Chemistry Commons^™

Picture Of A Chelate In Exchange: The Crystal Structure Of Nahodotma, A 'Semi'-Hydrated Chelate, Katherine M. Payne, Edward J. Valente, Silvio Aime, Mauro Botta, Mark Woods

Chemistry Faculty Publications and Presentations

Crystallography generally only provides static structural information. This can render it an ineffective technique for probing dynamic solution state processes. A crystal of HoDOTMA affords unique structures that effectively represent that of a lanthanide tetra-acetate chelate mid-way through the water exchange process.

Environmental And Energy Saving Technologies Of Vinyl Chloride Production, Mykola Kurta

USF Tampa Graduate Theses and Dissertations

Recently, because of the increase of environmental concerns in process design, the need to enhance conversion to product and prevent generation of wasteful byproducts in the reactor network has become urgent. This prevents high cost treatment and separation costs downstream in the process. Therefore, in this thesis I focus on making production of vinyl chloride monomer (VCM) more efficient and on possible ways of industrial organochlorine waste (OCW) recycling. In particular, in the first experiment, we investigate how catalyst and its structure can affect product output.

Infrared spectroscopy and X-ray diffraction analysis were utilized to investigate the structure of the …

Sector Expansion And Elliptical Modeling Of Blue-Gray Ovoids For Basal Cell Carcinoma Discrimination In Dermoscopy Images, Pelin Guvenc, Robert W. Leander, Serkan Kefel, William V. Stoecker, Ryan K. Rader, Kristen A. Hinton, Sherea Monica Stricklin, Harold S. Rabinovitz, Margaret C. Oliviero, Randy Hays Moss

Chemistry Faculty Research & Creative Works

Background: Blue-gray ovoids (B-GOs), a critical dermoscopic structure for basal cell carcinoma (BCC), offer an opportunity for automatic detection of BCC. Due to variation in size and color, B-GOs can be easily mistaken for similar structures in benign lesions. Analysis of these structures could afford accurate characterization and automatic recognition of B-GOs, furthering the goal of automatic BCC detection. This study utilizes a novel segmentation method to discriminate B-GOs from their benign mimics.

Methods: Contact dermoscopy images of 68 confirmed BCCs with B-GOs were obtained. Another set of 131 contact dermoscopic images of benign lesions possessing B-GO mimics provided a …

Exergetic Analysis Of Hydrogen Combustion Involving Electronically Excited Species, Devon Alan Washington

Wayne State University Dissertations

Plasma-assisted combustion (PAC) is a growing field of research that involves using nonthermal plasma (NTP) to enhance combustion. PAC research involves modeling reaction mechanisms and chemical kinetics. Exergy analysis of combustion devices focuses on combustion irreversibility, including mixing, internal heat transfer, and oxidation. This novel research project merges these two branches of research.

The focus of this work is the application of exergy analysis to PAC systems, to analyze the effect introducing NTP has on trends in exergy destruction associated with oxidation during hydrogen combustion. This was accomplished by developing a plug flow reactor model using the chemical simulation tool …

Colloidal Nano-Apatite Particles With Active Luminescent And Magentic Properties For Biotechnology Applications, Rajendra Kasinath, Kumar Ganesan

Environmental Engineering

Colloidal Nano-apatite Particles with Active Luminescent and Magentic Properties for Biotechnology Applications. The synthesis of functional nano-materials is a burgeoning field that has produced remarkable and consistent breakthroughs over the last two decades. Individual particles have become smaller and shown potential for well defined functionality. However, there are still unresolved problems, a primary one being the loss of functionality and novelty due to uncontrolled aggregation driven by surface energy considerations. As such the first design criteria to harness the true potential of nanoparticles is to prevent unwanted agglomeration by: (1) improving, and, if possible, (2) controlling aggregation behavior. This requires …

Online Learning In A Chemical Perceptron, Peter Banda, Christof Teuscher, Matthew R. Lakin

Computer Science Faculty Publications and Presentations

Autonomous learning implemented purely by means of a synthetic chemical system has not been previously realized. Learning promotes reusability and minimizes the system design to simple input-output specification. In this article we introduce a chemical perceptron, the first full-featured implementation of a perceptron in an artificial (simulated) chemistry. A perceptron is the simplest system capable of learning, inspired by the functioning of a biological neuron. Our artificial chemistry is deterministic and discrete-time, and follows Michaelis-Menten kinetics. We present two models, the weight-loop perceptron and the weight-race perceptron, which represent two possible strategies for a chemical implementation of linear integration and …

