Chemistry Commons^™

Determination Of 6-Benzylthioinosine In Mouse And Human Plasma By Liquid Chromatography–Tandem Mass Spectrometry, Lan Li, Yan Xu, David N. Wald, William Tse

Chemistry Faculty Publications

This paper described the development and validation of a liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for the quantitative determination of 6-benzylthioinosine (6BT), a novel myeloid leukemia differentiation-inducing agent, in mouse and human plasma. In this method, 2-amino-6-benzylthioinosine (2A6BT) was used as internal standard and ethyl acetate was used as organic solvent for the extraction of 6BT and internal standard from plasma samples. The extracted samples were separated on YMC ODS-AQ® column (2.0 mm × 50 mm), and the eluates from the column were monitored by the positive-electrospray-ionization tandem mass spectrometer (ESI+-MS/MS). Quantification of 6BT by internal calibration with 2A6BT was …

Fragmentation Properties Of Three-Membered Ring Heterocyclic Molecules By Partial Ion Yield Spectroscopy: C2h4o And C2h4s, Wayne C. Stolte, I. Dumitriu, S-W Yu, Gunnar Ohrwall, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigated the photofragmentation properties of two three-membered ring heterocyclic molecules, C₂H₄O and C₂H₄S, by total and partial ion yield spectroscopy. Positive and negative ions have been collected as a function of photon energy around the C 1s and O 1s ionization thresholds in C₂H₄O, and around the S 2p and C 1s thresholds in C₂H₄S. We underline similarities and differences between these two analogous systems. We present a new assignment of the spectral features around the C K-edge and the sulfur L_{2 …}

Development Of Chemometric Models And Calibration Transfer For Rapid Diesel And Jet Fuel Analysis Using Near Infrared Spectroscopy, Christopher Matthew Larkin

Chemistry & Biochemistry Theses & Dissertations

Fuel quality assurance and analysis, as it pertains to the United States armed forces, is crucial for maintaining operability and upholding safety regulations with respect to fuel class. Currently a great amount of effort, money and manpower are dedicated to this task as fuel analysis takes place in off-site laboratories where quality assessment and property determination is performed manually by highly qualified lab technicians. This presents the military with a logistics problem with respect to refueling, transport, and fuel storage as the typical tum-around time is 1-2 weeks. In this thesis it has been demonstrated that near-infrared spectroscopy, in conjunction …

Experimental And Theoretical Investigation Of Molecular Field Effects By Polarization-Resolved Resonant Inelastic X-Ray Scattering, Stephane Carniato, Renaud Guillemin, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

We present a combined theoretical and experimental study of molecular field effects on molecular core levels. Polarization-dependent resonant inelastic x-ray scattering is observed experimentally after resonant K-shell excitation of CF₃Cl and HCl. We explain the linear dichroism observed in spin-orbit level intensities as due to molecular field effects, including singlet-triplet exchange, and interpret this behavior in terms of population differences in the 2p_x,y,z inner-shell orbitals. We investigate theoretically the different factors that can affect the electronic populations and the dynamical R dependence of the spin-orbit ratio. Finally, the results obtained are used to interpret the L-shell …

Electrochemically Induced Free Radical Polymerization Of Methacrylic Acid And Fabrication Of Amperometric Glucose Biosensor, Sheng Wang, Ying Lei, Kang Shi

Journal of Electrochemistry

Electrochemically induced free radical polymerization of methacrylic acid was preliminarily investigated. Based on the electrochemical reduction of persulfate anion in phosphate buffer (pH 7.0) solution,the free radical polymerization of methacrylic acid was initiated to generate an ultrathin and biocompatible hydrogel layer on the gold electrode. At the meantime,glucose oxidase could be immobilized within the hydrogel film in the polymerization process. The resulting biosensor displayed an attractive performance.

