Chemistry Commons^™

Biochemical And Chemical Methods Of Key Derivation For Cryptographic Ciphers, Leif K. Mcgoldrick

Legacy Theses & Dissertations (2009 - 2024)

Cryptography is a vital component of digital communication and digital data in general. The use of cryptography is necessary to support the veracity of data and to protect it from outside parties with malicious intent. Cryptography focuses on two main facets that are vital for this goal: data encryption and user authentication. Encryption protects the data by transforming it into an encrypted text that would not allow someone access without having or breaking the encryption method that was used to make it. User authentication is a multiple part process that allows for one to be able to identify oneself to …

Utilizing Raman Spectroscopy And Chemometrics For Novel Medical Diagnostic Purposes, Nicole M. Ralbovsky

Legacy Theses & Dissertations (2009 - 2024)

Many problems exist within the myriad of currently employed diagnostic techniques. Further, an incredibly wide variety of procedures are used to identify an even greater number of diseases which exist in the world. There is a definite unmet clinical need to improve the diagnostic capabilities of these methods, including improving test sensitivity and specificity, objectivity and definitiveness, and reducing cost and how invasive a test is, with an interest in replacing multiple diagnostic methods with one powerful tool. That is, the development of a singular technique which can accurately and objectively diagnose a wide variety of diseases in a cost-effective …

Displacement Using Fentanyl And Bullet Analysis Using Atomic Absorption Spectroscopy, Henry Hance

Legacy Theses & Dissertations (2009 - 2024)

Opioids are substances that bind to opioid receptors in the central nervous system and can be endogenous, naturally occurring opium alkaloids derived from opium poppy or semi-synthetic and or synthetic compounds.1 Fentanyl is a synthetic opioid that has flooded the US market in the last decade. Synthetic opioid deaths increased by 100% from 2015 to 2016.2 The synthetic opioid is still used to treat severe chronic pain and during surgeries as an anesthetic, but has flooded the black market through illegal means. Fentanyl is prescribed in the forms of patches and lozenges, but can be abused and illegal sold in …

Nmr Based Studies Of Interactions Between Ribosomes And Glycolytic Enzymes, Devin Bryan Busch

Legacy Theses & Dissertations (2009 - 2024)

Recent research has been performed to better understand what implications ribosome-mediated quinary interactions have on cellular growth. These studies demonstrated that ribosomal binding to enzymes, and their cofactors, can cause significant changes in their enzymatic activity leading to a proposal that ribosome surfaces play a greater regulatory in cellular growth than thought of in the past. To widen the scope of investigations performed on these ribosomal-mediated quinary interactions, the regulatory enzymes associated in glycolysis (hexokinase, phosphofructokinase, and pyruvate kinase) were titrated into a solution of 70S E. coli ribosome and analyzed via 1H-15N-HSQC NMR. The perturbations of the peaks associated …

Investigation Of Underpotential Deposition Of Copper At Heated Gold Loop Screen-Printed Electrodes In A Variety Of Water Samples, Eun-Ju Lee

Legacy Theses & Dissertations (2009 - 2024)

To study the underpotential deposition (UPD) of copper, three different types of water samples (TraceSelect® Ultra-pure water, Indian pond water at University at Albany and tap water) are used at a heated gold loop screen-printed electrode (GLE), which is a new type of heated working electrode for voltammetry measurements that is able to directly detect the copper content in the water samples. The anodic stripping analysis of copper is performed with these gold loop electrodes at room temperature of 25 °C and electrode temperature of 80 °C at two different deposition potentials, -0.20 V and +0.10 V. Furthermore, the concentration …

Optimal Excitation Wavelength For Raman Spectroscopic Analysis Of Organic Gunshot Residue Evidence, Ashley Hull

Legacy Theses & Dissertations (2009 - 2024)

