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Advancements in detection for microcolumn separations

Posted on:2002-06-27Degree:Ph.DType:Dissertation
University:The University of North Carolina at Chapel HillCandidate:Fadgen, Keith EdwardFull Text:PDF
GTID:1468390011490245Subject:Chemistry
Abstract/Summary:
Correlation electrophoresis is a technique for improving the signal-to-noise ratio in less time as compared to traditional signal averaging. The jet flow gated injector is a sample injection device previously developed in our lab. Correlation experiments are presented using this injection device with a single point UV detector as well as a spatial imaging diode array detector.; The development of an injection differentiation routine is presented. When sample injections are performed to close to one another, the possibility arises for slower moving analytes to be overtaken by faster moving analytes from subsequent injections. Using the spatial imaging diode array detector, injection differentiation is possible. Initial finding for the utilization of the arithmetic, geometric, and harmonic mean for averaging across the array are presented. It is shown that thru the use of the harmonic mean, injection differentiation is possible.; Advancements of a contactless conductivity detector are presented. Conductivity measurements are made thru capacitive coupling/decoupling between the solution in the capillary and a pair of stainless steel cylinders surrounding the capillary. The use of a lock-in amplifier for signal isolation and amplification is discussed and compared to previous version of the detector. Signal response as a function of analyte concentration, excitation frequency, and excitation potential are discussed.; The conductivity detector is used as the basis for a new photothermal absorbance detector for microcolumn separations. Photothermal techniques measure changes in physical properties due to the absorption of light. If the analytes do not fluoresce, the absorption of energy is translated into heating the surrounding solution. The change in conductivity solution due to the heating effect is measured. Detector development, as well as initial findings with respect to laser power and chopping frequency are presented.; The final chapter presents two new method for plate parameter determination utilizing statistical moments. One of the large drawbacks to the use of statistical moments is the determination of the limits of integration. The first method presented utilizes an iterative approach for the determination of the endpoints. The other method uses threshold values for the initial determination of endpoints, then subsequent statistical moment calculations to determine the final endpoints.
Keywords/Search Tags:Detector, Determination
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