Computational Investigation Of Spin Traps Using Hybrid Solvation Models., Sai Sriharsha Manoj Konda

Electronic Theses and Dissertations

The cyclic nitrone 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), and the lesser known linear phenyl-N-tert-butylnitrone (PBN) and its phosphorylated analogues have been used as spin traps for the investigation of free radicals in biological systems. Theoretical work on these molecules suggests that there are important differences in their properties between biological systems and isolated molecules in the gas phase, most likely resulting from intra and intermolecular hydrogen bonding. Most dielectric solvation models such as the polarized continuum model and COSMO are incapable of direct determination of solvent-spin trap chemical interactions. To examine this, hybrid models incorporating COSMO for long range effects and discrete solvent …

Studies Of The Preparations And Use Of Sol-Gel For Enzyme Immobilization And Analytical Applications., Suzana Hamdan

Electronic Theses and Dissertations

Much attention has been paid to immobilization of enzymes to improve enzyme stability and permit its reuse. Glucose oxidase entrapment in different kinds of silica sol-gel matrices was investigated. The enzyme showed stable activity for 11 uses in the sol-gel with tetramethyl orthosilicate (TMOS) as precursor, and at least 7 uses in the sol-gel induced electrochemically with tetraethyl orthosilicate (TEOS) as precursor. The sol-gel made with TEOS as precursor and HCl as catalyst showed stability in enzyme activity for 11 uses but the activity decreases on the same sol-gel when modified with silica nanoparticles. Factors such as optimal incubation time …

Studies Of Capsaicinoids Contents Of Locally Grown And Commercial Chilies Using Reversed-Phase High Performance Liquid Chromatography., John Kailemia Muchena

Electronic Theses and Dissertations

Capsaicinoids are a class of compounds responsible for the "heat" of hot peppers. Capsaicin and dihydrocapsaicin have the highest burning effect. The aim of this work is to separate and quantify the two major capsaicinoids in fruits harvested at different stages of development and at different seasons. Simple and rapid HPLC method involves 73:27% methanol water mobile phase with C₁₈ stationary phase and UV-Vis detector set at 210 nm. The method showed good reproducibility with 1.74% - 4.72% relative standard deviations, a linear response within 0.65–45.5 and 0.25-17.5 μg/mL for capsaicin and dihydrocapsaicin, respectively. The method achieved average recovery …

Increased Control Over Gold Colloid Adsorption On Substrates For Colloid Displacement Lithography, Vara Prasad Reddy Sakampally

Masters Theses & Specialist Projects

Colloid displacement lithography is proving to be very effective in the designing of nanometer scale electronic devices. Precise control of the structure of matter at the nanometer scale has brought a revolutionary change in science and technology. The use of these nanometer scale devices ranges from the diagnosis of various diseases to cell repair to ultra strong materials. This research focused on optimizing the conditions for gold colloid particle adsorption for colloid displacement lithography, an expansion on gold colloid particle manipulation techniques using a scanned probe microscope. The system consists of a scrupulously cleaned glass surface that is coated with …

Continued Development Of An Empirical Function For Predicting And Rationalizing Protein–Protein Binding Affinities, Joseph Audie

Chemistry & Physics Faculty Publications

Here we summarize recent work on the continued development of our fast and simple empirical equation for predicting and structurally rationalizing protein–protein and protein–peptide binding affinities. Our empirical expression consists of six regression-weighted physical descriptors and derives from two key simplifying assumptions: (1) the assumption of rigid-body association and (2) the assumption that all contributions not explicitly considered in the equation make a net contribution to binding of ≈0 kcal. Within the strict framework of rigid-body association, we tested relative binding affinity predictions using our empirical equation against the corresponding experimental binding free energy data for 197 interface alanine mutants. …

Factors Affecting Redox Magnetohydrodynamics For Flow In Small Volumes, Matthew D. Gerner

