Chemistry Commons^™

Annealing Of Amorphous Fexco100-X Nanoparticles Synthesized By A Modified Aqueous Reduction Using Nabh4, Kyler J. Carroll, Daniel M. Hudgins, L. W. Brown Iii, S. D. Yoon, D. Heiman, V. G. Harris, Everett E. Carpenter

Chemistry Publications

FexCo100−x nanoparticles were synthesized by aqueous reduction in iron (II) sulfate and cobalt (II) sulfate using sodium borohydride and sodium citrate. The initial concentrations of iron and cobalt were varied while maintaining an overall metal concentration of 4.60 mM. Increasing the cobalt content from 0 to 100 at. % decreased the magnetization saturation from 152 to 48 emu/g, as determined by room temperature vibrating sample magnetometry. Annealing the samples at 450 and 600 °C showed an increase in crystallite size. Powder x-ray diffraction and transmission electron microscopy was performed to determine the phases and morphology of the materials.

Nonclassical Crystallization Of Amorphous Iron Nanoparticles By Radio Frequency Methods, Kyler J. Carroll, J. A. Pitts, Kai Zhang, A. K. Pradhan, E. E. Carpenter

Chemistry Publications

Amorphousironnanoparticles were synthesized using an aqueous reduction in iron(II) sulfate with sodium borohydride and sodium citrate. Various radio frequency (rf) exposure times were investigated in order to determine trends in nonclassical crystallization. RF times from 15 to 300 s revealed an increase in crystallite size from 5 to 60 nm, as determined by powde rx-ray diffraction. Also, solvent optimization revealed that ethanol produced the largest trends for increasing crystallite size without total oxidation of the samples. Magnetic characterization by room temperature vibrating sample magnetometry and high resolution transmission microscopy was performed to verify magnetic properties and particle morphology.

Synthetic Study Of Para-Substituted 5,6-Fused Ring Pyridazines, Justin Mobley

Mahurin Honors College Capstone Experience/Thesis Projects

Much of the focus in organic chemistry today is in area of green chemistry. With such large amounts of attention being paid to how do we create a more sustainable world, the focus has been to come up with new ways to not only create energy but to conserve energy and use recyclable products. One possible solution is through the use of organic and organometallic semiconductors. Due to their structural nature, organic semiconductors show similar conducting potential to that of metals such as copper with the potential to be more durable and more efficient. This project focuses strictly on the …

Sampling The Conformation Of Protein Surface Residues For Flexible Protein Docking, Patricia Francis-Lyon, S Gu, J Hass, N Amenta, P Koehl

Nursing and Health Professions Faculty Research and Publications

Background: The problem of determining the physical conformation of a protein dimer, given the structures of the two interacting proteins in their unbound state, is a difficult one. The location of the docking interface is determined largely by geometric complementarity, but finding complementary geometry is complicated by the flexibility of the backbone and side-chains of both proteins. We seek to generate candidates for docking that approximate the bound state well, even in cases where there is backbone and/or side-chain difference from unbound to bound states.

Results: We divide the surfaces of each protein into local patches and describe the effect …

The Growth And Evolution Of Thin Oxide Films On Δ-Plutonium Surfaces, Harry G. García Flores, David L. Pugmire

Department of Chemistry: Faculty Publications

The common oxides of plutonium are the dioxide (PuO₂) and the sesquioxide (Pu₂O₃). The nature of an oxide on plutonium metal under air at room temperature is typically described as a thick PuO₂ film at the gas-oxide interface with a thinner Pu₂O₃ film near the oxide-metal substrate interface. In a reducing environment, such as ultra high vacuum, the dioxide (Pu⁴⁺; O/Pu=2.0) readily converts to the sesquioxide (Pu³⁺; O/Pu=1.5) with time. In this work, the growth and evolution of thin plutonium oxide films is studied with x-ray …

Transition States In Ei Reactions, Charles A. Kingsbury

Department of Chemistry: Faculty Publications

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3-21G* to the MP2/6-31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O→σ*_{CH …}

Two-Dimensional To Three-Dimensional Structural Transition Of Gold Cluster Au 10 During Soft Landing On Tio 2 Surface And Its Effect On Co Oxidation, Hui Li, Yong Pei, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We investigate the possible structural transition of a planar Au₁₀ cluster during its soft landing on a TiO₂ (110) surface with or with no oxygen defects. The collision between the gold cluster and the oxide surface is simulated using the Car–Parrinello quantum molecular dynamics method. Both high-speed and low-speed conditions typically implemented in soft-landing experiments are simulated. It is found that under a high-speed condition, the gold cluster Au₁₀ can undergo a sequence of structural transitions after colliding with a defect-free TiO₂ (110) surface. When the TiO₂ (110) surface possesses oxygen vacancies, however, chemical bonds …

