Chemistry Commons^™

Micro- And Nanoparticles In Uv-Cured Thin Films, T. Christopher Corkery, Joseph Chan, Mike J. Idacavage, Elizabeth R. Gillies, Paul J. Ragogna

Chemistry Presentations

No abstract provided.

Bf3·Oet2 Catalyzed Reaction Of Donor-Acceptor Cyclobutanes With Terminal Alkynes: Single Step Access To 2,3-Dihydrooxepines, Ben P Machin, Brian L Pagenkopf

Chemistry Publications

In the presence of BF3˙OEt2 cyclobutane-1,1-diesters undergo a reaction with terminal alkynes to quickly access dihydro­oxepines.

Development Of Bioanalytical Methods For Clinical Applications And Drug Screening, Xiaohan Cai

ETD Archive

In the past decade, bioanalytical method development has become an integral part of clinical diagnosis, biomarker discovery, and drug discovery and development. The new and emerged bioanalytical technologies allow the quantitative and qualitative analysis of small molecules and biomolecules with high sensitivity and specificity. Specifically, the bioanalytical methods based on LC-MS and methylation-specific PCR are well suited for detecting low-abundance metabolites, proteins, and DNA in biofluids and tissues for biomarker investigation. They offer great clinical promises for early diseases diagnosis and therapeutic interventions. Besides, the LC-MS/MS quantitative method is essential for the estimation of pharmacokinetic and toxicological properties in drug …

Capillary Gradient Chromatofocusing-Mass Spectrometry;A Sensitive Approach For Protein Analysis, James Anthony Hribar

ETD Archive

Gradient chromatofocusing-mass spectrometry is a new technique for protein analysis recently introduced by our research group. Capable of separating and identifying proteins according to pI values and molecular weight, gradient chromatofocusing-mass spectrometry has been achieved by integrating a new ion-exchange chromatography technique called gradient chromatofocusing with a newly discovered buffer system that promotes mass spectrometry detection. Differing from traditional ion-exchange chromatography techniques, gradient chromatofocusing employs specific low molecular weight, volatile buffer components that are introduced onto an ion-exchange HPLC column by programming a binary gradient pumping system to deliver the correct proportions of acidic mobile phase to overcome buffering of …

Development Of Quantitative Lc-Ms/Ms Methods For The Pharmacological Studies Of Anti-Cancer Drugs, Lan Li

ETD Archive

In the development of anti-cancer drugs, it is essential to study the pharmacological profiles of the drugs. Among the analytical tools utilized in the pharmacological studies, LC-MS/MS has gained increased popularity due to its unequivocal sensitivity and specificity, as well as the ability of handling a wide variety of compounds with relatively simple sample preparation procedures. In this work, a brief review on the method rational, instrumentations, analytical method validation, and work flow of the method development was included. The processes of LC-MS/MS method development for the pharmacological studies of three anti-cancer drugs (i.e., methoxyamine, fludarabine, and 6-benzylthioinosine) were illustrated. …

Thermal Analysis As An Important Research Tool For Colleges And Universities, Jeffrey Allen Fruscella

ETD Archive

Three experiments were performed to demonstrate that thermal analysis is an important tool for use in colleges and universities for conducting scientific research. The first experiment used thermogravimetry, differential scanning calorimetry and thermal mechanical analysis to compare polymer resins from two ResinKits®, one from 1994 and the other from 2010. Analysis was done to determine if resins from the 1994 kit were viable standards. The experiments showed significant thermal differences between select resins and it was concluded that resins form the 1994 ResinKit® are no longer acceptable as standards.The second experiment used thermogravimetry and differential scanning calorimetry to determine the …

Factors Affecting Heme Transfer From "Gapdh": A Possible Heme Carrier Protein, Rajesh Vempati

ETD Archive

The aim of my research is to understand the mechanism of heme transfer by carrier proteins into heme proteins. The mechanism of heme insertion into proteins is poorly understood. Previous experiments reported from our lab identified GAPDH as a possible heme carrier protein involved in heme transfer (Ritu Chakravarti et al PNAS). This work focuses on 2 aspects of heme transfer. a.) Rate of transfer of heme from GAPDH to apomyoglobin. We examined the rate of transfer of native proto-heme and the analogue meso-heme. The results showed that the rate of heme transfer was twice as fast for meso-heme compared …

