General methodologies are elaborated for the modification of residual vinyl groups resulting from the polymerization of technical grade divinylbenzene to obtain polymer supported reagents, catalysts, protecting groups, separation media and chemosensors. These residual vinyl groups undergo anti-Markovnikov addition reactions via free-radical mechanisms to give polymer supported halides, sulfides, phosphines, phophonates, amines, silanes, carboxylic acid derivatives such as amides, amidines, esters and also b -diketones, crown ethers or acetals. Reaction of these pendant styryl units via electrophilic or nucleophilc mechanisms also give useful polymeric products. / Diels-Alder reactions of the pendant styryl units are also investigated, showing that these may react as dienophiles or, with the participation of the aromatic group, as a diene. Thus, one mole of diene such as hexachlorocyclopentadiene or 3,6-dipyridyl-1,2,4,5 tetrazine add per mole of alkene, or two moles of dienophile such as maleic acid derivatives add in a fashion analogous to the Wagner-Jauregg reaction. / Transition metal catalysed hydrosilylation of the substrate (vinyl)polystyrene using Co2(CO)8 gives exclusively dimethylene linked polymer supported dialkylchlorosilanes. These may be used to selectively protect primary hydroxyls in the presence of secondary or tertiary hydroxyls. Cleavage of the silyl ethers can be effected with aqueous acid, base or more conveniently with fluoride ions which then could be regenerated back to the polymeric silylchlorides using BCl3/CH2Cl2. / Resins bearing amino acid functionalities, obtained by free-radical addition of cysteine, may be converted to polymer supported azlactones which smoothly immobilize enzymes such as lipase, and retain their hydrolytic activity. / Functional polymer particles of nanometer dimensions bearing fluorescent molecular imprinted sites are obtained using a core-shell polymerization approach in conjunction with technique described above. The resulting clear particle dispersions show some ability to distinguish between molecules and even between enantiomers through weak interactions, as shown by fluorescence spectroscopy. / Small molecule fluorescent probes based on dimethylaminostyrylpyridinium salts are demonstrated to be useful fluorescent probes due to their great sensitivity to solution microviscosity. Caged derivatives are applied in microbial and cell cultures.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.34682 |
| Date | January 1997 |
| Creators | Stranix, Brent R. |
| Contributors | Darling, G. D. (advisor), Chin, B. J. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001617542, proquestno: NQ37028, Theses scanned by UMI/ProQuest. |
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