Amino modified magnetic halloysite nanotube supporting chloroperoxidase immobilization: enhanced stability, reusability,

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RESEARCH PAPER

Amino modified magnetic halloysite nanotube supporting chloroperoxidase immobilization: enhanced stability, reusability, and efficient degradation of pesticide residue in wastewater Xuefang Zhu1 · Xueting Fan1 · Yuting Wang1 · Quanguo Zhai1,2 · Mancheng Hu1,2 · Shuni Li1,2 · Yucheng Jiang1,2 Received: 29 July 2020 / Accepted: 28 September 2020 © Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract  Halloysite nanotube (HNT) is a natural bio-compatible and stable nanomaterial available in abundance at low-cost. In this work, HNT was modified by two strategies to make it suitable for supporting immobilization of chloroperoxidase (CPO). Firstly, ­Fe3O4 nanoparticles were deposited on HNT, so magnetic separation can be used instead of centrifugation. Then, the magnetic HNT was modified by 3-aminopropyltriethoxysilane (APTES), which can provide amine group on surface of HNT and meanwhile inhibit the agglomeration of magnetic HNT. Then, HNT-Fe3O4 -APTES was linked with branched polyethyleneimine (PEI) to provide more amino for binding with enzyme. The so-prepared CPO@HNT-Fe3O4-APTES-PEI showed enhanced enzyme loading, reusability, improved thermal stability and tolerance to organic solvents than free CPO. For example, after 10 repeated uses, CPO@HNT- F ­ e3O4-APTES-PEI can maintain 92.20% of its original activity compared with 65.12% of activity of CPO@HNT-APTES-PEI and 45.69% of activity of CPO@HNT. The kinetic parameters indicated the affinity and specificity of immobilized enzyme to substrate was increased. CPO@HNT-Fe3O4-APTES-PEI was very efficient when it was applied in the degradation of pesticides mesotrione in wastewater. The degradation efficiency can reach 90% within 20 min at range of 5–40 μmol·L−1. These results ensure the potential practical application of this bio-materials in wastewater treatment. Graphic Abstract

Keywords  Immobilization of enzyme · Modification of HNT · Stability · Reusability · Bio-degradation · Pesticide residues Extended author information available on the last page of the article

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Bioprocess and Biosystems Engineering

Introduction Halloysite clay nanotube (HNT) is a naturally biocompatible nanomaterial, which is much more cheap, stable, and is available abundantly compared with other nanomaterials, such as carbon nanotubes. HNT is formed by rolling flat sheets of kaolinite clay, having a 15 nm lumen, 50 − 70 nm external diameter, and length of 0.5 − 1 μm. These characteristics make it a good candidate for entrapping biomacromolecule by simple adsorption. Recently, HNTs are reported to be used as support for enzyme immobilization [1–5]. For example, Zhang and co-workers used natural halloysite nanotubes as support for immobilization of α-amylase and urease in channels of the nanotubes through physical adsorption in 2010 [6]. Then, they presented a hybrid-nanotubes formed by assembling chitosan onto the halloysite for immobilization of horseradish peroxidase in 2013 [7]. Besides chitosan, polydopamine is also often employed fo