Analytical Chemistry Commons^™

Stress Reduction For Pillar Filled Structures, Rebecca J. Nikolic, Adam Conway, Qinghui Shao, Lars Voss, Chin Li Cheung, Mushtaq A. Dar

Department of Chemistry: Faculty Publications

According to one embodiment, an apparatus for detecting neutrons includes an array of pillars, wherein each of the pillars comprises a rounded cross sectional shape where the cross section is taken perpendicular to a longitudinal axis of the respective pillar, a cavity region between each of the pillars, and a neutron sensitive material located in each cavity region.

Development Of Matrix Assisted Ionization Methods For Characterization Of Soluble And Insoluble Proteins From Native Environments By Mass Spectrometry, Ellen Dela Victoria Inutan

Wayne State University Dissertations

Matrix-assisted laser/desorption ionization (MALDI) and electrospray ionization (ESI) have made a huge impact in the analysis of biological materials. ESI has gained its popularity involving liquid based analysis, efficient fragmentation, chromatographic and electrophoretic separations but has a limitation for solubility restricted materials and surface analysis. MALDI is applicable to large biomolecule analysis and for surface methods useful for tissue imaging but is limited for structural characterization due to poor fragmentation and is ill suited for liquid based separation methods. The research presented here relates to new ionization methods that encompass the benefits of ESI and MALDI. These novel ionization methods …

Investigation Of Dopamine Dynamics In Bdnf+/- Mice Using In Vivo Microdialysis And Electrochemical Analysis Of Purine And Monoamine Molecules Using A Boron-Doped Diamond Electrode, Johnna A. Birbeck

Wayne State University Dissertations

The goal of the first study was to determine if a reduction in brain-derived neurotrophic factor (BDNF) levels in female mice lead to a dysregulation in their dopaminergic system. Through a series of in vivo microdialysis and slice voltammetry experiments, we have discerned that female BDNF^+/- mice are hyperdopaminergic similar to their male BDNF^+/- counterparts. The in vivo microdialysis method zero-net flux highlighted that female BDNF^+/- mice had increased extracellular dopamine (DA) levels, while stimulated regional release by high potassium potentiated DA release from vesicular mediated depolarization. Using the complementary technique of fast scan cyclic voltammetry, electrical …

Striatal Dopamine Dynamics Upon Manganese Accumulation, Madiha Khalid

Wayne State University Dissertations

STRIATAL DOPAMINE DYNAMICS UPON MANGANESE ACCUMULATION

by MADIHA KHALID

August 2013

Advisor: Dr. Tiffany Mathews

Major: Chemistry (Analytical)

Degree: Doctor of Philosophy

Although manganese (Mn) is fundamental for many biological processes, exposure to excess amounts leads to a neurological disorder termed manganism. Due to its symptomatic similarity to Parkinson's disease, as well its preferential accumulation in dopamine rich brain regions, alterations in the dopamine system are implicated in the onset of manganism. In my research, Mn overexposure is mimicked via subcutaneous administration of manganese chloride to C57BL/6 mice over the course of seven days using a protocol that has been …

Synthesis And Application Of Atp Analogs For Phosphorylation-Dependent Kinase-Substrate Crosslinking, Satish Kumar Garre Venkata Raghavendra

Wayne State University Dissertations

Phosphorylation is an important post-translational modification that plays a key role in a variety of signaling cascades and cellular functions. Kinases phosphorylate protein substrates in a highly regulated manner and are promiscuous. Understanding kinase-substrate specificity has been challenging and there is a need for new chemical tools. To this end we developed -phosphate modified ATP photocrosslinking analogs ATP-ArN3 and ATP-BP, that crosslink substrate and kinase in a phosphorylation dependent manner. We have successfully demonstrated that ATP-ArN3 and ATP-BP can be used with natural kinase and substrates using cell lysates in vitro. We used our approach to identify novel kinases of …

Studies Of Mercury In Water, Sediment, And Fish In Mississippi: Concentrations, Speciation, Cycling, And Isotopic Composition, Garry Brown

Electronic Theses and Dissertations

The goal of this project is to better understand the biogeochemical cycle of mercury (Hg) in Mississippi to aid those managing the resources and developing related policy. To that end, Hg levels were determined in a total of 202 fish from Enid, Sardis and Grenada Lakes; Enid and Grenada have fish consumption advisories due to Hg. In addition, total-Hg and methylmercury (MeHg) levels were determined in the inflow and outflows from Enid and Sardis Lakes and in bottom sediment and suspended solids in Enid Lake. Potential sources of Hg to Enid Lake were investigated, including precipitation and runoff from urban, …

