Este trabalho teve por objetivo estudar as interações do corante auramina O em suspensões aquosas de argilas naturais e sintéticas, correlacionando as diferenças de comportamento do corante com as propriedades das argilas estudadas. Estes sistemas podem ser futuramente empregados no desenvolvimento de materiais híbridos corante-argila fotoativos. A Auramina O foi estudada nas argilas, utilizando-se espectroscopia de absorção molecular na região do UV - visível e técnicas de fluorescência estática e dinâmica. A fluorescência da Auramina O aumenta após a adição do corante na argila, devido à adsorção das moléculas de corante na superfície externa das argilas, que restringe o movimento de torção da Auramina. Em períodos mais longos, as moléculas do corante migram para a região interlamelar das partículas de argila. A agregação das moléculas de corante pode ocorrer na região interlamelar, conduzindo à diminuição da emissão de fluorescência. Os rendimentos quânticos de fluorescência (ΦF) da auramina O nas argilas montmorilonitas naturais SAz-1, SWy-1, e nas argilas sintéticas Syn-1 e Laponita RDS são 0,015; 0,007; 0,016 e 0,017, respectivamente. Estes valores são maiores do que o rendimento quântico de fluorescência (ΦF) da auramina em solução aquosa e são da mesma ordem de grandeza do ΦF encontrado para solventes viscosos investigados como n-hexanol e n-heptanol (0,014 e 0,015). Estudos de espectroscopia de fluorescência resolvidos no tempo da Auramina adsorvida em argilas revelaram decaimentos multiexponenciais com componentes nas faixas de 25-36 ps, 219-362 ps e 1300-1858 ps. Os componentes de vida curtos podem ser atribuídos às espécies ligadas à superfície externa e os componentes de maior tempo de vida são atribuídos a moléculas do corante nos espaços interlamelares, que interagem fortemente com a argila. Parece claro que, a adsorção da Auramina nas argilas provoca uma redução significativa da taxa de conversão interna que envolve a difusão de rotação, de modo que o corante é bloqueado em uma geometria desfavorável para a conversão conformacional interna. / This thesis aims to study the auramine dye interactions in the aqueous suspensions of natural and synthetic clays, correlating dye behavioral differences with the properties of the studied clays. The spectroscopic behavior of Auramine O in aqueous suspensions of montmorillonite clays was studied using absorption and static and dynamic fluorescence techniques. The fluorescence of Auramine O increases immediately after mixing the dye solution with the suspension of clay due to its adsorption on the external surface of the clays, which restricts the torsional molecular motion of Auramine. At longer times, the dye molecules migrate into the interlamellar region of the clay particles. Aggregation of the dye molecules can occur in the interlayer region, leading to the decrease of the fluorescence emission. The fluorescence quantum yields (ΦF) of auramine O on the natural montmorillonites SAz-1, SWy-1, Syn-1 and Laponite clays were 0.015, 0.007, 0.016 and 0.017, respectively. These values are higher than the ΦF of auramine O in aqueous solution and are of the same order of magnitude of the ΦF found for viscous solvents such as n-hexanol and n-heptanol (0.014 and 0.015). Time-resolved fluorescence spectroscopy studies of adsorbed Auramine on clays revealed multi-exponential decays with components in the 25-36 ps, 219-362 ps and 1300-1858 ps ranges. The short-lived components can be attributed to species bound to external surface and the longer lifetime is assigned to dye molecules in interlayer spaces interacting strongly with the clay. It seems clear that the binding of Auramine to clays causes a significant reduction of the rate of internal conversion that does involve rotational diffusion, so that the clay will be locked in a conformational geometry unfavorable for internal conversion.

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.

Following the crash of a Norwegian Hercules aircraft on Rabots glaciär in the Kebnekaise mountain range in 2012, a field campaign was initiated in order to assess the fate of the hydrocarbon pollution in the system. It is hypothesized that soluble components of the aircraft fuel will be transported within the glacial meltwater. This thesis focuses on constraining the likely transit time and dispersion of the meltwater as a proxy for potential pollution pathways. Therefore, the hydrologic configuration of Rabots glaciär was studied during the ablation season 2013 by means of dye tracing experiments and discharge monitoring in the proglacial stream. The analyses of the dye return curves and stream monitoring suggest that Rabots glaciär exhibits a widely efficient drainage system towards the end of the ablation season, but with analyses revealing heterogeneity in the drainage system form. The seasonal evolution of efficiency was also assessed, showing an increase over time, although was hampered by early onset of melting before the field season began. There are different hydrological configurations on the north and south side of the glacier, possibly influenced by shading. The system on the north side is routing meltwater along the glacier bed over a long distance as indicated by the turbid outlet stream. Water routing on the southern side likely occurs through englacial channels. This configuration may be influenced by the thermal regime and distribution of cold surface layers. It has further been revealed that both systems are likely to be disconnected from each other. Pollution that is transported with the meltwater down from the crash site on the southern side does not reach the drainage system on the northern side. Besides revealing potential pathways for soluble hydrocarbon pollutants, this case study contributes to the previously very limited knowledge of Rabots glacial hydrology, and our general understanding of polythermal glacier hydrology.

