Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach

In recent years, increased attention has been given to the effective use of chitin nanofibers (ChNFs). We have developed a method to fabricate thinner chitin nanomaterials, called scale-down chitin nanofibers (SD-ChNFs), by a bottom-up procedure at the nanoscale level, with subsequent disintegration...

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Main Authors: Naoki Yamamoto, Masayasu Totani, Jun-ichi Kadokawa
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/1/16
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author Naoki Yamamoto
Masayasu Totani
Jun-ichi Kadokawa
author_facet Naoki Yamamoto
Masayasu Totani
Jun-ichi Kadokawa
author_sort Naoki Yamamoto
collection DOAJ
description In recent years, increased attention has been given to the effective use of chitin nanofibers (ChNFs). We have developed a method to fabricate thinner chitin nanomaterials, called scale-down chitin nanofibers (SD-ChNFs), by a bottom-up procedure at the nanoscale level, with subsequent disintegration by electrostatic repulsion. The surface modification of SD-ChNFs is anticipated to provide new properties and functions for their practical applications. Inspired by our previous reports, which found hydrophobicity in partially 2-deoxygenated (P2D-) amylose obtained by the glucan phosphorylase (GP)-catalyzed enzymatic copolymerization of α-<span style="font-variant: small-caps;">d</span>-glucose 1-phosphate/<span style="font-variant: small-caps;">d</span>-glucal as comonomers, this work investigated the hydrophobization of SD-ChNFs via an enzymatic approach. After the modification of maltooligosaccharide primers on SD-ChNFs was performed by a reductive alkylation toward ChNFs, the grafting of the P2D-amyloses was performed by GP-catalyzed enzymatic copolymerization. <sup>1</sup>H NMR analysis supported the production of P2D-amylose-grafted SD-ChNFs with different <span style="font-variant: small-caps;">d</span>-glucose/2-deoxy-<span style="font-variant: small-caps;">d</span>-glucose unit ratios on SD-ChNFs. The X-ray diffraction analysis of the products confirmed that the chain lengths and unit ratios of the grafted polysaccharides strongly affected the entire crystalline structures. Water contact angle measurements of the cast films of the products indicated that successful hydrophobization was achieved by the grafting of P2D-amylose chains with a sufficient chain length, a relatively high 2-deoxy-<span style="font-variant: small-caps;">d</span>-glucose unit ratio, and low crystallinity.
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spelling doaj-art-a11a51986c994493a0c15acf063d89232025-01-10T13:18:36ZengMDPI AGMolecules1420-30492024-12-013011610.3390/molecules30010016Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic ApproachNaoki Yamamoto0Masayasu Totani1Jun-ichi Kadokawa2Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065, JapanGraduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065, JapanGraduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065, JapanIn recent years, increased attention has been given to the effective use of chitin nanofibers (ChNFs). We have developed a method to fabricate thinner chitin nanomaterials, called scale-down chitin nanofibers (SD-ChNFs), by a bottom-up procedure at the nanoscale level, with subsequent disintegration by electrostatic repulsion. The surface modification of SD-ChNFs is anticipated to provide new properties and functions for their practical applications. Inspired by our previous reports, which found hydrophobicity in partially 2-deoxygenated (P2D-) amylose obtained by the glucan phosphorylase (GP)-catalyzed enzymatic copolymerization of α-<span style="font-variant: small-caps;">d</span>-glucose 1-phosphate/<span style="font-variant: small-caps;">d</span>-glucal as comonomers, this work investigated the hydrophobization of SD-ChNFs via an enzymatic approach. After the modification of maltooligosaccharide primers on SD-ChNFs was performed by a reductive alkylation toward ChNFs, the grafting of the P2D-amyloses was performed by GP-catalyzed enzymatic copolymerization. <sup>1</sup>H NMR analysis supported the production of P2D-amylose-grafted SD-ChNFs with different <span style="font-variant: small-caps;">d</span>-glucose/2-deoxy-<span style="font-variant: small-caps;">d</span>-glucose unit ratios on SD-ChNFs. The X-ray diffraction analysis of the products confirmed that the chain lengths and unit ratios of the grafted polysaccharides strongly affected the entire crystalline structures. Water contact angle measurements of the cast films of the products indicated that successful hydrophobization was achieved by the grafting of P2D-amylose chains with a sufficient chain length, a relatively high 2-deoxy-<span style="font-variant: small-caps;">d</span>-glucose unit ratio, and low crystallinity.https://www.mdpi.com/1420-3049/30/1/16chitin nanofiberenzymatic graftingglucan phosphorylasehydrophobizationreductive alkylation
spellingShingle Naoki Yamamoto
Masayasu Totani
Jun-ichi Kadokawa
Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
Molecules
chitin nanofiber
enzymatic grafting
glucan phosphorylase
hydrophobization
reductive alkylation
title Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
title_full Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
title_fullStr Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
title_full_unstemmed Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
title_short Hydrophobization of Chitin Nanofibers by Grafting of Partially 2-Deoxygenated Amyloses Through Enzymatic Approach
title_sort hydrophobization of chitin nanofibers by grafting of partially 2 deoxygenated amyloses through enzymatic approach
topic chitin nanofiber
enzymatic grafting
glucan phosphorylase
hydrophobization
reductive alkylation
url https://www.mdpi.com/1420-3049/30/1/16
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AT masayasutotani hydrophobizationofchitinnanofibersbygraftingofpartially2deoxygenatedamylosesthroughenzymaticapproach
AT junichikadokawa hydrophobizationofchitinnanofibersbygraftingofpartially2deoxygenatedamylosesthroughenzymaticapproach