Chemistry Commons^™

In Vivo Imaging Of Transport And Biocompatibility Of Single Silver Nanoparticles In Early Development Of Zebrafish Embryos, Kerry J. Lee, Prakash D. Nallathamby, Lauren M. Browning, Christopher J. Osgood, Xiao-Hong Nancy Xu

Chemistry & Biochemistry Faculty Publications

Real-time study of the transport and biocompatibility of nanomaterials in early embryonic development at single-nanoparticle resolution can offer new knowledge about the delivery and effects of nanomaterials in vivo, and provide new insights into molecular transport mechanisms in developing embryos. In this study, we directly characterized the transport of single silver nanoparticles into an in vivo model system (zebrafish embryos) and investigated their effects on early embryonic development at single-nanoparticle resolution in real time. We designed highly purified and stable (not aggregated and no photodecomposition) nanoparticles and developed single-nanoparticle optics and in vivo assays to enable the study. We …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU–includes Np, Pu, Am, and Cm) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership. In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in this new …

Structure And Biosynthesis Of Heat-Stable Antifungal Factor (Hsaf), A Broad-Spectrum Antimycotic With A Novel Mode Of Action, Fengan Yu, Kathia Zaleta-River, Xiangcheng Zhu, Justin Huffman, Jeffrey C. Millet, Steven D. Harris, Gary Y. Yuen, Xing-Cong Li, Liangcheng Du

Department of Chemistry: Faculty Publications

A screen for antifungal compounds from Lysobacter enzymogenes strain C3, a bacterial biological control agent of fungal diseases, has previously led to the isolation of heat-stable antifungal factor (HSAF). HSAF exhibits inhibitory activities against a wide range of fungal species and shows a novel mode of antifungal action by disrupting the biosynthesis of a distinct group of sphingolipids. We have now determined the chemical structure of HSAF, which is identical to that of dihydromaltophilin, an antifungal metabolite with a unique macrocyclic lactam system containing a tetramic acid moiety and a 5,5,6-tricyclic skeleton. We have also identified the genetic locus responsible …

Corrosion Studies On The Uss Arizona With Application To A Japanese Midget Submarine, Brent M. Wilson, Donald L. Johnson, Hans Vantilburg, Matthew A. Russell, Larry E. Murphy, James D. Carr, Robert J. De Angelis, David L. Conlin

Department of Chemistry: Faculty Publications

The assessment of corrosion on the USS Arizona included the pioneering development of a minimum-impact cost-effective technique to determine the corrosion rate of steel-hulled shipwrecks in seawater. The technique, with potential application worldwide, is illustrated in this paper with the application to a World War II Japanese midget submarine submerged in deep waters off the Oahu, Hawaii, coast.

Understanding Charged Aerosol Detection With High Performance Liquid Chromatography, Brian John Forsatz

Seton Hall University Dissertations and Theses (ETDs)

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Improved Nitrate Sensing Using Ion Selective Electrodes Based On Urea–Calixarene Ionophores, Benjamin Schazmann, Dermot Diamond

Articles

Urea–calix[4]arenes 1 and 2 were synthesised and incorporated into ISE membranes for assessment as sensors for inorganic anions in water. 1 revealed a strong response to all anions following the Hofmeister selectivity order. For ISEs of 2, the response to a portion of the anion series was suppressed, increasing the margin of selectivity of nitrate over chloride, a common interferant of nitrate in fresh and marine water samples. The performance of ISEs containing 2 was compared to commercially available alkylammonium nitrate ion-exchange salts used for nitrate sensing. Our ISEs performed favourably in terms of sensitivity, linear range and LOD performing …

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 stability of the association of iodine with FCC and NOM products were studied. Product distributions for the various matrices under various reaction conditions were examined in order to maximize the binding of iodine. The recovery of the iodine from the sequestration matrices was also examined, along with the conversion of the iodine to matrices more suitable for geological storage and/or use as transmutation targets.

The following are the specific research objectives and goals:

• Develop bench-scale experimental set-up and procedures for simulating plutonium extraction process (PUREX) head-end vapor phase.
• Develop experimental procedures for evaluating iodine sequestering methods using bench-scale procedures. …

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

Separations Campaign (TRP)

The objectives of this project are to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solution, and to use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborator, 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. Phase 3 has been partially completed. The tasks have been expanded …

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

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

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, 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 …

F-Element Electrochemistry In Room Temperature Ionic Liquids, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This proposal focuses on f-element electrochemistry in room temperature ionic liquids (RTILs). The ultimate goal is to fully characterize the oxidation/reduction of elements in RTILs to establish the baseline thermodynamic and kinetic data for these systems. The data will be used to critically evaluate the ability to use electrochemical methods for controlled, potential mediated, separation off-elements by electroplating on electrodes surfaces. Factors that will influence the ability to measure the redox processes in f-elements in RTIL solutions and electroplating on electrode surfaces include the structure, solubility, and stability of the target species in these solutions. These factors will be addressed …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the UREX separation scheme, providing data useful to modeling. The areas to be examined include the speciation of U and Pu with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK system. The complexation constants of U and Pu with tributylphosphate will be evaluated. In the TALSPEAK system, …

The Application Of Electrospray Ionization Coupled To Ultrahigh Resolution Mass Spectrometry For The Molecular Characterization Of Natural Organic Matter, Rachel L. Sleighter, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (> 3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (> 200000) techniques such as electrospray ionization (ESI) coupled …

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 …

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.

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 …

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 Pbo2, Hong-Lan Qi, Cheng-Xiao Zhang

Journal of Electrochemistry

A pre-oxidative amperometric glucose biosensor incorporated with carbon nanotube,ferrocenemonocarboxylic acid and PbO₂ was designed.The interferences coming from reduced substances,such as ascoribic acid and urine acid were eliminated by PbO₂.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^-1glucose.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.

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 …

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.