Introduction To Pharmaceutical Thermal Analysis: A Teaching Tool, Shravan Singh Thakur

ETD Archive

Significant Thermal Analysis-physical chemical data needs to be acquired by the new analyst whether an entry level chemist or a new function for the experienced pharmaceutical scientist. This teaching tool describes the introductory use of Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Thermomechanical Analysis (TMA) for characterizing pharmaceuticals. Optimum Experimental conditions for DSC, TGA and TMA will focus on collecting the best results and interpretations. Does the sample contain volatiles? Evaporation creates endothermic peaks, 2 water or solvent can lower the glass transition temperature (Tg) by up to 100°C and affect the crystallization temperature on cooling. The decomposition temperature …

Nmr Solution Structures Of Two Hairpins Of E. Coli 16s Rrna: The Effects Of Mutations And Chemical Modifications On Structure And Function Of Rrna, Yu Liu

Wayne State University Dissertations

The structures of two functional mutants, the UC (G690U, U697C) and the QM mutants (G690A, G693C, A695C, U697A) of the 690 hairpin of E. coli 16S ribosomal RNA were determined by NMR. The UC mutant and the QM mutant with high biological function are able to fold into structures that are isomorphous with the wild-type 690 hairpin sequence. The structural comparisons among the functional mutants and the wild-type provides structural validation for previously identified specific functional groups that are crucial for maintaining function of the 690 hairpin. The key groups for maintaining the structure and function of the 690 loop …

Exploring Potential Drug Target Sites In The Ribosome Using Cisplatin And Its Analogues, Keshab Rijal

Wayne State University Dissertations

Cis-diamminodichloridoplatinum (II), cisplatin, is an antitumor drug that has been used to treat several types of cancers. The reaction of cisplatin with DNA has been studied and discussed extensively in the literature; however, the effects of cisplatin on RNA function are poorly understood. In this thesis, two aspects of cisplatin, its preferred sites of interaction with RNA and its use as a chemical probe to gain accessibility information, were explored.

To understand the site-selectivity of cisplatin with RNA, model RNA constructs and full-length 16S rRNA were employed. The binding studies revealed a cisplatin preference for guanosine-rich sequences. Primer extensions in …

Synthesis Of N-Acetyl And C-Tert-Butyl Natural Amino Acid Substrates That Mimic Residues Of Polypeptides And Their Reactivity With [Feiv(O)(N4py)]2+: Kinetic And Mechanistic Investigations, Ashley Ann Campanali

Wayne State University Dissertations

This dissertation is divided into two chapters, the first chapter includes an introduction to reactive oxygen species and their reactions with proteins. The introduction also covers metal-based oxidants, including both heme and non-heme enzymes that activate dioxygen as well as complexes that mimic these enzymes. The work discussed in chapter one concerns the synthesis of amino acid substrates that mimic amino acid residues. Substrates synthesized were derived from Gln, Asn, Ile, Cys and Tyr. Once synthesized, these substrates were reacted with [FeIV(O)(N4Py)]2+ under pseudo-first order conditions. The mechanisms for the reactions of the most reactive substrates were investigated. Electron-transfer proton-transfer …

Study Of Protein-Rna Interactions Using Fluorescence Resonance Energy Transfer (Fret) And Single-Molecule Fret, Rajan Lamichhane

Wayne State University Dissertations

In the cell, RNA and protein, interact to form ribonucleoprotein complexes (RNPs) that have vital structural, catalytic and regulatory roles. Despite their functional importance, the mechanistic details and dynamics of RNPs are poorly understood. Single-molecule Fluorescence Resonance Energy Transfer (smFRET) techniques that provide information about heterogeneity and dynamic behaviors of molecules have been developed to investigate inter- and intra-molecular interactions. Here we have used FRET in combination with smFRET to study three very different RNP systems.