Synthesis And Characterization Of Transition Metal Arsenide Nanocrystals And The Metastability And Magneto-Structural Phase Transition Behavior Of Mnas Nanocrystals, Yanhua Zhang

Wayne State University Dissertations

This dissertation study focuses on (1) probing the magneto-structural phase transformation in nanoscale MnAs; (2) evaluation of the size-dependent phase stability of type-B MnAs (prepared by rapid injection); and (3) developing a general synthetic method for transition metal arsenide nanoparticles.

Discrete MnAs nanoparticles that adopt different structures at room temperature (type-A, α-structure and type-B, β-structure) have been prepared by the solution-phase arrested precipitation method. Atomic pair distribution and Rietveld refinement were employed on synchrotron data to explore the structural transitions of the bulk and nanoparticle samples, and these results were compared to AC magnetic susceptibility measurements of the samples. The …

A Highly Efficient Tio2-Xcx Nano-Heterojunction Photocatalyst For Visible-Light Induced Antibacterial Applications, Vinodkumar Etacheri, Michael Seery, Stephen Hinder, Georg Michlits, Suresh Pillai

Articles

Visible-light-induced antibacterial activity of carbon-doped anatase-brookite titania nano-heterojunction photocatalysts are reported for the first time. These heterostructures were prepared using a novel low temperature (100 °C) non-hydrothermal low power microwave (300 W) assisted method. Formation of interband C 2p states was found to be responsible for the band gap narrowing of the carbon doped heterojunctions. The most active photocatalyst obtained after 60 minutes of microwave irradiation exhibits a 2-fold higher visible-light induced photocatalytic activity in contrast to the standard commercial photocatalyst Evonik-Degussa P-25. Staphylococcus aureus inactivation rate constant for carbon-doped nano-heterojunctions and the standard photocatalyst was 0.0023 and -0.0081 min …

Specific Salt Effects On The Formation And Thermal Transitions Among Β-Lactoglobulin And Pectin Electrostatic Complexes, Stacey Ann Hirt

Open Access Theses

Factors of ion specificity and ionic strength (I~0-100) were studied in the electrostatic complex formation and protein particle formation by thermal treatment for a β-lactoglobulin and pectin system. ζ-potential showed β-lactoglobulin and pectin began to interact near pH 5.50 and interactions were strengthened with decrease in pH. Visible light turbidimetry and light scattering at 90° revealed a trend in critical pH transitions for electrostatic complex formation based on both the ionic strength and the anion of the salt species, while effects of the monovalent cation was insignificant. Critical pH values for complex formation and separation (pHc and pHΦ) decreased with …

Novel Resist Systems For Euv Lithography : Ler, Chain-Scission, Nanoparticle And More, Brian Cardineau

Legacy Theses & Dissertations (2009 - 2024)

Extreme Ultraviolet (EUV) lithography is currently the best option for replacing 193-nm lithography in future IC fabrication. For EUV to be successful, however, there are a number of challenges that must be overcome. Current resist designs struggle to meet the demands of future lithography nodes. We propose the best way to overcome these obstacles is through the design of novel resist systems.

The Effect Of Nanostructure On The Electrical Properties Of Metal Oxide Materials, Philip Zachary Rice

Legacy Theses & Dissertations (2009 - 2024)

Resistive random access memory (ReRAM) is a potential replacement technology for Flash and other memory implementations. Advantages of ReRAM include increased scalability, low power operation, and compatibility with silicon semiconductor manufacturing. Most of the ReRAM devices described to date have utilized thin film based metal oxide dielectrics as a resistive switching matrix. The goal of this dissertation project has been to investigate the resistive switching behavior of nanoparticulate metal oxides and to develop methods to utilize these materials in ReRAM device fabrication. To this end, nanoparticles of TiO₂ and HfO₂ were synthesized under a variety of conditions resulting …

Synthesis And Characterization Of Biodegradable Poly(Vinyl Esters) With Hdac Inhibitory Activity, Kyle Lawrence Horton