Gunshot residue (GSR) is a type of trace evidence that can often be recovered at violent crime scenes. There are two major types of GSR, organic gunshot residue (OGSR), and inorganic gunshot residue (IGSR). Traditional forensic analysis of GSR focuses on IGSR, although with the movement towards lead-free, or non-toxic ammunition, IGSR analysis has become less informative, as lead is a major component of IGSR analysis. Because of this, OGSR has been investigated to supplement the standard IGSR analysis methods. Previous work has shown Raman spectroscopy to be effective at identifying OGSR as well as a minimally destructive and specific …

Preparation And Characterization Of Light Sensitive Tetrafluoro-Lambda6-Sulfanyl-Containing Polymers, Kelly A. Bonetti

Legacy Theses & Dissertations (2009 - 2024)

The addition of the pentafluorosulfanyl (SF5) group to an unsaturated organic starting material became popular in the 1960s, following the widening commercial availability of SF5Cl and SF5Br. However, the free radical reaction conditions required limited a broader appreciation of this critical advance. Moreover, while important thermal, photochemical and free-radical initiated addition reactions were reported, the unique photosensitivity of these compounds was not well understood. In 2012, a scalable synthetic route was developed affording aryl-SF5-containing derivatives via a novel aryl-SF4Cl intermediate. As a result, a heightened interest in hypervalent fluorinated sulfur containing materials was renewed. In 2014, the visible light addition …

Development Of Dual Functional Dna/Rna Nanostructures For Drug Delivery, Vibhav Amit Valsangkar

Legacy Theses & Dissertations (2009 - 2024)

In addition to the traditional biochemical functions, DNA and RNA have been increasingly studied as building blocks for the formation of various 2D and 3D nanostructures. DNA has emerged as a versatile building block for programmable self-assembly. DNA-based nanostructures have been widely applied in biosensing, bioimaging, drug delivery, molecular computation and macromolecular scaffolding. A variety of strategies have been developed to functionalize these nanostructures. The major advantage is that DNA is a very stable molecule and its base-pairing properties can be easily utilized to control and program the formation of desired nanostructures. In addition, some of these DNA/RNA nanostructures have …

Mixed-Valent Heterometallic Molecular Precursors : Expansion Into 4d Transition Metals, Jesse Caleb Carozza

Legacy Theses & Dissertations (2009 - 2024)

Hydrogen fuel can provide an ideal carbon-free energy carrier wherever water is available, be that on Earth or throughout the solar system. The use of water electrolysis to split water molecules into contaminant-free hydrogen gas, suitable for use in fuel cells, and oxygen gas allows also for storage of excess electrical energy during periods of high production and low demand, and an easy path to release that stored energy when demand is high and active supply is low. However, liberating hydrogen from water is an energy-intensive process, and effective electrocatalysts that reduce the amount of energy wasted by the reaction …

Bioaffinity-Based Methods For Forensic, Biometric, And Clinical Purposes, Mindy Elizabeth Hair

Legacy Theses & Dissertations (2009 - 2024)

Biomarker analysis is a well-established discipline that involves the evaluation of biological samples for the presence of various substances indicative of personal attributes or illnesses. Sweat is one example of a biological fluid that is often overlooked for forensic and clinical analyses, even though it can contain DNA, various amino acids, and other low molecular weight compounds.1–3 The work presented in this dissertation focuses on the use of bioaffinity-based assays to quantify biomarkers in sweat for both forensic and clinical applications. The concentration of the biochemical content within an individual’s sweat are controlled by hormone-based metabolic pathways4 that fluctuate daily …

Metabolic Changes Associated With Adaptive Resistance To Daptomycin In Streptococcus Mitis-Oralis, Allison Parrett, Joseph M. Reed, Stewart G. Gardner, Nagendra N. Mishra, Arnold S. Bayer, Robert Powers, Greg A. Somerville

