Chemistry Commons^™

Effects Of Temperature On The Physicochemical Properties Of Traditionally Processed Vegetable Oils And Their Blends, Fn Ngassapa, Ss Nyandoroa, Tr Mwaisaka

Tanzania Journal of Science

The quality and stability of traditionally processed palm, sunflower and sesame oils and their blends as affected by temperature were evaluated by analyzing their physicochemical properties which included acid, saponification, peroxide, iodine values and refractive indices.. The initial quality of traditionally processed oils studied was found to be within the specifications of TZS and Codex requirements. The results further indicate that the quality of both unblended and blended traditionally processed vegetable oils deteriorate significantly at elevated temperatures (p < 0.05). However, the blends showed relatively better quality and stability than the unblended ones whereby the formulations of palm oil (PO) and sesame oil (SSO) appeared to be more stable than those of PO and sunflower oil (SO). This work suggests that blending of traditionally processed PO, SO and SSO improves the quality and stability of these oils.

Determination Of Lipophilic Extractives In Ionic Liquid Extracts Of Eucalyptus Pulp By Gas Chromatography - Mass Spectrometry, Kf Kilulyaa, Tam , Msagati, Bb , Mamba, Jc Ngila, T Bush

Tanzania Journal of Science

Lipophilic wood extractives composition is currently a big concern of pulp and paper industries as well as for the environmentalists due to their negative impacts on the quality of pulp and the environment. Because of the shortcomings of different extraction procedures using volatile organic solvents in capturing residual lipophilic extractives in pulp, this study reports on the use of ionic liquids as an effective approach for such extraction. The capacity of two ionic liquids; 1- butyl-3-methylimidazolium acetate and 1-butyl-3-methylimidazolium chloride to recover wood extractives was compared and it was observed that ionic liquid with chloride anion recovered a higher amount …

Molecularly Imprinted Polymer Technology: A Powerful, Generic, Facile And Cost Effective Alternative For Enantio-Recognition And Separation: A Glance At Advances And Applications, Jyn Philip, Dms Mosha

Tanzania Journal of Science

The emerging Molecularly Imprinted Polymer (MIP) technology has yielded proof of concept, harnessing nature’s fundamentals to yield recognition receptor mimics from the miniaturized basics, borrowing on the ground rules, but conveniently avoiding the complexity, fragility, instability, costs and ethics of animal based bio-affinity matrices. Thus, the impact of bio-sciences on the future of technology is not via direct use of the molecules, but rather the lessons learned. Molecular imprinting is a powerful specialty representing the generic, cost effective and facile alternative for preparation of synthetic custom-tailored receptors. It achieves this via creation of specific selective recognition sites for a pre-determined …

Computational Chemistry Capacity Building In An Underprivileged Context: Challenges, Outcomes And Perspectives, L Mammino

Tanzania Journal of Science

Computational chemistry is a fast developing branch of modern chemistry, focusing on the study of molecules to enable better understanding of the properties of substances. Its applications comprise a variety of fields, from drug design to the design of compounds with desired properties (e.g., catalysts with specific actions) and to ample overlaps with nanotechnology. However, despite its relevance, the presence of computational chemistry research in Sub-Saharan Africa is still scarce, practically absent in many institutions. Bridging the gap with the other continents requires the identification of capacity building options that may enable a rapid growth. The recent experience at the …

Theoretical Study Of Physiochemical Properties Of Insulin-Like Growth Factor 1, A Ilkhani

Tanzania Journal of Science

The computational approach to studying structural changes in a wide range of physical and biological problems, the empirical force fields, have great difficulty in simulating folding of Insulin-like Growth Factor 1 (IGF-1). In an effort to understand the conformational preferences that may be attributed to stereoelectronic effects, a number of computational studies were carried out. Monte Carlo, Molecular Dynamics and Langevin simulation methods by MM+, AMBER and OPLS force fields of calculations have been performed on IGF-1 as growth factors. The parameters of a minimized structure of IGF-1, calculated potential energy for important dihedral angles and the effect of temperature …

Comparison Of Chemical Nano Structure, Rheological And Mechanical Properties Of Long Oil Alkyd Resin Synthesized Using Polybasic Acids Catalyst, Ar Ilkhani

