Physical Sciences and Mathematics Commons^™

Synthesis Of Palladium-Based Electrocatalysis—From Pure Metal To Bimetallic Nanoparticles, Haijun Gao

Masters Theses

This thesis focuses on synthesis and characterization of palladium-based nanoparticles. Background information of the research in this thesis is provided in Chapter 1. Preparation and characterization of pure palladium nanoparticles are presented in Chapter 2. A fast and convenient method to prepare ultra small Pd nanoparticles via Pluronic P123 reduction is discussed in detail. Impregnation method and poly method are also studied in this chapter. Chapter 3 reports the studies of these methods to prepare ultra small bimetallic (bimetallic means a mixture of two metals) palladium-based nanoparticles. Oleylamine-mediated method used Pd nanoparticles prepared via P123 reduction as precursor. Ultra small …

Synthesis Of Di- And Trisubstituted Azulenes Using A Danheiser Annulation As The Key Step: An Advanced Organic Laboratory Experiment, Rebecca M. Thomas, Kevin M. Shea

Chemistry: Faculty Publications

This three-week advanced-level organic experiment provides students with an inquiry-based approach focused on learning traditional skills such as primary literature interpretation, reaction design, flash column chromatography, and NMR analysis. Additionally, students address higher-order concepts such as the origin of azulene’s blue color, the mechanism of the Danheiser annulation (step 1), identification of an unknown reaction byproduct, and rationalization of a selective electrophilic aromatic substitution reaction (step 2). Students are initially drawn in by the fascinating color of azulene and remain engaged by the intriguing questions that naturally occur during this investigation.

Effects Of Thiophene Units On Substituted Benzothiadiazole And Benzodithiophene Copolymers For Photovoltaic Applications, Ping Ding, Yingping Zou, Cheng-Che Chu, Dequan Xiao, Chain-Shu Hsu

Chemistry and Chemical Engineering Faculty Publications

Two conjugated copolymers, P1 and P2, comprising of benzodithiophene and 5, 6-dioctyloxy-benzothiadiazole (DOBT) derivatives with/without thiophene unit, were synthesized via Stille cross-coupling polymerization reaction. These copolymers are promising for the applications in BHJ solar cells due to their good solubilities， proper thermal stability and moderate hole mobility as well as low bandgap. The photovoltaic properties of the copolymers were investigated based on the blend of the different polymer/PC71BM weight ratio under AM1.5G illumination, 100 mW/cm2. The device with ITO/PEDOT:PSS/P2: PC71BM (1:2, w/w)/Ca/Al gave relatively better photovoltaic performance, with a power conversion efficiency of 1.55%.

Synthesis, Modeling, And Characterization Of Conducting Polymers, Geoffrey M. Spinks, Lianbin Zhao, Weihua Li, Yanzhe Wu, Dezhi Zhou, Gordon G. Wallace

Professor Weihua Li

This paper presents synthesis and characterization of polypyrrole based conducting polymers in terms of electronic and mechanical disciplines. Using the electrochemical polymerization approach, conducting polymer samples with different dimensions (length, width, and thickness) was fabricated. For each sample, both sinusoidal and step excitations were used to study its mechanical and electrical properties. An equivalent electric circuit based on constant phase element (CPE) is proposed to model such responses. Electrochemical impedance spectroscopy (EIS) method was used to identify the relationship between the dimensions of conducting polymers and model elements parameters.

Synthesis, Modeling, And Characterization Of Conducting Polymers, Geoffrey M. Spinks, Lianbin Zhao, Weihua Li, Yanzhe Wu, Dezhi Zhou, Gordon G. Wallace

Professor Weihua Li

This paper presents synthesis and characterization of polypyrrole based conducting polymers in terms of electronic and mechanical disciplines. Using the electrochemical polymerization approach, conducting polymer samples with different dimensions (length, width, and thickness) was fabricated. For each sample, both sinusoidal and step excitations were used to study its mechanical and electrical properties. An equivalent electric circuit based on constant phase element (CPE) is proposed to model such responses. Electrochemical impedance spectroscopy (EIS) method was used to identify the relationship between the dimensions of conducting polymers and model elements parameters.

