Chitosan-grafted halloysite nanotubes-fe3 o4 composite for laccase-immobilization and sulfamethoxazole-degradation

Avinash A. Kadam; Surendra K. Shinde; Gajanan S. Ghodake; Ganesh D. Saratale; Rijuta G. Saratale; Bharat Sharma; Seunghun Hyun; Jung Suk Sung

doi:10.3390/polym12102221

Chitosan-grafted halloysite nanotubes-fe₃ o₄ composite for laccase-immobilization and sulfamethoxazole-degradation

Avinash A. Kadam, Surendra K. Shinde, Gajanan S. Ghodake, Ganesh D. Saratale, Rijuta G. Saratale, Bharat Sharma, Seunghun Hyun, Jung Suk Sung

Division of Environmental Science and Ecological Engineering

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

A surface-engineered nano-support for enzyme laccase-immobilization was designed by grafting the surface of halloysite nanotubes (HNTs) with Fe₃ O₄ nanoparticles and chitosan. Herein, HNTs were magnetized (HNTs-M) by a cost-effective reduction-precipitation method. The synthesized HNTs-M were grafted with 0.25%, 0.5%, 1%, and 2% chitosan (HNTs-M-chitosan), respectively. Synthesized HNTs-M-chitosan (0.25%), HNTs-M-chitosan (0.5%), HNTs-M-chitosan (1%) and HNTs-M-chitosan (2%) were linked with glutaraldehyde (GTA) for laccase immobilization. Among these formulations, HNTs-M-chitosan (1%) exhibited the highest laccase immobilization with 95.13% activity recovery and 100.12 mg/g of laccase loading. The optimized material was characterized thoroughly by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analysis. The immobilized laccase (HNTs-M-chitosan (1%)-GTA-Laccase) exhibited higher pH, temperature, and storage stabilities. The HNTs-M-chitosan (1%)-GTA-Laccase possesses excellent reusability capabilities. At the end of 10 cycles of the reusability experiment, HNTs-M-chitosan (1%)-GTA-Laccase retained 59.88% of its initial activity. The immobilized laccase was utilized for redox-mediated degradation of sulfamethoxazole (SMX), resulting in 41%, 59%, and 62% degradation of SMX in the presence of 2,2^′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), guaiacol (GUA), and syringaldehyde (SA), respectively. Repeated SMX degradation (57.10% after the sixth cycle) confirmed the potential of HNTs-M-chitosan (1%)-GTA-Laccase for environmental pollutant degradation. Thus, we successfully designed chitosan-based, rapidly separable super-magnetic nanotubes for efficacious enhancement of laccase biocatalysis, which can be applied as nano-supports for other enzymes.

Original language	English
Article number	2221
Pages (from-to)	1-17
Number of pages	17
Journal	Polymers
Volume	12
Issue number	10
DOIs	https://doi.org/10.3390/polym12102221
Publication status	Published - 2020 Oct

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the the Korea government (MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of EnvironmentKorea governmentof Korea.(MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of Environment of Korea.

Publisher Copyright:
© 2020 by the authors. Licensee MDPI, Basel, Switzerland.

Keywords

Chitosan
Laccase-immobilization
Nano-engineered supports
Sulfamethoxazole degradation
Super-magnetic separation

ASJC Scopus subject areas

Chemistry(all)
Polymers and Plastics

Access to Document

10.3390/polym12102221

Cite this

@article{a37ded8be90c472a938660fb3f2a6c16,

title = "Chitosan-grafted halloysite nanotubes-fe3 o4 composite for laccase-immobilization and sulfamethoxazole-degradation",

abstract = "A surface-engineered nano-support for enzyme laccase-immobilization was designed by grafting the surface of halloysite nanotubes (HNTs) with Fe3 O4 nanoparticles and chitosan. Herein, HNTs were magnetized (HNTs-M) by a cost-effective reduction-precipitation method. The synthesized HNTs-M were grafted with 0.25%, 0.5%, 1%, and 2% chitosan (HNTs-M-chitosan), respectively. Synthesized HNTs-M-chitosan (0.25%), HNTs-M-chitosan (0.5%), HNTs-M-chitosan (1%) and HNTs-M-chitosan (2%) were linked with glutaraldehyde (GTA) for laccase immobilization. Among these formulations, HNTs-M-chitosan (1%) exhibited the highest laccase immobilization with 95.13% activity recovery and 100.12 mg/g of laccase loading. The optimized material was characterized thoroughly by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analysis. The immobilized laccase (HNTs-M-chitosan (1%)-GTA-Laccase) exhibited higher pH, temperature, and storage stabilities. The HNTs-M-chitosan (1%)-GTA-Laccase possesses excellent reusability capabilities. At the end of 10 cycles of the reusability experiment, HNTs-M-chitosan (1%)-GTA-Laccase retained 59.88% of its initial activity. The immobilized laccase was utilized for redox-mediated degradation of sulfamethoxazole (SMX), resulting in 41%, 59%, and 62% degradation of SMX in the presence of 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), guaiacol (GUA), and syringaldehyde (SA), respectively. Repeated SMX degradation (57.10% after the sixth cycle) confirmed the potential of HNTs-M-chitosan (1%)-GTA-Laccase for environmental pollutant degradation. Thus, we successfully designed chitosan-based, rapidly separable super-magnetic nanotubes for efficacious enhancement of laccase biocatalysis, which can be applied as nano-supports for other enzymes.",