Tanzania Journal of Science

In this research, chemical nano structures, rheological and mechanical properties of long oil alkyd resin which was synthesized using different polybasic acid catalysts have been studied. These catalyst were phosphoric acid, 1,2,4-benzene tricarboxylic acid and succinic acid. The new compounds were compared with reference formula of long oil alkyd resin. For this idea, same formula of clear air drying varnishes were prepared based on different long oil resins which have been synthesized using different catalysts and reference long oil alkyd resin. FTIR spectroscopy was employed to investigate the nano chemical structures of the resins and varnishes. The rheological properties of …

Adsorption And Electrooxidation Of Carbon Monoxide On Platinum Surfaces Modified With Sulfur, A. Mattox Mathew, W. Henney Matthew, Johnson Adam, Zou Shouzhong

Journal of Electrochemistry

Adsorbed sulfur is commonly considered as a reaction poison. However, small amounts of sulfur on platinum significantly increase the surface reactivity toward carbon monoxide (CO) electrooxidation. For the solution CO oxidation, the onset potential was shifted up to over 300 mV negative to that on S-free surface, and the extent of the negative potential shift increases with the sulfur coverage (X_s) up to about 0.6. The enhanced CO oxidation also depends on the solution pH. For the adsorbed CO, at low sulfur coverages (X_s < 0.3), the oxidation peak potential is about 40 mV negative to that of the corresponding clean Pt. However, at higher coverages, the peak potential is about 30 mV more positive. Surface-enhanced Raman spectra show that the adsorption of sulfur significantly redshifts the Pt-CO stretching frequency. These observations are explained by the weakening of the Pt-CO bond and the hindrance of CO diffusion by Sads.

Kinetic Study Of Photoelectrochemical Oxidation Of Lignin Model Compounds On Tio2 Nanotubes, Min Tian, Daniel Liba, Aicheng Chen

Journal of Electrochemistry

In this study, TiO₂ nanotubes were prepared via the electrochemical oxidation of titanium substrates in a non-aqueous electrolyte and their morphology and microstructures were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photoelectrochemical oxidation of two lignin model compounds, 1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanediol (DMP) and 3-hydroxy-1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanone (HDM), was investigated. A new band appeared at ~304 nm during the photoelectrochemical oxidation of DMP. The rate of DMP intermediate formation was amplified with the increase of initial concentrations, while it was diminished with increased temperature. Despite the similarity in structure between HDM and DMP, there are only small increases in absorbance …

Electrochemical Performance Of Screen-Printed Composite Coatings Of Conducting Polymers And Carbon Nanotubes On Titanium Bipolar Plates In Aqueous Asymmetrical Supercapacitors, Xiaohang Zhou, George Z. Chen

Journal of Electrochemistry

Composites of conducting polymers (polypyrrole and polyaniline) with acid treated multi-walled carbon nanotubes were formulated into printable aqueous inks, with the aid of functional additives (benzethonium chloride as a surfactant with or without polyvinyl alcohol as a binder). The inks were screen-printed as fairly uniform coatings of various mass loading densities and areas (up to 75 mg cm^-2 and 100 cm²) on thin titanium plates (0.1 mm in thickness). These screen-printed plates were used to fabricate both unit cell and multi-cell stack of asymmetrical supercapacitors with screen-printed negative electrodes of activated carbon (pigment black) in aqueous electrolytes …

Advances And Challenges Of Intermediate Temperature Solid Oxide Fuel Cells: A Concise Review, Sanping Jiang

Journal of Electrochemistry

Fuel cell is an electrochemical energy conversion device to directly convert the chemical energy of fuels to electricity. Among all types of fuel cells, solid oxide fuel cells (SOFCs) operating at intermediate temperatures of 600~800 ^oC offer an attractive option that is much more fuel flexible than low temperature fuel cells such as proton exchange membrane fuel cells, and is suitable for a wide range of applications. However, two main challenges remain towards the commercial viability and acceptance of the SOFC technologies: the cost and durability. Both are critically dependent on the process, fabrication, performance, chemical and microstructural stability …

Ternary Alloy Electrocatalysts For Oxygen Reduction Reaction, Jin Luo, Lefu Yang, Binghui Chen, Chuanjian Zhong

