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The aim of this research is to investigate and optimise the potential of capillary electrophoresis (CE) as a tool for the analysis of phytochemicals and the nutritional and health significance present in Brassica vegetables. These phytochemicals (phenolics and glucosinolates) have traditionally been analysed for high performance liquid chromatography, however CE, a relatively new technique, has been used increasingly in the last decade due to its many advantages such as superior resolving power, short analysis times and low solvent use. Yet one major drawback of CE is in its lack of detection sensitivity particularly when photometric (UV-VIS) detection is employed. In order to overcome this problem, online (in-capillary) pre-concentration of the phytochemicals of interest is currently being investigated.