keywords = "Chitosan, Laccase-immobilization, Nano-engineered supports, Sulfamethoxazole degradation, Super-magnetic separation",

author = "Kadam, {Avinash A.} and Shinde, {Surendra K.} and Ghodake, {Gajanan S.} and Saratale, {Ganesh D.} and Saratale, {Rijuta G.} and Bharat Sharma and Seunghun Hyun and Sung, {Jung Suk}",

note = "Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the the Korea government (MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of EnvironmentKorea governmentof Korea.(MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of Environment of Korea. Publisher Copyright: {\textcopyright} 2020 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2020",

month = oct,

doi = "10.3390/polym12102221",

language = "English",

volume = "12",

pages = "1--17",

journal = "Polymers",

issn = "2073-4360",

publisher = "MDPI AG",

number = "10",

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TY - JOUR

T1 - Chitosan-grafted halloysite nanotubes-fe3 o4 composite for laccase-immobilization and sulfamethoxazole-degradation

AU - Kadam, Avinash A.

AU - Shinde, Surendra K.

AU - Ghodake, Gajanan S.

AU - Saratale, Ganesh D.

AU - Saratale, Rijuta G.

AU - Sharma, Bharat

AU - Hyun, Seunghun

AU - Sung, Jung Suk

N1 - Funding Information: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the the Korea government (MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of EnvironmentKorea governmentof Korea.(MSIT) (NRF-2019R1G1A1009363) and the grant (2017001970003) from the Ministry of Environment of Korea. Publisher Copyright: © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2020/10

Y1 - 2020/10

N2 - A surface-engineered nano-support for enzyme laccase-immobilization was designed by grafting the surface of halloysite nanotubes (HNTs) with Fe3 O4 nanoparticles and chitosan. Herein, HNTs were magnetized (HNTs-M) by a cost-effective reduction-precipitation method. The synthesized HNTs-M were grafted with 0.25%, 0.5%, 1%, and 2% chitosan (HNTs-M-chitosan), respectively. Synthesized HNTs-M-chitosan (0.25%), HNTs-M-chitosan (0.5%), HNTs-M-chitosan (1%) and HNTs-M-chitosan (2%) were linked with glutaraldehyde (GTA) for laccase immobilization. Among these formulations, HNTs-M-chitosan (1%) exhibited the highest laccase immobilization with 95.13% activity recovery and 100.12 mg/g of laccase loading. The optimized material was characterized thoroughly by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analysis. The immobilized laccase (HNTs-M-chitosan (1%)-GTA-Laccase) exhibited higher pH, temperature, and storage stabilities. The HNTs-M-chitosan (1%)-GTA-Laccase possesses excellent reusability capabilities. At the end of 10 cycles of the reusability experiment, HNTs-M-chitosan (1%)-GTA-Laccase retained 59.88% of its initial activity. The immobilized laccase was utilized for redox-mediated degradation of sulfamethoxazole (SMX), resulting in 41%, 59%, and 62% degradation of SMX in the presence of 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), guaiacol (GUA), and syringaldehyde (SA), respectively. Repeated SMX degradation (57.10% after the sixth cycle) confirmed the potential of HNTs-M-chitosan (1%)-GTA-Laccase for environmental pollutant degradation. Thus, we successfully designed chitosan-based, rapidly separable super-magnetic nanotubes for efficacious enhancement of laccase biocatalysis, which can be applied as nano-supports for other enzymes.

AB - A surface-engineered nano-support for enzyme laccase-immobilization was designed by grafting the surface of halloysite nanotubes (HNTs) with Fe3 O4 nanoparticles and chitosan. Herein, HNTs were magnetized (HNTs-M) by a cost-effective reduction-precipitation method. The synthesized HNTs-M were grafted with 0.25%, 0.5%, 1%, and 2% chitosan (HNTs-M-chitosan), respectively. Synthesized HNTs-M-chitosan (0.25%), HNTs-M-chitosan (0.5%), HNTs-M-chitosan (1%) and HNTs-M-chitosan (2%) were linked with glutaraldehyde (GTA) for laccase immobilization. Among these formulations, HNTs-M-chitosan (1%) exhibited the highest laccase immobilization with 95.13% activity recovery and 100.12 mg/g of laccase loading. The optimized material was characterized thoroughly by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analysis. The immobilized laccase (HNTs-M-chitosan (1%)-GTA-Laccase) exhibited higher pH, temperature, and storage stabilities. The HNTs-M-chitosan (1%)-GTA-Laccase possesses excellent reusability capabilities. At the end of 10 cycles of the reusability experiment, HNTs-M-chitosan (1%)-GTA-Laccase retained 59.88% of its initial activity. The immobilized laccase was utilized for redox-mediated degradation of sulfamethoxazole (SMX), resulting in 41%, 59%, and 62% degradation of SMX in the presence of 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), guaiacol (GUA), and syringaldehyde (SA), respectively. Repeated SMX degradation (57.10% after the sixth cycle) confirmed the potential of HNTs-M-chitosan (1%)-GTA-Laccase for environmental pollutant degradation. Thus, we successfully designed chitosan-based, rapidly separable super-magnetic nanotubes for efficacious enhancement of laccase biocatalysis, which can be applied as nano-supports for other enzymes.

KW - Chitosan

KW - Laccase-immobilization

KW - Nano-engineered supports

KW - Sulfamethoxazole degradation

KW - Super-magnetic separation

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U2 - 10.3390/polym12102221

DO - 10.3390/polym12102221

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