Particle Matter Measurements For Inspection/Maintenance Programs, Daniel Joseph Pope

Electronic Theses and Dissertations

Particle emissions from Heavy Duty Diesel Vehicles (HDDVs) are currently measured by opacity or dynamometer gravimetric analysis. The Electronic Tailpipe Particle Sensor (ETaPS) is an inexpensive measurement device purported to give real time response to particle mass and was proposed as a possible addition to Inspection/Maintenance (I/M) programs. There were three goals to this study. The first was to verify ETaPS response to particle mass of HDDV exhaust. Integrated ETaPS signal was plotted against filter weight from dynamometer gravimetric analysis and a correlation was found. The second goal was to find a correlation between ETaPS readings and the Remote Sensing …

Adsorption Efficiency And Partitioning Capabilty Of Surfactant Monolayers On Gold, Carrie Jo M. Pruitt

Mahurin Honors College Capstone Experience/Thesis Projects

We are investigating adsorption efficiencies of sodium dodecyl sulfate (SDS) from pH 7 phosphate buffer onto polycrystalline gold substrates using electrostatics as the primary driving force via electrochemical control of the gold surface potential. It is shown through surface capacitance measurements by electrochemical impedance spectroscopy that the adsorption occurs readily. Measurement of the adsorption isotherms of SDS onto the substrate via the change in surface capacitance as a function of the bulk concentration of SDS has allowed us to determine that the minimum concentration of SDS required for efficient adsorption is below 0.011 mM. The investigation of the influence of …

Pulsed Laser Deposition Of Graphite Counter Electrodes For Dye-Sensitized Solar Cells, Pavel Anzenbacher Jr., Krishna P. Acharya, Himal Khatri, Sylvain Marsillac, Bruno Ullrich, Mikhail Zamkov

Chemistry Faculty Publications

We report on pulsed laser deposition of graphite onto flexible plastic and conductive glass substrates for use as a counter electrode in dye-sensitized solar cells. The efficiency of as-prepared graphite electrodes was tested using CdS-sensitized solar cell architecture resulting in external quantum efficiency comparable to that of conventional platinum counter electrodes. This work highlights the possibility of using pulsed laser deposited graphite as a low-cost alternative to platinum, which could be fabricated both on flexible and rigid substrates. © 2010 American Institute of Physics.

Trace Gas And Particle Emissions From Domestic And Industrial Biofuel Use And Garbage Burning In Central Mexico, Ted J. Christian, Robert Yokelson, B. Cardenas, L. T. Molina, G. Engling, S. C. Hsu

Chemistry and Biochemistry Faculty Publications

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl(-), NO(3)(-), and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Global biofuel use has been estimated at over 2600 Tg/y. With several simple case studies we show that cooking fires can be a major, or the major, source of several gases and fine particles in developing countries. Insulated cook stoves with chimneys were earlier shown to reduce …

Laboratory Measurements Of Trace Gas Emissions From Biomass Burning Of Fuel Types From The Southeastern And Southwestern United States, I. R. Burling, Robert J. Yokelson, David W. T. Griffith, T. J. Johnson, P. Veres, J. M. Roberts, C. Warneke, S. P. Urbanski, J. Reardon, D. R. Weise, Wei Min Hao, J. De Gouw

Chemistry and Biochemistry Faculty Publications

Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. …

Evolution Of Trace Gases And Particles Emitted By A Chaparral Fire In California, S. K. Akagi, J. S. Craven, J. W. Taylor, G. R. Mcmeeking, Robert J. Yokelson, I. R. Burling, S. P. Urbanski, C. E. Wold, J. H. Seinfeld, H. Coe, M. J. Alvarado, D. R. Weise

Chemistry and Biochemistry Faculty Publications

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated down-wind plume in the first similar to 4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared …

Determining The Presence Of An Ignitable Liquid Residue In Fire Debris Samples Utilizing Target Factor Analysis, Kelly Mchugh

