Digital Commons Network^™

The Supercam Instrument Suite On The Mars 2020 Rover: Science Objectives And Mast-Unit Description, S. Maurice, R. C. Wiens, P. Bernardi, P. Caïs, S. Robinson, T. Nelson, O. Gasnault, J. -M. Reess, M. Deleuze, F. Rull, J. -A. Manrique, S. Abbaki, R. B. Anderson, Y. André, Stanley M. Angel, G. Arana, T. Battault, P. Beck, K. Benzerara, S. Bernard, Et. Al.

Faculty Publications

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2–7 m, while providing data at sub-mm to mm scales. We report …

Gcn5-Related N-Acetyltransferases (Gnats) With A Catalytic Serine Residue Can Play Ping-Pong Too, Jackson T. Baumgartner, Thahani S. Habeeb Mohammad, Mateusz P. Czub, Karolina A. Majorek, Xhulio Arolli, Cillian Variot, Madison Anonick, Wladek Minor, Miguel A. Ballicora, Daniel P. Becker Ph.D., Misty L. Kuhn

Chemistry: Faculty Publications and Other Works

Enzymes in the Gcn5-related N-acetyltransferase (GNAT) superfamily are widespread and critically involved in multiple cellular processes ranging from antibiotic resistance to histone modification. While acetyl transfer is the most widely catalyzed reaction, recent studies have revealed that these enzymes are also capable of performing succinylation, condensation, decarboxylation, and methylcarbamoylation reactions. The canonical chemical mechanism attributed to GNATs is a general acid/base mechanism; however, mounting evidence has cast doubt on the applicability of this mechanism to all GNATs. This study shows that the Pseudomonas aeruginosa PA3944 enzyme uses a nucleophilic serine residue and a hybrid ping-pong mechanism for catalysis instead …

Synthesis And Characterization Of Regioregular Cross-Conjugated Poly(Thienylene Vinylene)S, Yousef M. Katba Bader

Chemistry and Chemical Biology ETDs

Poly(thienylene vinylene)s (PTVs) is special a class of conjugated polymers (CPs) that show remarkable optoelectronic properties and promising applications. The main reason that hinders their application, is the lack of synthetic methodologies for preparing new derivatives with various functionality. Developing new PTVs with improved structures based on structure-property relationships increases the potential of utilizing this type of polymers in advanced applications. Most available preparation methods lead to regio-random PTVs (ra-PTVs) structures due to the different placement of the sidechain in the polymer backbone, which results in reduced crystallinity. In this study, we developed a novel strategy that produces a series …

Broken-Hearted” Carbon Bowl Via Electron Shuttle Reaction: Energetics And Electron Coupling, Gabrielle A. Leith, Allison M. Rice, Brandon J. Yarbrough, Preecha Kittikhunnatham, Abijai Mathur, Nicholas A. Morris, Megan J. Francis, Anna A. Berseneva, Poonam Dhull, Richard D. Adams, M. Victoria Bobo, Aaron A. Vannucci, Mark D. Smith, Sophya Garashchuk, Natalia B. Shustova

Faculty Publications

Unprecedented one-step CC bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such …

Anion–Anion Interactions In Aerogen-Bonded Complexes. Influence Of Solvent Environment, Anna Grabarz, Mariusz Michalczyk, Wiktor Zierkiewicz, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are applied to the question as to whether a AeX₅− anion (Ae = Kr, Xe) can engage in a stable complex with another anion: F−, Cl−, or CN−. The latter approaches the central Ae atom from above the molecular plane, along its C₅ axis. While the electrostatic repulsion between the two anions prevents their association in the gas phase, immersion of the system in a polar medium allows dimerization to proceed. The aerogen bond is a weak one, with binding energies less than 2 kcal/mol, even in highly polar aqueous solvent. The complexes are …

Determination Of The Traits In Leguminous Crops Under Saline Condition, Tojiddin Kuliev, Karomat Ismailova

Karakalpak Scientific Journal

In this study, the variability and determination of genetic traits for winter legume crop varieties the Vostok-55 (Pisum arvense L) and Mirzachul-1 (Vicia villoza Roth L) were investigated under moderate saline soil condition. Results show that the weight of the bean was marked as variable and highly deterministic, and the height of the plants was the most stable. The selection of plants based on these traits is the most effective way of salinity. Both variety the forage pea Vostok-55 and vetch Mirzachul-1 is highly recommended as a sideration and forage crop in saline lands.