Department of Chemistry: Faculty Publications

Background: Viridans group streptococci of the Streptococcus mitis-oralis subgroup are important endovascular pathogens. They can rapidly develop high-level and durable non-susceptibility to daptomycin both in vitro and in vivo upon exposure to daptomycin. Two consistent genetic adaptations associated with this phenotype (i.e., mutations in cdsA and pgsA) lead to the depletion of the phospholipids, phosphatidylglycerol and cardiolipin, from the bacterial membrane. Such alterations in phospholipid biosynthesis will modify carbon flow and change the bacterial metabolic status. To determine the metabolic differences between daptomycin-susceptible and non- susceptible bacteria, the physiology and metabolomes of S. mitis-oralis strains 351 (daptomycin-susceptible) and 351-D10 (daptomycin …

Application Of Synthesized Copper Nanoparticles Using Aqueous Extract Ofziziphus Mauritiana L. Leaves As A Colorimetric Sensor For The Detection Of Ag$^{+}$, Roomia Memon, Ayaz Ali Memon, Syed Tufail Hussain Sherazi, Siraj Uddin, Aamna Balouch, Muhammad Raza Shah, Sarfaraz Ahmed Mahesar, Kauser Rajar, Muhammad Hassan Agheem

Turkish Journal of Chemistry

The presented work demonstrates the preparation of copper nanoparticles (CuNPs) via aqueous leaves extract of Ziziphus mauritiana L. (Zm) using hydrazine as a reducing agent. Various parameters such as volume of extract, concentration of hydrazine hydrate, concentration of copper chloride, and pH of the solution were optimized to obtain Ziziphus mauritiana L. leaves extract derived copper nanoparticles (Zm-CuNPs). Brownish red color was initial indication of the formation of Zm-CuNPs while it was confirmed by surface plasmon resonance (SPR) band at wavelength of 584 nm using ultraviolet-visible (UV-vis) spectroscopy. Synthesized Zm-CuNPs were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron …

Corrosion And Wear Behaviour Of Highly Porous Ti-Tib-Tin$_{\Mathbf{X}}$ In Situ Composites In Simulated Physiological Solution, Fati̇h Toptan

Turkish Journal of Chemistry

Highly porous Ti matrix composites can be a solution for some of the major clinical concerns for the load bearing implants such as low tribocorrosion resistance, stress shielding, and lack of biological anchorage. In order to respond to these needs, highly porous Ti-TiB-TiN$_{x}$ in-situ composites were synthesized by pressureless sintering using BN as reactant and urea as space holder. Corrosion behaviour was investigated at body temperature, in phosphate buffer saline solution (PBS), by measuring open circuit potential (OCP) and cyclic polarization. Wear behaviour was studied in PBS by reciprocating against a 10 mm diameter alumina ball under 3 N of …

Blue Tio2 Nanotube Arrays As Semimetallic Materials With Enhanced Photoelectrochemical Activity Towards Water Splitting, Naeimeh Sadat Peighambardoust, Umut Aydemir

Turkish Journal of Chemistry

In the past years there has been a great interest in self-doped TiO2 nanotubes (blue TiO2 nanotubes) compared to undoped ones owing to their high carrier density and conductivity. In this study, blue TiO2 nanotubes are investigated as photoanode materials for photoelectrochemical water splitting. Blue TiO2 nanotubes were fabricated with enhanced photoresponse behavior through electrochemical cathodic polarization on undoped and annealed TiO2 nanotubes. The annealing temperature of undoped TiO2 nanotubes was tuned before cathodic polarization, revealing that annealing at 500 °C improved the photoresponse of the nanotubes significantly. Further optimization of the blue TiO2 nanotubes was achieved by adjusting the …

Soil Degradation And Erosion, Anthany Ravanh

Natural Sciences Student Research Presentations

No abstract provided.

The Link Between Soil And Cancer, Adrianna (Annie) Althaus

Natural Sciences Student Research Presentations

No abstract provided.

