Construction of a smart microgel glutathione peroxidase mimic based on supramolecular self-assembly

Abstract

In an effort to construct smart artificial glutathione peroxidase (GPx) featuring high catalytic activity in an efficient preparation process, an artificial microgel GPx (PPAM-ADA-Te) has been prepared using a supramolecular host-guest self-assembly technique. Herein, 6,6'-telluro-bis(6-deoxy-β-cyclodextrin) (CD-Te-CD) was selected as a tellurium-containing host molecule, which also served as the crosslinker for the scaffold of the supramolecular microgel. And an adamantane-containing block copolymer (PPAM-ADA) was designed and synthesized as a guest building block copolymer. Subsequently, PPAM-ADA-Te was constructed through the self-assembly of CD-Te-CD and PPAM-ADA. The formation of this self-assembled construct was confirmed by dynamic light scattering, NMR, SEM and TEM. Notably, PPAM-ADA-Te not only exhibits a significant temperature responsive catalytic activity, but also features the characteristic saturation kinetics behaviour similar to that of a natural enzyme catalyst. We demonstrate in this paper that both the hydrophobic microenvironment and the crosslinker in this supramolecular microgel network played significant roles in enhancing and altering the temperature responsive catalytic behaviour. The successful construction of PPAM-ADA-Te not only provides a novel method for the preparation of microgel artificial GPx with high catalytic activity but also provides properties suitable for the future development of intelligent antioxidant drugs.

Facile Construction of Microgel based Biomimetic Glutathione Peroxidase with Temperature Responsive Catalytic Activity

“…They pioneered in exploring the catalytic mechanism of natural GPx and providing various biomimetic GPx scaffolds as antioxidant drugs. These biomimetic GPxs were mainly constructed based on small molecules, macromolecules, supramolecular assemblies, proteins, and inorganic nanomaterials …”

“…However, they presented a limitation in elucidating the catalytic mechanism of natural GPx due to the difficulty in simulating the synergistic catalysis process. In order to address this issue, hyperbranched polymers, block polymers, microgels and other macromolecules were used to construct biomimetic GPxs due to the facile tailor of the scaffold structure and the easy modification with various catalytic elements. The diverse structures and catalytic elements provided conveniences for the synergistic catalysis of biomimetic GPx.…”

“…Besides, the biomimetic GPx based on macromolecular polymers could be industrialized easily . Therefore, considerable efforts have been devoted to construct biomimetic GPxs based on macromolecular polymers . Additionally, supramolecular could be also modified with various catalytic elements for simulating GPx .…”

“…Therefore, considerable efforts have been devoted to construct biomimetic GPxs based on macromolecular polymers . Additionally, supramolecular could be also modified with various catalytic elements for simulating GPx . To some extent, however, the strict preparation conditions of supramolecular assemblies and the complicated synthesis process of supramolecular assembling units limited the efficient construction of these biomimetic GPxs and their further industrial application.…”

“…In order to increase the catalytic activity of biomimetic GPx and elucidate the synergistic catalytic mechanism of natural GPx, our groups have constructed some efficient biomimetic GPxs using block polymers, graft polymers, supramolecular polymers and microgels as scaffolds. Recently, the smart biomimetic GPx with a intelligently regulated catalytic activity has been developed to respond the need of intelligent regulation for ROS concentration .…”