Synthesis And Characterization Of Graphene Oxide, Jeremy A. Waddell, Arthur Cheng, Bin Chen

STAR Program Research Presentations

Graphene, a single atomic layer of sp² carbon atoms, has gotten a lot of attention from the scientific community because of its excellent mechanical and electronic properties. The mechanical exfoliation methods used to obtain graphene nanosheets are not effective for large scale manufacturing, so scalable synthesis approaches from structurally similar compounds are of great scientific interest. Graphene oxide is one such compound which is synthesized through the oxidation of graphite powder. The oxidation was performed using a modification of the previous experimental procedure. After synthesis, the powder was fabricated into graphene oxide films through vacuum filtration and transfer to …

Synthesis Of 1,1-Dialkyhydrazines And Their Hydroxyl Radical Degradation In Aqueous Environments, Benjamin F. Strong

Masters Theses

Determination of hydroxyl radical rate constants are essential to ensure adequate degradation of contaminants in wastewater. Hydrazines are an important class of organic contaminants and are the focus of this research. Ten 1,1-dialkylhydrazines are synthesized by the zinc reduction of the corresponding N-nitrosamines. Their hydroxyl radical rate constants are determined using the linear accelerator at the Notre Dame Radiation Laboratory at pH 4, 7, and 10.

Their rate constants are found to depend on the protonation state of the molecule. At pH 4 the molecules are fully protonated and hydrogen atom abstraction is favored from the alkyl chains. At …

Thermoelectric Properties Of Silicon Germanium: An In-Depth Study To The Reduction Of Lattice Thermal Conductivity, Daniel Thompson

All Dissertations

Thermoelectric materials provide a solid state route for the direct conversion between thermal and electrical energy. Hence, thermal gradients can be used to generate power of up to several KW, or driven DC power can be used to pump heat in or out of a system. Recent pushes in thermoelectric research are for power generation materials with higher efficiency. These materials can be used to recover energy from the waste heat of vehicles' exhaust systems, and as power generators for extraterrestrial exploration when coupled with a radioactive heat source.
The goal of this dissertation will be to demonstrate a new …

The Synthesis And Structural Characterization Of Metal Oxide Nanoparticles Having Catalytic Applications, Stacey Janel Smith

Theses and Dissertations

Nanotechnology is blossoming into one of the premiere technologies of this century, but the key to its progress lies in developing more efficient nanosynthesis methods. Variations in synthetic technique, however, can cause variations in size, structure, and surface characteristics, thereby altering the physical properties and functionality of the particles. Careful structural characterizations are thus essential for understanding the properties and appropriate applications for particles produced by new synthetic techniques.In this work, a new ‘solvent-deficient’ method is presented for the synthesis of an unprecedentedly wide range of metal oxide nanomaterials including at least one metal oxide from each group in Groups …

The Synthesis Of A Homologous Series Of Alkyl Lumazines And Their Application To The Dispersion Of Carbon Nanotubes, William P. Kopcha

Master's Theses

In this thesis, the synthesis of a series of alkyl lumazine surfactants (LC_n) is reported. Their application to the dispersion of both CoMoCAT and HiPco single-walled carbon nanotubes (SWNTs) is examined in detail and the thermal stability and chirality selection properties of dispersions made with these surfactants were compared both between themselves and with an alkyl flavin surfactant (FC₁₂). Lumazine alkyl chain length exhibited some control over the quality and the quantity of SWNTs dispersed. LC₁₀ was deemed most appropriate for comparison with FC₁₂ based on considerations of solubility and nanotube individualization. …

I. Synthesis Of Β-Sitosterol And Phytosterol Esters; Ii. New Methodology For Singlet Oxygen Generation From 1,1-Dihydroperoxides, Jiliang Hang

Department of Chemistry: Dissertations, Theses, and Student Research

Phytosterols are steroid compounds structurally similar with cholesterol and vary in the nature of carbon side chain. β-Sitosterol is commercially available in preparative amount only as mixtures with other phytosterols. New semipreparative synthesis of pure β-sitosterol and sidechain-modified phytosterols is discussed in this dissertation. This new synthesis is achieved via a temporary masking of the stigmasterol 5,6-alkene as an epoxide. Following performance of the desired modification, the alkene is regenerated through a mild deoxygenation. Preparation of phytosterol esters for cholesterol metabolism study is also discussed in this dissertation.