Development Of Analytical Methods For Toxic Inhaled Hazards (Tih) And Their Metabolites, Obed Adu Gyamfi

Electronic Theses and Dissertations

Toxic inhalation hazards (TIHs), such as methyl isocyanate (MIC) and hydrogen cyanide (HCN), are noxious gases and vapors that are harmful, and often deadly, to humans. However, because of their low cost and high reactivity, they are extensively used for industrial productions, creating risk of exposure for both industrial workers (e.g., occupational exposure) and civilians (e.g., accidental release during transport). The illicit use of TIHs, including as terrorist agents, is also concerning. Considering the rapid toxicity of TIHs and the danger they pose to both human and animal lives, there is a critical need to develop of analytical methods for …

Synthesis And The Genetic Encoding Of Novel Lysine Post-Translational Modifications, Sahan A. Galbada Liyanage

Theses and Dissertations

Post-translational modifications (PTMs) play a significant role in regulating cell signaling and regulating the inner cellular environment. The study of PTMs and their primary biological functions is critical for the development of new medicines targeting the pathways and biomolecules responsible for the PTMs.

Previous studies revealed the direct coupling of the β -hydroxybutyryl lysine (K_BHB) modification with the gene expression. K_BHB in histone proteins links metabolism to epigenetics and gene expression and enables to study in-depth, how cell metabolism controls the gene expression and vice versa. Similar novel histone modification, K_Lac, attracts a special interest …

Nanodiamonds And Carbon Nano-Onions Ceramic Composites And Their Applications, Ibrahim Munkaila Abdullahi

Masters Theses

"Luminescent nanodiamonds are photostable non-blinking fluorescent biocompatible, non-toxic, functional Zable materials made from high-pressure high temperature (HPHT) microcrystalline diamonds. For long, the scientific community has been investigating for a clean, efficient and cost-effective technique to reduce the size of fluorescent microcrystalline diamond into nanodiamonds. Their color center, responsible for the fluorescent properties are crucial for their applications, including biomedical imaging, nano sensing, quantum computing etc, and therefore should not be affected significantly by the method of size reduction applied. A novel size reduction technique that is based on explosive fragmentation was developed and the corresponding fragmented diamonds obtained were characterized …

Reactions Of First-Row Transition Metal Complexes In Bis(Alkoxide) Ligand Environments With Diazoalkanes: Formation Of Carbenes Versus Reductive Coupling To Form Bridging Tetrazenes, Amanda Grass

Wayne State University Dissertations

This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) Å, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ½ complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. …

Synthesis Of Bradyrhizose And The Equatorial Glycosides Of 3-Deoxygenation-D-Mango-Oct-2-Ulosonic Acid, Philemon O. Ngoje

Wayne State University Dissertations

ABSTRACT

SYNTHESIS OF BRADYRHIZOSE AND THE EQUATORIAL GLYCOSIDES OF 3- DEOXY-D-MANNO-OCT-2-ULOSONIC ACID

Chapter one provides a general view on the background to the research in two parts. The first part begins with an introduction on the significance of the lectin-carbohydrate interactions in leguminous plants. Then the structure and role of O-antigen lipopolysaccharides in the symbiotic nitrogen cycle, and the mechanism and significance of the cycle in leguminous plants growth are introduced. The role, isolation and characterization of bradyrhizose are also introduced; and the previous syntheses of bradyhizose and of related bicyclic compounds presented.

The second part of chapter one starts …

Characterization Of Clear Coat And Base Coat Automotive Paint Analysis Using Dart-Hrms And Comparison Of Ftir Spectroscopy, Py-Gc-Ms, And Dart-Hrms For Clear Coat Analysis, Kaitlin Jones

Electronic Theses and Dissertations, 2020-2023

Current techniques used to analyze automotive paint samples include microscopy, fourier – transform infrared (FTIR) spectroscopy, and pyrolysis gas chromatography - mass spectrometry (Py-GC-MS). These techniques are performed in the respective order listed above. Out of the three techniques currently used in this field, the one that has the highest discriminatory power is py-GC-MS; however, this technique is time consuming and destructive toward the sample. One hundred automotive paint samples were analyzed using FTIR, Py-GC-MS and direct analysis in real time-high resolution mass spectrometry (DART-HRMS) to determine how DART-HRMS compared to Py-GC-MS in terms of discriminatory capability. DART-HRMS takes approximately …

