PhD opportunity - Redox Biocatalysis in Deep Eutectic Solvents

Project Description Redox reactions in Deep Eutectic Solvents have received relatively little attention. The huge potential to explore the activity of redox enzymes in eutectic solvents is the focus of this project. The initial part of the project will focus on the use of amine oxidases and will subsequently extend to use of alcohol dehydrogenases. Dehydrogenases have a history of applications in fine chemistry for enantiomeric resolution. The potential to examine both enzymes in tandem as part of a cascade will also be explored. The conversion of an amine to the corresponding aldehyde is synthetically useful in organic chemistry provided the enzyme can utilise a wide range of substrates. The use of DES can lead to enhanced “promiscuity” of enzyme active sites thereby facilitating the use of a wide range of substrates. The extent of this broadening of specificity will be explored in this study. A search of the literature revealed that few attempts to examine the effects of ionic liquids on these enzymes have been reported. Basic questions surround the use of this reaction in low water media. Dehydrogenases have similarly been neglected due to their need for expensive cofactors although some examples have been reported. A little known dismutation reaction which uses very little cofactor can be exploited. This allows aldehyde oxidation to the carboxylate. The advantage of this reaction is the ability of the enzyme to regioselectively modify an amino group and to exhibit enantioselectivity for chiral synthesis while recycling the cofactor. This reaction is especially interesting since its aldehyde substrate is the product of amine oxidase oxidations allowing for the development of cascade transformations. These enzymes can work in tandem to synthesise specific chemicals enantioselectively. The dismutation will produce an alcohol as well as an aldehyde.

Student Requirements for this Project. A degree in Chemistry, Biochemistry, Biotrechnology, Biocatalysis or equivalent ideally with experience of biocatalysis or a relevant related area.

Fully Funded (scholarship, fees, materials) Funding agency Science Foundation Ireland Student Stipend per annum € 17,250-23,000 Materials & Travel Budget per annum € 4,000 Fees covered by the funding Duration of funding 48 months

If you are interested in submitting an application for this project, please complete an Expression of Interest.

forms.office.com/Pages/ResponsePage.aspx?id=yxdjdkjpX06M7Nq8ji_V2hiTno1vZnVJip0jxPLsgu9UN0JWSjA5REk3M1FFTTFGSEwzVzNQNklJMS4u

www.tudublin.ie/research/discover-our-research/research-institutes-centres-and-groups/green-chemistry-biocatalysis/about/

Deadline to submit an application 01/06/2023