Analytical Chemistry Commons^™

Optimization Of Sample Preparation In Matrix-Assisted Laser Desorption/Ionization (Maldi) Mass Spectrometry Of Macromolecules, Evgenia Akhmetova

Graduate Theses and Dissertations

New method for the matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) and Fourier transform mass spectrometry (MALDI-FTMS) analysis of low molecular weight polyvinyl acetate (PVAc) was developed and then applied to the characterization of commercially available chewing gum. The optimization of MALDI analysis of PVAc was achieved by investigating the influence of sample preparation variables such as the choice of solvent and choice of matrix-analyte ratio. It was demonstrated that the use of ethyl acetate as a solvent and 2,5-Dihydroxybenzoic acid as a matrix yielded the highest signal intensity for the pure polymer sample. The application of TOF technique did not …

Characterization By Nmr Of Reactants And Products Of Hydrofluoroether Isomers, Cf3(Cf2)3och3 And (Cf3)2c(F)Cf2och3, Reacting With Isopropyl Alcohol, Howard Knachel, Vladimir Benin, William E. Moddeman, Janine C. Birkbeck, Thomas A. Kestner, Tayna L. Young

Chemistry Faculty Publications

The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the ¹H and ¹⁹F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine …

Surface Tethered Pamam Dendrimers On Controlled Pore Glass As Color Release Sensors For Phosphates, Chang Liu

Master's Theses

Poly(amidoamine) dendrimer (PAMAM) are highly branched macromolecules with reactive amine groups in their interior and exterior. PAMAM dendrimers were attached to controlled pore glass (CPG) surfaces in order to create new functionalized surfaces and used as platforms for UV-vis and fluorescent sensing of phosphate substrates via indicator displacement assays (IDA).

CPG surfaces were first modified with different sized PAMAM dendrimers (generation 3.0, 4.0, and 5.0), then reacted with two strong metal-chelators: aminofunctionalized terpyridine (synthesized from 2,2’:6’,2’’-terpyridine) and Nα-Nα-bis(carboxymethyl)-L-lysine (Lys-NTA). First of all, Cu(II) metal ion binding capacities were measured on the surfaces. Second, two terminal group density tests, amine assay …

Effect Of Leaving Ligands Of Platinum(Ii) Diamine Complexes On Dna And Protein Residues, Ramya Kolli

Masters Theses & Specialist Projects

Platinum compounds are widely used drugs in cancer treatments. Although DNA is the biological target, reaction of platinum compounds with proteins is also potentially significant. Our objective is to study the effects of leaving ligands on the relative reactivity between 5'-GMP (guanosine 5' phosphate), a key DNA target, and N-Acetyl - L-Methionine (N-AcMet), a key protein target. We have used NMR spectroscopy to monitor reactions with N-AcMet and 5'-GMP added to a platinum complex to see which products are formed preferentially. Previous research showed that both a non-bulky complex such as [Pt(en)(D₂O)₂]²⁺ [en=ethylenediamine], and a …

Study Of Immobilizing Cadmium Selenide Quantum Dots In Selected Polymers For Application In Peroxyoxalate Chemiluminescence Flow Injection Analysis, Christopher S. Moore

Electronic Theses and Dissertations

Two batches of CdSe QDs with different sizes were synthesized for immobilizing in polyisoprene (PI), polymethylmethacrylate (PMMA), and low-density polyethylene (LDPE). The combinations of QDs and polymer substrates were evaluated for their analytical fit-for-use in applicable immunoassays. Hydrogen peroxide standards were injected into the flow injection analyzer (FIA) constructed to simulate enzyme-generated hydrogen peroxide reacting with bis-(2,4,6-trichlorophenyl) oxalate.