Singlet oxygen (¹O₂) is the lowest excited state …

Ferrocene Constrained Helical Peptides Via On-Resin Cyclization, Thomas A. Mcteague

Senior Theses and Projects

Previous research within the Curran group has demonstrated that ferrocene may be used as an organometallic constraint to induce the formation of α-helices in short peptides which traditionally possess undefined conformations. Through strategic placement of lysine residues at the i and i+3 positions within the peptide, such a constraint was accomplished via the crosslinking of the lysine side chains to ferrocene dicarboxylic acid chloride in solution phase synthesis. The aim of this work was to develop a method for solid phase peptide synthesis (SPPS) for the synthesis of these ferrocene-constrained helices. In particular, we seek to develop a method in …

The Density Factor In The Synthesis Of Carbon Nanotube Forest By Injection Chemical Vapor Deposition, R. W. Call, C. G. Read, C. Mart, T. -C. Shen

T. -C. Shen

Beneath the seeming straight-forwardness of growing carbon nanotube(CNT) forests by the injection chemical vapor deposition(CVD) method, control of the forest morphology on various substrates is yet to be achieved. Using ferrocene dissolved in xylene as the precursor, we demonstrate that the concentration of ferrocene and the injection rate of the precursor dictate the CNT density of these forests. However, CNT density will also be affected by the substrates and the growth temperature which determine the diffusion of the catalyst adatoms. The CNT growth rate is controlled by the temperature and chemical composition of the gases in the CVD reactor. We …

High-Yield Cell-Free Protein Synthesis For Site-Specific Incorporation Of Unnatural Amino Acids At Two Sites, Kiyoshi Ozawa, Karin V. Loscha, Kekini V. Kuppan, Choy Theng Loh, Nicholas E. Dixon, Gottfried Otting

Faculty of Science - Papers (Archive)

Using aminoacyl-tRNA synthetase/suppressor tRNA pairs derived from Methanocaldococcus jannaschii, an Escherichia coli cell-free protein production system affords proteins with site-specifically incorporated unnatural amino acids (UAAs) in high yields through the use of optimized amber suppressor tRNA_CUA opt and optimization of reagent concentrations. The efficiency of the cell-free system allows the incorporation of trifluoromethyl-phenylalanine using a polyspecific synthetase evolved previously for p-cyanophenylalanine, and the incorporation of UAAs at two different sites of the same protein without any re-engineering of the E. coli cells used to make the cell-free extract.

Large Scale Synthesis Of V-Shaped Rutile Twinned Nanorods, Weigang Lu, Britain Bruner, Gilberto Casillas, Jibao He, Miguel Jose-Yacaman, Patrick J. Farmer

Australian Institute for Innovative Materials - Papers

V-shaped rutile twinned nanorods (VRTNs) with different aspect ratios were synthesized on large scale using a one-pot organic solvothermal method. Although several different types of VRTNs were produced, (101) twinned nanorods were the major product with minor amounts of (301) twins and straight nanorods. STEM, TEM and XRD characterizations show that [001] is the growth direction of VRTNs, with surfaces dominated by {110} facets. Intermediate formation of both brookite and anatase nanorods provides dual pathways to VRTNs’ growth: one path in which anatase seeds trigger and promote brookite nanorod growth; and a second path in which anatase nanorods are formed …

The Synthesis, Structures And Reactions Of Zinc And Cobalt Metal-Organic Frameworks Incorporating An Alkyne-Based Dicarboxylate Linker, Andrew D. Burrows, L C. Fisher, David M. Hodgson, Mary F. Mahon, Naomi Cessford, Tina Duren, Christopher Richardson, S P. Rigby

Faculty of Science - Papers (Archive)