Synthesis Of The Microbial Polysaccharide Gellan From Dairy And Plant-Based Processing Coproducts, Thomas P. West

Faculty Publications

The purpose of this review is to provide both background about the microbial polysaccharide gellan and, more specifically, to examine bacterial gellan synthesis on dairy and plant-based processing coproducts. The anionic heteropolysaccharide gellan is known to be synthesized by Sphingomonas elodea strain ATCC 31461 [1,2]. Although originally classified as Pseudomonas elodea, this strain was reclassified as a species of Sphingomonas [3,4]. Structurally, the water-soluble gum gellan exists as a tetrasaccharide composed of 20% glucuronic acid, 60% glucose and 20% rhamnose [5–7]. The native form of gellan has been shown to contain acetyl and L-glyceryl groups. These substituents need to be …

Ratiometric Near-Infrared Fluorescent Probes Based On Hemicyanine Dyes Bearing Dithioacetal And Formal Residues For Ph Detection In Mitochondria, Yunnan Yan, Yibin Zhang, Shuai Xia, Shulin Wan, Tara Vohs, Marina Tanasova, Rudy Luck, Haiying Lui

Michigan Tech Publications, Part 1

Ratiometric near-infrared fluorescent probes (AH+ and BH+) have been prepared for pH determination in mitochondria by attaching dithioacetal and formal residues onto a hemicyanine dye. The reactive formyl group on probe BH+ allows for retention inside mitochondria as it can react with a protein primary amine residue to form an imine under slightly basic pH 8.0. Probes AH+ and BH+ display ratiometric fluorescent responses to pH changes through the protonation and deprotonaton of a hydroxy group in hemicyanine dyes with experimentally determined pKa values of 6.85 and 6.49, respectively. Calculated pKa values from a variety of theoretical methods indicated that …

Protonation Of Methyl Phenyl Porphyrin Isomers Using Uv Spectroscopy, Mamiko Swanson, Isabel De Angelis, Harsh Chheda, Rushi Patel, Raahil Shah, Shreya Patel, Maria Ballester Ph.D.

Chemistry and Physics Faculty Proceedings, Presentations, Speeches, Lectures

The protonation of methyl phenyl porphyrin isomers was studied through UV vis spectroscopy using trifluoroacetic acid (TFA), a strong organic acid. Protonation was achieved by titration of the porphyrin in toluene and toluene/methanol (90:10). A wavelength shift from the free base Soret to the protonated Soret confirms the formation of the dication. The resulting UV spectra was used to calculate an apparent pKa value of each free base porphyrin isomer. Addition of methanol to the porphyrin solution decreased the average pKa values of the Soret and Q-bands for each porphyrin. This could be an indication of a stabilizing monocation, not …

Comparisons Of Silver Nanoparticle Synthesis Methods By Microwave And Non-Microwave Using Hydrogen Gas As A Reducing Agent, Sofia Erech Hanapin

Honors Theses

Synthesis and characterization of silver nanoparticles are of current interest. This research project describes a simple and rapid synthesis of silver nanoparticles upon reduction of Silver (I) oxide (Ag2O) by molecular hydrogen (H2) at elevated temperature (70 – 100 °C) and a pressure of > 1 atmosphere by heating the aqueous mixture using a common kitchen microwave. This reaction generates naked silver colloids that contain no foreign stabilizers other than metal particles in aqueous media. Its application of an antibacterial effect was monitored by using biological cultures using the Kirby-Bauer Test.

Thermodynamic Analysis Of Pamam Dendrimer Synthesis, Ryutaro Einar Jacobson

Honors Theses

The objective of this research was to determine kinetic and thermodynamic data about the reaction between ethylene diamine and methyl acrylate which is used in the production of PAMAM dendrimers. Establishing a rate law and finding values such as rate constant, activation energy, and Arrhenius coefficient will help in determining the best possible conditions for the reaction. A rate law was established through the method of initial rates, comparing the rates of reactions with different initial concentrations to one another. Additional reactions were run with active cooling to observe the effects on rate and reaction progress, and finally reactions were …

Finding Optimal Opa-Iblc Derivatized Amino Acid Analysis Parameters With Three-Dimensional Fluorometric Scans For Hplc Method Validation, Aaron Jacobs

