Year of Publication

2009

Degree Name

Doctor of Philosophy (PhD)

Document Type

Dissertation

College

Arts and Sciences

Department

Chemistry

First Advisor

Dr. Robert A. Lodder

Abstract

Modern analytical instrumentation is capable of creating enormous and complex volumes of data. Analysis of large data volumes are complicated by lengthy analysis time and high computational demand. Incorporating real-time analysis methods that are computationally efficient are desirable for modern analytical methods to be fully utilized. The use of modern instrumentation in on-line pharmaceutical process validation, remote sensing, and astrobiology applications requires real-time analysis methods that are computationally efficient.

Integrated sensing and processing (ISP) is a method for minimizing the data burden and sensing time of a system. ISP is accomplished through implementation of chemometric calculations in the physics of the spectroscopic sensor itself. In ISP, the measurements collected at the detector are weighted to directly correlate to the sample properties of interest. This method is especially useful for large and complex data sets. In this research, ISP is applied to acoustic resonance spectroscopy, near-infrared hyperspectral imaging and a novel solid state spectral imager. In each application ISP produced a clear advantage over the traditional sensing method.

The limitations of ISP must be addressed before it can become widely used. ISP is essentially a pattern recognition algorithm. Problems arise in pattern recognition when the pattern-recognition algorithm encounters a sample unlike any in the original calibration set. This is termed the false sample problem. To address the false sample problem the Bootstrap Error-Adjusted Single-Sample Technique (BEST, a nonparametric classification technique) was investigated. The BEST-ISP method utilizes a hashtable of normalized BEST points along an asymmetric probability density contour to estimate the BEST multidimensional standard deviation of a sample. The on-line application of the BEST method requires significantly less computation than the full algorithm allowing it to be utilized in real time as sample data is obtained. This research tests the hypothesis that a BEST-ISP metric can be used to detect false samples with sensitivity > 90% and specificity > 90% on categorical data.

Included in

Chemistry Commons

Share

COinS