Journal of Electrochemistry

Proton exchange membrane fuel cell represents an important electrochemical energy conversion device with many attractive features in terms of efficiency of energy conversion and minimization of environmental pollution. However, the large overpotential for oxygen reduction reaction at the cathode and the low activity, poor durability and high cost of platinum-based catalysts in the fuel cells constitute a focal point of major barriers to the commercialization of fuel cells. The development of nanostructured catalysts shows promises to addresses some of the challenging problems. The ability to engineer the composition and nanostructure of nanoalloy catalysts is important for developing active, robust and …

Electrocatalytic Activity Of Palladium Nanocatalysts Supported On Carbon Nanoparticles In Formic Acid Oxidation, Jie Huang, Zhiyou Zhou, Yang Song, Xiongwu Kang, Ke Liu, Wancheng Zhou, Shaowei Chen

Journal of Electrochemistry

Palladium nanostructures were deposited onto carbon nanoparticle surface by a chemical reduction method. Transmission electron microscopic studies showed that whereas the resulting metal-carbon (Pd-CNP) nanocomposites exhibited a diameter of 20 to 30 nm, the metal components actually showed a cauliflower-like surface morphology that consisted of numerous smaller Pd nanoparticles (3 to 8 nm). Electrochemical studies showed that the effective surface area of the Pd-CNP nanoparticles was about 40% less than that of Pd black, possibly because the Pd nanoparticles were coated with a layer of carbon nanoparticles; yet, the Pd-CNP nanocomposites exhibited marked enhancement of the electrocatalytic activity in formic …

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 …

Polymorphism And Polyamorphism In Bilayer Water Confined To Slit Nanopore Under High Pressure, Jaeil Bai, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A distinctive physical property of bulk water is its rich solid-state phase behavior, which includes 15 crystalline (ice I–ice XIV) and at least 3 glassy forms ofwater, namely, low-density amorphous, highdensity amorphous, and very-high-density amorphous (VHDA). Nanoscale confinement adds a new physical variable that can result in a wealth of new quasi-2D phases of ice and amorphous ice. Previous computer simulations have revealed that when water is confined between two flat hydrophobic plates about 7–9 Å apart, numerous bilayer (BL) ices (or polymorphs) can arise [e.g., BL-hexagonal ice (BL-ice I)]. Indeed, growth of the BL-ice I through vapor deposition on …

A Novel Route To Organonitrites By Pd-Catalyzed Cross-Coupling Of Sodium Nitrite And Potassium Organotrifluoroborates, Mohammad Al-Masum, Nabil Saleh, Tasfia Islam

Chemistry Faculty Research

Microwave irradiated palladium-catalyzed cross-coupling reaction of potassium styryltrifluoroborates and sodium nitrite gives the corresponding styryl nitrites in high yields. Potassium aryltrifluoroborates also furnish aryl nitrites under same reaction condition. This unprecedented cross-coupling is an interesting development and has the potential to lead to new nitration protocols.

Facile Molten-Salt Synthesis Of Double Perovskite La2bmno 6 Nanoparticles, Yuanbing Mao

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Crystalline double perovskite La2BMnO6 (B = Ni and Co) nanoparticles with an average grain size of ∼64 nm were successfully prepared using a facile, environmentally friendly, scalable molten-salt reaction at 700 °C in air. Their composition and structural and magnetic properties have been characterized.

A Comparison Of Boltzmann And Gibbs Definitions Of Microcanonical Entropy For Small Systems, Randall B. Shirts

Faculty Publications

Two different definitions of entropy, S= klnW, in the microcanonical ensemble have been competing for over 100 years. The Boltzmann/Planck definition is that W is the number of states accessible to the system at its energy E (also called the surface entropy). The Gibbs/Hertz definition is that W is the number of states of the system up to the energy E (also called the volume entropy). These two definitions agree for large systems but differ by terms of order N^-1 for small systems, where N is the number of particles in the system. For three analytical …

Ultra-Stable Protein-Polymer Bioconjugates, Kyle S. Cole

Master's Theses

No abstract provided.

Synthesis And Characterization Of Complexes Of [Rh2(Nphcoch3)4] And Nitriles., Jennie Tan

Undergraduate Honors Theses

The rhodium carboxamide [Rh2(NPhCOCH3)4]L (L=axial ligand), has applications as a catalyst for carbenoid transformations. To explore the nature of the rhodium-carbene bond, studies between Rh2(NPhCOCH3)4 and nitriles were proposed. Trials of the benzonitrile, o-tolunitrile, and m-tolunitrile have been performed and characterized on the 2,2-trans [Rh2(NPhCOCH3)4] complex via NMR spectroscopy, IR spectroscopy, and X-ray crystallography.