Graduate Theses and Dissertations

Lab-on-a-chip technologies offer the possibility of developing analytical devices that are low-cost, portable, disposable, fast, and operable by non-technical personnel. Such devices require automated methods to manipulate ultra-small volumes (picoliters) of samples and solution, including pumping, stirring, and positioning. Current methods for ultra-small volume microfluidics have limitations that restrict their use including high voltage requirements, disadvantageous flow profiles or rates, and relatively complicated fabrication due to mechanical parts. Redox magnetohydrodyanmics (RMHD) that utilizes permanent magnets for portability shows promise as a micropump with ease of switching flow direction, no moving parts, compatibility with both aqueous and non-aqueous solutions, low voltages …

The Use Of Fourier Transform (Ft) Surface-Enhanced Raman Scattering For Biochemical Analysis, Robert Butler Jeffers

Chemistry & Biochemistry Theses & Dissertations

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique that has created exciting opportunities in the field of bioanalytical chemistry, where it combines ultrasensitive detection of biologically relevant molecules with vibrational spectroscopy. Due to the difficulties in preparing reproducible SERS active substrates, SERS has been mainly used as a qualitative tool. In order for SERS to be utilized as a viable tool for quantitative analysis, simple, facile SERS substrates which generate clean, highly reproducible signals must be developed. This dissertation deals with the evaluation of three different methods of SERS that led to the development of a novel substrate for …

Arsenic And Selenium Distribution In Coal-Fired Plant Samples, Pauline Rose Hack Norris

Masters Theses & Specialist Projects

Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES.

This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and …

Investigation Of Photophysical And Photochemical Processes In Conjugated Polymer Nanoparticles By Single Particle And Ensemble Spectroscopy, Craig Szymanski

All Dissertations

Single molecule imaging has emerged as a powerful tool in a range of applications, but the field is limited by a lack of fluorescent probes with sufficient brightness and photostability for many demanding applications such as tracking of single biomolecules in cells and tissues at video rate with 1 nm spatial resolution. Conjugated polymers hold great promise as a solution to these issues, with a high density of π electrons and variety of chemistries, allowing efficient and tunable absorption of light. This dissertation describes the development and characterization of a novel type of nanoparticle composed of conjugated polymer called CPdots. …

The Synthesis And Systematic Evaluation Of Modified Polymeric Foams And Electrically Conductive Polyimide/Carbon/Metal Films, John Macharia Kinyanjui

UNLV Theses, Dissertations, Professional Papers, and Capstones

Thermally processed PU foams are examined as a function of processing temperatures (25, 45, 65, and 85°C) at the side, middle, and center of a simple cylindrical mold. The PU foams show both chemical and morphological differences as a function of the processing temperature and radial position within the mold. Thermal degradation of uretoneimine structures, the emergence of carbodiimide structures, and extent of reaction of isocyanate groups are measured using photoacoustic FTIR spectroscopy. Chemical gradients and morphology differences between the side, middle, and center of the molded foam are observed for all processing temperatures. The data indicate that thermal activation …

Fundamental Aspects Of Small Molecules And Macromolecules On Poly(Ethylene Terephthalate) Capillary-Channeled Polymer Fibers, Christine Straut

All Dissertations

Stationary phases and adsorbents are continually being developed to enhance separations in high performance liquid chromatography (HPLC). Polymeric stationary phases have gained popularity due to their ability to be employed over a large pH range and because they are more chemically robust when compared to silica based phases. Capillary-channeled polymer (C-CP) fibers are an alternative to traditional porous packed bed beads. These fibers have a unique geometry with increased the surface area/volume ratios when compared to cylindrical fibers. Very unique characteristics are realized in the use of the C-CP fibers, including drastically reduced backpressures and selection of solute-surface interaction through …

The Separation And Indentification Of Polyoxometalate Mixtures, Stephanie Peterson

Honors Capstones

Capstone submitted as a graduate requirement for the BSU Honors Program.

