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New approaches to the design of redox catalysts for use in immunohistochemical imaging

Lunn, Rebecca Jayne. 2006. New approaches to the design of redox catalysts for use in immunohistochemical imaging. PhD Thesis, Cardiff University.

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Abstract

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.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
ISBN: 9781303207693
Date of First Compliant Deposit: 30 March 2016
Last Modified: 12 Feb 2016 23:15
URI: http://orca.cardiff.ac.uk/id/eprint/56132

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