Tuning Dynamics, Sterics, And Ion Conductivities In Reticular Materials, Demetrius Vazquez-Molina

Electronic Theses and Dissertations, 2020-2023

The goal of this thesis is to synthesize libraries of organic building blocks with systematic functionalizations for tuning dynamics and steric traits in crystalline frameworks. Chapter 1 will introduce the materials being studied, their targeted applications, and a brief outline of each chapter will also be included. Chapters 2 explores the impact of mechanical processing in Covalent Organic Frameworks (COFs) from the point of view of crystallographic effects and pressure induced preferred orientation. This chapter also studies solid-state ionic conduction for Li ions in crystallographically aligned COFs studied by solid-state NMR and Electrochemical Impedance Spectroscopy (EIS), we observed fast ionic …

Route Exploration And Synthesis Of The Reported Pyridone-Based Pdi Inhibitor Stk076545, Eric Greve, Sergey V. Lindeman, Christina Scartelli, Lin Lin, Robert Flaumenhaft, Chris Dockendorff

Chemistry Faculty Research and Publications

The enzyme protein disulfide isomerase (PDI) is essential for the correct folding of proteins and the activation of certain cell surface receptors, and is a promising target for the treatment of cancer and thrombotic conditions. A previous high-throughput screen identified the commercial compound STK076545 as a promising PDI inhibitor. To confirm its activity and support further biological studies, a resynthesis was pursued of the reported β-keto-amide with an N-alkylated pyridone at the α-position. Numerous conventional approaches were complicated by undesired fragmentations or rearrangements. However, a successful 5-step synthetic route was achieved using an aldol reaction with an α-pyridone allyl …

Enhanced Light Harvesting Ability In Zeolitic Imidazolate Frameworks Through Energy Transfer From Cds Nanowires, Yixuan Zhou, Wenhui Hu, Sizhuo Yang, Jier Huang

Chemistry Faculty Research and Publications

Zeolitic imidazolate frameworks (ZIFs) represent a novel class of porous crystalline materials that have demonstrated potential as light harvesting materials for solar energy conversion. In order to facilitate their application in solar energy conversion, it is necessary to expand their absorption further into the realm of the solar spectrum. In this work, we report the incorporation of semiconductor cadmium sulfide nanowires (CdS NWs) into ZIF-67 (CdS@ZIF-67), where a broader region of the solar spectrum can be absorbed by CdS NWs and relayed to ZIF-67 through an energy transfer (EnT) process. Using steady-state emission and time resolved emission and absorption spectroscopy, …

Antifungal Defense Molecules From Bacterial Symbionts Of North American Trachymyrmex Ants, Georgia Scherer

CMC Senior Theses

Defensive symbioses, in which microbes provide molecular defenses for an animal host, hold great potential as untapped sources of therapeutically useful antibiotics. Fungus-growing ants use antifungal defenses from bacterial symbionts to suppress pathogenic fungi in their nests. Preliminary chemical investigations of symbiotic bacteria from this large family of ants have uncovered novel antifungal molecules with therapeutic potential, such as dentigerumycin and selvamicin.

In this study, the bacterial symbionts of North American Trachymyrmex fungus-growing ants are investigated for antifungal molecules. Plate-based bioassays using ecologically-relevant fungal pathogens confirmed that these bacteria have antifungal activity. In order to purify and identify the antifungal …

Development Of Smartphone-Based Ecl Sensor For Dopamine Detection: Practical Approaches, Hyun J. Kwon, Elmer Rivera, Mabio R. Cohelo Neto, Daniel Marsh, Jonathan Swerdlow, Rodney Lee Summerscales, Padma P. Tadi Uppala