Oregon Nmr Consortium: A Collaboratory For Nmr Data Acquisition And Processing, R. Carlisle Chambers

Faculty Publications - Department of Biological & Molecular Science

The Oregon NMR consortium was created to provide access to a modern, high-field 400 MHz NMR spectrometer for students and faculty at several two-year and small four-year institutions. Students use both on-site and remote access to conduct their NMR experiments. Remote access involves connecting to the NMR console over the Internet. Features of the consortium are described, including the details of remote access, sample transport, and data processing. This paper also discusses the impact that the access to the NMR spectrometer has had on student achievement of several learning goals in the organic chemistry courses at the partner institutions.

Investigation Of Drinking Water/Beverage Contaminants Within The Beverage Industry, Elizabeth Hobbs

Theses

The impact of water resource quality has influenced the community worldwide. It is an on-going target for water suppliers to produce suitable drinking water and the beverage industry to provide suitable water for the production of beverages. This diligence will ensure the consumer is provided with a product safe for consumption. The research and analytical techniques explored in this thesis may be of benefit to the beverage industry for the monitoring of inorganic contaminants present in water and carbonated soft drinks. The occurrence of certain contaminants in drinking water has become a major issue in the water industry in recent …

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.

The Bench Synthesis Of Silver Nanostructures Of Variable Size And An Introductory Analysis Of Their Optical Properties, Aoife Power, Tony Betts, John Cassidy

Articles

A laboratory practical was designed for use by both undergraduate and second level students to demonstrate the synthesis and characterisation of tuneable silver colloids. It clearly illustrates the novel optical properties of silver nanoparticles compared to the bulk metal. The synthesis is both rapid and repeatable, and can be conducted on the laboratory bench at room temperature.

Raman Spectroscopy For The Identification Of Body Fluid Traces : Mixtures And Contaminations, Race And Gender Differentation, Aliaksandra Sikirzhytskaya

Legacy Theses & Dissertations (2009 - 2024)

Body fluid traces are an important type of forensic evidence, which play a significant role in the reconstruction of a violent crime and often help to identify a victim or suspect based on DNA analysis. Despite a great need, there is no a single method, which could identify multiple body fluids. In addition, majority of current methods are destructive for the evidence. For about eight years, our laboratory has been working on the development of a new nondestructive method for identification of body fluid traces based on Raman microspectroscopy combined with advanced statistics. High differentiation power of the method has …

Vibrational Spectroscopic Analysis Of Gunshot Residue : A Novel Approach For Detection And Characterization, Justin J. Bueno

Legacy Theses & Dissertations (2009 - 2024)

Due to the increasing prevalence of firearm related crimes, there is a need for an all-encompassing analytical technique which can rapidly detect and analyze trace crime scene firearm evidence. There are several forms of ballistics and trace evidence associated with firearm offenses. Historically, the most neglected piece of evidence has ironically been the most prevalent. Each firearm discharge produces a so called gunshot residue (GSR) sample, expelling dust and particles numbering from hundreds to thousands throughout the shooting environment. The detection of GSR at a crime scene or on a suspect is critical for determining what actually happened during a …

Assessment Of Human Exposure To Perchlorate And Perfluoroalkyl Substances In The United States : Biomonitoring And Environmental Monitoring Approaches, Qian Wu

Legacy Theses & Dissertations (2009 - 2024)

Perchlorate is an oxidant in solid fuels and explosives and is produced in large quantities worldwide. Perchlorate is a ubiquitous environmental contaminant and is present in water, food, indoor environment and humans. Human exposure to perchlorate is a concern due to its ability to disrupt the thyroid gland functions.

Raman Spectroscopic Analysis Of Body Fluids : Species Differentiation And The Effect Of Substrate Interference And Laser Power, Gregory Keith Mclaughlin

Legacy Theses & Dissertations (2009 - 2024)

Several recent discoveries demonstrate that Raman spectroscopy has a unique capability to characterize body fluid traces in a forensic capacity. This approach has thus garnered interest in the forensic community since 2008, when a proof of concept experiment established that blood, semen, vaginal fluid, sweat and saliva are easily differentiable through their Raman spectra. Several possible methods of identification have been described in the literature, one approach uses chemometrical models, and another applies recently formulated multidimensional Raman signatures. The analytical sampling method and the identification procedure provide several desirable traits for the field of forensic science. In particular, Raman spectroscopy …

