Design, synthesis and studies of radical and radical ion probes [Elektronische Ressource] : from enzyme investigations to electroactive surfactants / vorgelegt von Mukul Lal

Design, Synthesis and Studies of Radical and Radical Ion Probes: From Enzyme Investigations to Electroactive Surfactants DISSERTATION zur Erlangung des Grades eines Doktors der Naturwissenschaften vorgelegt von Mukul Lal M.Sc. geb. am 28.Mai 1973 in Hyderabad, Indien. eingereicht beim Fachbereich 8 der Universität Siegen Siegen 2004 Gutachter: Prof. Dr. M. Schmittel Prof. Dr. H. Ihmels Tag der mündlichen Prüfung: 21-01-2005 urn:nbn:de:hbz:467-1954 Ph. D. Thesis of Mukul Lal Design, Synthesis and Studies of Radical and Radical Ion Probes: From Enzyme Investigations to Electroactive Surfactants Abstract The present work is centered at understanding the mechanistic details of the coenzyme B 12dependent enzymes such as diol and glycerol dehydratase that are known to involve radical and radical ionic intermediates in transforming vicinal diols to carbonyl compounds. The work aims on translating such reactive intermediates to relatively long lived ones (making use of beta cleavage leading to persistent radical or electron transfer processes) thereby enabling their spectroscopic detection. A number of modified enzyme substrates attached with groups such as ferrocene, quinone and 2,2,6,6-tetramethylpiperidinoxy were synthesised and were investigated.