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The interfacial behaviour of two amphiphillic poly iso-butenyl succinic anhydride (PIBSA)-derived surfactants and the effect of their interaction with various nitrate salts on the stability of a water-in-oil type emulsion has been investigated. The adsorption of the esterification product of PIBSA and coco-diethanolamide (PICDEA) and of Experse-70 (E-70) at the equilibrated aqueous-fuel oil interface was investigated via the measurement of interfacial tension using the ring detachment method.The interfacial pressure of PICDEA decreased in the presence of excess unreacted coco-diethanolamide (CDE) and for both PICDEA and E-70 interfacial pressure decreased with an increase in the length of the poly iso-butenyl (PIB) hydrocarbon tail. Interfacial tension-concentration curves and the Gibbs Equation were used to determine surfactant surface excess concentration and the packing efficiency of the surfactant in the interphase. The double hydrocarbon PICDEA molecule was found to occupy a larger interfacial area than the single hydrocarbon E-70 molecule. The pH of the aqueous phase effects the interfacial activity and nature of, PICDEA and E-70 at the interface. PICDEA is protonated at pH values less than 4.6 and deprotonated at higher pH values. E-70 is neutral at low pH and deprotonated at pH values greater than approximately 2.The effect of sodium, calcium and ferric nitrate salts on the interfacial free energy of the surfactant saturated interface was also determined. The interfacial tension at the E-70 aqueous nitrate interface was dependent on ionic strength alone with a general decrease in interfacial free energy as nitrate concentration was increased. In the case of PICDEA, however, a surfactant-cation orientation effect was observed. The divalent Ca2+ cation attracts two adjacent PICDEA anions resulting in the adverse interaction of hydrocarbon tails in the interphase. This produces an interface with a higher than expected interfacial free energy. The Na+ cation produces an interface with a more energetically stable orientation. PICDEA in the presence of a ferric nitrate solution (pH 1 to 2) is protonated and therefore the univalent nitrate anion forms the counterion layer at the positively charged surfactant interface. Stability studies were carried out on aqueous nitrate salt in diesel emulsions using PICDEA as the stabilizing surfactant. Droplet coalescence rates were determined from droplet size distribution data in the presence of varying concentrations of sodium, calcium and ferric nitrate salts. Droplets were sized microscopically at progressive time intervals and the rate of coalescence determined from the change in droplet concentration with time. Coalescence was found to follow two or more consecutive first order reactions. After an initial period of rapid droplet coalescence, involving small droplets with diameters of 5~m and less, a droplet distribution is attained conducive to a more stable emulsion which then undergoes a slower rate of coalescence involving larger droplets. The effect of the nitrate salt type on the initial droplet coalescence rate (in order of increasing rate) is as follows: Ca2+< Na+< Fe3+. The opposite trend was observed for the slower long term rate of coalescence, i.e. Fe3+< Na+< Ca2+. These trends are explained in terms of the surfactant cation orientation effect, the effect of the droplet's radius of curvature on the potential energy barrier against coalescence and the effect of the droplet distribution of the emulsion system. / Thesis (M.Sc.)-University of Natal, Durban, 1990.

The electropolymerisation of a range of indole derivatives results in the formation of redox active films. These redox films have been observed to be highly luminescent. Earlier studies have investigated electrochemical and photophysical properties, for potential applications such as fast response potentiometric sensors or novel materials for light emitting devices. The work in this thesis extends this approach to electrochemical and computational studies of a range of novel redox-active aromatic systems. This work has exploited the continuing increase of computing power, employing powerful quantum computational models to complement and augment electrochemical methods. Density Functional Theory has been used to show that prediction of oxidation potentials in good agreement with experimental values is achievable for a wide range of aromatic systems. Calculation of the electron spin density of the radical cations has also helped to elucidate the likely coupling locations for the formation of electroactive layers. It is observed that the nature of substituents and additional hetero groups to the aromatic systems can have a profound effect on electron spin density distributions. The redox-active species formed from indole dimers and 5-methylindolocarbazole have also been characterised. The species formed from electropolymerisation of 5- methylindolocarbazole has been found to be a mixture of three isomers of a 5- methylindolocarbazole dimer. Full characterisation of the product of the electropolymerisation of indole dimers was not possible; fluorescence work however suggests this to be a species with a greater degree of conjugation than either indole dimers or trimers. It is thought likely that this product is either a tetramer or longer chain polymer. This work demonstrates the applicability of a combination of computational and electrochemical methods to the characterisation of novel heteroaromatic systems.

We present a recalibration of the M-BH-sigma(star) relation, based on a sample of 16 reverberation-mapped galaxies with newly determined bulge stellar velocity dispersions (sigma(star)) from integral-field spectroscopy (IFS), and a sample of 32 quiescent galaxies with publicly available IFS. For both samples, sigma(star) is determined via two different methods that are popular in the literature, and we provide fits for each sample based on both sets of sigma(star). We find the fit to the active galactic nucleus sample is shallower than the fit to the quiescent galaxy sample, and that the slopes for each sample are in agreement with previous investigations. However, the intercepts to the quiescent galaxy relations are notably higher than those found in previous studies, due to the systematically lower sigma(star) measurements that we obtain from IFS. We find that this may be driven, in part, by poorly constrained measurements of bulge effective radius (r(e)) for the quiescent galaxy sample, which may bias the sigma(star) measurements low. We use these quiescent galaxy parameterizations, as well as one from the literature, to recalculate the virial scaling factor f. We assess the potential biases in each measurement, and suggest f = 4.82 +/- 1.67 as the best currently available estimate. However, we caution that the details of how sigma(star) is measured can significantly affect f, and there is still much room for improvement.