High-Performance Flexible Solid-State Supercapacitors Based On Mno2-Decorated Nanocarbon Electrodes, Yang Gao, Yun Shen Zhou, Min Qian, Hao Ming Li, Jody G. Redepenning, Li Sha Fan, Xiang Nan He, Wei Xiong, Masoud Majhouri-Samani, Lan Jiang, Yongfeng Lu

Department of Chemistry: Faculty Publications

Flexible energy storage units are highly desired to meet the ever-increasing demands for flexible electronics. In this paper, highly flexible solid-state supercapacitors are fabricated using MnO₂-decorated nanocarbon electrodes and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide–poly(vinylidene fluoride)- hexafluoropropylene ([EMIM][NTf2]–PVdF(HFP)) gel electrolytes. The flexible electrodes are prepared by electrodepositing MnO₂ onto the carbon nanotube/carbon nanoonion (CNT/CNO) films. CNT/CNO films have a large surface area for MnO₂ deposition and work as mechanical supports with high flexibility and light weight. CNOs act as spacers to separate CNTs, introducing mesopores inside the CNT/CNO films for preventing pore blocking during MnO₂ deposition. The supercapacitor exhibits …

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

An Expanded Genetic Code In Mammalian Cells With A Functional Quadruplet Codon, Wei Niu, Peter G. Schultz, Jiantao Guo

Department of Chemistry: Faculty Publications

We have utilized in vitro evolution to identify tRNA variants with significantly enhanced activity for the incorporation of unnatural amino acids into proteins in response to a quadruplet codon in both bacterial and mammalian cells. This approach will facilitate the creation of an optimized and standardized system for the genetic incorporation of unnatural amino acids using quadruplet codons, which will allow the biosynthesis of biopolymers that contain multiple unnatural building blocks.

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …

Ultrasensitive Analysis Of Binding Affinity Of Hiv Receptor And Neutralizing Antibodies Using Solution-Phase Electrochemiluminescence Assay, Xiao-Hong Nancy Xu, Zhaoyang Wen, William J. Brownlow

Chemistry & Biochemistry Faculty Publications

Binding of a few ligand molecules with its receptors on cell surface can initiate cellular signaling transduction pathways, and trigger viral infection of host cells. HIV-1 infects host T-cells by binding its viral envelope protein (gp120) with its receptor (a glycoprotein, CD4) on T cells. Primary strategies to prevent and treat HIV infection is to develop therapies (e.g., neutralizing antibodies) that can block specific binding of CD4 with gp120. The infection often leads to the lower counts of CD4 cells, which makes it an effective biomarker to monitor the AIDS progression and treatment. Despite research over decades, quantitative assays for …

Method Development For A Chemical And Biological Analysis Of Glucocorticoids In Wastewater, Maria Carmen Lozano

Open Access Theses & Dissertations

Glucocorticoids are a class of steroid hormones that can either be produced synthetically or naturally by the adrenal glands. The synthetic glucocorticoids are highly prescribed in the United States for their anti-inflammatory and immunosuppressive properties to treat a variety of ailments and diseases; however, these have been implicated in a number of adverse human conditions such as obesity, metabolic syndrome, immune-suppression, delayed puberty, adrenal insufficiency and Cushing Syndrome, among others. Ongoing research has shown that synthetic and natural hormones are transported to aquatic environments via mammalian excretion or wastewater effluent, and as a result, the release of glucocorticoids into the …

Single-Stranded Dna Scanning And Deamination With Single-Molecule Resolution, Padhuk Gamarala Senavirathne

Wayne State University Dissertations

SINGLE-STRANDED DNA SCANNING AND DEAMINATION WITH SINGLE-MOLECULE RESOLUTION

by

GAYAN SENAVIRATHNE

December 2013

Advisor: Dr. David Rueda & Dr.Ashok Bhagwat

Major: Chemistry (Analytical)

Degree: Doctor of Philosophy

APOBEC3G (Apo3G) and Activation-Induced cytidine Deaminase (AID) are the most notable members of APOBEC enzymes, a family of cytidine (C) deaminases with crucial functions in the immune system. In T cells, Apo3G deaminates C in viral cDNA to halt the replication of HIV 1 strains lacking viral infectivity factor (vif). In B cells, AID is required for the diversification of antibodies through initiation of somatic hypermutation (SHM), and class switch recombination (CSR), by …

Development Of A Screening Protocol Of Antiprotozoal Activity Against Acanthameoba Castellanii, Chelsey Stewart