Electrochemical Properties Of Functionalized Carbon Nanotubes And Their Applications In Analysis Of 6-Mercaptopurine, Bao-Yi Lu, Yan-Yan Lai, Hong Li

Journal of Electrochemistry

The electrochemical behaviors and adsorption properties of single-walled carbon nanotubes such as SWNT,SWNT-COOH,and SWNT-OH and multi-walled carbon nanotubes including MWNT,MWNT-COOH,and MWNT-OH modified at a graphite electrode have been investigated by using [Fe(CN)₆]^3-anion and [Co(phen)₃]³⁺ cation.It was shown that shows good redox reversibility of [Fe(CN)₆]^3-/4-reactions on the existed carbon nanotubes(CNT) modified electrode.Based on the strong adsorptive property of [Co(phen)₃]³⁺ on the CNT surface,the [Co(phen)₃]³⁺/CNT modified graphite electrode can be obtained by progressive potential sweeping and developed to monitor quantitatively 6-mercaptopurine(6-MP).The adsorption capacity of …

A Conducance Detection System Applying Constant Current Source For Ion Chromatography, Hua-Bin Chen, Wei-Xiong Huang, Rong-Zong Hu

Journal of Electrochemistry

Being different from bipolar pulse technique,a new type conductivity detection circuit system applying constant current source for ion chromatography was designed which effectively reduces the complexity of bipolar pulse technique,accurately and intelligently completes the signal amplification,collection,processing and spectrum displaying.In this article the detection principle and the hardware of the system were described and the experimental results with accurate and reliable measurements were shown.

Development And Validation Of An Empirical Free Energy Function For Calculating Protein–Protein Binding Free Energy Surfaces, Joseph Audie

Chemistry & Physics Faculty Publications

In a previous paper, we described a novel empirical free energy function that was used to accurately predict experimental binding free energies for a diverse test set of 31 protein–protein complexes to within ≈1.0 kcal. Here, we extend that work and show that an updated version of the function can be used to (1) accurately predict native binding free energies and (2) rank crystallographic, native-like and non-native binding modes in a physically realistic manner. The modified function includes terms designed to capture some of the unfavorable interactions that characterize non-native interfaces. The function was used to calculate one-dimensional binding free …

Classification And Cluster Analysis Of Complex Time-Of-Flight Secondary Ion Mass Spectrometry For Biological Samples, Stephen E. Reichenbach, Xue Tian, Qingping Tao, Alex Henderson

School of Computing: Conference and Workshop Papers

Identifying and separating subtly different biological samples is one of the most critical tasks in biological analysis. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is becoming a popular and important technique in the analysis of biological samples, because it can detect molecular information and characterize chemical composition. ToF-SIMS spectra of biological samples are enormously complex with large mass ranges and many peaks. As a result the classification and cluster analysis are challenging. This study presents a new classification algorithm, the most similar neighbor with a probability-based spectrum similarity measure (MSN- PSSM), which uses all the information in the entire ToF- SIMS …

Application Of Multiple Mass Spectrometric Techniques In The Isolation, Determination And Characterisation Of The Marine Toxins; Azaspiracid, Keith O'Callaghan

Theses

The Azaspiracids are a class of polyether marine biotoxins that present a significant health risk to consumers of shellfish. Since their discovery in the late 1990s several human intoxications have been reported, and traced to Irish shellfish farms resulting in closures or harvest rejections. As such incidents involving azaspiracid shellfish poisoning have a major socio-economic impact on communities that rely on shellfish farming revenues.