Honors Theses

Three-dimensional fluorometric scans of OPA-IBLC derivatized glutamic acid and histidine solutions revealed that decreasing concentration maintained maximum λem but produced different maximum λex. In pH 0.4 M sodium borate buffer (pH 10.4), 50 μM derivatized amino acid solutions had maxima around 350- to 450-nm λex-λem where 12.5 μM solutions had maxima around 230- to 450-nm λex- λem. In the lower concentration, the λex peak at 230 nm was about 80% higher than 350 nm. Thus, collecting spectra with 230 nm λex would provide better LOD and LOQ. Results inform HPLC standard concentrations since differential quenching effects may produce non-linear calibration …

Detection Of Gold Cysteine Thiolate Complexes On Gold Nanoparticles With Time-Of-Flight Secondary Ion Mass Spectrometry, Yolanda Hedberg, Jonas Hedberg, Valentin Romanovski, Elena Romanovskaia, Heng-Yong Nie

Chemistry Publications

Gold (Au) nanoparticles (NPs) are widely used in nanomedical applications as a carrier for molecules designed for different functionalities. Previous findings suggested that biological molecules, including amino acids, could contribute to the dissolution of Au NPs in physiological environments and that this phenomenon was size-dependent. We, therefore, investigated the interactions of L-cysteine with 5-nm Au NPs by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). This was achieved by loading Au NPs on a clean aluminum (Al) foil and immersing it in an aqueous solution containing L-cysteine. Upon rinsing off the excessive cysteine molecules, ToF-SIMS confirmed the formation of gold …

Influence Of Monovalent And Divalent Ions In The Conformational Change Of Caspase-Cleaved Par-4 (Cl-Par-4) Tumor Suppressor Protein, Krishna K. Raut, Komala Ponniah, Steven M. Pascal

College of Sciences Posters

Prostate apoptosis response-4 (Par-4) is a pro-apoptotic tumor suppressor protein. We have shown that this 38 kDa full-length Par-4 (Fl-Par-4) protein is predominantly intrinsically disordered in vitro. In vivo, Par-4 is cleaved by caspase-3 at Asp-131 to generate a 24 kDa functionally active cleaved Par-4 (cl-Par-4) fragment. The cl-Par-4 protein inhibits the NF-κB-mediated cell survival pathway and causes selective apoptosis in various tumor cells. Our laboratory is interested in how the disorder-order balance within Fl-Par-4 and cl-Par-4 may be related to the balance between cell survival and cell death. Currently, we are using biophysical techniques such as circular …

Visible Light Generation And Mechanistic Investigation Of High-Valent Metal-Oxo Species Supported By Different Ligands, Seth Ellis Klaine

Masters Theses & Specialist Projects

Numerous transition metal catalysts have been designed as biomimetic model compounds for the active site of metalloenzymes found throughout Nature, most notably cytochrome P450 monooxygenases that carry out the oxidative transformations of organic substrates with near-perfect chemo-, regio-, and stereo-selectivity. The primary active oxidants in catalytic and enzymatic cycles are fleeting high-valent metal-oxo intermediates where the oxo ligand can transfer to an organic substrate in a process known as oxygen atom transfer (OAT).

In the present work, porphyrin-manganese(III), salen-chromium(III), and salenmanganese( III) derivatives were successfully synthesized and spectroscopically characterized using 1H NMR and UV-Vis spectroscopies. A facile photochemical approach was …

Synthesis And Catalytic Oxidation Of Organic Substrates By Light-Harvesting Metalloporphyrins, Christian Alcantar

Masters Theses & Specialist Projects

note: Some notation in this abstract may not appear exactly as formatted in the thesis.

In this work, ruthenium, iron, and manganese light-harvesting metalloporphyrins have been successfully synthesized to serve as biomimetic models of the active site of Cytochrome P450 for the development of a green and efficient oxidation catalyst. The covalent introduction of light-harvesting boron-dipyrrin (BODIPY) fluorophores on the porphyrin macrocycle allows for the absorption of a broader range of visible light in addition to that captured by the porphyrin aromatic system alone. It is expected that this core-antenna system will increase the absorbed light energy and transfer it …

Ph-Sensitive Chitosan Nanoparticles For Salivary Protein Delivery, Yi Zhu, Lina M. Marin, Yizhi Xiao, Elizabeth R. Gillies, Walter L. Siqueira

Chemistry Publications

Salivary proteins such as histatins (HTNs) have demonstrated critical biological functions directly related to tooth homeostasis and prevention of dental caries. However, HTNs are susceptible to the high proteolytic activities in the oral environment. Therefore, pH-sensitive chitosan nanoparti-cles (CNs) have been proposed as potential carriers to protect proteins from enzymatic degradation at physiological salivary pH. Four different types of chitosan polymers were investigated and the optimal formulation had good batch to batch reproducibility, with an average hydrodynamic diame-ter of 144 ± 6 nm, a polydispersity index of 0.15 ± 0.04, and a zeta potential of 18 ± 4 mV at …