Linear correlations between hydrogen peroxide and chemilumenscent intensities yielded regression values greater than 0.9750 for hydrogen peroxide concentrations between 1.0 x 10^-4 M and 1.0 x 10^-1 M. The developed technique’s LOD was approximately 10 ppm. Variability of the prepared …

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils

Chemistry Faculty Publications

One way to improve fuel efficiency in today’s jet aircraft engines is to create an environment for higher operating temperatures and speeds. New and improved lubricants and bearing materials must be developed to remain stable in these elevated operating temperatures. Three lubricants, with varying amounts of tricresyl phosphate added as an anti-wear/extreme pressure additive were tested on two different stainless steels at varying temperatures ranging from 300 °C to 350 °C in vacuum. Significant decomposition of the lubricant base-stocks and the phosphate ester additive did occur in most of the trials resulting in the formation of carboxylic acids and phenols. …

Polymers For Dna Binding, Sue Yuan Li

Seton Hall University Dissertations and Theses (ETDs)

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Separation Of Tc From U And Development Of Metallic Tc Waste Forms, Edward Mausolf

UNLV Theses, Dissertations, Professional Papers, and Capstones

The isotope Technetium-99 (⁹⁹Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t_1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO₄]^-, Tc represents long-term concern to the biosphere. Various options have been considered to manage ⁹⁹Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric …

An Electrochemical Impedance Spectroscopic Study Of Cuf2/Moo3/C Cathode Composites, Yue-Li Shi, Nan Wu, Ming-Fang Shen, Jia-Qun Dong, Quang-Chao Zhuang, Li Jiang

Journal of Electrochemistry

Composite electrode of CuF₂/MoO₃/C was fabricated through high energy mechanical milling. The properties of CuF₂/MoO₃/C were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), galvanostatic charge-discharge measurements, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the grain sizes of CuF₂ and MoO₃ after milling were 200 ~ 300 nm, and the initial discharge capacity of CuF₂/MoO₃/C was 647 mAh·g^-1 at room temperature and at a current density of 10 mA·g^-1. However, the …

Current Development Of Quantum Dots Based Electrochemiluminescence Immunosensors, Ling-Ling Li, Qian Lu, Jun-Jie Zhu

Journal of Electrochemistry

Electrochemiluminescence exhibits the merits of both luminescence and electrochemistry analysis, and has been extensively employed in biosensors. Quantum dots are considered one of the three main kinds of electrochemiluminescence luminophores due to their unique properties. This paper briefly reviews the classification and signal amplification technology of quantum dots based electrochemiluminescence immunosensors. Future research trends are also suggested.

Reliable Peak Selection For Multisample Analysis With Comprehensive Two-Dimensional Chromatography, Stephen E. Reichenbach, Xue Tian, Akwasi A. Boateng, Charles A. Mullen, Chiara Cordero, Qingping Tao

School of Computing: Faculty Publications

Comprehensive two-dimensional chromatography is a powerful technology for analyzing the patterns of constituent compounds in complex samples, but matching chromatographic features for comparative analysis across large sample sets is difficult. Various methods have been described for pairwise peak matching between two chromatograms, but the peaks indicated by these pairwise matches commonly are incomplete or inconsistent across many chromatograms. This paper describes a new, automated method for postprocessing the results of pairwise peak matching to address incomplete and inconsistent peak matches and thereby select chromatographic peaks that reliably correspond across many chromatograms. Reliably corresponding peaks can be used both for directly …

A Computational Study Of The Vibrational Spectra Of Mono-Nitrated Fluoranthenes, Jorge Ojeda

Undergraduate Research Conference

No abstract provided.

