Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation

Recently, cellulose and other biomass nanofibers (NFs) have been increasingly utilized in the design of sustainable materials for environmental, biomedical, and other applications. However, the past literature lacks a comparison of the macromolecular and nanofibrous states of biopolymers in various...

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Main Authors: Taisei Kawate, Yehao Wang, Kayee Chan, Nobuyuki Shibata, Yuya Doi, Yuichi Masubuchi, Anatoly Zinchenko
Format: Article
Language:English
Published: MDPI AG 2024-09-01
Series:Gels
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Online Access:https://www.mdpi.com/2310-2861/10/9/604
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author Taisei Kawate
Yehao Wang
Kayee Chan
Nobuyuki Shibata
Yuya Doi
Yuichi Masubuchi
Anatoly Zinchenko
author_facet Taisei Kawate
Yehao Wang
Kayee Chan
Nobuyuki Shibata
Yuya Doi
Yuichi Masubuchi
Anatoly Zinchenko
author_sort Taisei Kawate
collection DOAJ
description Recently, cellulose and other biomass nanofibers (NFs) have been increasingly utilized in the design of sustainable materials for environmental, biomedical, and other applications. However, the past literature lacks a comparison of the macromolecular and nanofibrous states of biopolymers in various materials, and the advantages and limitations of using nanofibers (NF) instead of conventional polymers are poorly understood. To address this question, hydrogels based on interpolyelectrolyte complexes (IPECs) between carboxymethyl cellulose nanofibers (CMCNFs) and chitosan (CS) were prepared by ele+ctrostatic cross-linking and compared with the hydrogels of carboxymethyl cellulose (CMC) and CS biopolymers. The presence of the rigid CMCNF altered the mechanism of the IPEC assembly and drastically affected the structure of IPEC hydrogels. The swelling ratios of CMCNF-CS hydrogels of ca. 40% were notably lower than the ca. 100–300% swelling of CMC-CS hydrogels. The rheological measurements revealed a higher storage modulus (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>G</mi></mrow><mrow><mo>′</mo></mrow></msup></mrow></semantics></math></inline-formula>) of the CMCNF-CS hydrogel, reaching 13.3 kPa compared to only 3.5 kPa measured for the CMC-CS hydrogel. Further comparison of the adsorption characteristics of the CMCNF-CS and CMC-CS hydrogels toward Cu<sup>2+</sup>, Cd<sup>2+</sup>, and Hg<sup>2+</sup> ions showed the slightly higher adsorption capacity of CMC-CS for Cu<sup>2+</sup> but similar adsorption capacities for Cd<sup>2+</sup> and Hg<sup>2+</sup>. The adsorption kinetics obeyed the pseudo-second-order adsorption model in both cases. Overall, while the replacement of CMC with CMCNF in hydrogel does not significantly affect the performance of such systems as adsorbents, CMCNF imparts IPEC hydrogel with higher stiffness and a frequency-independent loss (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>G</mi></mrow><mrow><mo>″</mo></mrow></msup></mrow></semantics></math></inline-formula>) modulus and suppresses the hydrogel swelling, so can be beneficial in practical applications that require stable performance under various dynamic conditions.
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spelling doaj-art-00a4bf14f9ed4313b975b3deb2fd40e82025-08-20T01:55:31ZengMDPI AGGels2310-28612024-09-0110960410.3390/gels10090604Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental RemediationTaisei Kawate0Yehao Wang1Kayee Chan2Nobuyuki Shibata3Yuya Doi4Yuichi Masubuchi5Anatoly Zinchenko6Graduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, JapanGraduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, JapanGraduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, JapanNagoya Municipal Industrial Research Institute, Nagoya 456-0058, JapanGraduate School of Engineering, Nagoya University, Nagoya 464-8601, JapanGraduate School of Engineering, Nagoya University, Nagoya 464-8601, JapanGraduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, JapanRecently, cellulose and other biomass nanofibers (NFs) have been increasingly utilized in the design of sustainable materials for environmental, biomedical, and other applications. However, the past literature lacks a comparison of the macromolecular and nanofibrous states of biopolymers in various materials, and the advantages and limitations of using nanofibers (NF) instead of conventional polymers are poorly understood. To address this question, hydrogels based on interpolyelectrolyte complexes (IPECs) between carboxymethyl cellulose nanofibers (CMCNFs) and chitosan (CS) were prepared by ele+ctrostatic cross-linking and compared with the hydrogels of carboxymethyl cellulose (CMC) and CS biopolymers. The presence of the rigid CMCNF altered the mechanism of the IPEC assembly and drastically affected the structure of IPEC hydrogels. The swelling ratios of CMCNF-CS hydrogels of ca. 40% were notably lower than the ca. 100–300% swelling of CMC-CS hydrogels. The rheological measurements revealed a higher storage modulus (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>G</mi></mrow><mrow><mo>′</mo></mrow></msup></mrow></semantics></math></inline-formula>) of the CMCNF-CS hydrogel, reaching 13.3 kPa compared to only 3.5 kPa measured for the CMC-CS hydrogel. Further comparison of the adsorption characteristics of the CMCNF-CS and CMC-CS hydrogels toward Cu<sup>2+</sup>, Cd<sup>2+</sup>, and Hg<sup>2+</sup> ions showed the slightly higher adsorption capacity of CMC-CS for Cu<sup>2+</sup> but similar adsorption capacities for Cd<sup>2+</sup> and Hg<sup>2+</sup>. The adsorption kinetics obeyed the pseudo-second-order adsorption model in both cases. Overall, while the replacement of CMC with CMCNF in hydrogel does not significantly affect the performance of such systems as adsorbents, CMCNF imparts IPEC hydrogel with higher stiffness and a frequency-independent loss (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>G</mi></mrow><mrow><mo>″</mo></mrow></msup></mrow></semantics></math></inline-formula>) modulus and suppresses the hydrogel swelling, so can be beneficial in practical applications that require stable performance under various dynamic conditions.https://www.mdpi.com/2310-2861/10/9/604nanofibersinterpolyelectrolyte complexhydrogelrheologymetal ion adsorption
spellingShingle Taisei Kawate
Yehao Wang
Kayee Chan
Nobuyuki Shibata
Yuya Doi
Yuichi Masubuchi
Anatoly Zinchenko
Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
Gels
nanofibers
interpolyelectrolyte complex
hydrogel
rheology
metal ion adsorption
title Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
title_full Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
title_fullStr Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
title_full_unstemmed Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
title_short Polyion Hydrogels of Polymeric and Nanofibrous Carboxymethyl Cellulose and Chitosan: Mechanical Characteristics and Potential Use in Environmental Remediation
title_sort polyion hydrogels of polymeric and nanofibrous carboxymethyl cellulose and chitosan mechanical characteristics and potential use in environmental remediation
topic nanofibers
interpolyelectrolyte complex
hydrogel
rheology
metal ion adsorption
url https://www.mdpi.com/2310-2861/10/9/604
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