Analytical Chemistry Commons^™

Absolute Configuration And Biosynthesis Of Pahayokolide A From Lyngbya Sp. Strain 15-2 Of The Florida Everglades, Li Liu

FIU Electronic Theses and Dissertations

Pahayokolides A-D are cytotoxic cyclic polypeptides produced by the freshwater cyanobacterium Lyngbya sp. strain 15-2 that possess an unusual β-amino acid, 3-amino-2,5,7,8-tetrahydroxy-10-methylundecanoic acid (Athmu). The absolute configuration of pahayokolides A-D was determined using advanced Marfey’s method. It was also confirmed that a pendant N-acetyl-N-methyl leucine moiety in pahayokolide A was absent in pahayokolides B and pahayokolides C-D were conformers of pahayokolide A. Feeding experiments indicated that the biosynthesis of the Athmu sidechain arises from leucine or α-ketoisovalerate, however could not be further extended by three rounds of condensation with malonate units. Putative four peptide and one unique polyketide synthetases in …

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 …

Developing Novel Electrospray Ionization Mass Spectrometry (Esi Ms) Techniques To Study Higher Order Structure And Interaction Of Biopolymers, Agya K. Frimpong

Open Access Dissertations

Mass spectrometry has enjoyed enormous popularity over the years for studying biological systems. The theme of this dissertation was to develop and use mass spectrometry based tools to solve five biologically oriented problems associated with protein architecture and extend the utility of these tools to study protein polymer conjugation. The first problem involved elucidating the false negatives of how proteins with few basic residues, forms highly charged ions in electrospray ionization mass spectrometry (ESI MS). This study showed that the unfolding of polypeptide chains in solution leads to the emergence of highly charged protein ions in ESI MS mass spectra, …

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.

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 …

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 …

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. …

Room Temperature Tunable Energy Transfer Systems In Different Solvents, Zhonghua Guo

Electronic Theses and Dissertations

The focus of this thesis is on d⁸ and d¹⁰ metal-metal interactions, e.g. weak bonding in homometallic and heterometallic systems in liquid solutions, the tunability of luminescent energy due to the variation of metal-metal interaction strength in different solvents and different concentrations, as well as energy transfer from the luminescent energy tunable d⁸ and d¹⁰ metal ions clusters as donor ions to the lanthanide ions as acceptor ions at room temperature. First, energy transfer has been studied between dicyanoaurate(I) luminescent nanocluster donor ions and Eu³⁺ and Tb³⁺ acceptor ions in aqueous solutions. The emission …

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 …

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 …

Exploiting The Versatility Of Ionic Liquids In Separation Science: Determination Of Low-Volatility Aliphatic Hydrocarbons And Fatty Acid Methyl Esters Using Headspace Solid-Phase Microextraction Coupled To Gas Chromatography, Yunjing Meng, Veronica Pino, Jared L. Anderson

Jared L. Anderson

The determination of high-molecular weight aliphatic hydrocarbons and fatty acid methyl esters possessing high boiling points and low vapor pressures was performed using a headspace solid-phase microextraction gas chromatography (HS-SPME-GC) method comprised entirely of ionic liquids (ILs). The method utilizes three independently structurally engineered ILs in which the imparted physical and chemical properties make them compatible with the requirements of each component of the method. Component one is composed of a thermally stable IL solvent used to increase the equilibrium concentration of analytes in the HS, component two is a SPME sorbent coating based on a polymeric ionic liquid (PIL) …

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 …

Ionic Liquids Containing The Tris(Pentafluoroethyl)Trifluorophosphate Anion: A New Class Of Highly Selective And Ultra Hydrophobic Solvents For The Extraction Of Polycyclic Aromatic Hydrocarbons Using Single Drop Microextraction, Cong Yao, William R. Pitner, Jared L. Anderson

Jared L. Anderson

A new class of ionic liquids (ILs) containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion are paired with imidazolium, phosphonium, and pyrrolidinium cations and used as extraction solvents in direct immersion single drop microextraction (SDME) studies coupled to high performance liquid chromatography (HPLC). The selectivity and sensitivity of the extraction method can be tuned and manipulated by varying the cationic component of the IL, thereby providing larger enrichment factors for a variety of analytes, including polycyclic aromatic hydrocarbons (PAHs). Compared to other hydrophobic ILs containing the hexafluorophosphate (PF6−) and bis[(trifluoromethyl)sulfonyl]imide (NTf2−) anions, FAP-based ILs are significantly more hydrophobic and hydrolytically stable permitting them …

