The development of an apoferritin-based artificial metalloenzyme for catalysis of sulfide oxidation

Hoteit, Camille (2018) The development of an apoferritin-based artificial metalloenzyme for catalysis of sulfide oxidation. MPhil thesis, University of Nottingham.

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Abstract

The development of artificial metalloenzymes is an expanding field, involving various protein scaffolds and incorporating a wide range of transition-metal catalysts. Due to its pH-dependent disassembling properties, apoferritin has been used extensively for various purposes. However, very few studies reported its use as a scaffold for the design of artificial metalloenzymes.

This study investigated the development of an apoferritin-based artificial metalloenzyme, based on covalent conjugation with a manganese-salen complex, applied to the catalysis of sulphide oxidation.

A mouse recombinant heavy-chain apoferritin mutant, containing a unique and reactive cysteine, in position 68, pointing towards its hollow core, was expressed and purified. A manganese-salen bearing a maleimide linker was synthesised and covalently linked to apoferritin’s cysteine 68, via a Michael addition reaction.

The catalytic activity towards the enantioselective oxidation of thioanisole was assessed in both organic and aqueous media and has resulted in pH-dependent activity and enantioselectivity, with up to 69 % conversion and 17 % ee, due to the reassembling of the conjugated apoferritin nanocapsule.

However, background reactions exhibited high yields in certain conditions and the stability of the apoferritin-based artificial metalloenzyme was extremely relative at pH ranges where native apoferritin was supposed to be stable. Therefore, further research is recommended to improve three key features of this catalyst: stability, enantioselectivity and reactivity.

Item Type: Thesis (University of Nottingham only) (MPhil)
Supervisors: Pordea, Anca
Thomas, Neil R.
Keywords: Artificial metalloenzyme; Biocatalysis; Apoferritin; Salen; Sulfoxidation
Subjects: T Technology > TP Chemical technology
Faculties/Schools: UK Campuses > Faculty of Engineering
Item ID: 53544
Depositing User: Hoteit, Camille
Date Deposited: 12 Dec 2018 04:40
Last Modified: 08 Feb 2019 08:46
URI: http://eprints.nottingham.ac.uk/id/eprint/53544

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