Publication Date

2004

Document Type

Dissertation/Thesis

First Advisor

Lin, C. T. (Chhui-Tsu)

Degree Name

Ph.D. (Doctor of Philosophy)

Department

Department of Chemistry and Biochemistry

LCSH

Chemical detectors--Design and construction

Abstract

Sol-gels have unique advantages over many materials in terms of sensor design and construction. The practical design of optical sensors utilizing transition metal ion dopants (or using organic dopants for the detection of transition metals) in the sol-gel matrix is the subject of the dissertation work presented. Three sensors were constructed using the sol-gel matrix. One sol-gel matrix for the encapsulation of metal nanoparticles is presented. A thiolated silane is the basis for the detection of nickel (II) and cobalt (II) ions. The sensor described changes from clear and colorless to blood red in the presence of cobalt (II) ions and from clear and colorless to brown in the presence of nickel (II) ions. The detection limits of the sensors are 2.8 × 10ˉ⁴ mM (280 nM) for Co²⁺ and 7.7 × 10ˉ⁵ mM (77 nM) for Ni²⁺. The stabilization of noble metal nanoparticles in a sol-gel matrix was achieved using bis[3-(triethoxysilyl)propyl]-tetrasulfide in a tetramethyl orthosilicate matrix. This matrix has the ability to stabilize gold nanoparticles and has limited success stabilizing silver nanoparticles. This stabilization is of importance for rational material design using the unique properties of nanoparticles. A charge-transfer-based sol-gel optical detector was constructed for a chemical warfare agent analogue of HD. The ligand-to-metal charge transfer was shown between Cu²⁺ and 2-chlororethyl methyl sulfide. The color changes from sky blue to canary yellow when the charge transfer complex was present. The detection limits for the HD sensor were determined to be 0.03 μL per 1.5 mL sensor volume (200 μM). A sensor utilizing a nickel (II) center was produced for a nerve agent analogue of VX. The observed color change is from a faint green to a brown color. The detection limit of the VX sensor is 3.4 × 10ˉ³ mM. From the VX sensor, a double sensor for HD and VX was also constructed using a dual-sensing center of Cu²⁺ and Ni²⁺. The Cu²⁺ detects the HD analogue with a limit of 0.06 μL per 1.5 mL sensor volume (400 μM) and the Ni²⁺ detects the VX analogue with a DL of 3.0 × 10ˉ³ mM.

Comments

Includes bibliographical references (pages 207-211).

Extent

xiii, 211 pages (some color pages)

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type

Text

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