A Determination Of The Aspartame Content In Select Diet Beverages, Jorge Ojeda

Undergraduate Research Conference

Millions of dollars are spent every year on diet beverages and there has been much controversy on the contents in these beverages, mainly the artificial sweetener aspartame. It is known that aspartame is included in many diet beverages, but the actual amount of aspartame used is not listed in the nutritional facts or provided by the beverage manufacturers. For this reason, the aspartame content of various soft drinks, Coke Zero, Pepsi Max, Diet Pepsi, and Pepsi Next, was analyzed and compared to a calibration plot utilizing Diet Coke as a standard. Diet Coke was used due to the unavailablity of …

Study And Identification Of Environmental Nanoparticles In Governors State University (Gsu's) Agricultural Fields, Ekta Desai

All Capstone Projects

Main purpose of this project is to study nanoparticles in Governors State University’s agricultural field and design experimental protocol for the same. Nanoparticles have one dimension that measures between 1 - 100 nanometers or less. Nanoparticles are widely used in day to day life such as in medicines, textiles, manufacturing and cosmetics. Due to their wide use, they can enter environment through many ways such as accidental spills during handling. Waste water treatment plant disposal serves as a main source of their entrance into the environment. Analysis of nanoparticles in environmental samples presents a number of challenges, including separation and …

Folic Acid And Its Receptors, Jacqueline Spreadbury

All Capstone Projects

Folic acid, also known as folate or vitamin B9, is essential for various functions in the human body and life as we know it. Folate is the compound that occurs naturally in food, and folic acid is the synthetic form of this vitamin. Chemically speaking, folic acid has the hydrogen (H+) attached to the compound whereas folate is the conjugate, having lost the hydrogen (H+). Structure, Functions of Folate, Folic Acid in Bacteria, Folate Receptors, and Folic Acid Receptor in Macrophages are discussed in this literature review project. (abstract by OPUS staff)

Synthesis Of A Folate Conjugated Fluorescent Imaging Dye, Daniel Bonner

All Capstone Projects

In recent years methods of selective targeting of pathologic cells have become increasingly important for both detection and treatment of various cancers. The use of folic acid as a selective therapeutic and targeting agent for cancer cells is becoming ever more significant. This is due to the well characterized up regulation of folate receptors for cancer cells.

In this experiment we focus on the development of a new folate conjugate dye by using a small fluorescent molecule known as Oregon Green 514 for fluorescent imaging of cancer cells. To obtain this objective we I inked folate with Oregon green 514 …

Uhplc In The Analysis Of Drug Components, Rana Chandra Sekhar Reddy Pulagam

All Capstone Projects

The main objective of this article is to highlight the new trends that have emerged in the enhancement of the HPLC which have given rise to the use of UHPLC. This innovative tool is much more reliable and effective as compared to HPLC, in the investigation of many chemical compounds. In this article, special insight is given on the changes that have been made with regards to both instruments. In this article focus is also placed on the implementation of UPLC in various fields of interest, in order to enhance the processes for which it is utilized. The pros and …

Development Of Method For Detection Of Lead In Samples Collected From Keweenaw Peninsula Mines, Michigan In Collaboration With Environmental Biology Research Students, Sindhu Reddy Aaireddy

All Capstone Projects

Mining is one of the most important industries and a main cause of global pollution due to release of heavy metals into air, water, and soil. Some of these elements are persistent in the environment for years and bioaccumulation in living organisms causing toxic effects. Such elements are known as PBTs (persistent, bioaccumulate and toxic). The nature of toxicity depends on the properties, size of population exposed to it and period of exposure. For this reason, we are interested in developing a method to detect heavy metals in soil samples, mine tailings, plant and animal samples collected from surroundings of …

Mass Spectral Imaging For Analysis Of Pharmaceutical Ingredients, Abdul Majid Mohammed

All Student Theses and Dissertations

Mass spectral imaging (MS-imaging) is a modern technique used for the analysis and characterization and distribution of pharmaceutical ingredients , drugs, peptidies, lipids, and other bioactive species in tissue section/ Tissue prints. Although now widely accepted, there remains a host of competing and complementary techniques including DESI, MALDI, SIMS, and DART ionization techniques that allow the researchers to obtain appreciable ion intensities for mapping purposes. Instrumentation further is, rapidly advancing with significant progress in TOF, ion trap, and quadrupole instrumentation for mapping. In this review, I will examine the current status and role of MS-imaging with emphasis on analysis of …

Metal-Organic And Supramolecular Architectures Based On Mechanically Interlocked Molecules, Isurika Rosini Fernando

Dissertations

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials.

Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, …

Monolayer-Protected Nanoparticle Doped Xerogels As Functional Components Of Amperometric Glucose Biosensors, Michael Hartley Freeman, Jackson R. Hall, Michael C. Leopold

Chemistry Faculty Publications

First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during …

Combination And Applications Of Time-Resolved Surface Plasmon Resonance Spectroscopy And Electrochemical Methods, Yu Bao, Yan Mao, Wei Wang, Zheng-Gang Li, Li Niu

Journal of Electrochemistry

Electrochemical-surface plasmon resonance (EC-SPR) technique, developed in recent years, is a new technology which combines time-resolved surface plasmon resonance spectroscopy and electrochemical methods. Surface plasmon resonance (SPR) is a physical phenomenon generated by optical coupling using a metallic thin film and is very sensitive to optical analysis. The principles of SPR and EC-SPR are briefly introduced and the applications of the combination of SPR spectroscopy with electrochemical techniques are reviewed in this paper. This new technology has been widely used in such research areas as reaction dynamics, biochemical sensors, electrode/electrolyte interfaces, kinetic parameters and bimolecular interactions.

An In Situ Ftir Spectroelectrochemical Study On Methanol Oxidation At Pt-Mo2C/Gc Catalyst, Hai-Ping Huang, Xi-Yu Yao, Pei-Kang Shen

Journal of Electrochemistry

A 40% Pt on Mo₂C/GC catalyst has been prepared by ion exchange method. The mechanism of methanol electrooxidation on Pt-Mo₂C/GC and commercial Pt/C catalysts in acidic media was studied by cyclic voltammetry, XRD measurements and in-situ Fourier transform infrared spectroelectrochemistry. The results revealed that the Pt nanoparticles were uniformly dispersed on Mo₂C/GC with an average particle size of 3 nm. The cyclic voltammetric and chronopotentiometric experiments indicated that Pt-Mo₂C/GC catalyst exhibited a better performance for methanol oxidation than that of Pt/C in acid solution. A negative shift over 90 mV of the …

Utilizing Nmr Spectroscopy And Molecular Docking As Tools For The Structural Determination And Functional Annotation Of Proteins, Jaime Stark

Department of Chemistry: Dissertations, Theses, and Student Research

With the completion of the Human Genome Project in 2001 and the subsequent explosion of organisms with sequenced genomes, we are now aware of nearly 28 million proteins. Determining the role of each of these proteins is essential to our understanding of biology and the development of medical advances. Unfortunately, the experimental approaches to determine protein function are too slow to investigate every protein. Bioinformatics approaches, such as sequence and structure homology, have helped to annotate the functions of many similar proteins. However, despite these computational approaches, approximately 40% of proteins still have no known function. Alleviating this deficit will …

Preliminary Simulation Study On Classification Of Large Molecules By Newly Designed Cascade Type Differential Mobility Analyzer (Ctdma), Chenxi Zhu

Student Theses and Dissertations

Differential mobility analyzer (DMA), coupled with other instrumentation analyzers, such as mass spectrometry (MS), can classify size, masses and shapes by their different gas-phase electrophoretic mobility. In order to obtain the high resolution in classifying large particles (50 kD ~ 1 MD), our laboratory designed several versions of cylindrical cascade type differential mobility analyzers (CTDMA). Because CTDMAs consist of two cylindrical particle classifiers in one housing, target particles are guided through "gaps" and "stairs", a unique feature to this new particle classification device. Two modes of operation--outward cross flow mode and no-cross flow mode--both reduce the flow rate in the …

Overexpression Of Human Fatty Acid Transport Protein 2/Very Long Chain Acyl-Coa Synthetase 1 (Fatp2/Acsvl1) Reveals Distinct Patterns Of Trafficking Of Exogenous Fatty Acids, Elaina M. Melton, Ronald Cerny, Concetta C. Dirusso, Paul N. Black

