ADV SYNTH CATAL, 368, 11, e70452: 1-17 (2026)

IF 4,0

Exploring Diverse Glycone Preferences of Aspergillus rutinosidases

Jitka Brouzdová, Lucie Petrásková, Katerina Brodsky, Natalia Kulik, Helena Pelantová, Martina Hurtová, Andrea Vopálenská, Kristýna Slámová, Pavla Bojarová, Vladimír Křen

 Abstract

Fungal rutinosidases are retaining diglycosidases that release rutinose from flavonoid glycosides, catalyzing valuable transglycosylation reactions. We systematically compare the substrate specificity and synthetic capabilities of two structurally characterized fungal rutinosidases from Aspergillus niger (AnRut) and A. oryzae (AoRut), across a panel of natural, modified, and non-natural glycosides. AnRut displays remarkable glycone promiscuity, efficiently hydrolyzing not only rutinosides and β-glucopyranosides but also β-galactopyranosides, β-xylopyranosides, and α-L-arabinopyranosides. AnRut also processes diglycosides, such as rutinosides and isomaltosides. It catalyzes transglycosylations with non-natural glycosides as donors, glycosylating alcoholic and phenolic acceptors, including transfer of β-D-galacto-, β-D-xylo-, and α-L-arabinopyranosyl residues. In contrast, AoRut exhibits a narrower substrate range: it recognizes rutinosides and selected monoglycosides as substrates but does not hydrolyze most other diglycosides. Unexpectedly, AoRut catalyzes efficient transglycosylation using p-nitrophenyl β-D-galactopyranoside and pNP-α-L-arabinopyranoside as donors, producing novel β-galacto- and α-L-arabinopyranosides of various phenolic acceptors. Both enzymes also catalyze donor self-condensation products, such as pNP-β-D-glucopyranosyl-(1→3)-β-D-glucopyranoside and pNP-β-D-xylopyranosyl-(1→3)-β-D-xylopyranoside and pNP-β-D-xylopyranosyl-(1→2)-β-D-xylopyranoside (only AoRut). Notably, this is the first reported case of a rutinosidase glycosylating a sugar acceptor. These findings reveal distinct glycone preferences and mechanistic features of the two enzymes and significantly expand the repertoire of glycosides accessible through fungal rutinosidases, highlighting their utility for synthesizing novel carbohydrate derivatives.

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