title: Construction of a smart temperature-responsive GPx mimic based on the self-assembly of supra-amphiphiles.
abstract: Glutathione peroxidase (GPx) is a major defense against hydroperoxides as a kind of seleno-enzyme that protects cells from oxidative damage. A supramolecular vesicle with controllable GPx activity and morphology has been successfully constructed by the self-assembly of supra-amphiphiles formed by host-guest recognition between cyclodextrin and adamantane derivatives. By introducing thermosensitive poly(N-isopropylacrylamide) (PNIPAM) scaffolds and the catalytic moiety selenium into adamantane and cyclodextrin, respectively, the complex of catalysis-functionalized cyclodextrin with thermosensitivity-functionalized adamantane directed the formation of a supramolecular vesicle which acted as a GPx mimic at 37 °C. The self-assembled nanoenzyme exhibited an obvious temperature responsive characteristic and high GPx-like catalytic activity promoting the reduction of hydrogen peroxide (H2O2) with glutathione (GSH) as the reducing substrate at 37 °C. However, the vesicle disassembled when the temperature decreased to 25 °C due to the transition of PNIPAM between the coil and the globule. Interestingly, the catalytic activity changed along with the transformation of morphologies. The vesicle structure self-assembled at 37 °C provided the favorable microenvironment for the enzymatic reaction, hence we successfully developed a temperature-responsive nanoenzyme model. Moreover, the catalytic activity of the thermosensitive GPx mimic exhibited excellent reversibility and typical saturation kinetics behaviour similar to a natural enzyme catalyst. It is assumed that the proposed GPx model not only has remarkable advantages such as easy functionalization and facile preparation but also provided a new way to develop intelligent responsive materials.
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Huixin
authors.initials: H
authors.lastname: Zou
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Hongcheng
authors.initials: H
authors.lastname: Sun
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Liang
authors.initials: L
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Linlu
authors.initials: L
authors.lastname: Zhao
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Jiaxi
authors.initials: J
authors.lastname: Li
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Zeyuan
authors.initials: Z
authors.lastname: Dong
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Quan
authors.initials: Q
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Jiayun
authors.initials: J
authors.lastname: Xu
authors.affiliation: State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China. junqiuliu@jlu.edu.cn.
authors.forename: Junqiu
authors.initials: J
authors.lastname: Liu
mesh_terms: D000180:Acrylic Resins / Q000737:chemistry; D000218:Adamantane / Q000737:chemistry; D002384:Catalysis; D003505:Cyclodextrins / Q000737:chemistry; D005978:Glutathione / Q000737:chemistry; D005979:Glutathione Peroxidase / Q000737:chemistry / Q000378:metabolism*; D006358:Hot Temperature; D006861:Hydrogen Peroxide / Q000737:chemistry; D049329:Nanostructures / Q000737:chemistry*; D013501:Surface-Active Agents / Q000737:chemistry*
chemical_list: D000180:Acrylic Resins; D003505:Cyclodextrins; D013501:Surface-Active Agents; C052970:poly-N-isopropylacrylamide; D006861:Hydrogen Peroxide; D005979:Glutathione Peroxidase; D005978:Glutathione; D000218:Adamantane