Alternative splicing is a highly regulated biological process that plays a crucial role in proteomic diversity in eukaryotes. One splicing regulator, PTB, has been …

New Insights Into The Mechanism Of Dna Replication On Unmodified And Benzo[A]Pyrene Modified Templates Using Surface Plasmon Resonance, Richard George Federley

Wayne State University Dissertations

DNA synthesis is critical to cell survival, and the enzyme DNA polymerase has had a great deal of time to evolve efficient strategies to perform synthesis. A variety of effects are induced by the identity of the incoming dNTP, and its ability to effectively base pair with the templating base. The presence of the next correct dNTP is known to induce a conformational change of the polymerase and lead to an increase in KF-DNA binding. Conversely, the presence of an incorrect dNTP is shown to lead to a destabilization and reduction in the levels of KF-DNA complexes formed. Using surface …

Laser-Assisted Single-Molecule Refolding, Rui Zhao

Wayne State University Dissertations

Non-coding RNAs must fold into precise secondary and tertiary structures in order to perform the biological functions. Due to the flexibility of RNA, the RNA folding energy landscape can be rugged and full of local minimum (kinetic trap). To provide a means to study kinetically trapped RNAs, we have developed a new technique combining single-molecule FRET detection with laser induced temperature jump. We have calibrated the magnitude of the temperature jump with 1˚C accuracy using gold micro-size sensor. The accuracy of temperature calibration was confirmed by close agreement between single-molecule and bulk DNA duplex melting experiments.

HIV 1 DIS RNAs …

Astrochemical Dynamics: Fundamental Studies Relevant To Titan's Atmosphere, Wilson Kamundia Gichuhi

Wayne State University Dissertations

This work presents results of primary fundamental photodissociation and state-specific ion-molecule dynamical studies that are relevant to understanding the formation and growth mechanisms of unsaturated hydrocarbon molecules, haze layers and aerosols in Titan's upper atmosphere. In the diacetylene dimer, it is shown, via laboratory studies combined with electronic structure calculations that the photodissociation of the dimer readily initiates atomic hydrogen (H) loss and atomic H transfer reactions forming two prototypes of resonantly stabilized free radicals, C8H3 and C4H3, respectively. In ethylamine cation, high-level ab initio calculations identify the complex dissociation pathways for the ground state CH3CH2NH2+ radical cation at 233.3 …

Artificial And Natural Nucleic Acid Self Assembling Systems, Marcus Wood

Wayne State University Dissertations

Nucleic acids are good candidates for nanomachine construction. They participate in all the processes of life, and so can function as structural building blocks and dynamic catalysts. However, to use nucleic acids as nanomachines, a better understanding of their material properties, how to design structures using them, and their dynamics is needed. We have tried to address these issues, in a small way, with nucleic acid force field development, an attempt at nanostructural design and synthesis using DNA, and a study of the RNA/protein regulatory dynamics of the tryptophan regulatory attenuation protein.

Development Of Chemical Inducers Of Dimerization For Screening Competitive Histone Deactelyase Inhibitors, Emily Lynn Aubie

Wayne State University Dissertations

Histone Deacetylase (HDAC) proteins are transcriptional regulators that affect histone proteins, which are involved in packaging of DNA into chromosomes. HDACs have been linked to the proliferation of cancer through their role in transcriptional regulation. Due to these findings, HDAC inhibitors have been explored as anti-cancer agents. Several HDAC inhibitors are currently in various stages of clinical trials, and the inhibitor suberoyl anilide hydroxamic acid (SAHA) has been FDA approved for treatment of cutaneous T-Cell lymphoma. Currently, most of the known HDAC inhibitors are non-selective, which causes non-specific binding to the active sites of all HDAC isoforms, including those not …

Synthesis And Characterization Of Metal Chalcogenide Nanostructured Materials For Thermoelectric Applications, Shreyashi Ganguly

Wayne State University Dissertations

The synthesis and characterization of metal chalcogenide nanostructured materials with the potential to exhibit enhanced thermoelectric (TE) properties is reported. The tellurides, specifically PbTe and Bi⊂2⊂Te⊂3⊂ (Bi⊂2⊂Te⊂3⊂–Sb⊂2⊂Te⊂3⊂ alloys) were selected as these are well established TE materials in bulk form. The approaches used for nanostructuring are (1) sol-gel assembly of discrete nanoparticles of PbTe, Bi⊂2⊂Te⊂3⊂, and Bi⊂2⊂Te⊂3⊂–⊂2⊂Te⊂3⊂ alloys, and (2) formation of heterostructured nanocomposites of PbTe nanoparticles in bulk Bi⊂2⊂Te⊂3⊂ (p– or n–doped) matrices.