Ronald Cerny Publications

In mammals, the fatty acid transport proteins (FATP1 through FATP6) are members of a highly conserved family of proteins, which function in fatty acid transport proceeding through vectorial acylation and in the activation of very long chain fatty acids, branched chain fatty acids and secondary bile acids. FATP1, 2 and 4, for example directly function in fatty acid transport and very long chain fatty acids activation while FATP5 does not function in fatty acid transport but activates secondary bile acids. In the present work, we have used stable isotopically labeled fatty acids differing in carbon length and saturation in cells …

High-Pressure Cryogelation Of Nanosilica And Surface Properties Of Cryosilicas, V M. Gun'ko, V V. Turov, V I. Zarko, G P. Prykhod'ko, O S. Remez, R Leboda, J Skubiszewska-Zieba, E M. Pahklov, Jonathan Blitz

Faculty Research and Creative Activity

Silica cryogels (cryosilicas) in a powder state were synthesized with different concentrations of fumed silica A-300 (CA-300 = 5-20 wt.%), sonicated in aqueous suspension, then frozen at -14 oC at different pressures in a high-pressure stainless steel reactor (a freezing bomb), and dried in air at room temperature. To analyze the effects of low temperature and high pressure, samples were also prepared at -14 oC or room temperature and standard pressure. The structural and adsorption properties of the powder materials were studied using nitrogen adsorption, high-resolution transmission electron microscopy, infrared spectroscopy, thermogravimetry, low-temperature 1H NMR spectroscopy and thermally stimulated depolarization …

High-Pressure Cryogelation Of Nanosilica And Surface Properties Of Cryosilicas, V Gun'ko, V Turov, V Zarko, G Prykhod'ko, O Remez, R Leboda, J Skubiszewska-Zieba, E Pahklov, Jonathan Blitz

Faculty Research and Creative Activity

Silica cryogels (cryosilicas) in a powder state were synthesized with different concentrations of fumed silica A-300 (CA-300 = 5-20 wt.%), sonicated in aqueous suspension, then frozen at -14 oC at different pressures in a high-pressure stainless steel reactor (a freezing bomb), and dried in air at room temperature. To analyze the effects of low temperature and high pressure, samples were also prepared at -14 oC or room temperature and standard pressure. The structural and adsorption properties of the powder materials were studied using nitrogen adsorption, high-resolution transmission electron microscopy, infrared spectroscopy, thermogravimetry, low-temperature 1H NMR spectroscopy and thermally stimulated depolarization …

A Facile, Low-Cost Route For The Preparation Of Calcined Porous Calcite And Dolomite And Their Application As Heterogeneous Catalysts In Biodiesel Production, Rui Wang, Hu Li, Fei Chang, Jiafeng Luo, Milford A. Hanna, Daoyang Tan, Deyu Hu, Yuping Zhang, Baoan Song, Song Yang

Department of Chemistry: Faculty Publications

Despite their potential for biodiesel synthesis, directly calcined minerals rich in magnesium/calcium carbonates are used at the expense of large amounts of the catalyst, high alcohol loading, long processing times, and severe conditions. We report a facile and low-cost route for preparing calcined porous calcite (CPC) and dolomite (CPD) via simple thermal decomposition of the reaction mixtures of natural calcite and dolomite with stearic acid. CPC and CPD, both of which have porous structures, were compared with previously reported catalysts and examined as promising heterogeneous base catalysts under mild conditions. A 40% increase in conversion through CPC and CDC was …

Re2o7-Catalyzed Reaction Of Hemiacetals And Aldehydes With O-, S-, And C-Nucleophiles, Wantanee Sittiwong, Michael W. Richardson, Charles E. Schiaffo, Thomas J. Fisher, Patrick H. Dussault

Department of Chemistry: Faculty Publications

Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re₂O₇ or a Brønsted acid.