Recent evidence suggests that azaspiracid poisoning events may become more commonplace. With this increased risk the understanding of azaspiracids mode of action and biological targets becomes crucial. To support these endeavours effective analytical methods need to …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Raman Spectroscopy Of Body Fluids : A Nondestructive Identification Technique For Forensic Applications, Kelly Virkler

Legacy Theses & Dissertations (2009 - 2024)

The analysis of body fluid evidence during forensic investigations is a complicated process, yet it is a critical step in determining the key facts of a crime. There is no doubt that DNA analysis is an extremely useful tool that can identify a suspect or victim, but crime scene investigators must first locate and identify potential body fluid stains that can be collected for DNA analysis. Current screening tests are destructive to the sample and can give false positive results, so a nondestructive technique such as Raman spectroscopy, that can possibly confirm the presence of a particular fluid, could lend …

Genetically Engineered Repetitive Polypeptides : Design, Synthesis, Characterization, And Applications, Natalya I. Topilina

Legacy Theses & Dissertations (2009 - 2024)

This work is dedicated to the investigation of protein folding with the emphasis on the aggregation and amyloid fibrils formation. The focus of the research is to elucidate the relationship between polypeptide chain sequence and folding/aggregation properties. For this purpose, i) libraries of the de novo macromolecular repetitive β-sheet forming polypeptides were designed, and ii) the strategy for their rapid creation was developed. The strategy enables retention of a basic polypeptide core, yet allowing variations in the repetitive sequence, degree of polymerization and distribution of specific amino acids. The polypeptides were expressed in E. coli, purified, and characterized by various …

Measurement Of Atmospheric Ammonia Species : Development, Validation, And Field Applications Of An Analytical Method, Jian Hou

Legacy Theses & Dissertations (2009 - 2024)

Ammonia is the primary base in the atmosphere. It reacts readily with atmospheric acids such as sulfuric acid, nitric acid, and hydrochloric acid to form ammonium salts that occur predominantly in the fine aerosol particle (PM2.5) fraction. The ability to measure ammonia species (NHx, the sum of gaseous NH₃ and particulate NH₄+) is essential for the investigation of atmospheric behaviors of NHx. In this dissertation work, a highly sensitive technique has been developed for the measurement of atmospheric NHx species. The method is based on aqueous scrubbing of the atmospheric NH₃ and NH₄+ using …

Biomonitoring For Exposure To Trace Elements In Utero : Analysis Of The Human Placenta, Pamela Catherine Kruger

Legacy Theses & Dissertations (2009 - 2024)

The placenta forms in eutherian mammals, and is responsible for the nutrition of the developing fetus. However, maternal exposure to environmental pollutants both before and during pregnancy may result in the passage of toxins through the placental barrier and into fetal tissues. The placenta is the only organ derived from both maternal and fetal tissues, and establishes a link between the fetus and the environmental exposures of the mother. The analysis of placentae for the presence of environmental pollutants offers the possibility of exposure measurements in both the mother and the developing fetus. Specifically, trace element determination in human placentae …

Immobilization Method For Producing Active Α1-Acid Glycoprotein, David S. Hage, Hai Xuan

Department of Chemistry: Faculty Publications

A method and kit for immobilization of a glycoprotein. The method may include activating an affinity Support. The affinity Support may be activated by reacting the affinity Support with a compound that is reactive with one or more functional groups included within the glycoprotein. The method may also include oxidizing the glycoprotein in which oxidation conditions are selected to yield an oxidized glycoprotein that is biologically active and contains a Sufficient number of reactive aldehyde groups for coupling to a Support. For example, the oxidized glycoprotein may include five reactive aldehyde groups. In addition, the method may include reacting the …

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.

Partial Ion Yield Sspectroscopy Around The Cl 2p And C 1s Ionization Thresholds In Cf3cl, D. Ceolin, Maria Novella Piancastelli, Wayne C. Stolte, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We present a partial ion yield experiment on freon 13, CF₃Cl, excited in the vicinity of the C 1s and Cl 2p ionization thresholds. We have collected a large amount of cationic fragments and a few anionic fragments at both edges. We have observed a strong intensity dependence of Rydberg transitions with ion fragment size for the CF_nCl⁺ and CF_n⁺/F⁺ (n=0–3) series at both the Cl 2p and C 1s ionization edges. Selectivity in the fragmentation processes involving the C–Cl and C–F bonds are highlighted by the intensities of the C …