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A highly stable nanocomposite of antioxidant activity was developed by immobilization of a superoxide dismutase-mimicking metal complex on copolymer-functionalized nanoclay. The layered double hydroxide (LDH) nanoclays were synthesized and surface modification was performed by adsorbing poly(vinylpyridine-b-methacrylic acid) (PVPMAA). The effect of the adsorption on the charging and aggregation properties was investigated and the copolymer dose was optimized to obtain stable LDH dispersions. The LDH-PVPMAA hybrid particles showed high resistance against salt-induced destabilization in aqueous dispersions. Copper(II)-histamine (Cu(Hsm)(2)) complexes were immobilized via the formation of dative bonds between the metal ions and the nitrogen atoms of the functional groups of the copolymer adsorbed on the particles. Changes in the coordination geometry of the complex upon immobilization led to higher superoxide radical anion scavenging activity than the one determined for the non-immobilized complex. Comparison of superoxide dismutase (SOD)-like activity of the obtained hybrid LDH-PVPMAA-Cu(Hsm)(2) with the nanoclay-immobilized SOD enzyme revealed that the developed composite maintained its activity over several days and was able to function at elevated temperature, while the immobilized native enzyme lost its activity under these experimental conditions. The developed nanocomposite is a promising antioxidant candidate in applications, where high electrolyte concentration and elevated temperature are applied. (C) 2019 Elsevier Inc. All rights reserved.
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Esther Amstad, Alvaro Lino Boris Charlet, Raffaele Mezzenga