Magister Scientiae Dentium - MSc(Dent) / Introduction: Micro-leakage and enamel demineralization is still a major challenge in dental practice. It can lead to formation of demineralization lesions around and beneath the adhesive–enamel interface (Mali et al., 2006). Enamel demineralization adjacent to orthodontic brackets is one of the risks associated with orthodontic treatment. The prevention of demineralization during orthodontic treatment is therefore essential for aesthetic reasons and to circumvent the onset of caries. Aim: To assess micro-leakage and enamel demineralization around orthodontic direct attachments (brackets) using three different orthodontic cements. Materials and methods: In this in-vitro study, intact (non carious) extracted human premolars were used to compare the micro-leakage and enamel demineralization of three different cements (Fuji Ortho LC, Rely X luting 2 and Transbond XT). The dye penetration technique was used to evaluate micro-leakage on extracted human premolars. Micro-hardness testing was performed on 21 teeth to determine enamel demineralization. Sixty teeth were randomly divided into 3 groups of twenty teeth each. Direct attachments were cemented on each tooth using 3 different cements; Fuji Ortho LC (GC Fuji II LC GC Corporation Tokyo, Japan), (group 1), Rely X luting 2 cement (3M ESPE dental product, USA), (group 2), Transbond XT Light Cure (3M Unitek, Monrovia, Calif), (group 3). After the orthodontic direct attachments were fitted, they were exposed to 500 thermo-cycles between 5°C and 55°C, with a dwell time of 15 seconds in a buffered (pH 7) 1% methylene blue dye solution (Grobler et al, 2007). The specimens were viewed under a stereomicroscope (Nikon, Japan) at magnification of 40 times. Photographs of each specimen were taken with a Leica camera (Leica DFC 290 micro-systems, Germany) fitted onto a stereomicroscope. The ACDsee photo editing programme was used to transfer the photographs to a computer to measure the dye penetration along the enamel–adhesive and adhesive–bracket interfaces, both on the gingival and occlusal edge at × 40 magnification. For the demineralization sample, 21 teeth were divided into 3 groups of seven teeth each, where direct attachments were cemented using each of the 3 cements, group 1, Fuji Ortho LC (GC Fuji II LC GC Corporation Tokyo, Japan); group 2, Rely X luting 2 cement (3M ESPE dental product, USA) and group 3, Transbond XT Light Cure (3M Unitek, Monrovia, Calif). A digital hardness tester with Vickers diamond indenter (Zwick RoellIndentec (ZHV; Indentec UK) was used to measure surface micro-hardness of enamel before and after attaching the brackets. Ten indentations were made on the enamel surface of each tooth before bonding the brackets with a 300g load applied for 15 seconds to establish the baseline hardness value. After de-bonding the brackets, the hardness was measured again in the same area as mentioned above to determine the degree of enamel demineralization (softening). Result: The result showed statistically significantly lower levels of micro-leakage for Transbond XT (P= <0.001). The amount of micro-leakage on the margins was significantly higher in the gingival portion (P <0.05) as compared with the occlusal margin. Enamel micro-hardness tests before bonding using the three different cements showed that the variances are not significantly different (Chi-squared = 3.051, df = 2, p-value = 0.218). However, the micro-hardness tests done after bonding and thermo-cycling was statistically significantly different (Chi-squared = 13.435, df = 2, p-value = 0.001). Clearly, the Transbond XT group had less hardness, implying greater demineralization than the Fuji Ortho LC and Rely X luting 2 groups. Two sample t-tests show that mean value for the Fuji Ortho and Rely X luting 2 were not significantly different from each other (t = -0.636, df = 12, p-value = 0.537). The mean value for Transbond XT differed significantly from both the other two means: Transbond XT vs Fuji Ortho LC (t = 3.249, df = 6.9, p-value = 0.014). Transbond XT vs Rely X luting 2 (t = 3.493, df = 6.8, p-value = 0.011). Conclusions: This study showed that Fuji Ortho LC and Rely X luting 2 show more micro-leakage than Transbond XT. However Transbond XT had significant lower micro-leakage, less hardness (greater demineralization) than the Fuji Ortho LC and Rely X luting 2. This may have been due to the fluoride release which significantly reduces demineralization. Therefore the Fuji Ortho LC and Rely X luting 2 may be recommended for prevention of demineralization during orthodontic treatment.

