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Encapsulation of Microperoxidase-8 in MIL-101(Cr)-X Nanoparticles: Influence of Metal–Organic Framework Functionalization on Enzymatic Immobilization and Catalytic Activity

  • Effrosyni Gkaniatsou
    Effrosyni Gkaniatsou
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
  • Rémy Ricoux*
    Rémy Ricoux
    Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
    *E-mail:. [email protected]
    More by Rémy Ricoux
  • Kalani Kariyawasam
    Kalani Kariyawasam
    Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
  • Ingrid Stenger
    Ingrid Stenger
    Groupe d’étude de la matière condensée, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
  • Benhui Fan
    Benhui Fan
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
    More by Benhui Fan
  • Narjès Ayoub
    Narjès Ayoub
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
  • Samanta Salas
    Samanta Salas
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
  • Gilles Patriarche
    Gilles Patriarche
    Université Paris-Saclay, CNRS, Centre de Nanosciences et de Nanotechnologies, 91120 Palaiseau, France
  • Christian Serre
    Christian Serre
    Institut des Matériaux Poreux de Paris, UMR 8004 CNRS Ecole Normale Supérieure, Ecole Supérieure de Physique et de Chimie Industrielles de Paris, PSL Research University, 75005 Paris, France
  • Jean-Pierre Mahy
    Jean-Pierre Mahy
    Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
  • Nathalie Steunou
    Nathalie Steunou
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
  • , and 
  • Clémence Sicard*
    Clémence Sicard
    Institut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France
    *E-mail: [email protected]
Cite this: ACS Appl. Nano Mater. 2020, 3, 4, 3233–3243
Publication Date (Web):March 11, 2020
https://doi.org/10.1021/acsanm.9b02464
Copyright © 2020 American Chemical Society

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    Abstract

    Abstract Image

    Microperoxidase 8 (MP8) was immobilized within MIL-101(Cr) bearing terephthalate linkers with functionalized groups (-NH2 and -SO3H). A synthesis protocol for MIL-101(Cr)-SO3H that avoids the use of toxic Cr(VI) and HF was developed. The electrostatic interactions between the MP8 molecules and the MOF matrices were found to be crucial for a successful immobilization. Raman spectroscopy revealed the dispersion of the immobilized MP8 molecules in MIL-101(Cr)-X matrices as monomers without aggregation. The presence of functional groups resulted in higher amounts of immobilized MP8 in comparison to the bare MIL-101(Cr). The catalytic activity of MP8@MIL-101(Cr)-NH2 per material mass was higher than that for MP8@MIL-101(Cr). The presence of free amino groups can thus improve the immobilization efficiency, leading to a higher amount of catalytically active species and improving the subsequent catalytic activity of the heterogeneous biocatalysts. MP8@MIL(Cr)-X also successfully catalyzed the selective oxidation of thioanisole derivatives into sulfoxides.

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