SYNTHESIS AND DEVELOPMENT OF SILICON ANALOG OF FLUORESCEIN FLUOROPHORES AND ESTERIFICATION CATALYSTS

Author

Narsimha Sattenapally, Southern Illinois University CarbondaleFollow

Date of Award

12-1-2012

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Scott, Colleen

Second Advisor

Gao, Yong

Abstract

The synthesis and development of new materials and the improvement of the existing materials are a continuous quest for scientists. There is a constant need for new materials that have more advantages over the existing ones. The research to develop new materials can be appreciated in high magnitude, as the new materials improve the livelihood. In this dissertation, we are presenting our progress in developing new materials, such as fluorescence fluorophores as probes, and esterification catalysts. In the first part of the dissertation, the synthesis and characterization of a novel silicon analog of fluorescein (silyl fluorescein) was studied in detail. The photo-physical properties and toxicity studies of these fluorophores are also discussed. Compared to fluorescein, silyl fluorescein displayed a 90 nm longer wavelength in its absorption and emission. Silyl fluorescein showed good solubility in water and organic solvents, and has a considerable fluorescence quantum yield compared to fluorescein. Silyl fluorescein was found to be moderately toxic under light and non-toxic in dark, where as fluorescein toxicity was found to be greater than silyl fluorescein both in the dark and under light. Two probes from our novel silyl fluorescein fluorophore were developed and studied. SIF HySOx is probe for hypochlorous acid (HOCl), which is a reactive oxygen species (ROS) found in cells that are stressed due to various diseases. The HOCl probe was synthesized and its photo-physical properties were studied. It was found to be selective and sensitive only to HOCl. A fluoride probe (DTBDMS SIF P) was also developed from silyl fluorescein. Its synthesis and photo-physical properties were also studied. The probe displayed excellent selectivity and sensitivity to fluoride (TBAF) in the presence of other halides and bases. Future directions on novel fluorophore are briefly mentioned. Second part of the dissertation is focused on the screening of two organic esterification catalysts which were synthesized by Dr. Liu and Dr. Wong. The catalysts which are synthesized from pyridine and dinitrobenzene moieties were screened with several carboxylic acids and alcohols. Catalyst 8-4 was shown to be moderately active in the esterification of carboxylic acids and alcohols. It has no selectivity in the esterification of primary, secondary, tertiary alcohols, and the carboxylic acids that are attached to those carbons. Catalyst 9-1 however, was more efficient in the esterification of carboxylic acids and alcohols. Catalyst 9-1 displayed selectivity in the esterification of primary, over secondary, over tertiary alcohols, and the carboxylic acids that are attached to those carbons. Catalyst 9-1 gave up to 95% isolated yields.