Electronic Theses and Dissertations

Current fire debris analysis procedure involves using the chromatographic patterns of total ion chromatograms, extracted ion chromatograms, and target compound analysis to identify an ignitable liquid according to the American Society for Testing and Materials (ASTM) E 1618 standard method. Classifying the ignitable liquid is accomplished by a visual comparison of chromatographic data obtained from any extracted ignitable liquid residue in the debris to the chromatograms of ignitable liquids in a database, i.e. by visual pattern recognition. Pattern recognition proves time consuming and introduces potential for human error. One particularly difficult aspect of fire debris analysis is recognizing an ignitable …

Black Writing Ink Analysis By Direct Infusion Electrospray Mass Spectroscopy, Christopher M. Moody

Electronic Theses and Dissertations

An optimized method of extraction, an instrumental analysis method and data analysis was proposed for black writing inks based on direct infusion electrospray-mass spectrometry (ESI-MS). The sampling and analysis method is both minimally destructive and able to assess differences in inks from a reference collection of thirty ballpoint, gel, and rollerball inks. The methanol extracts of ink on paper samples were analyzed with three direct infusion (ESI-MS) methods. Each method varied scan voltage negative and positive, ESI fragmentor applied voltage (+120V, +0V, and -120V), and mobile phase additive. Direct infusion ESI-MS analysis, followed by pair-wise comparisons of the observed ion …

Single Step Morphology-Controlled Synthesis Of Silver Nanoparticles, Vinodkumar Etacheri, Reenamole Georgekutty, Michael Seery, Suresh Pillai

Articles

Silver nanoparticles having different size and plasmon resonances were synthesized through a single step aqueous based method. The current procedure was based on the reduction of silver ions by ascorbic acid in the presence of sodiumborohydride and trisodium citrate. Triangular colloidal nanoparticles having different plasmon resonances (and hence different size and colours) were synthesized by varying only the concentration of ascorbic acid. These nanoparticles were found to be stable without using any surfactants or polymers. This study revealed a strong correlation between particle growth and concentration of constituent chemicals. Crystallinity and phase purity of the silver samples were investigated through …

Design, Synthesis And Characterization Of Oriented Glyco-Affinity Macroligands For Glyco-Capturing, Glycomics And Glycoproteomics Applications, Srinivas Chalagalla

ETD Archive

Cell surface carbohydrates existing as parts of glycoproteins, glycolipids, and other conjugates present the first information about cell to the outside world and are intimately involved in various biological events such as intercellular communication, and molecular and cellular targeting. However, mechanisms of most processes at the molecular level are still unclear. Therefore, it is very important to develop carbohydrate-specific binding molecules for rapid, efficient, sensitive purification and accurate analysis of complex carbohydrate structures as well as their functions. Furthermore, carbohydrate-specific binding molecules can be expected to be used in medical diagnostic applications for carbohydrate biomarkers. In this thesis study, oriented …

Dna Mutation/Methylation Screening Method For Colon Cancer Screening, Wei Meng

ETD Archive

Cancer is a result of unregulated cell growth. For all types of cancer currently studied, the transition from a healthy cell to a malignant tumor cell is a step-by-step process which requires mutation in at least several oncogenes and tumor suppressor genes together. Another cancer early event is DNA methylation. Cancer-related DNA methylation focuses on promoter hypermethylation of the certain genes. The DNA mutation and methylation profile can serve as biomarkers for diagnosing early stage of cancer. Colorectal cancer is the third most common cancer type in the United States and has been well studied. The essential mechanism of cancer …

Molecular Basis Of The Role Of Kindlin 2 In Cell Adhesion, Hettiarachchige Dhanuja Deepamalee Perera

ETD Archive

Kindlins are a novel family of cytoskeleton proteins that plays an important role in the activation of heterodimeric integrin transmembrane receptors. These receptors play a vital role in cell adhesion, cell migration and other cellular processes. The Kindlin protein family consists of three homologous proteins, Kindlin 1, 2 and 3 with differential tissue distribution and varying expression levels in human. Mutations of Kindlin 1 protein are clinically linked to Kindler Syndrome. Kindlin 2 knockdown studies have shown embryonic lethality in mouse, but no diseases have been clinically testified. Kindlin 3 mutations are associated with bleeding disorders, e.g. LADIII. Talin is …

Human Prostate Cancer Cell Apoptosis Induced By Interferon-Y And Double-Stranded Rna And Studies On The Biological Roles Of Transmembrane And Coiled-Coil Domains 1, Haiyan Tan

ETD Archive

No abstract provided.

