Electrostatic Interaction-Induced Formation of Enzyme-on-MOF as Chemo-Biocatalyst for Cascade Reaction with Unexpectedly Acid-Stable Catalytic Performance

ACS Appl Mater Interfaces. 2019 Oct 9;11(40):36782-36788. doi: 10.1021/acsami.9b13080. Epub 2019 Oct 1.

Abstract

Combining biocatalytic and chemocatalytic reactions in a one-pot reaction not only avoids the tedious isolation of intermediates during the reactions but also provides a desirable alternative to extend the range of catalytic reactions. Here, we report a facile strategy to immobilize an enzyme, glucose oxidase (GOx), on PCN-222(Fe) induced by electrostatic interaction in which PCN-222(Fe) serves as both a support and chemocatalyst. The immobilization was confirmed through ζ potential measurement, confocal laser scanning microscopy, Fourier transform infrared spectrometry, and UV-vis spectroscopy. This chemo-biocatalyst was applied to a cascade reaction to catalyze glucose oxidation and ABTS (ABTS = 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (or pyrogallol) oxidation. The catalytic kinetics studies show that these chemo-biocatalytic cascade reactions obey the Michaelis-Menten equation, which indicates that the cascade reactions follow the typical enzymatic dynamic regulation process. Interestingly, GOx/PCN-222(Fe) exhibits an exceptional acid-stable catalytic performance as evidenced by circular dichroism spectroscopy where no significant structure change was observed toward acidic solutions with different pH values. GOx/PCN-222(Fe) also displays desirable recyclability since no significant loss of conversion rates was found after six repeated reactions. This work presents a convenient strategy to construct metal-organic framework based chemo-biocatalysts, which may find potential applications in sensing and nanomachines.

Keywords: Acidic stability; Cascade reaction; Electrostatic interaction; Enzymes; Metal−organic frameworks.

MeSH terms

  • Biocatalysis*
  • Enzyme Stability
  • Enzymes, Immobilized / metabolism
  • Glucose / metabolism
  • Glucose Oxidase / metabolism*
  • Glucose Oxidase / ultrastructure
  • Metal-Organic Frameworks / chemical synthesis
  • Metal-Organic Frameworks / chemistry*
  • Oxidation-Reduction
  • Static Electricity*

Substances

  • Enzymes, Immobilized
  • Metal-Organic Frameworks
  • Glucose Oxidase
  • Glucose