to absorb microwaves and convert it into other forms of energy. This research investigates the effects of carbon nanotube absorption of microwaves and initiation of styrene monomer polymerization. Grignard reactions are used to …

Analysis Of Microdroplets And Microorganisms By Single Entity Electrochemistry, Junaid U. Ahmed

Theses and Dissertations

Single Entity Electrochemistry (SEE) is an emerging electrochemical technique that has been used to characterize discrete entities by measuring the change in current or potential during individual stochastic events (collision or adsorption) of an entity with an ultramicroelectrode (UME) of similar dimensions. The shape and magnitude of the SEE signal depend on the underlying mechanism of interaction with the UME surface. There is a critical need for quantitative models that correlate the SEE signal with properties of the entity-UME system, including effects of acquisition instrumentation, to prevent misinterpretation of data.

This research focused on integrated experiments and simulations to quantify …

Elucidating Mechanisms For S-Nitrosoglutathione Reductase Activity And Control In Plants Using O-Aminobenzoyl-S-Nitrosoglutathione And A Novel Photo-Sensitive Probe, Leslie Ventimiglia

Electronic Theses and Dissertations

S-nitrosoglutathione reductase, (GSNOR) is widely accepted as the master regulator of stress through NO signaling and protein S-nitrosylation. GSNOR mediates stress response through the catalysis of its principal substrate S-nitrosoglutathione (GSNO). The instigation of various stressors in plants cause observable changes in plant phenotype, which are associated with changes in GSNOR activity. There are no current methods for measuring GSNOR activity directly in living plants. In this paper, a previously developed fluorogenic pseudo-substrate for human GSNOR, OAbz-GSNO, was applied to the Solanum lycopersicum plant model. OAbz-GSNO was identified as a promising novel pseudo- substrate to study changes …

Fluorescent Labelling Of Ribosomal Rna In Live Mammalian Cells, Amir Agharezaee

Legacy Theses & Dissertations (2009 - 2024)

This thesis describes a bio-orthogonal chemistry-based approach for new methods of fluorescence labelling of RNA in live HeLa cells via an IEDDA reaction of TCO with tetrazine. The key step of the approach is synthesis of two nucleobase analogues which were modified with TCO and a masked 5′-phosphate group using aryl phosphonamidite chemistry. Synthesis of tubercidin and uridine analogues were considered in this investigation for incorporation into RNA in live HeLa cells. Synthetic approach was successful at installing the handle containing TCO to tubercidin and uridine to make compounds 12 and 21 respectively (the synthesis of both of which are …

Discrimination Between Human And Non-Human Blood Using Raman Spectroscopy And A Self-Reference Algorithm For Forensic Purposes : Method Expansion And Validation, Harrison Dickler

Legacy Theses & Dissertations (2009 - 2024)

Determining whether the origin of a bloodstain is human or non-human is an important capability of a forensic investigation. In their pioneering work, Bian et al. (Journal of biomedical optics, 2017) introduced a self-reference peak algorithm for the analysis of bloodstain Raman spectra and demonstrated a great potential of this approach for differentiating human and nonhuman blood. However, this work only used three non-human species in the creation of their model. This study investigates the capability of a self-referencing peak algorithm to discriminate between human and 18 non-human species based on the Raman spectra of blood samples. The intensity ratios …

Methodology Studies For Dearomatized Dimer And Beta-Lactone-Mediated Native Chemical Ligation In Organic Synthesis, Xinhao Fan

Legacy Theses & Dissertations (2009 - 2024)

Chapter 1: Dimers of naphthalenol derivatives were synthesized by photocatalysis, cobalt(II) acetylacetonate. Several functional groups were tolerant of its skeleton. This novel dimer was connected through a reversible sigma bond. Its reversibility was confirmed by chiral HPLC and 1H-NMR experiments. Through EPR and Stern-Volmer quenching experiments, we proposed the reaction mechanism. The reversibility property can be potentially beneficial in polymers, self-healing, and memory materials.Chapter 2: We report an epimerization-free native chemical ligation reaction by β-lactone-mediated peptides. This approach can achieve Thr-Xaa efficiently and rapidly. Besides, it has a broad side-chain tolerance. Through the competition reaction experiment, it was demonstrated that …

Synthesis Of Oligonucleotides Containing Unnatural Backbone And Regulation Of Crispr Activity Using Inverse Electron Demand Diels-Alder Chemistry, Alyssa Hoy

Legacy Theses & Dissertations (2009 - 2024)

This thesis describes the synthesis of an oligonucleotide containing an unnatural neutralbackbone. The backbone was constructed using bio-orthogonal inverse electron demand Diels- Alder chemistry between trans-cyclooctene (TCO) and tetrazine (Tz). A TCO phosphoramidite was synthesized and attached to solid support for strand propagation. Uridine monomers containing either bis-TCO or bis-Tz were also synthesized. The oligonucleotide strand was formed by sequential ligation of the bis-Tz and bis-TCO monomers. The oligonucleotide was analyzed using mass spectrometry. This thesis also describes the synthesis of sgRNAs containing non-canonical nucleobases, m1A, m6A, s2U and s4U using the ‘split-and-click’ methodology. The synthetic sgRNAs were assembled using …

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

Legacy Theses & Dissertations (2009 - 2024)

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

Uio-Type Metal-Organic Framework Derivatives As Sorbents For The Detection Of Gas-Phase Explosives, Matthew Ryan Sherrill

Legacy Theses & Dissertations (2009 - 2024)

The detection of energetic compounds – better known to the public as explosives – has is an important cornerstone of counterterrorism and homeland security . While significant advances have been achieved for the detection of trace explosives in various matrices such as soil, wastewater, and clothing, the detection of explosives in the gas phase remains challenging due to their infamously low vapor pressures. In this thesis, we leverage the high sensitivity of direct analysis in real-time mass spectrometry (DART-MS) and the microporosity of metal-organic frameworks (MOFs) to adsorb and therefore concentrate explosives from the vapor phase and subsequently detect them …