Defense Date

1999

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Sarah C. Rutan

Abstract

In this research, a hidden node pruning algorithm was developed for an artificial neural network (ANN) that automatically determined a more efficient size of the hidden layer, caused the ANN to resize itself, and then continued to train using a standard back-propagation algorithm. The hidden-node pruning algorithm was based on determining the number of significant eigenvalues present in the matrix of values produced by the hidden layer, starting with an excessive number of hidden nodes.

Eight sulfonylurea herbicides were used as the target analytes in this study. The ability of an ANN to simplify the sample preparation needed for analysis using a liquid chromatograph/particle beam/mass spectrometer (LC/PB/MS) was evaluated.

The results derived from this research demonstrated that ANNs allow the clean-up procedure to be simplified, while still obtaining reliable identification of the sulfonylurea herbicides in complex matrices such as soil. Specifically, this was accomplished by using retention times from the LC and MS when the herbicides were injected individually in pure forms combined with MS data obtained from extracted samples. This information was used by a trained neural network to identify sulfonylurea herbicides as both individual components and components in a mixture.

Two different neural networks were created. One was trained with a single mass spectrum from each herbicide, resulting in an 8-training-sample network, and one was trained with five mass spectra of each herbicide, resulting in a 40-training-sample network. Both ANNs had 47 input nodes and eight output nodes. Starting with an excess of 20 hidden nodes, the networks resized themselves to contain 6 hidden nodes for the 8-training-sample network and 7 hidden nodes for the 40-training-sample network. An optimum sum-squared error (SSE) goal was determined to be 0.3 for the 8-training-sample network by using a statistical t-test . to establish the smallest SSE where the standard error of prediction was not significantly greater than the standard error of calibration. Results demonstrated that the 8-training-sample ANN performed just as well as the 40-training-sample ANN. When compared to the Hewlett-Packard probability-based matching (HP- PBM) library searching system, both neural networks out-performed the HP-PBM system in the identification of unknown mass spectra.

Comments

Scanned, with permission from the author, from the original print version, which resides in University Archives.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

2-23-2018

Included in

Chemistry Commons

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