In this study a presentation of the technology behind dye-sensitized solar cells, their design as well as the role of the different parts of the cell. The characterization of the cell is divided into four sections namely: the characterization of the paste required to make the TiO2 film and its optical properties using SEM-EDX and XRD analytical techniques; Analysis of the various absorptions of three Ru-based dyes using UV-Vis spectroscopy, Photoluminescence and Fourier Transform Infra-Red spectroscopy; the characterization and the analyses of the entire cell using Electrochemical Impedance Spectroscopy. The nine cells were prepared by examining RuL2(CN)2 , RuL2(NCS)2 or N3 dye and RuL2(NCS)2 TBA+ or N719 dye. [L = 2,2'-bipyridyl-4,4'-dicarboxylic acid ;TBA = tetra-butyl ammonium] were combined with three electrolytes namely: Z–150 , AN–50 and PN–50. The Iodolyte PN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called propionitrile (PN). The Iodolyte AN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called acetonitrile (AN). The Iodolyte Z–150 is an iodide based low viscosity electrolyte with 150 mM of tri-iodide dissolved in a solvent called 3-methoxypropionitrile (MPN) and with additives such an ionic liquid, malkylbenziimidazole and guanidine thiocyanate. A solar simulator was utilized with which the standard solar irradiation can be created in laboratory conditions. The fill factors as well as overall performance efficiencies of the these cells are quite low < 1.0%,.

Over the past decade, intensive academic and commercial interests have been paid on compounds possessing photochemical properties, namely for their preparation, chemical properties, high efficiency and potential low-cost. Compounds having intense photochemical properties gained great interest due to wide range of potential applications. The sensitizers are one of the key components for high power-conversion efficiency in the dye sensitized solar cells (DSSCs). They are the core components in the organic light-emitting devices (OLEDs) due to their ability to emit light with the wavelengths largely red- shifted from their absorption wavelength. Ruthenium based sensitizers have been tagged “molecular light switches” because, although the fluorescence of these complexes in aqueous solutions is negligible, it increases of greater than 10000 fold in the presence of DNA. Many polypyridyl and dipyrido phenazine ruthenium complexes have achieved high power conversion efficiencies and therefore are of practical interest. Several research groups stated that the dipyrido phenazine ligand may be thought of as comprising two components: a bipyridyl unit and a phenazine unit. These two subunits behave essentially separately, with many molecular orbitals being localised over only one subunit and a redox properties of central phenazine moiety in the dipyrido phenazine ligand are important for the photochemical applications. Therefore a phenazine ligand was selected as a model for the present investigation. The chemistry of phenazine ligand is mostly limited to the late transition metal and f - element complexes. Our laboratory has a rich backgroung in the aluminum and early transition metal chemistry. The aluminum chemistry and early transition metal chemistry are of great interest since aluminum and early transition metal complexes are environmentally friendlier and cheaper than the late transition metal compounds. Another drawback of the ruthenium-based sensitizers is the lack of absorption in the red region of the visible spectrum, and also low molar extinction coefficients. An essential requirement for efficient conversion of solar energy is the good spectral match of the sensitizer absorption to the emission spectrum of solar radiation. In this regard, the ruthenium sensitizers’ spectral response in the lower energy regions is not sufficient. The current project has three parts. In the first part we collected and reviewed known literature regarding the certain classes of non-innocent ligands containing the six-membered carbon- nitrogen heterocycles and regarding the ligands potentially important for the photochemical applications. We also reviewed all available to the data information about the complexes supported by the phenazine ligand. In the second part we have investigated interaction of alkylaluminum compounds and phenazine and observed reduction of phenazine accompanied by formation of dialuminum cage type compounds containing two formally mononegative phenazine ligand. The derivatization of phenazine has been also observed. It resulted in formation of compounds having a stable organic radical. In a third part of our project we have explored interaction of phenazine or thiophenazine with the alkylaluminum compounds and chromium dichloride. The reaction in the three component system resulted in reduction of phenazine ligand and lead to the heterometallic Cr(II) - aluminum complexes containing a formally dinegative phenazine or thiophenazine ligands. When a large excess of triethylaluminum was taken, reduction of phenazine and chromium has been observed leading to the heterometallic multinuclear Cr(I) - aluminum complex containing a formally dinegative phenazine ligands and two chromium atoms in one complex in the rare oxidation state one.

