Sandwiching multiple dehydrogenases and shared cofactor between double polyelectrolytes for enhanced communication of cofactor and enzymes

Regeneration and reutilization of cofactors remain as the biggest challenge facing the industrial application of cofactor-dependent redox, while efficient communication and synergism between enzymes and cofactors are the major requirements for implementation of such processed. Inspired by swinging arms facilitating multistep catalytic transformations in nature, polyelectrolytes-based artificial swinging arms were introduced to a multienzyme system by coaxial electrospinning technology. The poly(allylamine hydrochloride) (PAH), pre-dissolved in the core-phase solution, would penetrate across the shell of hollow nanofibers, thus act as artificial swinging arms and enable effective tethering and retention of the enzymes and cofactors on the outer surface of nanofibers via the ion-exchange interactions. With further intercalary insertion of another negatively charged polyelectrolyte poly(styrene sulfonate) (PSS), a sandwich-like structure was formed on the outer surface of the hollow nanofiber. It was found that PSS layer not only effectively prevented the leaking of enzymes and cofactors, the double-polyelectrolytes also imposed crowding and confinement effects on the sandwiched multienzymes, thus the communication of the dehydrogenases and the shared cofactors were further facilitated. The methanol yield obtained with the sandwiched multienzymes system reached to 98.27%, which was 2.72-fold higher than that of the free system, and even 1.52-fold higher than that without PSS layer. (C) 2018 Elsevier B.V. All rights reserved.