Part I: Pyrrolidine derivatives were attached a methoxy group on a-C position of pyrrolidine-ring via anodic oxidation. Followed with alkylation and series of transformation under Lewis acids to obtain tropane alkaloids. Part II: Application of intramolecular radical cyclization toward the synthesis of aporphine alkaloids. Tributyltinhydride and AIBN were used to generate aryl radicals. Trapping of aryl radicals with unsaturated alkenes led to products.

published_or_final_version / Chemistry / Master / Master of Philosophy

A novel way of producing nanostructures in the past decade has been through the use of an anodized alumina template. This template has dense, self-ordered nanometric pores that grow in the oxide as the aluminum is being anodized. This technique is a fairly new method of processing nanostructures, and much study and research is presently being done to understand the formation mechanisms of the highly ordered pores. Ultra-pure aluminum foil and pure aluminium single crystal plates were anodized to create porous anodized alumina, and using it as a template to electro-deposit Nickel nanostructures. The effects different anodizing parameters have on oxide creation were studied, and the results obtained from studying the effects of substrate purity and texture of the anodized aluminum substrate on the morphology of the alumina template, through the use of X-ray diffraction and scanning electron microscopy. / Nickel nanowires were prepared by DC electrodeposition inside the porous alumina template with a gold-palladium coating serving a conductive base. The nanowires have a diameter of 65 nm, and their length depends on the deposition time. The nanowires can uphold a position perpendicular to the substrate by partially dissolving the alumina template. They also have a tendency to gather together once the template is partially removed.

Thesis (M. S.)--Mechanical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Bert Bras; Committee Member: David Rosen; Committee Member: Jeannette Yen

>Magister Scientiae - MSc / Platinum Group Metals (PGMs), particularly palladium (Pd), platinum (Pt) and rhodium (Rh) have been identified as pollutants in the environment due to their increased use in catalytic converters and mining in South Africa (as well as worldwide). Joining the continuous efforts to alleviate this dilemma, a new electrochemical sensor based on a nanoparticle film transducer has been developed to assess the level of these metals in the environment. The main goal of this study was to exploit the capabilities of nanostructured material for the development and application of an adsorptive stripping voltammetric method for reliable quantification of PGMs in environmental samples. In the study reported in this thesis, glassy carbon electrode (GCE) and screen-printed carbon electrode (SPCE) surfaces were modified with conducting films of nanostructured reduced graphene oxide-antimony nanoparticles (rGO-SbNPs) for application as electrochemical sensors. The rGO-SbNPs nanocomposite was prepared by Hummer`s synthesis of antimony nanoparticles in reaction medium containing reduced graphene oxide. Sensors were constructed by drop coating of the surfaces of the carbon electrodes with rGO-SbNPs films followed by air-drying. The nanocomposite material was characterised by: scanning and transmission electron miscroscopies; FTIR, UV-Vis and Ramanspectrosocopies; dc voltammetry; and electrochemical impedance spectroscopy. The real surface area of both electrodes were studied and estimated to be 1.66 × 10⁶ mol cm⁻² and 4.09 × 10³ mol cm⁻² for SPCE/rGO-SbNPs and GCE/rGO-SbNPs, respectively. The film thickness was also evaluated and estimated to be 0.36 cm and 1.69 × 10⁻⁶ cm for SPCE/rGO-SbNPs and GCE/rGO-SbNPs, respectively. Referring to these results, the SPCE/rGO-SbNPs sensor had a better sensitivity than the GCE/rGO-SbNPs sensor. The electroanalytical properties of the PGMs were first studied by cyclic voltammetry followed by indepth stripping voltammetric analysis. The development of the stripping voltammetry methodology involved the optimisation of experimental conditions such as selection of adequate supporting electrolyte, choice of pH and /or concentration of supporting electrolytes, deposition potential, deposition time, stirring conditions. The detection of Pd(II), Pt(II) and Rh(III) in environmental samples were performed SPCE/rGO-SbNPs and GCE/rGO-SbNPs at the optimised experimental conditions For the GCE/rGO-SbNPs sensor, the detection limit was found to be 0.45, 0.49 and 0.49 pg L⁻¹ (S/N = 3) for Pd(II), Pt(II) and Rh(III), respectively. For the SPCE/rGO-SbNPs sensor, the detection limit was found to be 0.42, 0.26 and 0.34 pg L⁻¹ (S/N = 3) for Pd(II), Pt(II) and Rh(III), respectively. The proposed adsorptive differential pulse cathodic stripping voltammetric (AdDPCSV) method was found to be sensitive, accurate, precise, fast and robust for the determination of PGMs in soil and dust samples. The simultaneous determination of PGMs was also investigated with promising results obtained. The AdDPCSV sensor performance was compared with that of inductive coupled plasma mass spectroscopy (ICP-MS) for the determination of PGM ions in soil and dust samples. It was found that though the metals could be determined by ICP-MS technique, it was limited from the standpoints of sensitivity, ease of operation and versatility compared to the AdDPCSV sensor. This study has show cased the successful construction and application of novel SPCE/rGO-SbNPs and GCE/rGO-SbNPs AdDPCSV sensors forthe determination of PGMs in environmental samples (specifically roadside dust and soil samples). The study provides a promising analytical tool for monitoring PGMs pollutants that are produced by automobiles and transported in the environment.

