Alkaline lipase from Pseudomonas fluorescens non-covalently immobilised on pristine versus oxidised multi-wall carbon nanotubes as efficient and recyclable catalytic systems in the synthesis of Solketal esters

Abstract

In order to produce effective and recyclable catalysts for enantioselective transesterification in the industrial applications, alkaline lipase from Pseudomonas fluorescens was non-covalently immobilised (ca. 6 wt%) on pristine multi-wall carbon nanotubes (MWCNTs) and oxidised MWCNTs (O-MWCNTs) using an adsorption technique. Mesoporous silica modified with n-octyl groups was used as a reference support. Irreversible transesterifications of three vinyl esters (acyl donors) by racemic Solketal with a chromatographically (GC) traced kinetics were selected as model reactions. The undertaken comparative studies revealed that different morphology and chemical functionalisation of the supports led to various enzyme loadings, catalytic activities and enantioselectivities. MWCNT-lipase emerged as the exceptionally active (yield up to 98%, t=1h, 1320 Ug(-1), i.e. 9 times more active than native enzyme) whereas lipase immobilised on O-MWCNTs as the most enantioselective system, particularly for longer acyl chain esters (e.e. up to 72% after 30 min at yield of 20%, 340 Ug(-1)). Moreover, the activity of all nanotube-based catalysts after 10 cycles of transesterification remained practically unchanged. The differences in performance of MWCNTs and O-MWCNTs as solid supports were found to be based on geometry of pores, dominating hydrophobic interactions and absence/presence of the surface polar groups. Due to an excellent activity and reusability of the nanotube-lipase catalysts one can propose (O-)MWCNT as supports of a prospective industrial relevance.

Keywords: Alkaline lipase; Enantioselectivity; Immobilisation; Multi-wall carbon nanotubes; Solketal esters; Transesterification.