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. 2020 May 20;5(21):12329-12338.
doi: 10.1021/acsomega.0c01067. eCollection 2020 Jun 2.

Glucose Oxidase Immobilized on Magnetic Zirconia: Controlling Catalytic Performance and Stability

Angela K Haskell  1 , Aleksandrina M Sulman  2 , Ekaterina P Golikova  3 , Barry D Stein  4 , Maren Pink  1 , David Gene Morgan  1 , Natalya V Lakina  2 , Alexey Yu Karpenkov  3 , Olga P Tkachenko  5 , Esther M Sulman  2 , Valentina G Matveeva  2   3 , Lyudmila M Bronstein  1   6   7
Affiliations

Glucose Oxidase Immobilized on Magnetic Zirconia: Controlling Catalytic Performance and Stability

Angela K Haskell et al. ACS Omega. .

Abstract

Here, we report the structures and properties of biocatalysts based on glucose oxidase (GOx) macromolecules immobilized on the mesoporous zirconia surface with or without magnetic iron oxide nanoparticles (IONPs) in zirconia pores. Properties of these biocatalysts were studied in oxidation of d-glucose to d-gluconic acid at a wide range of pH and temperatures. We demonstrate that the calcination temperature (300, 400, or 600 °C) of zirconia determines its structure, with crystalline materials obtained at 400 and 600 °C. This, in turn, influences the catalytic behavior of immobilized GOx, which was tentatively assigned to the preservation of GOx conformation on the crystalline support surface. IONPs significantly enhance the biocatalyst activity due to synergy with the enzyme. At the same time, neither support porosity nor acidity/basicity shows correlations with the properties of this biocatalyst. The highest relative activity of 98% (of native GOx) at a pH 6-7 and temperature of 40-45 °C was achieved for the biocatalyst based on ZrO2 calcined at 600 °C and containing IONPs. This process is green as it is characterized by a high atom economy due to the formation of a single product with high selectivity and conversion and minimization of waste due to magnetic separation of the catalyst from an aqueous solution. These and an exceptional stability of this catalyst in 10 consecutive reactions (7% relative activity loss) make it favorable for practical applications.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
TEM images of ZrO2-600 (a) and IO-ZrO2-600 (b).
Figure 2
Figure 2
XRD patterns of ZrO2-300 (a), ZrO2-400 (b), ZrO2-600 (c), and IO-ZrO2-400 (d).
Figure 3
Figure 3
STEM dark-field image (a) and EDS maps of IO-ZrO2-600 for Fe (b), Zr (c), O (d) and superposition of Fe and Zr (e) and Fe, Zr, and O (f). Scale bar is 100 nm.
Figure 4
Figure 4
Liquid N2 adsorption–desorption isotherms (a,c) and pore sizes distributions (b,d) of ZrO2-600 and IO-ZrO2-600s.
Scheme 1
Scheme 1. Schematic Representation of GOx Immobilization on the Magnetic Support
Figure 5
Figure 5
Effect of pH (a) and temperature (b) on the relative activity of native and immobilized GOx.
Figure 6
Figure 6
Relative activity of immobilized GOx in reuse.
Figure 7
Figure 7
Long-term incubation stability at 50 °C.
See this image and copyright information in PMC

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