Contents: a. The oxidation of metals by atomic and molecular oxygen -- b. Calculation of the heats of formation of point defects in some transition metal oxides.

Anodic oxidation of a commercial dye, methylene blue (MB), from aqueous solutions using an electrochemical cell is reported. Data are provided on the effects of eight different types of supporting electrolytes, concentration of electrolytes, initial dye concentration, current and electrolytic time on the percentage removal of methylene blue. Anodic oxidation was found to be effective in achieving the removal of methylene blue from aqueous solutions. The optimised electrolytic conditions, for the removal of methylene blue (MB), were applied to the removal of azure A (AA), azure B (AB), azure C (AC), toluidine blue 0 (TBO), new methylene blue (NMB), dimethyl methylene blue (DMMB), thionine (TH), methylene green (MG), methyl violet (MV), Nile blue (NB), neutral red (NR), acridine orange (AO) and resorufin (RS) from aqueous solutions containing sodium chloride. Results indicated that between 84 to 100% of each dye of phenothiazine was removed during 60 minutes of electrolysis. The percentage removals for the phenothiazine dyes followed the following decreasing order: (MG ≈ MV) > (DMMB ≈ AA) > (AB ≈ AC ≈ NMB) > TBO > TH. However, the azine, acridine and oxazine dyes showed between 98 to 99% colour removal and the following decreasing order: NB ≈ NR > AO ≈ RS. Strongly electron withdrawing substituents such as nitro group or carbonyl group increases the degradation of the phenothiazine chromophore, whereas the electron donating groups such as amino and alkyl amino groups decrease the degradation. Anodic oxidation studies were extended to the destruction of eight permitted food colours, with azo and triarylmethane chromophore, from aqueous solution containing either sodium chloride or sodium sulphate as a supporting electrolyte. Again, sodium chloride was found to be the best supporting electrolyte and between 97 to 100% colour removal was achieved after 60 minutes of electrolysis. The percentage removal for the single azo based colourants followed the following increasing order: carmoisine > sunset yellow FCF > amaranth > ponceau 411 > tartrazine. However, the binary and ternary mixtures of food colour showed the following increasing order: blue > green > yellow food colours. The extractions and applications of 54 different types of natural dyes (53 from plants and one from animal origin) are evaluated using simple techniques. The extracted natural dyes were applied in dyeing three types of textile fabrics viz: a) paj silk, b) brushed cotton twill and c) crystallized shimmering satin. The effects of two eco-friendly mordants (alum and iron) on the dyeing process were compared with the dyeing process without mordants. The colour fastness to wash and light (both natural and artificial sun light) of these natural dyes were also assessed. The results showed that out of the 54 dyestuffs studied, 32 plants are potentially able to produce marketable natural dyes. These dyes produced good colour and met minimal performance standards for colour fastness to light and washing. The addition of mordants generally increased the fastness properties. Silk gave the best performance of dyeing uptake and stability. Cotton gave the poorest fastness properties. The overall results showed that, considering molecular associations, the fastness properties were of the order: anthraquinones and tannins> indigoid > flavones> flavonols > flavanols> carotenoids> anthocyanins. Anodic oxidation studies were extended to the destruction of ten natural dyes from aqueous solutions containing either sodium chloride or sodium sulphate as a supporting electrolyte. Anodic oxidation was effective in achieving the removal of green tea (35%), spinach (69%), Langdale yellow and turmeric (95%), carmine, saffron, henna (97%), beetroot, karkade and sumac (98%). However, TOC measurements and the UV analyses indicated that some organic intermediate compounds were formed in the presence of sodium chloride.

Under suitable conditions anodic metal oxidation leads to growth of complex porous structures. The initiation and growth of these structures is an interesting and challenging task for electrochemical modelling. One must identify chemical reactions in a multi-phase framework, derive a proper partial differential equations and solve them in time dependent domains. In this work, electrochemical model for the oxide growth in nano scales is presented. Physically motivated equations are formulated with precise mathematical meaning and existence of solutions is studied. Electrostatic potential fulfilling high-field conduction law and interfacial jump conditions is sought for. Numerical discretization is performed with the use of finite element method and free boundaries are tracked with characteristic level-set functions. Basic mechanism governing the growth of porous structures is given and numerical experiments are explained on it's basis. This thesis presents novel contributions to the electrochemical and mathematical picture of nanopores growth.

In this thesis the corrosion resistance of two types of steel materials were evaluated, Corten A as a representative of WS (weathering steel) and the corrosion resistance of anti-corrosion protection formed by the zinc coating. The different kinetics of corrosive processes was found during the NSS test. WS steel exposed to 400 hours of NSS laboratory test showed growth of the corrosion rate, however, after this period of time there has been a significant decline in this rate. Conversely, when using Zn as anodic protection, the corrosion losses decrease linear up to 300 hours of exposure, but after this time there was a relatively significant linear increase in corrosion rate. During measurements on existing VHV pylons they were measured corrosion decreases of steel and Zn anti-corrosion protection. Normal corrosion rate for weathering steel with 10 m.a-1 and for Zn corrosion loss 1.8 m.a-1 were found. Technical and economic assessment were evaluated using variant of new poles with Zn surface layer and revitalization of existing pylons from WS steel. With regard to all aspects obtained from laboratory tests and economic assessments, friendlier version of revitalization of existing VHV pylons from WS steel using a sufficient corrosion resistance of these steels were found out.

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