Analytical Chemistry Commons^™

Incorporation Of Capillary-Channeled Polymer (C-Cp) Fibers Into Micropipette Tips For Solid Phase Extraction With Applications In Bioanalysis, Donald Fornea

All Theses

Solid phase extraction (SPE), is a widely used sample preparation method that is currently experiencing a surge in research interest, clever architecture/format development, and stationary phase characterization.1-3 SPE devices commonly exist in syringe, cartridge, disk, and micropipette tip formats.4 Micropipette tip SPE has enhanced the determination of proteins by electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS) by handling micro-liter volumes of sample and buffer removal/solvent exchange.5-7 Buffers have deleterious effects on ionization taking place in MS sources due to preferential ionization, ion suppression effects, and the formation of adduct species competing for ionization in …

Characterization Of Capillary-Channeled Polymer Fibers As Stationary Phases For High-Performance Liquid Chromatography Of Macromolecules, Dwella Nelson

All Dissertations

Capillary-channeled polymer (C-CP) fibers are being developed and characterized as high-performance liquid chromatography (HPLC) stationary phases for reversed-phase separations of proteins. Conventional porous phases are not well suited for separating large macromolecules due to the slow diffusivity of the molecules, large diffusional distances, and stagnant mobile phase zones within the column. Stationary phases are continually being developed to address the challenges associated with HPLC of proteins and other macromolecules in general. C-CP fiber stationary phases are an alternative to conventional bead technology and offer a variety of chemical and physical advantages. The fibers can be selected for their chemical functionality …

Statistical Thermodynamics And Kinetics Of Dna Multiplex Hybridization Reactions, Albert S. Benight, M. T. Horne, D. J. Fish

Chemistry Faculty Publications and Presentations

A general analytical description of the equilibrium and reaction kinetics of DNA multiplex hybridization has been developed. In this approach, multiplex hybridization is considered to be a competitive multichannel reaction process: a system wherein many species can react both specifically and nonspecifically with one another. General equations are presented that can consider equilibrium and kinetic models of multiplex hybridization systems comprised, in principle, of any number of targets and probes. Numerical solutions to these systems for both equilibrium and kinetic behaviors are provided. Practical examples demonstrate clear differences between results obtained from more common simplex methods, in which individual hybridization …

Stm Tip-Induced Nanostructuring-Replacement Method To Construct Pt Surface Nanostructures, Jin-Gang Wang, Jing Tang, Zhao-Bin Chen, Bing-Wei Mao

Journal of Electrochemistry

STM tip-induced surface nanostructuring based on "Jump-to-contact" mechanism is a nanostructuring technique that has the highest resolution in aqueous solutions.However,for metals that have high cohesive energy,atoms would transfer from surface to tip instead,which limits the wide application of this technique.In this paper,we present a two-step Nanostructuring-Replacement method to construct metal nanoclusters that cannot be obtained directly via the "Jump-to-contact" mechanism.The method is demonstrated to construct Pt nanoclusters that are of great interest in catalysis and electrocatalysis but cannot be constructed via the "Jump-to-contact" mechanism.Since Cu is the most intensively studied and successful system in the tip-induced nanostructuring,it is utilized as …

Electrochemical Behavior Of Tanshinoneⅱa And Its Determination, Guang-Wen Li, Xin-Hua Lin, Xiao-Yan Lin

Journal of Electrochemistry

The electrochemical behavior of TanshinoneⅡA was investigated by voltammetry at a glassy carbon electrode.And Differential Pulse Voltammetric method for determination of TanshinoneⅡA was developed.In pH 4.0 acetate buffer solution,the relationship between oxidation peak current of Differential Pulse Voltammetric and the concentration of Tanshinone ⅡA was linear in the range of 3.0×10 ~(-7)～2.0×10 ~(–5) mol·L~(-1).The detection limit had been estimated as 2.0×10~(-8) mol·L~(-1).The interference of other components in the preparation could be efficiently eliminated by the glassy carbon electrode.This method can be used for the determination of TanshinoneⅡA in real sample with satisfactory results