Wayne State University Theses

HDAC inhibitors are known to have anti-inflammatory properties. HDAC inhibitors are used in combination with Oct4 to generate induced pluripotent stem cells. I hypothesized that polyesters based on simple aliphatic HDAC inhibitors like valproic acid (VPA) and phenylbutyric acid (PBA) can serve as alternatives to existing polyester biomaterials with improved anti-inflammatory properties and as scaffolds for generation of iPSCs when used in combination with layer-by-layer thin films delivering reprogramming transcription factors. Vinyl ester of phenylbutyric acid (VEPA) and vinyl ester of valproic acid (VEVA) were synthesized from their carboxylic acid precursors using an iridium complex catalyst at yields as high …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …

Parametric Study Of Reaxff Simulation Parameters For Molecular Dynamics Modeling Of Reactive Carbon Gases, Benjamin David Jensen

Dissertations, Master's Theses and Master's Reports - Open

Abstract

Studies Of Functionalized Nanoparticles For Smart Self-Assembly And As Controlled Drug Delivery, Xiaochu Ding

Dissertations, Master's Theses and Master's Reports - Open

This dissertation is related to the studies of functionalized nanoparticles for self-assembly and as controlled drug delivery system. The whole topic is composed of two parts. In the first part, the research was conducted to design and synthesize a new type of ionic peptide-functionalized copolymer conjugates for self-assembly into nanoparticle fibers and 3D scaffolds with the ability of multi-drug loading and governing the release rate of each drug for tissue engineering. The self-assembly study confirmed that such peptide-functionalized amphiphilic copolymers underwent different self-assembly behavior. The bigger nanoparticles were more easily assembled into nanoparticle fibers and 3D scaffolds with larger pore …

Purification Of Sodium Sulfate By Crystallization, Perla Teresita Torres

Open Access Theses & Dissertations

Sodium sulfate can be recovered from a dilute solution by concentrating it by conventional water treatment techniques like reverse osmosis and electrodialysis; however, those processes also concentrate impurities like arsenic. The sodium sulfate would have commercial use if it can be recovered in an arsenic-free form. This study demonstrated that sodium sulfate could be separated from impurities using slow cooling crystallization in a novel apparatus developed and designed during the experimentation. This device is called a heat exchanger crystallizer and allows slow cooling crystallization in order to grow pure crystals of sodium sulfate decahydrate. Crystals grown in the heat exchanger …

Preparation Of Cobalt/Nickel Molybdenum Sulfide Catalysts Supported By Aqueous Media Soluble Multi-Wall Carbon Nanotubes., Hassan Ahmad Bleibel

Open Access Theses & Dissertations

Multi-walled carbon nanotubes (MWCNTs) have been subjected to chemical treatment in order to introduce hydrophilic functional groups on their surfaces. These covalently bonded groups did enhance the solubility of MWCNTs in aqueous media as expected. Functionalized MWCNTs were characterized using FTIR, Raman spectroscopy, TGA, X-ray diffraction, dispersion test and TEM. Then, functionalized MWCNTs were incorporated in the hydrothermal synthesis method of transition metal sulfide catalysts (CoMo, NiMo, and Ethylenediamine-CoMo Sulfides). Catalysts were characterized using X-ray diffraction, TEM, SEM, N2 Gas adsorption-desorption, elemental analysis, and Hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT). The objective was to study the functionalized MWCNTs' effect; being …

Method Development For A Chemical And Biological Analysis Of Glucocorticoids In Wastewater, Maria Carmen Lozano

Open Access Theses & Dissertations

Glucocorticoids are a class of steroid hormones that can either be produced synthetically or naturally by the adrenal glands. The synthetic glucocorticoids are highly prescribed in the United States for their anti-inflammatory and immunosuppressive properties to treat a variety of ailments and diseases; however, these have been implicated in a number of adverse human conditions such as obesity, metabolic syndrome, immune-suppression, delayed puberty, adrenal insufficiency and Cushing Syndrome, among others. Ongoing research has shown that synthetic and natural hormones are transported to aquatic environments via mammalian excretion or wastewater effluent, and as a result, the release of glucocorticoids into the …

Novel Copper (Ii) Mediated Transfection Nano-Systems And Biological Properties Of Pyridinium Surfactants, Sarit Pal