The Lyme Disease Spirochete In Tick Species Collected From Warren County, Kentucky, Cheryl C. Onwu

Mahurin Honors College Capstone Experience/Thesis Projects

The overall goal of this present study was to determine the prevalence of the Lyme disease spirochete, Borrelia burgdorferi, in south central Kentucky. A survey of ticks collected from a single location in Warren County, Kentucky was conducted between the months of April and June, 2010. A total of 293 ticks were collected. Three species were identified: 264 (91.7 %) of the ticks were Amblyoma americanum, 18 (6.6%) were Dermacentor variabilis, and 1 (0.35%) was Ixodes scapularis. The ten remaining ticks were immature nymphs and could not be identified. After identifying the species and sex of …

Reaction Of Halogenated Hydrocarbons With Cysteine And Nucleotides, Brittany S. Morgan

Mahurin Honors College Capstone Experience/Thesis Projects

Our objective is to develop a simple, inexpensive model to better understand the biologically relevant reactions of halogenated hydrocarbons and characterize them by NMR spectroscopy. We currently have a model that mimics the adduct created by the reaction of ethylene dibromide (a known toxin and carcinogen) with cysteine and guanosine 5’-monophosphate. Early attempts led to side products including ethylene oxide and ethylene glycol; however, our most promising method to date reacts cysteine with 2-bromoethanol in sodium methoxide/methanol followed by reaction of the 2-hydroxyethyl adduct with HCl and later with guanosine 5’-monophosphate. By reacting other halogenated hydrocarbons through the same method, …

Synthesis And Characterization Of Metallocorrole And Metalloporphyrin Complexes For Catalytic Oxidations, Zhibo Yuan

Mahurin Honors College Capstone Experience/Thesis Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in nature, namely the cytochrome P450 enzymes. Metal porphyrin complexes have been the center of research as catalysts in this context. This study focuses on the synthesis of porphyrin and corrole macrocyclic ligands and the corresponding ruthenium and iron complexes which are fully characterized by UV-vis and NMR spectroscopies.

The catalytic oxidation reactions towards organic sulfides by these metal complexes were also studied. Two ruthenium porphyrin complexes …

Water-Soluble Deep-Cavity Cavitands: Synthesis, Molecular Recognition, And Interactions With Phospholipid Membranes, Sarah E. Ioup

LSU New Orleans Theses and Dissertations

Water-soluble deep-cavity cavitands provide a rare opportunity to study self-assembly driven by the hydrophobic effect. These molecular hosts dimerize in the presence of certain guest molecules to form water-soluble molecular capsules. These systems have given rise to numerous novel chemical phenomena and have potential use in drug delivery. The host octaacid (OA) has been particularly well-characterized, but studies are limited to basic pH because of limited host solubility.

Herein we report an improved synthesis of OA and the syntheses of three new water-soluble deep-cavity cavitands. The new hosts are soluble at neutral pH, increasing relevance for biological studies. The new …

Interactions Of Aqueous Ag+ With Fulvic Acids: Mechanisms Of Silver Nanoparticle Formation And Investigation Of Stability, Nathaniel F. Adegboyega, Virender K. Sharma, Karolina Siskova, Radek Zboril, Mary Sohn, Brian J. Schultz, Sarbajit Banerjee

Chemistry and Chemical Engineering Faculty Publications

This study investigated the possible natural formation of silver nanoparticles (AgNPs) in Ag+ −fulvic acid (FA) solutions under various environmentally relevant conditions (temperature, pH, and UV light). Increase in temperature (24−90 °C) and pH (6.1−9.0) of Ag+ −Suwannee River fulvic acid (SRFA) solutions accelerated the appearance of the characteristic surface plasmon resonance (SPR) of AgNPs. The rate of AgNP formation via reduction of Ag+ in the presence of different FAs (SRFA, Pahokee Peat fulvic acid, PPFA, Nordic lake fulvic acid, NLFA) and Suwannee River humic acid (SRHA) followed the order NLFA > SRHA > PPFA > SRFA. This order was found to be …