Significance Of Polycyclic Aromatic Hydrocarbons (Pahs) And Petroleum Biomarker Compounds In Contaminated Passaic River Sediments, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lower Passaic River (northeastern New Jersey) flows through one of the most densely populated regions of the United States. The area’s long history of industrial activity is reflected in the complex and variable hydrocarbon composition of the river sediments. Sediments from river bottom grab samples at Newark and a 30 cm deep core at Kearny were subjected to thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). This technique offers a practical alternative for rapid, inexpensive analysis, simply employing milligram quantities of dry, disaggregated sediment, avoiding the use of hazardous organic solvents. For each sample, a total of 181 hydrocarbons and organosulfur compounds …

Pre-Oxidative Amperometric Glucose Biosensor Incorporated With Carbon Nanotube And Pbo_(2), Hong-Lan Qi, Cheng-Xiao Zhang

Journal of Electrochemistry

A pre-oxidative amperometric glucose biosensor incorporated with carbon nanotube,ferrocenemonocarboxylic acid and PbO_(2) was designed.The interferences coming from reduced substances,such as ascoribic acid and urine acid were eliminated by PbO_(2).The oxidative current is linear at the potential of +0.40 V(vs.SCE) to the concentration of glucose in the range from 0.50 to 20 mmol·L~(-1),and the detection limit of glucose is 0.1 mol L~(-1).The relative standard deviation is 3.3% for seven successive assays at 5.0 mmol·L~(-1)glucose.This biosensors have been applied to determination of the glucose in serum with satisfying results.

Reversed-Phase Hplc Determination Of Citral In Locally Grown Lemon Grass Harvested At Different Season., Mahmoud Al-Shaer

Electronic Theses and Dissertations

A simple HPLC procedure for the quantitative determination of citral, the major fragrant component in the lemon grass, has been developed. The procedure involves a C-8 stationary phase using a 90:10 methanol: water pH 5 mobile phase containing 0.25% 1-octanesulfonic acid and an UV detector (set at 233 nm). The lemon grass leaves were harvested fresh at different times of the year and were soaked in methanol for 48 hours without any mechanical assistance to extract the citral and other methanol soluble components. The method showed good reproducibility with relative standard deviation of 2.8% and 10.8% for two different sets …

Determination Of Cholesterol In Foods By Flow Injection Analysis With Perroxyoxalate Chemiluminescence., Abisake Feleke

Electronic Theses and Dissertations

Cholesterol is an important biological molecule with many important functions. However, high serum cholesterol is a health hazard. Thus analysis of cholesterol is important and many analytical techniques have been developed. The objectives of the proposed research are to develop an economical, rapid method for the determination of total cholesterol with good selectivity and enhanced sensitivity. For evaluation of proposed flow injection analysis with peroxyoxalate chemiluminescence (FIA-POCL) method, figures of merit such as accuracy, precision, and linear dynamic range will be assessed. The proposed procedure was then applied to the determination of total cholesterol in foods. The procedure was linear …

Criticality Studies Of Dilute Plutonium Mixtures For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of higher actinides (HA, includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel has been identified as a requirement to construct prototype plants such as the Engineering-Scale Demonstration (ESD) and the Advanced Fuel Cycle Facility (AFCF) for the Global Nuclear Energy Partnership (GNEP). GNEP is a program to develop a worldwide consensus to enable the expanded use of economical, environmental nuclear energy to meet growing electricity demand. In this program and the Advanced Fuel Cycle R&D program (AFC) that supports it, we are developing economic …

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report January-March 2006, Spencer M. Steinberg

Separations Campaign (TRP)

Project Highlights:

• Established that iodide can be oxidized by MnO₂ to I₂ at pHs of 4-8 and moderate temperature.

• Demonstrated that p-hydroxybenzoic acid can be iodinated by MnO₂ and KI at pHs of 2-8.

• Established that humic acids can be iodinated by MnO₂ and iodide at room temperature in pH range of 4-8.