Study Of Drug Delivery Behavior Through Biomembranes Using Thermal And Bioanalytical Techniques, Hareesha Reddy Venumuddala

ETD Archive

This Master of Science thesis encompasses two projects in chemical pharmaceuticals. The first is a study of excipients and the added new information collected beyond Thermal Gravimetric Analysis and Differential Scanning Calorimetry from Dielectric Analysis. These new properties enhance our global knowledge of excipients by thermal analytical methods. Excipients, the inactive ingredients in formulated drugs, aid different functions of the active pharmacy ingredient, the drugs. Low temperature transitions, by DEA including melting of frozen solvents, e.g. water, are more definitive than observed by low temperature DSC. Millions of dollars are expended annually on pharmaceutical testing to qualify excipients for fully …

Disintegration Of Tablets And Capsules Measured By Isothermal Thermal Mechanical Analysis And Macrophotography, Visweswararao Badipatla

ETD Archive

The current United States Pharmacopoeia (USP) test for tablet and encapsulated drug disintegration does not specify the initial disintegration time and provides limited information on the disintegration process itself. An isothermal Thermal Mechanical Analysis (IsoTMA) method is presented to measure the rate and initial time of drug disintegration, that is, the mechanical collapse of the gelatin capsule or the solid tablet. This method monitors changes in the dimensions of the formulated drugs during their disintegration in a liquid. Dimensional changes can be followed as a function of time, temperature, applied stress and pH. Some of the drugs studied were Olanzapine®, …

Temporal And Spatial Variations In Freshwater 14C Reservoir Effects: Lake Mývatn, Northern Iceland, Philippa L. Ascough, G. T. Cook, M. J. Church, E. Dunbar, Á. Einarsson, Thomas H. Mcgovern, A. J. Dugmore, Sophia Perdikaris, H. Hastie, A. Friðriksson, H. Gestsdóttir

School of Global Integrative Studies: Faculty Publications

Lake Mývatn is an interior highland lake in northern Iceland that forms a unique ecosystem of international scientific importance and is surrounded by a landscape rich in archaeological and paleoenvironmental sites. A significant freshwater reservoir effect (FRE) has been identified in carbon from the lake at some Viking (about AD 870–1000) archaeological sites in the wider region (Mývatnssveit). Previous accelerator mass spectrometry (AMS) measurements indicated this FRE was about 1500–1900 ¹⁴C yr. Here, we present the results of a study using stable isotope and ¹⁴C measurements to quantify the Mývatn FRE for both the Viking and modern periods. …

Transition Metal-Mediated Higher-Order Cycloaddition Reactions: Application To The Total Synthesis Of Complex Natural Products, Bilal Abou Aleiwi

Wayne State University Dissertations

ABSTRACT

TRANSITION METAL-MEDIATED HIGHER-ORDER CYCLOADDITION REACTIONS: APPLICATION TO THE TOTAL SYNTHESIS OF COMPLEX NATURAL PRODUCTS

by

BILAL ABOU ALEIWI

October 2010

Advisor: Dr. James H. Rigby

Major: Chemistry (Organic)

Degree: Doctor of Philosophy

Chromium (0)-mediated [6ð + 2ð] and [6ð + 2ð + 2ð] cycloaddition reactions between cyclic trienes and alkynes is reported. The development, investigation and the application of these reactions in the total synthesis of complex ring systems and natural products is described. Two natural products, namely, ∆ 9(12) -Capnellene and Echinopines A and B were targeted.

An investigation led to the successful development of a methodology to …

Experimental And Theoretical Analysis Of The Electronic Behavior In Five-Coordinate Iron(Iii) And Six-Coordinate Cobalt(Iii) Complexes With Electroactive Phenol-Rich Ligands, Marco Mathieu Allard

Wayne State University Dissertations

Three 5 coordinate high-spin Iron(III) complexes containing pentadentate N2O5 ligands were synthesized and characterized, namely, (1) [FeIII(L1)] and (2) [FeIII(L2)]. Structural differences in ligand design,N,N,N'-tris(3,5-di-tert-butyl-2-hydroxybenzyl)benzene-1,2-diamine for (1) and N,N,N'-tris-(3,5-di-tert-butyl-2-hydroxybenzyl)-N'-methyl-benzene-1,2-diamine for (2), result in complexes that due to their forced geometry, asymmetry, and slightly different electronic structures are able to foster phenoxyl radicals although show a sensitive dependence to both the solvent and the electrolyte system in the cyclic voltammetry. In the presence of TBAClO4 (1) exhibits a two-electron oxidation, whereas in the presence of TBAPF6 (2), , shows three distinct phenolato/phenoxyl radical couples. Both (1) and (2) were redox-cycled 30 …