Aerogels and xerogels of PbTe nanoparticles were synthesized by sol–gel assembly of discrete nanoparticles, leading to interconnected networks of nanoparticles and pores. The PbTe aerogel exhibited …

Synthesis, Redox Properties, And Langmuir Monolayer Formation Of Selected 3d- And 4d- Metalloamphiphiles, Sree Ramadevi Shanmugam

Wayne State University Dissertations

Transition metals containing amphiphilic compounds integrate various geometric, electronic, magnetic, and electrochemical properties together with the film forming properties. These compounds thereby find potential towards the fabrication of responsive films. This dissertation confers the synthesis and analysis of film forming properties of various redox-active metalloamphiphiles. Two new azido and thiocyanto bridged copper-based amphiphiles were synthesized and characterized by IR, UV-visible, and EPR spectroscopies, mass spectrometry, cyclic voltammetry, and elemental analysis. The redox studies show that both these complexes exhibit redox reversibility with only the azido bridged complex showing good redox cycling of about 50 times with minimal decomposition of less …

Structure Function Analysis Of An Adp-Ribosyltransferase Type Iii Effector And Its Rna-Binding Target In Plant Immunity, Byeong-Ryool Jeong, Yan Lin, Anna Joe, Ming Guo, Christin Korneli, Huirong Yang, Ping Wang, Min Yu, Ronald Cerny, Dorothee Staiger, James R. Alfano, Yanhui Xu

Ronald Cerny Publications

Background: HopU1 ADP-ribosylates GRP7, suppressing plant immunity.

Results: The HopU1 structure has two novel loops required for GRP7 recognition, and HopU1 ribosylates GRP7 at an arginine in position 49 disrupting its function.

Conclusion: HopU1 targets a conserved arginine in GRP7, disabling its ability to bind immunity-related RNA.

Significance: The mechanistic details of how HopU1 recognizes its substrate reveal how HopU1 contributes to pathogenesis.

Establishing An Interdepartmental Fluorescent Microscopy Facility, Marcy Kelly, David Zuzga, Nigel Yarlett

Cornerstone 3 Reports : Interdisciplinary Informatics

No abstract provided.

Interdisciplinary Computational Projects Utilizing The Hpc Cluster, Demos Athanasopoulos

Cornerstone 3 Reports : Interdisciplinary Informatics

No abstract provided.

The Complexity Of Reform Efforts In Science Curriculum And Instruction: A Case Study Of The Illinois Mathematics And Science Academy Chemistry Teacher, Tang Wee Teo

IMSA History

This study explores how teacher-initiated site-based reform in a specialized STEM school is conceptualized and enacted, how and why curriculum reform ideas change in the process of enactment, what qualities of teacher agency are entailed, how these qualities are acquired, interplayed, become generative, and/or are influenced to effect different curriculum reform outcomes, and how different conditions support and further teacher agency to make a more defensible curriculum.

In a critical case study of a highly experienced and qualified science teacher, I follow a teacher who initiated efforts to reform the advanced chemistry curriculum. This teacher wanted to make the curriculum …

Illicit Drug Analysis By Using Ultra-Short Pulses (Thz Spectroscopy), Canan Karaalioglu

Cornerstone 3 Reports : Interdisciplinary Informatics

No abstract provided.