The reaction of zinc(II) nitrate and 4,4′-ethynylenedibenzoic acid (H₂edb) in DMF at 80 °C gave the metal–organic framework material [Zn₄O(edb)₃(H₂O)₂]·6DMF 1 in which edb ligands connect Zn₄O centres into a doubly-interpenetrated cubic network with a similar topology to observed with other linear dicarboxylates in the IRMOF series. Analysis of the nitrogen isotherm revealed the material to have a BET surface area of 1088 m² g⁻¹, which is approximately one-third of the value calculated from GCMC simulations, suggesting incomplete activation or pore blocking in the activated …

Synthesis And Anti-Leukaemic Activity Of Pyrrolo[3,2,1-Hi]Indole-1,2- Diones, Pyrrolo[3,2,1-Ij]Quinoline-1,2-Diones And Other Polycyclic Isatin Derivatives, Lidia Matesic, Julie M. Locke, Kara Vine, Marie Ranson, John B. Bremner, Danielle Skropeta

Faculty of Science - Papers (Archive)

To further expand the structure–cytotoxic activity relationships of isatin derivatives and to reduce flexibility in substituent groups at nitrogen, 20 analogues incorporating a ring system between the N1 and C7 atoms of isatin were prepared using a variety of synthetic strategies. This yielded pyrroloindole-, pyrroloquinoline-, pyrroloacridine-, pyrrolophenanthridine- and benzopyrrolophenanthridine-based systems with embedded isatin moieties, the latter possessing a novel carbon skeleton. These compounds were subsequently assessed for their in vitro cytotoxicity against human U937 lymphoma cells, with the brominated pyrroloacridine dione 27 showing the most promising activity (IC50 3.01 μM) after 24 h.

Synthesis, Properties And Water Permeability Of Swnt Buckypapers, L J. Sweetman, L Nghiem, I Chironi, G Triani, Marc In Het Panhuis, St F. Ralph

Faculty of Science - Papers (Archive)

The ability of macrocyclic ligands to facilitate formation of dispersions of single-walled carbon nanotubes (SWNTs) was investigated using a combination of absorption spectrophotometry and optical microscopy. Vacuum filtration of aqueous dispersions containing SWNTs and various macrocyclic ligands (derivatised porphyrin, phthalocyanine, cyclodextrin and calixarene) afforded self-supporting membranes known as buckypapers. Microanalytical data and energy dispersive X-ray spectra were obtained for these buckypapers and provided evidence for retention of the macrocyclic ligands within the structure of the membranes. The electrical conductivities of the membranes varied between 30 ± 20 and 220 ± 60 S cm−1, while contact angle analysis revealed they all …

Total Synthesis Of A Virotoxin And Analogs For Conformational Studies, Benson Jumba Edagwa

LSU Doctoral Dissertations

This dissertation describes the first total synthesis of alloviroidin in trace amounts, along with that of three analogs containing L-proline (Pro), trans-3-hydroxyproline (3-Hyp) or cis-4-hydroxyproline (4-hyp) residue substituting for 2,3-trans-3,4-trans-dihydroxyproline in the natural product. We report herein an efficient strategy that provides a dipeptide containing a (2S,4S)-4,5-dihydroxyleucine (dihyLeu) residue, including a diastereoselective dihydroxylation. Nα-Carbobenzyloxy-(2S)-4,5-dehydroleucine was coupled with valine ethyl ester to give a dipeptide that was subjected to a Sharpless asymmetric dihydroxylation to introduce the diol. The relative configuration at C4 was assigned as S by X-ray crystallography after derivatization as an α-amino-γ-lactone hydrochloride salt. The preparation of the 2-(methylsulfonyl)tryptophan …

Botppi, A New Wittig Salt Used In The Synthesis Of 12-(S)-Hydroxy-Eicosatetraenoic Acid [12-(S)-Hete], Michael A. Christiansen, Merritt B. Andrus

Chemistry and Biochemistry Faculty Publications

An efficient route to (Z)-(8-benzyloxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or BOTPPI, is disclosed, complete with full experimental details, NMR spectra, and HRMS data. BOTPPI serves as a surrogate for (Z)-(8-methoxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or MOTPPI, a Wittig salt previously used in two 12-HETE syntheses. BOTPPI has the advantage over MOTPPI of being derived from a sequence for which every intermediate is UV-active and amenable to large-scale chromatographic purification. A formal asymmetric total synthesis of 12-(S)-HETE is also reported, involving a stereoselective phase-transfer catalyzed (PTC) alkylation in its key step.

