This master thesis deals with the issue of production of wooden toy in the company Detoa Albrechtice. The aim was to prepare an analysis of the current state of the company, including a description of the existing production proces. Based on this analysis, it was designed several variants of possible solutions. Because of the scope of work has been chosen one optimal solution. This option in more detail processed. The thesis also includes an option to extend the range of existing production The results obtained are shortly economic evaluation.

This Thesis utilises vibrational spectroscopy in combination with multivariate and two-dimensional analytical techniques to probe the interactions of a biopolymer in water-based systems. Chapter 1: This Chapter gives an introduction to the Thesis and briefly outlines the experimental tech- niques used to study biopolymeric systems before covering the theory and implementation of the multivariate and two-dimensional methods used. A brief introduction to carrageenan, the biopolymer of interest, is then given. Chapter 2: The general experimental procedures are discussed together with the development of a new low-temperature ATR system, which allows very precise control and variation of sample tem- perature. The latter is key to many of the measurements and analyses reported in this thesis. The ATR system is stable to 0.01 C over a temperature range of -30 to 80 C. Many of the tech- niques used within this thesis rely on the Matlab environment. Analysis methods that are not commercially available have been programmed as part of my work. The theoretical background is discussed and the scripts for these functions are included in the Appendix. Chapter 3: Three commercially available carrageenans, k-, i- and l-carrageenan are studied with infrared spectroscopy. The carrageenan solutions are cooled from ca. 80 to 10 C. k- and i-carrageenan undergo a gelation transition during the cooling and this is investigated with a variety of analysis methods. The gelation transition can be monitored with FTIR allowing insight into the struc- tural rearrangement of the biopolymer as a function of temperature. The spectral transitions are probed with multivariate (PCA & MCR) and two-dimensional (2DCOS, MW2D & PCMW2D) techniques. Structural rearrangement for k- and i-carrageenan is observed, with various sulfate based modes showing the most intense changes to temperature. As cooled from 80 to 10 C, k- and i-carrageenan showed sulfate vibrational modes changing predominantly before vibrations associated with the backbone of the polyelectrolyte (C-O-C), indicating a sequential order to the molecular rearrangement occurring during the gelation transition. Chapter 4: Investigation of a 2 % i-carrageenan in H2O is frozen and probed with infrared spectroscopy using a modified low-temperature ATR accessory. The sample is cooled past it’s freezing point and is then subjected to short term, constant temperature storage. Changes in structure of the water and carrageenan are observed as a function of time post-freezing. Analysis by multivariate, two-dimensional and band fitting routines is applied, allowing the post freezing spectral perturbations to be monitored. Several spectral changes within the fingerprint region occur at a different rate, these have been proposed as vibrations associated with the backbone and pro- truding groups of i-carrageenan showing di↵erent processes in response to being frozen. Initially post-freezing, large changes in the O-H stretch region for H2O are observed, before subsiding and and followed by changes in the structure of carrageenan. These effects suggests an interaction between i-carrageenan and ice. Chapter 5: The use of a confocal Raman microscope, installed at Unilever’s Colworth facility has been used to investigate i-carrageenan in frozen systems. A gradient temperature stage allows formation of ice-fronts and a variety of these type of systems are probed. Changes in the concentration of carrageenan are seen dependant on the movement of the ice-front. Progressing an ice front into a gelled (unfrozen) section of the sample results in a large increase in carrageenan concentration at the ice-front. This indicates that the slow growth of the ice crystal is excluding the carrageenan and causing a freeze-concentration effect at the ice-front.

The development of optical multidimensional spectroscopic techniques has opened up new possibilities for the study of biological processes. Ultrafast two-dimensional ultraviolet spectroscopy experiments have determined the rates of tryptophan → heme electron transfer and excitation energy transfer for the two tryptophan residues in myoglobin. Here we show that accurate prediction of these rates can be achieved using Marcus theory in conjunction with time dependent density functional theory (TDDFT). Key intermediate residues between the donor and acceptor are identified, and in particular the residues Val68 and Ile75 play a critical role in calculations of the electron coupling matrix elements. Our calculations demonstrate how small changes in structure can have a large effect on the rates, and show that the different rates of electron transfer are dictated by the distance between the heme and tryptophan residues, while for excitation energy transfer the orientation of the tryptophan residues relative to the heme is important. The absorption and fluorescence spectroscopy of a series of porphyrin based systems have been studied. The range of systems has been selected in order to investigate the influence of both the electronic and geometric configuration on the photophysical properties. The origin of the bathochromic shift in the absorption and fluorescence spectra of substituted porphyrins is attributed to both steric distortions of the ring and electronic effects of the substituents. Three DFT based approaches have been used to model and calculate these properties. The approach using the maximum overlap method (MOM) predicted the largest discrepancy from Excited States of Porphyrins experimental results whilst TDDFT calculated shifts within 0.05 eV of experimental values. Finally a third method labelled as a ‘hybrid’ approach has been used, where the MOM is employed to optimise excited state geometries and single point TDDFT calculations are used to evaluate the vertical excitation energies. This approach improves on the excitation energies predicted by the MOM but does not improve on the values that a full TDDFT calculation produced. However, this ‘hybrid’ approach is computationally less demanding. There is distinct trade-off between accuracy and feasibility of calculations, where this ‘hybrid’ method of MOM and TDDFT becomes beneficial and useful. High resolution spectra of both free base and metallocentred complexes of porphyrin are calculated for the Q band region. Calculations on the vibronic structure of porphyrin are performed using DFT and TDDFT. Both Franck–Condon (FC) and Herzberg–Teller (HT) approaches have been used to predict the frequency and intensity of vibronic bands in the simulated absorption spectra with respect to the S0 → S1 electronic transition as the summation of contributions from both schemes characterise the electronic transitions and provide a high resolution description of the Q-band. Chapter five shows that the first electronic transition into the singlet excited state is vibronically active in the Qx region of the absorption spectrum, in good agreement with experimental data. The HT scheme appears to have more significant contributions and provides more insight into resolving the vibrationally active area of the absorption spectra. HT contributions to the electronic transition dipole moments are essential to assign the weak vibrational transitions and reproduce the experimental spectral profile. In order to provide a detailed account of the vibronic structure it is necessary to assign the vibrational transitions using both HT and FC schemes. The importance of theoretical calculations are highlighted here and can help the general understanding of the photophysical properties of porphyrins.