The Electrochemical Separation Of Curium And Americium: Quaterly Report January - March, 2006, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. For two and a half years, research has been actively performed on this project, and is currently on schedule for the proposed timelines.

Progress:

• The electrochemical characterization of Ce and Eu complexed with EDTA, NTA, and Citrate has been completed.

• Synthesis of the polymer substrate and the chelating ligand is underway. Approximately 50 grams of disulfide has been produced to produce the chelating thiol group required for the last set of studies.

• Gold substrates have been prepared to perform …

In-Situ Detection Of The Effect Of Brighter In The Solution For Nickel And Phosphor Alloy, Jian Zheng, Ning Li, De-Yu Li, Guo-Feng Cui

Journal of Electrochemistry

In this work,the gold-plated mica was used for the substrate,the concentration of 5% of normal plating solution for the nickel was used as the mother solution,and the effect for the deposition by the brighter with ECSTM was in-situ detected.The solution for deposition without the brighter has no brightness,though the values of the roughness and the H_(A-V) have reduced in evidence after deposition;the solution for deposition with the complete brighter although has great brightness,the values of the roughness and the H_(A-V) have increased(after) deposition;the solution for deposition with the half brighter has a moderate effect on the H_(A-V) and (brightness).Hence,the brighter …

Femtosecond Nuclear Motion Of Hcl Probed By Resonant X-Ray Raman Scattering In The Cl 1s Region, Marc Simon, Loic Journel, Stephane Carniato, Richard Taieb, I. Minkov, Faris Gel'mukhanov, P. Salek, H. Agren, Renaud Guillemin, Wayne C. Stolte, A. C. Hudson, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations.

Evaluation Of The Vaporization, Fusion, And Sublimation Enthalpies Of The 1-Alkanols: The Vaporization Enthalpy Of 1-, 6-, 7-, And 9-Heptadecanol, 1-Octadecanol, 1-Eicosanol, 1-Docosanol, 1-Hexacosanol, And Cholesterol At T = 298.15 K By Correlation Gas Chromatography, Gary Nichols, Sasha Kweskin, Margaret Frericks, Sarah Reiter, Gin Wang, Jennifer Orf, Brett Carvallo, Dorothea Hillesheim, James Chickos

James Chickos

No abstract provided.

Education And Training Of Bs Analytical Chemists For Entry-Level Positions In Industry: A Survey, Julian Tyson, Angela M. Fahey

Chemistry Department Faculty Publication Series

Surveys, in 1993 and 2003, of industrial employers of BS analytical chemists show that respondents consider employees’ abilities to work as a team member, solve problems, write and communicate orally, work safely with a positive ethic, perform calculations, and apply basic chemical principles to be the most important. There is dissatisfaction with the preparation of graduates with regard to communications skills, safety training, and problem-solving abilities. Respondents also indicated that graduates should have had hands-on experience with a variety of chromatographic and spectroscopic techniques as well as some techniques not commonly encountered in the teaching laboratory, such as auto-titration, microwave …

Investigation Of Coke Deposition And Coke Inhibition By Organosulfur Compounds In The Pyrolysis Of Naphtha In The Jet Stirred Reactor System, D Salari, A Niaei, J Towfighi, P Panahi, Reza Nabavi

Seyed Reza nabavi

No abstract provided.

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of nuclear waste. Iodine-129, a long-lived fission product formed by both commercial nuclear power generation and nuclear weapons production, is released when reprocessing nuclear fuel. Since iodine can be concentrated in the human thyroid, any uncontrolled release of iodine may result in an increased rate of thyroid cancer in the exposed population. For this reason, recovery of iodine is important for implementing any nuclear transmutation strategy.

The stability of the association of iodine with FCC and NOM products are studied. Product …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in aqueous solution and use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborators, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed Phases 1 and 2.

The following were specific goals for this year:

• To develop a fundamental …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The research objectives of this project are as follows:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration (by the addition of NaNO₃), actinide ion concentration, temperature, and time.
• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.