College Of Natural Sciences Newsletter, April 2021, College Of Natural Sciences

College of Natural Sciences Newsletters and Reports

Volume 2, Issue 4

Page 1 Dean's Message
Page 2 & 3 Awards & Recognition
Page 4 Student Spotlight: Allsion Bjornstad
Page 5 Research Spotlight: Dr. Vondruska & Students
Page 6 Department Head Interviews
Page 7 Media Coverage of CNS
Page 8 Open PRAIRIE Data
Page 9 Student Club Spotlight: BMGSA
Page 10 Then & Now: Urban Geography

Raman Spectroscopy Using A Monolithic Spatial Heterodyne Raman Spectrometer For Planetary Exploration, Abigail M. Waldron

Theses and Dissertations

Raman spectroscopy is a vibrational technique that provides detailed molecular and structural information for organic and inorganic molecules and minerals, and is uniquely suited for spacecraft applications, in the search for chemical indicators of life. This is why NASA sent two Raman spectrometers to Mars on the Mars 2020 Perseverance rover, as part of the SuperCam and SHERLOC instruments. The Raman spectrometers on Perseverance are conventional dispersive instruments that have been engineered to survive the harsh conditions of spaceflight. Future missions could benefit from smaller, more robust designs, especially missions to the Jovian planets, Jupiter and Saturn, their moons, asteroids …

Characterization Of Uranium, Lead, And Rare Earth Element Pollution In Natural Soils And Sediments, Hope Rasmussen

Civil and Environmental Engineering Theses and Dissertations

Heavy metals in the environment add to the global burden of pollution, negatively impacting public health and ecosystem resilience. This study included projects regarding uranium (U), lead (Pb), and rare earth elements (REE) in natural samples, due to their known toxicity, ubiquity, and relevance in context to recent pollution trends. The first project focused on testing the potential of using a hydroxyapatite product as a remediation solution for U-contaminated groundwater and soil at an EPA Superfund site. The results showed that the U was sequestered in a highly crystalline mineral form within the solids, guiding the EPA to specify the …

Biophysical Characterization Of The Par-4 Tumor Suppressor: Evidence Of Structure Outside The Coiled Coil Domain And Interactions With Platinum Chemotherapeutics, Andrea Megan Clark

Chemistry & Biochemistry Theses & Dissertations

Prostate apoptosis response-4 (Par-4) is an apoptosis-inducing tumor suppressor protein. Full-length Par-4 has previously been shown to be a predominantly intrinsically disordered protein (IDP) under neutral conditions, with significant regular secondary structure evident only within the C-terminal coiled coil domain. However, IDPs can gain ordered structure through the process of induced folding, which often occurs under non-neutral conditions. Previous work has shown that the Par-4 leucine zipper, which is a subset of the C-terminal coiled coil domain, is disordered under neutral conditions, but forms a dimeric coiled coil at acidic pH. Increase in ionic strength was also shown to increase …

Evaluating The Role Of The Stringent Response Mechanism In Clostridioides Difficile Survival And Pathogenesis, Astha Pokhrel

Chemistry & Biochemistry Theses & Dissertations

The human pathogen Clostridioides difficile is increasingly tolerant of multiple antibiotics and causes infections with a high rate of recurrence, creating an urgent need for new preventive and therapeutic strategies. The stringent response, a universal bacterial response to extracellular stresses, governs antibiotic survival and pathogenesis in diverse organisms but has not previously been characterized in C. difficile. This dissertation explores the ability of C. difficile to mount the stringent response. The bacteria encode a full-length, canonical bifunctional Rel/Spo Homolog or RSH enzyme. C. difficile RSH is incapable of utilizing GTP as a substrate but readily synthesizes putative 5’-pGpp-3’ alarmones. …

Computational And Experimental Investigation Into The Determinants Of Protein Structure, Folding, And Stability In The Β-Grasp Superfamily, John T. Bedford Ii

Chemistry & Biochemistry Theses & Dissertations

Elucidating the mechanisms of protein folding and unfolding is one of the greatest scientific challenges in basic science. The overarching goal is to predict three-dimensional structures from their amino acid sequences. Understanding the determinants of protein folding and stability can be facilitated through the study of evolutionarily related but diverse proteins. Insights can also be gained through the study of proteins from extremophiles that may more closely resemble the primordial proteins. In this doctoral research, three aims were accomplished to characterize the structure, folding and unfolding behavior within the β-grasp superfamily. We propose that the determinants of structure, stability, and …

