Strategies for Transferring Photobiocatalysis to Continuous Flow Exemplified of Acids

The challenges of light-dependent biocatalytic transformations of lipophilic substrates in aqueous media are manifold. For instance, photolability of the catalyst as well as insufficient light penetration into the reaction vessel may be further exacerbated by a heterogeneously dispersed substrate. Light penetration may be addressed by performing the reaction in continuous flow, which allows two modes of applying the catalyst: (i) heterogeneously, immobilized on a carrier, which requires light-permeable supports, or (ii) homogeneously, dissolved in the reaction mixture. Taking the light-dependent photodecarboxylation of palmitic acid catalyzed by fatty-acid photodecarboxylase from Chlorella variabilis (CvFAP) as a showcase, strategies for the transfer of a photoenzyme-catalyzed reaction into continuous flow were identified. A range of different supports were evaluated for the immobilization of CvFAP, whereby Eupergit C250 L was the carrier of choice. As the photostability of the catalyst was a limiting factor, a homogeneous system was preferred instead of employing the heterogenized enzyme. This implied that photolabile enzymes may preferably be applied in solution if repair mechanisms cannot be provided. Furthermore, when comparing different wavelengths and light intensities, extinction coefficients may be considered to ensure comparable absorption at each wavelength. Employing homogeneous conditions in the CvFAP-catalyzed photo-decarboxylation of palmitic acid afforded a space-time yield unsurpassed by any reported batch process (5.7 g center dot L-1 center dot h-1, 26.9 mmol center dot L-1 center dot h-1) for this reaction, demonstrating the advantage of continuous flow in attaining higher productivity of photobiocatalytic processes.

Automated summary

The challenges of light-dependent biocatalytic transformations of lipophilic substrates in aqueous media are addressed through continuous flow reactions. The immobilization of the catalyst on a carrier or using a homogeneous system is determined by the photostability of the catalyst. Homogeneous conditions in the CvFAP-catalyzed photodecarboxylation of palmitic acid achieved a high space-time yield, demonstrating the advantage of continuous flow for photobiocatalytic processes.