No abstract / Dissertation LLM--University of Pretoria, 2014 / hb2014 / Mercantile Law / unrestricted

No abstract available. / Dissertation (LLM)--University of Pretoria, 2010. / Mercantile Law / unrestricted

This paper entitled Capital Rules in terms of the Companies Act no.71 of 2008 is submitted in partial fulfillment of the requirements for the degree of Master of Laws (LLM) majoring in Corporate Law. The topic is motivated by the recent change in our company law ushered by the new Companies Act no.71 of 2008. The new Act sets forth to repeal, in the near future, the Companies Act no.61 of 1973. It is trite that the 1973 Act, which has regulated our company law for over thirty (30) years, was old and outdated. Several attempts were made to resuscitate it so as to bring it to par with prevailing international trends in company law. This is evidenced by the numerous amendments to the 1973 Act over the years, particularly between the years 1998 and 1999 when company law trends were experiencing a dimensional shift through out the world. However, these attempts boiled down to ‘pouring new wine into an old skin’. Ultimately, it became imperative that the entire Act be reviewed and hence the enactment of the Companies Bill which later became the new Companies Act of South Africa. The new Act comes with major changes in the company law system. Like any new legislation, some of these changes still need to be revisited while others still need time to settle into our legal system. This paper, as the title depicts, focuses on the changes introduced by the new Act in the sphere of Capital Rules. To a great extent, the new Act is clear on its position regarding the principle of capital maintenance. Capital rules no longer apply as exceptions to the common law rule as was the case under the 1973 Act. The rules are unambiguously stated in the new Act in sections 45, 46 and 48. The Board of Directors is endowed with power to authorize a company to, inter alia, <ul><li> provide financial assistance to a related or inter-related company,</li> <li> acquire its own shares or those of a related or inter-related company,</li> <li> issue shares at a discount and</li> <li> declare and pay out dividends.</li> </ul> All things done in terms of the new Act are subject to the company’s solvency and liquidity. Any act done that is inconsistent with the Act is void and to be deemed void, the court has to declare such act void (section 218 of the Companies Act no.71 of 2008). This paper seeks to highlight the problems anticipated in light of the changes imported by the new Company law dispensation. Some positive changes have also been observed and these too are highlighted herein. The findings herein are not conclusive as this paper addresses only one specific aspect, Capital Rules, the Act itself is much broader and covers a wide aspect of company law. It is my wish to see other areas of research develop from this paper and more importantly, to see amendments on the Act being implemented in due course. / Dissertation (LLM)--University of Pretoria, 2011. / Mercantile Law / unrestricted

The objective of this study is to do critical analysis if the new Companies Act, with specific reference capital maintenance rules. Furthermore, this study will compare the current Companies Act with the new Companies Act, with a specific focus on sections 44, 45 and 48 of the new Companies Act and their comparison to sections 38, 85 and 226 of the current Companies Act. The next objective is to establish what impact the new piece of legislation will have on South African companies and whether the deficiencies in the current Companies Act have been addressed by the new Companies Act. The final objective is to establish whether this new piece of legislation gives adequate protection for the shareholders of a company. This study will focus on certain aspects of capital maintenance and excludes a comprehensive study of the capital maintenance rules, as the focus will be on certain sections in the current Companies Act and also the new Companies Act. This study will focus on the comparison between the new and current Companies Act. Furthermore, the focus will also be on the protection of the creditors of a company when analysing the different sections of the current companies act and the new companies act. / Dissertation (LLM)--University of Pretoria, 2011. / Mercantile Law / unrestricted

No abstract available. / Dissertation (LLM)--University of Pretoria, 2013. / Mercantile Law / unrestricted

No abstract available. / Dissertation (LLM)--University of Pretoria, 2013. / Mercantile Law / unrestricted

Active Galactic Nuclei (AGN) are cores of distant protogalaxies, with a supermassive blackhole at the center surrounded by an accretion disk, and bipolar jets. Blazars, a subset of AGN, have their jets aligned with our line of sight. Emission from blazars is highly variable on all timescales and frequencies. Microvariability refers to rapid continuum variations that arise within the jet. Bhatta et al. (2013) suggest a modified Kirk, Rieger, \& Mastichiadis (1998) model (KRM) to explain microvariability. The KRM model assumes that when shock waves passes though the jet, each turbulent cell encountered produces a pulse of emission characterized by cell size, local density enhancement, and magnetic field strength. NASA's \kepler\ has monitored optical emission from four AGN. We use the modified KRM model to analyze micro-variations in these \kepler\ data. The distribution of cell sizes computed from these data is consistent with the distribution expected from a turbulent plasma.