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Homogeneous Connectivity Of Potential Energy Network In A Solidlike State Of Water Cluster, Takuma Akimoto, Toshihiro Kaneko, Kenji Yasuoka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A novel route to the exponential trapping-time distribution within a solidlike state in water clusters is described. We propose a simple homogeneous network (SHN) model to investigate dynamics on the potential energy networks of water clusters. In this model, it is shown that the trappingtime distribution in a solidlike state follows the exponential distribution, whereas the trapping-time distribution in local potential minima within the solidlike state is not exponential. To confirm the exponential trapping-time distribution in a solidlike state, we investigate water clusters, (H₂O)₆ and (H₂O)12, by molecular dynamics simulations. These clusters change dynamically from …

Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai-Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

Porous Polymer Coatings As Substrates For The Formation Of High-Fidelity Micropatterns By Quill-Like Pens, Michael Hirtz, Marcus Lyon, Wenqian Feng, Andrea E. Holmes, Harald Fuchs, Pavel A. Levkin

Department of Chemistry: Faculty Publications

We explored the potentials of microarray printing using quill-like microcantilevers onto solid supports that are typically used in microspot printing, including paper, polymeric nitrocellulose and nylon membranes. We compared these membranes with a novel porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) support (HEMA) with narrow pore size distribution in the 150 nm range, which demonstrated advantages in pattern definition, spot homogeneity, and consistent spot delivery of different dyes (phloxine B and bromophenol blue) with diameters of several micrometres. The bromophenol blue arrays on HEMA support were used to detect the presence of bovine serum albumin (BSA). In the presence of BSA, …

Single Transcriptional And Translational Preq1 Riboswitches Adopt Similar Pre-Folded Ensembles That Follow Distinct Folding Pathways Into The Same Ligand-Bound Structure, Krishna C. Suddala, Arlie J. Rinaldi, Jun Feng, Anthony M. Mustoe, Catherine D. Eichhorn, Joseph A. Liberman, Joseph E. Wedekind, Hashim M. Al-Hashimi, Charles L. Brooks Iii, Nils G. Walter

Department of Chemistry: Faculty Publications

Riboswitches are structural elements in the 50 untranslated regions of many bacterial messenger RNAs that regulate gene expression in response to changing metabolite concentrations by inhibition of either transcription or translation initiation. The preQ₁ (7-aminomethyl-7-deazaguanine) riboswitch family comprises some of the smallest metabolite sensing RNAs found in nature. Once ligand-bound, the transcriptional Bacillus subtilis and translational Thermoanaerobacter tengcongensis preQ₁ riboswitch aptamers are structurally similar RNA pseudoknots; yet, prior structural studies have characterized their ligand-free conformations as largely unfolded and folded, respectively. In contrast, through single molecule observation, we now show that, at nearphysiological Mg²⁺ concentration and pH, …

Iodonium Cyclophanes For Secure Arene Functionalization, Stephen Dimagno

Department of Chemistry: Faculty Publications

This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Supercharging: An Investigation Into The Effects Of External Amino Acid Residue Charge On The Solubility And Internal Electric Character Of Bound Ligands In A Heme-Binding De Novo-Designed Protein, Cooper French

Dissertations and Theses

De novo protein design offers many interesting prospects both as a means to better understand natural protein dynamics and as a potential resource in biomedical and industrial applications. In this work I describe the modification of a simple, well-characterized heme-binding protein by altering side chain residue identities on the hydrophilic surface of the protein to produce variants with a range of net external charges. These charge modifications had a significant impact on nearly every measurable character of the protein. This work establishes the hard limits of supercharging within our experimental protein scaffold system, demonstrating that excessive positive charge increased the …

Chemical Analysis Of Ophthalmic Solutions, Pagagiotis Tavlarakis

Seton Hall University Dissertations and Theses (ETDs)

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Studies Of Organic Compounds Spreading Over High Energy Surfaces, Lingbo Lu

Theses and Dissertations--Chemistry

Spreading plays an important role in coating, lubrication, printing and etc. During the spreading process, a liquid thin film forms prior to the expansion of a liquid drop. This thin film is called a precursor film. It not only changes the spreading mechanism, but impacts the wettability of a liquid. Early studies on the precursor films showed the films were stacked in a terraced structure, and the radius of each layer of the films was proportional to the square root of time. Optical techniques such as ellipsometry, X-ray diffraction and X-ray reflectivity solved the conformations of liquid molecules at the …