Open Access Theses & Dissertations

Efficacy of gene therapy is relied upon the improvement of gene delivery vectors into mammalian cells. Although viral-based polynucleotide carriers are still considered as the most common method for gene delivery but the cost effectiveness, nonspecific lethal immune response has evoked the renaissance of non-viral synthetic delivery systems. An initial discovery by Felgnar et al showed Cationic Liposomes (CLs) (having an overall positive charge) when mixed with DNA to form CL-DNA complexes can enhance the transfer of polynucleotides into cells followed by its expression. Presently, a flurry of experimental works is taking place for the better understanding of structural characterization …

Transformations, Bioavailability And Toxicity Of Manufactured Zno Nanomaterials In Wastewter, Sewwandi Rathnayake

Theses and Dissertations--Plant and Soil Sciences

In order to properly evaluate the ecological and human health risks of ZnO Manufactured nanomaterials (MNMs) released to the environment, it is critical to understand the likely transformation products in the wastewater treatment process and in soils receiving biosolids. To address this critical knowledge gap, we examined the transformation reactions of 30 nm ZnO MNMs in single component and multi-component systems, with phosphate and natural organic matter (NOM). We also assessed the influence of nano ZnO transformation on the bioavailability, and toxicity of ZnO transformation products to Triticum aestivum. The data revealed that ZnO MNMs react with phosphate at …

Qualitative And Quantitative Analysis Of Lignocellulosic Biomass Using Infrared Techniques: A Mini-Review, Feng Xu, Jianming Yu, Tesfaye Tesso, Floyd Dowell, Donghai Wang

United States Department of Agriculture-Agricultural Research Service / University of Nebraska-Lincoln: Faculty Publications

Current wet chemical methods for biomass composition analysis using two-step sulfuric acid hydrolysis are time-consuming, labor-intensive, and unable to provide structural information about biomass. Infrared techniques provide fast, low-cost analysis, are non-destructive, and have shown promising results. Chemometric analysis has allowed researchers to perform qualitative and quantitative study of biomass with both near-infrared and mid-infrared spectroscopy. This review summarizes the progress and applications of infrared techniques in biomass study, and compares the infrared and the wet chemical methods for composition analysis. In addition to reviewing recent studies of biomass structure and composition, we also discuss the progress and prospects for …

Self-Assembling Of Gold Nanoparticles Array For Electro-Sensing Applications, Islam M. Al-Akraa Dr, Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

A colloidal solution of citrate-stabilized gold nanoparticles (AuNPs) with an average size of ca. 2.6 nm has been prepared, characterized and further implemented in electro-sensing applications. This colloidal solution of AuNPs has been prepared via the reduction of NaAuCl4 with sodium tetrahydroborate (NaBH4) using trisodium citrate as a stabilizer. The optical properties of this solution have been studied with UV–Vis spectroscopy. Next, these AuNPs have been immobilized onto a polycrystalline Au (poly-Au) electrode with the assistance of benzenedimethanethiol (BDMT), which served as a binder. Attention has been taken to ensure the formation of a compact impermeable layer of BDMT on …

Model For Acid-Base Chemistry In Nanoparticle Growth (Mabnag), Taina Yli-Juuti, Kelley Barsanti, L. Hildebrandt Ruiz, Antti-Jussi Kieloaho, U. Makkonen, Tuukka Petäjä, Taina Ruuskanen, Markku Kulmala, Ilona Riipinen

Civil and Environmental Engineering Faculty Publications and Presentations

Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential …

Novel Microwave Assisted Synthesis Of Zns Nanomaterials, Suresh Pillai, Michael Seery, Damian Synnott, John Colreavy, Stephen Hinder

Articles

A novel ambient pressure microwave-assisted technique is developed in which silver and indium modified ZnS is synthesised. The as prepared ZnS is characterised by X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy and luminescence spectroscopy. This procedure produced crystalline materials with particle sizes below 10 nm. The synthesis technique leads to defects in the crystal which induce mid energy levels in the band gap and lead to indoor light photocatalytic activity. Increasing the amount of silver causes a phase transition from cubic blende to hexagonal phase ZnS. In a comparative study, when the ZnS cubic blende is heated in a conventional …