A Minimum-Impact Method For Measuring Corrosion Rate Of Steel-Hulled Shipwrecks In Seawater, Matthew A. Russell, David L. Conlin, Larry E. Murphy, Donald L. Johnson, Brent M. Wilson, James D. Carr

Chemistry Department: Faculty Publications

Current research on USS Arizona is focused on a minimum-impact technique for calculating corrosion rate of the battleship’s steel hull by analysing physical and chemical properties of marine encrustation covering the exposed hull. An equation is derived that allows concretion thickness, density, and total iron content to be used to calculate corrosion rate of steel hull plate.

Novel Derivatizing Agents For The Determination Of Methylmercury By Gas Chromatography Using Electron Capture Detection, Crystal Marie Irwin

Dissertations, Theses, and Masters Projects

No abstract provided.

A Chloride Selective Calix[4]Arene Optical Sensor Combining Urea Functionality With Pyrene Excimer Transduction, Benjamin Schazmann, Dermot Diamond

Articles

A neutral 2-site chloride selective compound has been developed (3), based on a 1,3- alternate tetrasubstituted calix[4]arene providing a preorganised supramolecular scaffold. The resultant supramolecular cavity is amongst the first to combine urea functional groups bridged with single methylene spacers to pyrene moieties. It combines a naturally and synthetically proven H-bonding system with the elegant ratiometric fluorescent signalling properties of an intramolecular pyrene excimer system, triggered by conformational changes upon anion coordination. The excimer emission of 3 is quenched, with a simultaneous rise in the monomer emission solely by the chloride anion amongst a wide variety of anions tested. 3 …

Development Of A Calix[4]Arene Sensor For Soft Metals Based On Nitrile Functionality, Benjamin Schazmann, Dermot Diamond

Articles

The current work is amongst the first to examine the potential usefulness of the nitrile functional group in potentiometric analytical sensors for soft metals. Nitrile functionality has hereby been incorporated into a calix[4]arene skeleton to give a series of new cation selective hosts. The analytical sensing behaviour of these hosts was examined by Ion Selective Electrode (ISE) based potentiometry. In all cases a preference for soft metals was observed, explained primarily in terms of soft–soft compatibility between calix[4]arene nitrile hosts and metal guests in combination with a classical ‘lock and key’ best fit mechanism. Hosts 2, 3 and 4 showed …

The Determination Of Probes For The Indirect Detection Of Anions In Capillary Zone Electrophoresis Using Light Emitting Diode Detection, Peter Ashley Balding

Theses : Honours

This study investigated the potential of a number of compounds to act as probes for the indirect detection of inorganic and organic anions separated by capillary zone electrophoresis and using light emitting diodes (LED) as the light source. Desirable characteristics of the probe anion included: high molar absorptivity, moderate to high electrophoretic mobility, and having a wavelength of maximum absorbance near the maximum emission wavelength of a LED. A preliminary study led to the evaluation of eleven possible compounds. Two of these, p-nitrophenol and 4-hydroxy-3,5-dinitrobenzoic acid were selected for further study as they fulfilled the criteria previously mentioned. The optimised …

Automated Peak Identification For Time -Of -Flight Mass Spectroscopy, Haijian Chen

Dissertations, Theses, and Masters Projects

The high throughput capabilities of protein mass fingerprints measurements have made mass spectrometry one of the standard tools for proteomic research, such as biomarker discovery. However, the analysis of large raw data sets produced by the time-of-flight (TOF) spectrometers creates a bottleneck in the discovery process. One specific challenge is the preprocessing and identification of mass peaks corresponding to important biological molecules. The accuracy of mass assignment is another limitation when comparing mass fingerprints with databases.;We have developed an automated peak picking algorithm based on a maximum likelihood approach that effectively and efficiently detects peaks in a time-of-flight secondary ion …

Preparation Of Conducting Polyaniline/Nylon 6 Blend Fiber By Wet Sppinning Technique, A Mirmohseni, D Salari, Reza Nabavi

Seyed Reza nabavi

No abstract provided.