Switchable Nanozyme Activity of Porphyrins Intercalated in Layered Gadolinium Hydroxide

In this study, organo-inorganic nanohybrids <b>LHGd-MTSPP</b> with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (<b>MTSPP</b>, M = 2H, Zn(II) and Pd(II)) into g...

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Bibliographic Details
Main Authors: Maria A. Teplonogova, Marina V. Volostnykh, Alexey D. Yapryntsev, Madina M. Sozarukova, Yulia G. Gorbunova, Ekaterina D. Sheichenko, Alexander E. Baranchikov, Vladimir K. Ivanov
Format: Article
Language:English
Published: MDPI AG 2022-12-01
Series:International Journal of Molecular Sciences
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Online Access:https://www.mdpi.com/1422-0067/23/23/15373
Description
Summary:In this study, organo-inorganic nanohybrids <b>LHGd-MTSPP</b> with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (<b>MTSPP</b>, M = 2H, Zn(II) and Pd(II)) into gadolinium layered hydroxide (<b>LHGd</b>). The combination of powder XRD, CHNS analysis, FT-IR, EDX, and TG confirmed the layered structure of the reaction products. The basal interplanar distances in <b>LHGd-MTSPP</b> samples were 22.3–22.6 Å, corresponding to the size of an intercalated tetrapyrrole molecule. According to SEM data, <b>LHGd-MTSPP</b> hybrids consisted of individual lamellar nanoparticles 20–50 nm in thickness. The enzyme-like activity of individual constituents, <b>LHGd-Cl</b> and sulfoporphyrins <b>TSPP</b>, <b>ZnTSPP</b> and <b>PdTSPP</b>, and hybrid <b>LHGd-MTSPP</b> materials, was studied by chemiluminescence analysis using the ABAP/luminol system in phosphate buffer solution. All the individual porphyrins exhibited dose-dependent antioxidant properties with respect to alkylperoxyl radicals at pH 7.4. The intercalation of free base <b>TSPP</b> porphyrin into the <b>LHGd</b> preserved the radical scavenging properties of the product. Conversely, in <b>LHGd-MTSPP</b> samples containing Zn(II) and Pd(II) complexes, the antioxidant properties of the porphyrins changed to dose-dependent prooxidant activity. Thus, an efficient approach to the design and synthesis of advanced <b>LHGd-MTSPP</b> materials with switchable enzyme-like activity was developed.
ISSN:1661-6596
1422-0067