Previous work in our group has been directed towards the synthesis of crown-ethers for use in the selective complexation of metal ions and as chiral ligands for use in asymmetric catalysis. The development of a modular approach to macrocycle assembly has enabled the synthesis of a library of pyridine-based macrocycles possessing multiple donor sites where chirality was readily introduced from simple amino acids.The nucleophilic ring opening of aziridines 181, 193 or 194, allowed the highly selective synthesis of thioether-based spacers and macrocycles. Extension of this basic approach to the synthesis of seleno-crown ethers was also investigated. The use of chiral-pool starting materials derived from D- or L-alanine, provided access to optically pure macrocycles. The use of the Sharpless-Huisgen 'click' reactions allowed the attachment of a carbohydrate residue directly to a macrocycle via a triazole unit. We hope to attach a macrocycle, carbohydrate residue and azo dye together, to be able to examine further diseases such as Alzheimer's. We have so far succeeded in attaching a macrocycle and sugar to a central scaffold by performing a one-pot double 'click' reaction. The distance between the points of attachment of the chromophore to the macrocycle metal binding site is probably, in this first generation sensor, too great to enable a metal-macrocycle binding event to be reported.

This thesis describes both batch and continuous processes for water treatment by adsorption with electrochemical regeneration of the adsorbent using an airlift reactor. The process is based on the adsorption of dissolved organic pollutants onto a graphite intercalation compound (GIC) adsorbent and subsequent electrochemical regeneration of the adsorbent by anodic oxidation of the adsorbed pollutant. Batch experiments were carried out to determine the adsorption kinetics and equilibrium isotherm for a sample contaminant, the organic dye Acid Violet 17 on the GIC (Nyex®1000) adsorbent. The adsorption capacity was found to be around 1 ± 0.05 mg/g. The rate of adsorption appeared to follow pseudo-second order kinetics. The increase in the rate adsorption with temperature indicated an activation energy of around 4.2 KJ/mole, suggesting that the mechanism of adsorption was physisorption. It was demonstrated that the adsorbent could be regenerated by anodic oxidation of the adsorbed dye in a simple electrochemical cell. The GIC adsorbent recovered its initial adsorption capacity after 40 to 60 min of treatment at a current density of 10 mA/cm2, corresponding to a charge passed of 12 to 15 C/g of adsorbent. The charge passed is consistent with that expected for mineralisation of the dye suggesting that the dye was removed and destroyed with high charge efficiency. Experiments were carried out to investigate the characterisation and performance of the continuous process, where water is treated continuously in a fluidised adsorption zone and the adsorbent is circulated through a moving bed electrochemical regeneration cell. The adsorbent circulation rate, the residence time distribution (RTD) of the reactor, and water treatment performance by continuous adsorption and electrochemical regeneration were studied. The RTD behaviour could be approximated as a continuously stirred tank. It was found that greater than 90% removal at feed concentrations of up to 100 mg/L were achieved using a single pass through a large continuous treatment unit by adsorption and electrochemical regeneration with a flow rate of 0.25 L/min. In a smaller continuous treatment unit 98% removal at feed concentrations of up to 66 mg/L were achieved in a single pass with a flow rate of 0.24 L/min. Steady state and dynamic models have been developed for the continuous process performance, assuming full regeneration of the adsorbent in the moving bed electrochemical cell. Experimental data and modelled predictions (using parameters for the adsorbent circulation rate, adsorption kinetics and isotherm obtained experimentally) of the dye removal achieved were found to be in good agreement. A higher dye removal was found with a co-current PFR model, but a number of tank in series (n CSTRs) was found to give higher contaminant removal for the same total adsorption zone volume. It was also found that the predicted number of stages of batch adsorption / regeneration required to achieve 99.9% AV17 removal was halved when the adsorptive capacity of the adsorbent was doubled. Similarly the predicted number of continuous CSTR adsorption / electrochemical regeneration process units required in series to achieve 99% AV17 removal was reduced by more than two thirds when the adsorptive capacity of the adsorbent was doubled.

With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless, noisy signals were obtained that prevented the ability of detecting OH at the expected few ppms concentrations. Further optimization of the experimental setup is required.

No description available.