Faculty Publications

In this work, a compact, mobile phone-based ECL sensor apparatus was developed using the phone cameras, screen-printed electrodes (SPE), and mobile app for dopamine detection. Methods of DC voltage application for ECL reaction were comprehensively studied from the mobile phone itself or external power. Under optimized sensing conditions, with disposable carbon SPE and 20 mM coreactant tri-n-propylamine (TPrA), acceptable repeatability and reproducibility were achieved in terms of relative standard deviation (RSD) of intra- and interassays, which were 6.7 and 5.5%, respectively. The biochemical compound dopamine was measured due to its ECL quenching characteristics and its clinical importance. The …

Synthesis Of Chromium(Ii) Complexes With Chelating Bis(Alkoxide) Ligand And Their Reactions With Organoazides And Diazoalkanes, Sudheer S. Kurup, Richard J. Staples, Richard Lord, Stanislav Groysman

Open Access Publishing Support Funded Articles

Synthesis of new chromium(II) complexes with chelating bis(alkoxide) ligand [OO]Ph (H2[OO]Ph = [1,1′:4′,1′’-terphenyl]-2,2′’-diylbis(diphenylmethanol)) and their subsequent reactivity in the context of catalytic production of carbodiimides from azides and isocyanides are described. Two different Cr(II) complexes are obtained, as a function of the crystallization solvent: mononuclear Cr[OO]Ph(THF)2 (in toluene/THF, THF = tetrahydrofuran) and dinuclear Cr2([OO]Ph)2 (in CH2Cl2/THF). The electronic structure and bonding in Cr[OO]Ph(THF)2 were probed by density functional theory calculations. Isolated Cr2([OO]Ph)2 undergoes facile reaction with 4-MeC6H4N3, 4-MeOC6H4N3, or 3,5-Me2C6H3N3 to yield diamagnetic Cr(VI) bis(imido) complexes; a structure of Cr[OO]Ph(N(4-MeC6H4))2 was confirmed by X-ray crystallography. The reaction of Cr2([OO]Ph)2 with …

Voltammetry And Spectroelectrochemistry Of Tcnq In Acetonitrile/Rtil Mixtures, Abderrahman Atifi, Michael D. Ryan

Chemistry Faculty Research and Publications

Understanding the solvation and ion-pairing interactions of anionic substrates in room-temperature ionic liquids (RTIL) is key for the electrochemical applications of these new classes of solvents. In this work, cyclic voltammetry and visible and infrared spectroelectrochemistry of tetracyanoquinodimethane (TCNQ) was examined in molecular (acetonitrile) and RTIL solvents, as well as mixtures of these solvents. The overall results were consistent with the formation of RTIL/acetonitrile nanodomains. The voltammetry indicated that the first electrogenerated product, TCNQ⁻, was not incorporated into the RTIL nanodomain, while the second electrogenerated product, TCNQ²⁻, was strongly attracted to the RTIL nanodomain. The visible …

Nonheme Iron–Thiolate Complexes As Structural Models Of Sulfoxide Synthase Active Sites, Danushka M. Ekanayake, Anne A. Fischer, Maya E. Elwood, Alexandra M. Guzek, Sergey V. Lindeman, Cordina V. Popescu, Adam T. Fiedler

Chemistry Faculty Research and Publications

Two mononuclear iron(II)–thiolate complexes have been prepared that represent structural models of the nonheme iron enzymes EgtB and OvoA, which catalyze the O₂-dependent formation of carbon–sulfur bonds in the biosynthesis of thiohistidine compounds. The series of Fe(II) complexes reported here feature tripodal N₄ chelates (L^A and L^B) that contain both pyridyl and imidazolyl donors (L^A = (1H-imidazol-4-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine; L^B = N,N-bis((1-methylimidazol-2-yl)methyl)-2-pyridylmethylamine). Further coordination with monodentate aromatic or aliphatic thiolate ligands yielded the five-coordinate, high-spin Fe(II) complexes [Fe^II(L^A)(SMes)]BPh …