Development And Applications Of Thioacids In Peptide Chemistry And Exploration Of Methods Toward The Stereochemical Elucidation And Synthesis Of Virgineone, Kasinath Sana

Wayne State University Dissertations

ABSTRACT

DEVELOPMENT AND APPLICATIONS OF THIOACIDS IN PEPTIDE CHEMISTRY AND EXPLORATION OF METHODS TOWARD THE STEREOCHEMICAL ELUCIDATION AND SYNTHESIS OF VIRGINEONE

by

KASINATH SANA

December 2010

Advisor: David Crich

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation describes investigations toward the development of methods for the synthesis of peptidyl thioacids and thioesters, with particular emphasis on applications in peptide chemistry, and the exploration of methods toward the assignment of the relative and absolute configuration of virgineone and its total synthesis.

The first part of chapter one introduces the general characteristics and reactivity of thioacids, and describes their potential for application …

Synthetic Levers Enabling Control Of Phase, Size And Morphology In Transition Metal Phosphide Nanoparticles (Fe, Ni), Elayaraja Muthuswamy

Wayne State University Dissertations

ABSTRACT

SYNTHETIC LEVERS ENABLING CONTROL OF PHASE, SIZE AND MORPHOLOGY IN TRANSITION METAL PHOSPHIDE NANOPARTICLES (FE, NI)

by

ELAYARAJA MUTHUSWAMY

May 2011

Advisor:Dr. Stephanie L. Brock

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation study focuses on (1) development of a synthetic strategy to control phase in nanoscale iron phosphides; (2) extension of the developed phase control strategy to the nanoscale nickel phosphide system with simultaneous control on size and morphology and (3) illustration of the enhanced reactivity of nanoscale oxide systems.

A synthetic strategy to control phase in nanoscale iron phosphides was developed to prepare phase-pure samples of …

Dechalcogenative Allylic Selenosulfide And Disulfide Rearrangements For Cysteine Modification And Glycoligation, Venkataraman Subramanian

Wayne State University Dissertations

This thesis describes investigations directed at the development of methods for the selenosulfide and disulfide rearrangements for the permanent functionalization of thiols, and in particular of cysteine and carbohydrate based thiols. Emphasis is placed on the newly invented silver mediated allylic desulfurative rearrangement for the primary modification of thiols and the synthesis of complex oligosaccharide mimics.

Chapter one introduces the concept of chemoselective ligations for the modification of macromolecules like carbohydrates and proteins. It overviews the native and non-native ligation techniques for their modification of such entities with a attention focusing on thiol based ligation techniques. The later part of …

Metal Chalcogenide Nanocrystal Assembly: From Synthesis To Applications, Qinghong Yao

Wayne State University Dissertations

This dissertation study is focused on (1) the application of an oxidation-induced sol-gel assembly method to formation of CdTe aerogels; (2) extension of existing aerogel compositions and properties by an alternative synthetic approach: cation-exchange reactions; and (3) probing the functionality of CdSe aerogels as optical sensors of Lewis base analytes.

Highly porous CdTe aerogels were successfully synthesized by sol-gel assembly of CdTe nanocrystals with thiolate or nonthiolate (phosphine oxide) ligated surfaces by treatment with tetranitromethane. Both phosphine oxide-capped and the thiolate-capped aerogels exhibit similar structure, morphology and porosimetry properties, suggesting that precursor ligation does not have a no major effect …

Synthesis And Characterization Of Metal Complexes Containing Tetrazolate, Poly(Tetrazolyl)Borate, And Aryl Pentazole Ligands As High Energy Density Materials, Dongmei Lu

Wayne State University Dissertations

Heavier alkaline earth metal tetrazolates have been prepared as cryatals contain aqua ligands and as anhydrous powders, and were characterized by spectral and analytical methods. Potassium bis(tetrazolyl)borate complexes K(BH₂(RCN₄)₂)(H₂O)_n (R = H, Me, NMe₂, and NiPr₂) and their 18-crown-6 adducts have been synthesized. In the solid state, complexes where R = H and Me have B-N bonds to the nitrogen atoms proximal to the carbon atom, whereas those with R = NMe₂ and NiPr₂ possess isomeric B-N bonds to the nitrogen atoms distal to the …