Novel applications of optical analytical techniques have been demonstrated in three general areas, namely application of broadband cavity enhanced absorption spectroscopy (BBCEAS) to the detection of liquid phase analytes, the use of total luminescence spectroscopy to discriminate between different type of teas and the development of an optical sensor to detect ammonia gas, based on the fluorescence quenching of a dye immobilised in a sol gel matrix. A simple BBCEAS setup has been developed with a view to perform sensitive visible wavelength measurements on liquid phase solutions. In the present work a simple low-cost experimental setup has been demonstrated for the measurement of the visible spectra of representative liquid-phase analytes in a 2 mm quartz cuvette placed at normal incidence to the cavity mirrors. Measurements on Ho3+ and sudan black with a white LED and the R ≥ 0.99 mirrors covered a broad wavelength range (~250 nm) and represents the largest wavelength range covered to date in a single BBCEAS experiment. The sensitivity of the technique as determined by the best αmin value was 5.1 x 10-5 cm-1 and was obtained using the R ≥ 0.99 mirrors. The best limit of detection (LOD) for the strong absorber brilliant blue-R, was approximately 620 pM. The optical setup was then optimised for the application of BBCEAS detection to an HPLC system. A 1 cm pathlength HPLC cell with a nominal volume of 70 l was used in this study. The cavity was formed by two R ≥ 0.99 plano-concave mirrors with a bandwidth of ~ 420 – 670 nm. Two analytes rhodamine 6G and rhodamine B were chosen for separation by HPLC, as they were chemically similar species with distinctive visible spectra and would co-elute in an isocratic separation. The lowest value of min obtained was 1.9 x 10-5 cm-1. The most significant advantage of the HPLC-BBCEAS study over previous studies arose from the recording of the absorption spectrum over a range of wavelengths. It was demonstrated that the spectral data collected could be represented as a contour plot which was useful in visualising analytes which nearly co-eluted. The LOD values for the two analytes studied indicated that the developed HPLC-BBCEAS setup was between 54 and 77 times more sensitive than a commercial HPLC system. For improved sensitivity and lower detection limits the low cost BBCEAS setup was used with a significantly longer 20 cm pathlength cell where the mirrors were in direct contact with the liquid phase analyte. This also reduced interface losses. The experiments were carried out using both R 0.99 and R 0.999 mirrors. The lowest αmin value obtained in this study was 2.8 x 10-7 cm-1 which is the lowest reported value to date for a liquid phase measurement, making this study the most sensitive liquid phase absorption measurement reported. The lowest LOD recorded was 4.6 pM, and was obtained for methylene blue with the R 0.999 mirrors. A novel application of total luminescence spectroscopy to discriminate between different types of teas objectively was also investigated. A pattern recognition technique based on principal component analysis (PCA) was applied to the data collected and resulted in discrimination between both geographically similar and dissimilar teas. This work has shown the potential of fluorescence spectroscopy to distinguish between seven types of teas from Africa, India, Sri Lanka and Japan. Geographically similar black teas from 15 different plantation estates in Sri Lanka were also studied. The visualisation technique allowed the separation of all 11 types of teas when the first two principal components were utilised. The final part of the thesis describes the development of an optical sensor for the detection of ammonia gas. The operation of the sensor depended on the fluorescence quenching of the dye 9 amino acridine hydrochloride (9 AAH) immobilised in a sol gel matrix. It was also shown that the sensor response was not affected by the presence of acidic gases such as HCl and SO2. The final version of the sensor made use of dual channel monitoring to improve the sensitivity of the sensor. Measurements using diluted mixtures of ammonia gas in the range 5 -70 ppm showed that the response of the sensor was nonlinear, with the sensitivity increasing at lower concentrations. The measurement of the baseline noise allowed the LOD to be estimated at ~400 ppb.
|Date of Award||12 Jun 2009|
|Supervisor||Meez Islam (Supervisor), Zulfiqur Ali (Supervisor) & Steve Connolly (Supervisor)|