Bf2obn∙Oet2: A Novel Lewis Acid And Its Use In A Regio- And Stereo-Selective Opening Of Trisubstituted Epoxides And Its Application Towards Amphidinolide C, Nicholas A. Morra, Brian Pagenkopf

Chemistry Publications

The generation of a new Lewis acid (BF2OBn·OEt2) has been reported, and its usefulness has been demonstrated in the regio- and stereoselective ring-opening of trisubstituted epoxides. This Lewis acid is one in a series of new Lewis acids generated from BF3·OEt2 that display varying levels of Lewis acidity. When paired with a modified Shi epoxidation protocol, highly functionalized propionate units, such as those found in a wide variety of natural products, can be accessed. In conjunction with a Mukaiyama oxidative cyclization employing our second generation catalyst Co(nmp)2, this procedure ultimately culminated in the shortest and highest yielding route towards the …

Impact Of Post-Synthesis Modification Of Nanoporous Organic Frameworks On Selective Carbon Dioxide Capture, Timur İslamoğlu

Theses and Dissertations

Porous organic polymers containing nitrogen-rich building units are among the most promising materials for selective CO2 capture and separation applications that impact the environment and the quality of methane and hydrogen fuels. The work described herein describes post-synthesis modification of Nanoporous Organic Frameworks (NPOFs) and its impact on gas storage and selective CO2 capture. The synthesis of NPOF-4 was accomplished via a catalysed cyclotrimerization reaction of 1,3,5,7-tetrakis(4-acetylphenyl)adamantane in Ethanol/Xylenes mixture using SiCl4 as a catalyst. NPOF-4 is microporous and has high surface area (SABET = 1249 m2 g-1). Post-synthesis modification of NPOF-4 by nitration afforded (NPOF-4-NO2) and subsequent reduction resulted …

Dissolved Organic Matter Composition And Bioavailability Reflect Ecosystem Productivity In The Western Arctic Ocean, Yuan Shen, Cedric Fichot, Ronald Benner

Faculty Publications

Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High concentrations and yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting …

Microfluidic Devices With Integrated Sample Preparation For Improved Analysis Of Protein Biomarkers, Pamela Nsang Nge

Theses and Dissertations

Biomarkers present a non-invasive means of detecting cancer because they can be obtained from body fluids. They can also be used for prognosis and assessing response to treatment. To limit interferences it is essential to pretreat biological samples before analysis. Sample preparation methods include extraction of analyte from an unsuitable matrix, purification, concentration or dilution and labeling. The many advantages offered by microfluidics include portability, speed, automation and integration. Because of the difficulties encountered in integrating this step in microfluidic devices most sample preparation methods are often carried out off-chip. In the fabrication of micro-total analysis systems it is important …

An Investigation Of Urban Mobile Source Aerosol Using Optical Properties Measured By Crdt/N: Diesel Particulate Matter And The Impact Of Biodiesel, Monica Elizabeth Wright

Dissertations and Theses

Mobile source emissions are a major contributor to global and local air pollution. Governments and regulatory agencies have been increasing the stringency of regulations in the transportation sector for the last ten years to help curb transportation sector air pollution. The need for regulations has been emphasized by scientific research on the impacts from ambient pollution, especially research on the effect of particulate matter on human health. The particulate emissions from diesel vehicles, diesel particulate matter (DPM) is considered a known or probable carcinogen in various countries and increased exposure to DPM is linked to increased cardiovascular health problems in …

Acid-Base Catalysis In Proton-Coupled Electron Transfer Reactions (Pcet): The Effects Of Brönsted Bases On The Oxidation Of Glutathione And Hydroquinone, Ramos Jonnathan Medina

Theses and Dissertations

This thesis presents the results and discussion of the investigation of the effects of Brönsted bases on the kinetics and thermodynamics of two proton-coupled electron transfer processes: the mediated oxidation of glutathione and the electrochemical oxidation of hydroquinone. Proton-coupled electron transfer (PCET) is the name given to reactions that involve the transfer of electron(s) accompanied by the exchange of proton(s). PCETs are found in many chemical and biological processes, some of current technological relevance such as the oxygen reduction reaction in fuel cells, which involves the transfer of four electrons and four protons (4e-, 4H+); or the splitting of water …