Helix-sense-selective polymerization of poly(3-methyl-4vinylpyridine) have been carried out using the DPEDAHLi

There is mounting evidence that supermassive black holes (SMBHs) form and grow in bulgeless galaxies. However, a robust determination of the fraction of active galactic nuclei (AGNs) in bulgeless galaxies, an important constraint to models of SMBH seed formation and merger-free models of AGN fueling, is unknown, since optical studies have been shown to be incomplete for AGNs in low-mass galaxies. In a recent study using the Wide-field Infrared Survey Explorer, we discovered hundreds of bulgeless galaxies that display mid-infrared signatures of extremely hot dust suggestive of powerful accreting massive black holes, despite having no signatures of black hole activity at optical wavelengths. Here we report X-ray follow-up observations of J122434.66+555522.3, a nearby (z = 0.052) isolated bulgeless galaxy that contains an unresolved X-ray source detected at the 3 sigma level by XMM-Newton with an observed luminosity uncorrected for intrinsic absorption of L2-10 (keV) = (1.1 +/- 0.4) x 10(40) erg s(-1). Ground-based near-infrared spectroscopy with the Large Binocular Telescope and multiwavelength observations from ultraviolet to millimeter wavelengths together suggest that J1224+5555 harbors a highly absorbed AGN with an intrinsic absorption of N-H > 10(24) cm(-2). The hard X-ray luminosity of the putative AGN corrected for absorption is L2-10 keV similar to 3 x 10(42) erg s(-1), which, depending on the bolometric correction factor, corresponds to a bolometric luminosity of the AGN of L-bol 6 x 10(43)-3 x 10(44) erg s(-1). and a lower mass limit for the black hole of M-BH similar or equal to 2 x 10(6) M-circle dot, based on the Eddington limit. While enhanced X-ray emission and hot dust can be produced by star formation in extremely low metallicity environments typical in dwarf galaxies, J1224+5555 has a stellar mass of similar to 2.0 x 10(10) M-circle dot and an above solar metallicity (12 + logO/H = 9.11), typical of our WISE-selected bulgeless galaxy. sample. While collectively. these observations suggest the presence of an AGN, we caution that identifying obscured AGNs in the low-luminosity regime is challenging. and often requires multiwavelength observations. These observations suggest that low-luminosity AGNs can be heavily obscured and reside in optically quiescent galaxies, adding to the growing body of evidence that the fraction of bulgeless galaxies with accreting black holes may be significantly underestimated based on optical studies.

In this Thesis I present simulation- and theory-based studies of pattern formation and growth in collections of micro-organisms, in particular bacterial colonies. The aim of these studies is to introduce simple models of the 'micro-scale' behaviour of bacterial cells in order to study the emergent behaviour of large collections of them. To do this, computer simulations and theoretical techniques from statistical physics, and in particular non-equilibrium statistical physics, were used, as the systems under study are far from thermodynamic equilibrium, in common with most biological systems. Since the elements making up these sytems - the micro-organisms - are active, constantly transducing energy from their environment in order to move and grow, they can be viewed as `active matter' systems. First, I describe my work on a generalization of an archetypal model of active matter - the Vicsek model of flocking behaviour - in which the speed of motion of active particles depends on the local density of particles. Such an interaction had previously been shown to be responsible for some forms of pattern formation in bacterial colonies grown on agar plates in the laboratory. Simulations and theory demonstrated a variety of pattern formation in this system, and these results may be relevant to explaining behaviour observed in experiments done on collections of molecular motors and actin fibres. I then go on to describe work on modelling pattern formation and growth in bacterial biofilms - dense colonies of cells growing on top of solid surfaces. I introduce a simple simulation model for the growth of non-motile cells on a flat surface, whereby they move only by growing and pushing on each other as they grow. Such colonies have previously been observed experimentally to demonstrate a transition from round to 'branched' colonies, with a pattern similar to diffusion-limited aggregation. From these simulations and analytical modelling, a theory of the growth of such colonies is developed which is quite different from previous theories. For example, I find that the colony cannot grow at a constant speed if the cells are not compressible. Finally, I present some results on genetic drift and evolution in growing bacterial colonies. Genetic drift is greatly enhanced in colonies which are expanding in space, as only a few individuals at the edge of the population are able to pass on their genes onto their progeny. The individual-based simulations of biofilms described above are used to analyse which factors - such as the shape of the colony, the thickness of the growing layer of cells, and the interactions between the cells - affect the rate of genetic drift and the probability of fixation of beneficial mutations. This has implications, for example, for the evolution of antibiotic resistance in such colonies.