Biophysical And Structural Studies On Telomeric G-Quadruplexes From Tetrahymena Thermophila, Dana Beseiso , '21

Senior Theses, Projects, and Awards

G-quadruplexes (GQs) are non-canonical DNA structures composed of stacks of stabilized guanine tetrads (G-tetrads). GQs are highly diverse structures that can be categorized by their strand directionality, number of G-tetrads, and loop types among other parameters. Due to their high guanine content, GQs are expected to fold in regions such as telomers or oncogene promoters. They are thus firmly established as biologically viable targets for the development of anticancer therapeutics. In order to harvest GQs’ therapeutic potential, extensive structural studies are required to elucidate the structures’ diverse topologies alone and in complex with selective ligands. Towards this goal, this thesis …

Use Of Anthraquinone Derivatives And Methods Of Efficient Syntheses, Alex Crespo

Senior Honors Theses

While the bromination of aromatic compounds is a well-researched topic, AQ and hydroxy substituted AQ derivatives, with two carbonyl groups acting as strong deactivators for electrophilic substitution, are notoriously difficult to brominate.¹¹ Although there are well defined ways to brominate an AQ or hydroxy substituted AQ dating back to 1921,¹² in order to synthesize more complex AQ derivatives, a method for halogenating AQ derivatives already bonded to more complicated or unstable functional groups is needed in order for the compound to carry out desirable activities. This represents an area of great need in research. The purpose of this …

Hydrogen-Bonded Clusters: A Study Of The Elusive Anisole-Ammonia And Anisole-Water 1:1 Complexes, John Lawrence Loman

Master's Theses (2009 -)

The hydrogen bond is one of the most important and versatile interactions found in most subsets of chemistry and biology. This interaction is responsible for reactions and characteristic properties of the systems in thereof. This interaction is just one of several available non-covalent interactions that can occur and over the past several decades of molecular spectroscopy studies, the definition of the hydrogen bond has become broader compared to the “classic” definition. To accurately study the hydrogen-bonding in these systems can be quite challenging due to the size and complexity of the molecules involved, as well as the other interactions that …

Molecular Basis Of Xenobiotic Metabolism And Resistance In Tetranychus Urticae, Leily Daneshian

Theses and Dissertations

Invasive pest species are a major cause of crop loss around the world and adversely affect the agricultural industry. We are focusing on Tetranychus urticae (two-spotted spider mite; TSSM), which is a polyphagous pest that targets more than 1100 plant species. The TSSM alone causes a loss of roughly $1.6 billion per year globally due to acaricide resistance. It is developing resistance to most acaricides due to rapid growth and reproduction. Therefore, new acaricides are needed to combat TSSM resistance and infestation [1]. To address this problem, four enzymes of TSSM, intradiol ring cleavage dioxygenases, a glutathione S-transferase, a β …

Fabrication Of Chemically-Functionalized 3dprinted Porous Scaffolds For Biomedical Applications, Eiman Hamed Alblooshi

Theses

Hard tissues, such as bone and teeth, are natural composites of collagen nanofibers that are reinforced by inorganic calcium phosphate Nano crystallites, in the form of nanocomposites. The interlocking between these components in hard tissues explains their unique characteristics. Bone is mainly classified into two major types; compact and cancellous depending on the extent of porosity. Fractures in the compact bone can be treated using bone fixation implants, such as rods, screws, and plates, or can be totally replaced by bone implants if complete substitution is required. Cancellous bone, on the other hand, is highly porous and its substitution with …

Levels Of Testosterone Esters In Camel Hair, Aysha Khalid Alraeesi

Theses

Doping and steroid use represent a serious threat to animal health and can even lead to their untimely and painful death. However, doping is an acute problem in today's animal racing world, particularly in camel racing. Testosterone and its ten esters (benzoate, valerate, isocaproate, hexahydrobenzoate, decanoate, undecanoate, laurate, enanthate, cypionate, and caproate) are of utmost importance because when they are administered to animals it is difficult to measure them efficiently. The levels of testosterone and its esters in camels and other animals are typically determined using urine and blood tests. The aim of this study was to develop and validate …

Reversing The Regioselectivity Of Indole Addition To Cyclic Unsymmetrical Oxyallyl Cations: Construction Of Diaryl Quaternary Centers, Thomas Davis Curry Ii

Honors Capstones

No abstract provided.