One-Pot Synthesis Of Colloidal Silicon Quantum Dots And Surface Functionalization Via Thiol-Ene Click Chemistry, Xiaoyu Cheng, Richard Gondosiswanto, Simone Ciampi, Peter J. Reece, J Justin Gooding

Australian Institute for Innovative Materials - Papers

A solution method for preparing surface functionalized colloidal silicon quantum dots (SiQDs) is presented. SiQDs prepared by this method are reasonably monodispersed and can be further functionalized via thiol-ene click reactions to introduce specific functionalities (i.e. -NH2, -COOH, -SO 3 -, alkane, alkene).

Ferroelectric And Ferromagnetic Nanofibers: Synthesis, Properties And Applications, A Jalalian, A M. Grishin, S X. Dou

Australian Institute for Innovative Materials - Papers

As first time, ferroelectric (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃ (BCTZ), biocompatible (Na_0.5K_0.5)NbO₃ (NKN), and ferromagnetic Y3Fe5O12 (YIG) nanofibers were synthesized by sol-gel assisted electrospining technique. Non-woven, bead-free 100 μm long fiber mat was formed from close-packed nanocrystals after calcination in air at 800°C (BCTZ and NKN) and 1100°C (YIG). BCTZ fibers are 200 nm in width whereas NKN and YIG fibers have smaller 50-100 nm diameter. X-ray diffraction and Raman spectroscopy show that BCTZ and NKN crystallized in tetragonal and rhombohedral polar phases in the vicinity of morphotropic phase boundary. …

Synthesis And Electrochemical Characterization Of Lifepo4/C-Polypyrrole Composite Prepared By A Simple Chemical Vapor Deposition Method, Qiang Gong, Yu-Shi He, Yang Yang, Xiao Zhen Liao, Zi-Feng Ma

Australian Institute for Innovative Materials - Papers

A LiFePO₄/C-polypyrrole (LiFePO₄/C-PPy) composite as a high-performance cathode material is successfully prepared through a simple chemical vapor deposition (CVD) method. According to the transmission electron microscope (TEM) analysis, the surface of the LiFePO₄/C is surrounded with PPy in the LiFePO₄/C-PPy composite. The as-prepared LiFePO₄/C-PPy material shows outstanding rate capability at 20°C and good cycle performance at 55°C in comparison with those of the bare LiFePO₄/C material against Li anode. After 700 cycles, the discharge capacity of LiFePO₄/C-PPy could still remain 110 mA h g⁻¹ with …

The Synthesis Of Lamellar Nano Mgb2 Grains With Nanoimpurities, Flux Pinning Centers And Their Significantly Improved Critical Current Density, Zongqing Ma, Yongchang Liu, Qi Cai

Australian Institute for Innovative Materials - Papers

MgB2 superconductors with unique microstructures were rapidly fabricated at low temperatures, and exhibited significantly improved critical current density (Jc). According to the microstructure observations, the prepared samples consisted of lamellar nano MgB2 grains with many embedded nanoimpurities (about 10 nm). The formation of these lamellar nano MgB2 grains is associated with the presence of a local Mg-Cu liquid at sintering temperatures as low as 575°C. The ball milling treatment of the original powders also plays a positive role in the growth of lamellar grains. Based on an analysis of the relationship between resistivity and temperature, the lamellar nano MgB2 grains …

Synthesis Of The Novel Benzothiazole Compounds From 7-Benzylidenebicyclo [3.2.0] Hept-2-En-6-Ones And 2-Aminobenzenethiol, Esra Findik

Turkish Journal of Chemistry

Synthesis of the 2-(2-styrylcyclopent-3-enyl)benzo-[d]thiazoles (6a-i) is reported for the first time. Reaction of 7-benzylidenebicyclo [3.2.0] hept-2-en-6-ones (3a-i) and 2-aminobenzenethiol (4) in the presence of p-TsOH as a catalyst, in ethanol under reflux, resulted in the formation of novel 2-(2-styrylcyclopent-3-enyl)benzo[d]thiazoles in high yields.