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 …

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. …

Simultaneous Quantitation Of Multiple Classes Of Organohalogen Compounds In Fish Oils With Direct Sample Introduction Comprehensive Two-Dimensional Gas Chromatography And Time-Of-Flight Mass Spectrometry, Eunha Hoh, Steven J. Lehotay, Kristin C. Pangallo, Katerina Mastovska, Helen L. Ngo, Christopher M. Reddy, Walter Vetter

Kristin Pangallo

Capabilities Of Direct Sample Introduction-Comprehensive Two-Dimensional Gas Chromatography-Time-Of-Flight Mass Spectrometry To Analyze Organic Chemicals Of Interest In Fish Oils., Eunha Hoh, Steven J. Lehotay, Katerina Mastovska, Helen L. Ngo, Walter Vetter, Kristin C. Pangallo, Christopher M. Reddy

Kristin Pangallo

Linear Free Energy Relationship Correlations For Room Temperature Ionic Liquids: Revised Cation-Specific And Anion-Specific Equation Coefficients For Predictive Applications Covering A Much Larger Area Of Chemical Space, Laura M. Sprunger, Jennifer Gibbs, Amy Proctor, William E. Acree Jr., Michael H. Abraham, Yunjing Meng, Cong Yao, Jared L. Anderson

Jared L. Anderson

Previously reported ion-specific equation coefficients for both the Abraham general solvation model and Goss modified Abraham model are updated using recently measured activity coefficient, gas chromatographic retention factor, and solubility data for solutes dissolved in room temperature ionic liquids (RTILs). Reported for the first time are equation coefficients for 1-propyl-2,3-dimethylimidazolium cation, and octylsulfate and thiocyanate anions. In total nine sets of cation-specific and eight sets of anion-specific equation coefficients have been determined for each model. The derived correlations describe the 976 experimental gas-to-RTIL partition coefficients to within a standard deviation of 0.12 log units and the 955 experimental water-to-RTIL partitions …

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.

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 [Co(phen)3]3+ on the multi-walled carbon nanotubes is higher than that of single-walled carbon nanotubes.For the carbon nanotubes with …

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 …

Abc's Of Dew (Adi) Software, John Pickle

STEM Digital

Introduction to three color light, pixels, DEW (ADI) tools

Androgen-Stimulated Udp-Glucose Dehydrogenase Expression Limits Prostate Androgen Availability Without Impacting Hyaluronan Levels, Qin Wei, Robert Galbenus, Ashraf Raza, Ronald Cerny, Melanie A. Simpson

Ronald Cerny Publications

UDP-glucose dehydrogenase (UGDH) oxidizes UDP-glucose to UDP-glucuronate, an essential precursor for production of hyaluronan (HA), proteoglycans, and xenobiotic glucuronides. High levels of HA turnover in prostate cancer are correlated with aggressive progression. UGDH expression is high in the normal prostate even though HA accumulation is virtually undetectable. Thus, its normal role in the prostate may be to provide precursors for glucuronosyltransferase enzymes, which inactivate and solubilize androgens by glucuronidation. In this report, we quantified androgen dependence of UGDH, glucuronosyltransferase, and HA synthase expression. Androgen dependent and independent human prostate cancer cell lines were used to test the effects of UGDH …

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

Chemistry Department: 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 …

A Multi-Step Nmr Screen For The Identification And Evaluation Of Chemical Leads For Drug Discovery, Kelly A. Mercier, Matthew D. Shortridge, Robert Powers

Chemistry Department: Faculty Publications

A multi-step NMR based screening assay is described for identifying and evaluating chemical leads for their ability to bind a target protein. The multi-step NMR assay provides structure-related information while being an integral part of a structure based drug discovery and design program. The fundamental principle of the multi-step NMR assay is to combine distinct 1D and 2D NMR techniques, in such a manner, that the inherent strengths and weakness associated with each technique is complementary to each other in the screen. By taking advantage of the combined strengths of 1D and 2D NMR experiments, it is possible to minimize …

Anhydrous Fluoride Salts And Reagents And Methods For Their Production, Stephen G. Dimagno, Haoran Sun

Chemistry Department: Faculty Publications

Anhydrous organic fluoride salts and reagents prepared by a method comprising the nucleophilic Substitution of a fluorinated aromatic or fluorinated unsaturated organic compound with a salt having the formula: [Q_nM]^x+A_x^- in an inert polar, aprotic solvent; wherein M is an atom capable of supporting a formal positive charge, the n groups Q are independently varied organic moieties, n is an integer such that the [Q_nM] carries at least one formal positive charge, x is an integer defining the number of formal positive charge(s), +, carried by the [Q_nM], A^{- …}