Optimizing Electrode Design For Microbial Fuel Cells Used For Wastewater Treatment, Lindsay Nichols, John A. Hogan

STAR Program Research Presentations

Microbial fuel cells (MFC) utilize bacteria to generate an electrical current that can be used in the decomposition of sludge and human urine. In a MFC there is an anode (for oxidation of organic compounds), cathode (reduction of oxygen or carbon dioxide), and a proton exchange membrane (PEM, allows protons to migrate); reduction-oxidation reactions between the anode and cathode produce a measurable current. Bacteria that are found in sludge can be used to produce electrons in a voltaic cell, but optimizing conditions for harnessing the energy is crucial to making a MFC efficient. Research has shown that the ratios of …

Evolution Of Multispectral Aerosol Optical Properties In A Biogenically-Influenced Urban Environment During The Cares Campaign, Madhu Gyawali, W. Patrick Arnott, Rahul A. Zaveri, C. Song, Mikhail Pekour, B. Flowers, Manvendra K. Dubey, Ari Setyan, Qi Zhang, Joseph Harworth, James Gregory Radney, Dean B. Atkinson, S. China, Claudio Mazzoleni, Kyle Gorkowski, R. Subramanian, B. Tom Jobson, Hans Moosmüller

Chemistry Faculty Publications and Presentations

Ground-based aerosol measurements made in June 2010 within Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area are used to investigate the evolution of multispectral optical properties as the urban aerosols aged and interacted with biogenic emissions. Along with black carbon and non-refractory aerosol mass and composition observations, spectral absorption (ᵝabs), scattering (ᵝsca), and extinction (ᵝext) coefficients for wavelengths ranging from 355 to 1064nm were measured at both sites using photoacoustic (PA) instruments with integrating nephelometers and using cavity ring-down (CRD) instruments. The …

Development Of Novel Nano-Composite Membranes As Introduction Systems For Mass Spectrometers: Contrasting Nano-Composite Membranes And Conventional Inlet Systems, Luis Miranda

USF Tampa Graduate Theses and Dissertations

This dissertation presents the development of novel nano-composite membranes as introduction systems for mass spectrometers. These nano-composite membranes incorporate anodic aluminum oxide (AAO) membranes as templates that can be used by themselves or modified by a variety of chemical deposition processes. Two types of nano-composite membranes are presented. The first nano-composite membrane has carbon deposited within the pores of an AAO membrane. The second nano-composite membrane is made by coating an AAO membrane with a thin polymer film. The following chapters describe the transmission properties these nano-composite membranes and compare them to conventional mass spectrometry introduction systems. The nano- composite …

Model Pt- And Pd-Based Electrocatalysts For Low Temperature Fuel Cells Applications, Selasi Ofoe Blavo

USF Tampa Graduate Theses and Dissertations

In the search for alternative energy technologies, low temperature fuel cells continue to feature as technologies with the most promise for mass commercialization. Among the low temperature fuel cells, alkaline and proton exchange membrane fuel cells are the most popular. Alkaline fuel cells have typically been used for water generation as well as auxiliary power for space shuttles. Their bulkiness however makes them undesirable for other applications, especially in automobiles, where there is a great demand for alternative technologies to internal combustion engines. Proton exchange membrane fuel cells on the other hand possess numerous qualities including their compact size, high …

Electrocatalytic Oxidation Of Formic Acid On Pd/Ni Heterostructured Catalyst, Mingjun Ren, Liangliang Zou, Ju Chen, Ting Yuan, Qinghong Huang, Haifeng Zhang, Hui Yang, Songlin Feng

Journal of Electrochemistry

A Pd/Ni bimetallic nanostructured electrocatalyst was fabricated via a two-step reduction route. Owing to an epitaxial growth of Pd atoms on the surface of Ni nanoparticles, heterostructured Pd/Ni nanocomposites were formed and verified by high resolution transmission electron microscopy combined with energy-dispersion X-ray spectroscopy. X-ray diffraction confirmed that the as-prepared Pd/Ni nanocomposites possessed a single face-centered-cubic (fcc) Pd structure, probably due to a weaker diffraction intensity of metallic Ni and/or overlapping by that of Pd. The intrinsic catalytic activity on the Pd/Ni is higher than that on the Pd. Moreover, the durability of formic acid oxidation on the Pd/Ni was …