Stability Of Carboplatin And Oxaliplatin In Their Infusion Solutions Is Due To Self-Association, Anthony J. Di Pasqua, Deborah J. Kerwood, Yi Shi, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

Carboplatin and oxaliplatin are commonly used platinum anticancer agents that are sold as ready-to-use aqueous infusion solutions with shelf lives of 2 and 3 years, respectively. The observed rate constants for the hydrolysis of these drugs, however, are too large to account for their long shelf lives. We here use electrospray-trap mass spectrometry to show that carboplatin and oxaliplatin are self-associated at concentrations in their ready-to-use infusion solutions (∼27 mM and 13 mM, respectively) and, as expected, when the drug concentration is reduced to more physiologically relevant concentrations (100 μM and 5 μM, respectively) the association equilibrium is shifted in …

Development Of Biomarkers For Endocrine Disrupting Compounds In The Fathead Minnow, Pimephales Promelas, Tara Frare

Undergraduate Review

Organic waste compounds (OWC’s) are an environmental concern that can have adverse effects on humans, animals, and the environment. Ethinyl estradiol (EE2) is one common OWC and is an active ingredient in oral birth control pills. The presence of EE2 in aquatic environments and drinking water can be linked to decreased fertility and altered physiology in fish. I am developing Q-PCR biomarkers to detect changes in fish at low concentrations before adverse effects occur at higher concentrations. RNA was extracted from twenty fathead minnows that had not been exposed to OWC’s and will be used to synthesize cDNA. Thus far …

Identification Of Proteins That Interact With The Transcription Factor Emx2 In Developing Mouse Neocortex, Jennifer A. Groves

Undergraduate Honors Theses

Neocortex is the largest region of the cerebral cortex in the mammalian brain. It is composed of multiple functional areas that process discrete types of information including visual, somatosensory, and auditory input and motor control output. During embryonic development, the relative size of each area is determined by transcription factors such as EMx2. The goal of our work is to identify proteins that interact with Emx2 to influence its role in neocortical arealization, the process by which the specific areas of the neocortex are formed with discrete boundaries.

Emissions From Ethanol-Gasoline Blends: A Single Particle Perspective, Dabrina D. Dutcher, Mark R. Stolzenburg, Samantha L. Thompson, Juan M. Medrano, Deborah S. Gross, David B. Kittelson, Peter H. Mcmurry

Chemistry Faculty Work

Due to its agricultural origin and function as a fuel oxygenate, ethanol is being promoted as an alternative biomass-based fuel for use in spark ignition engines, with mandates for its use at state and regional levels. While it has been established that the addition of ethanol to a fuel reduces the particulate mass concentration in the exhaust, little attention has been paid to changes in the physicochemical properties of the emitted particles. In this work, a dynamometer-mounted GM Quad-4 spark ignition engine run without aftertreatment at 1,500 RPM and 100% load was used with four different fuel blends, containing 0, …

Thiomaleic Anhydride: A Linchpin For Organic Synthesis And Structural Verification Of A Nonprotein Antifreeze Oligosaccharide, Md Yeajur Rahaman Sardar

Wayne State University Dissertations

This dissertation consists of two parts of which the first develops the utility of α,β-unsaturated monothioanhydrides as a linchpins in multicomponent coupling reactions by processes involving addition to the double bond, cyclization onto the anhydride, and finally exploitation of the rich chemistry of the thioacid liberated in the cyclization. The second part of the thesis is concerned with verification of the structure of a nonprotein antifreeze oligosaccharide by the total synthesis of various authentic oligosaccharides and the comparison of spectroscopic data.

Chapter one starts with the introduction of the general characteristics and reactivity of thioacids, and their potential for application …

Chemical Synthesis Of Peptides And Peptide Thioesters, Indrajeet Sharma

Wayne State University Dissertations

This dissertation describes investigations toward the development of a new chemistry for the block synthesis of peptides and peptidyl thioesters. A direct approach for the Fmoc-SPPS of peptidyl thioesters is also delineated in this thesis.

In the first part of chapter one, the difficulty and importance of chemical synthesis of peptides is explained, and a brief survey of available methods is given. The second part of chapter one presents the challenges inherent in the synthesis of peptidyl thioesters by Fmoc-SPPS.

The second chapter outlines the investigations conducted towards the development of a new chemistry for epimerization-free block synthesis of peptides …