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Title: New approaches to the design of redox catalysts for use in immunohistochemical imaging
Author: Lunn, Rebecca Jayne
ISNI:       0000 0004 2749 7280
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2006
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This thesis investigates potential classes of compound for use as immunohistochemical markers. A range of ligands and their corresponding metal complexes have been screened for their ability to catalytically reduce silver ions in a Timm's type reaction. Chapter two focuses on the preparation and testing of bidentate tertiary phosphine metal complexes. The functionalised ligands, l,2-bis-diphenylphosphino-4-methoxy- benzene, l-diphenylphosphino-2 (diphenylphosphino)-methyl -4-methoxybenzene and the corresponding platinum complexes have been prepared. Platinum complexes of 1,2- bis diphenylphosphinoethane were also synthesised. These platinum complexes were found to reduce the silver in times ranging from 5 minutes to in excess of 30 minutes. Chapter three focuses on the preparation of marker systems based on platinum and palladium complexes of weso-tetraarylporphyrins. 5,10,15,20-Tetra(4- hydroxyphenyl)porphyrin and 5,10,15 -tri-(4-tolyl)-20-(4-hydroxyphenyl)porphyrin have been prepared from the corresponding anisole and 3,4,5-trimethoxybenzoic acid phenyl ester derivatives. A number of symmetrical and unsymmetrical porphyrins bearing aryl phosphate esters derived from diethyl-4-formylphenyl phosphate and diethyl-4-formyl-2- methoxyphenyl phosphate have been prepared. The reaction of 5,10,15,20-tetra-(4- hydroxyphenyl)porphyrin or 5,10,15,20-tetra-(4-hydroxy-3-methoxyphenyl)porphyrin with chloro diethylphosphate in the presence of either sodium hydride or triethylamine failed to afford the corresponding tetra-phosphorylated products. The reaction between 5,10,15,20- tetra-(4-hydroxyphenyl)porphyrin palladium and chlorodiethylphosphate in the presence of triethylamine afforded a mixture of phosphorylated products. None of the prepared complexes displayed the ability to reduce silver ions in a Timm's type reaction. Chapter four describes the design and synthesis of 4-phenyl-2,2':6',2"-terpyridines functionalised with a PEG chain terminating with a reactive group suitable for bio- conjugation. 4'- (2-(2- 2-(l,3-Dioxo-l,3-dihydro-isoindol-2-yl)-ethoxy -ethoxy)-ethoxy)- phenyl - 2,2':6',2"-terpyridine was prepared using two methods starting from either 4- hydroxybenzaldehyde or (4-hydroxyphenyl)-2,2':6',2"-terpyridine. Base hydrolysis converted the phthalimde moiety to the free amine which was subsequently treated with l,5-difluoro-2,4-dinitrobenzene. This ligand was not water soluble. The addition of two morpholinomethyl pendent groups via a Mannich reaction did not dramatically increase the solubility in water. A number of transition metal complexes were prepared and tested. Chapter five presents a novel one-pot synthesis of 'mixed' 7V-arylated 1,4,7- triazacyclononane (tacn) ligands. Using this methodology tacn ligands functionalised with two nitrophenyl groups and either a benzaldehyde (L32a), benzoic acid (L32ba), benzyl ester (L32Benzyi), alcohol (L32Aic), tolyl (L32T) or napthoquinone (L32Q) groups have been prepared in yields ranging between 39 and 64 %. Hydrogenation of L32t afforded L32tr. Reaction with Ni(II) perchlorate afforded the air stable complex Nin(L32TR) C104 2, which was found to catalyse the reduction of aqueous silver ions via a Timm' type reaction in 3 minutes. Attempts to attach both a porphyrin and a terpyridine sub-unit are also presented.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available