Synthesis, Cellular Studies, And Computational Analysis Of Porphyrin And Bodipy Conjugates With Affinity For Epidermal Growth Factor Receptor, Alecia Michelle Mccall

LSU Doctoral Dissertations

Chapter 1 is a description of the basic fundamental concepts of porphyrins and BODIPYs, (including synthetic methodologies), a general mechanism of the processes of EGFR, and computational concepts that are elaborated upon in future chapters. Chapter 2 is a discussion solely on the porphyrins that were synthesized to be used as fluorophores for EGFR-targeted conjugates, both peptidic and non-peptidic. The porphyrins were primarily synthesized via the Lindsey method as well as by O-alkylation of tetrahydroxy porphyrins. Synthesis of PEG linkages are discussed as well through three methodologies. Chapter 3 is a presentation of the synthesis, characterization, cellular studies, and computational …

Syntheses And Characterization Of Water-Soluble Phythalocyanines For Diagnosis And Treatment Of Cancer, Benson Getenga Ongarora

LSU Doctoral Dissertations

Ongarora, Benson Getenga, B.S., Moi University, 2005 Doctor of Philosophy, Fall Commencement, 2012 Major: Chemistry Syntheses and Characterization of Water-Soluble Phthalocyanines for Diagnosis and Treatment of Cancer Dissertation directed by Professor M.Graҫa H. Vicente Pages in dissertation, xi. Words in abstract, 251. ABSTRACT Chapter 1 describes the general properties of phthalocyanines, synthesis of metallo-phthalocyanines, their photophysical features and their uses. The concepts of PDT and targeted therapeutics are also introduced. Chapter 2 describes the syntheses, characterization, photophysical studies and biological evaluation of cationic phthalocyanines. The trimethylaminophenoxy substituted phthalocyanines were synthesized through statistical condensation method, which gave a statistical mixture of …

Synthesis, Characterization, And Antioxidant Activities Of New Trisubstituted Triazoles, Kemal Sancak, Yasemi̇n Ünver, Di̇lek Ünlüer, Esra Düğdü, Gülcan Kör, Fati̇h Çeli̇k, Emrah Bi̇ri̇nci̇

Turkish Journal of Chemistry

A series of new 4-(3,4dimethoxyphenethyl)-3,5-akyl/aryl-4H- 1,2,4-triazoles (3a-g) were obtained by reaction of ethyl N'-(alkylidene/arylidene)hydrazonate (1) and 2-(3,4-dimethoxy phenyl)ethanamine (2). Compounds 4d, e, and g were synthesized from the reaction of corresponding compounds 3d, e, and g with BBr_3, respectively. The 10 new compounds synthesized were characterized by elemental analyses, IR, ^1H-NMR, and ^{13}C-NMR spectral data. The structure of compound 3g was inferred through IR, ^1H-, ^{13}C-NMR, elemental analyses, and X-ray spectral techniques. In addition, the newly synthesized chemicals were screened for their antioxidant properties. Among the chemicals tested, 4d, e, and g exhibited the highest degree of antioxidant activity.

Synthesis Of 3-Pyrroline-2-Ones From Amino Acids And An Aryl Amine, Nezi̇re Saygili, Cemi̇l Aydoğan

Turkish Journal of Chemistry

The conversion of the amino group of amino dicarboxylicacid esters and an aryl amine into N-substituted pyrrolinone derivatives with dimethoxydihydrofurane is described. The conversion also occurs with serine methylester but it decomposes very quickly.

Recent Applications Of The Simple Hydrocarbon Cyclooctatetrene As A Starting Material For Complex Molecule Synthesis, Kevin W. Glaeske, William Donaldson

Chemistry Faculty Research and Publications

Cyclooctatetraene [COT], a simple non-aromatic cyclic polyene, is capable of undergoing a variety of oxidation and cycloaddition reactions to afford polycyclic structures. In addition, complexation of COT or the cycloaddition products with transition metals facilitates bond formation. Recent developments in the reactivity of COT and application to the synthesis of naturally occurring and non-naturally occurring compounds is reviewed.