Application of ionic liquids for the functional materialization of chitin

Kadokawa, Jun‐ichi

doi:10.1039/d2ma00101b

Cited by 18 publications

(9 citation statements)

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“…Based on the above background, we aimed to develop an efficient and facile chitin acylation procedure under homogeneous conditions. Almost quantitative degrees of substitution (DSs) of the produced chitin ester derivatives were successfully obtained by the reaction of chitin with acyl chlorides coexisting with pyridine/ N,N -dimethyl-4-aminopyridine (DMAP) as base/catalyst in an ionic liquid solvent,1-allyl-3-methylimidazolium bromide (AMIMBr), based on the observation that ionic liquids are identified as good solvents for polysaccharides, such as chitin. − However, the resulting derivatives (single chitin esters) did not exhibit thermoplasticity and melt processability, ascribed to the construction of intrinsic chitin crystals in these derivatives, even by the derivatization of hydroxy groups by acyl substituents. The acetamido groups that remained in these chitin ester derivatives facilitated intermolecular hydrogen bonding, resulting in the formation of chitin crystals.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Thermoplastic Mixed Chitin Esters

Shigenobu,

Nakashima,

Kadokawa

2023

Biomacromolecules

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Mixed chitin esters, that is, chitin benzoate stearates, exhibiting thermoplasticity, were synthesized by the acylation of chitin using benzoyl and stearoyl chlorides in the presence of pyridine and N,N-dimethyl-4-aminopyridine for 1 h + 24 h at 100 °C in an ionic liquid, 1-allyl-3-methylimidazolium bromide. IR and 1H NMR spectroscopic analyses confirmed the formation of the desired chitin benzoate stearates. Powder X-ray diffraction analysis of the products indicated that the crystalline structures of the chitin main-chains and stearoyl side-chains were strongly affected by the benzoyl/stearoyl substituent ratios. Introducing a small number of benzoyl groups, in addition to a large ratio of stearoyl groups, contributed to disrupting the intrinsic chitin crystals and enabling the chitin main chains and stearoyl side chains to form regularly controlled layered and parallel arrays, respectively. The resulting products exhibited meting points, associated with regular stearoyl packings, and formed melt-pressed films during the melt-pressing process. These results suggest that chitin benzoate stearates with appropriate benzoyl/stearoyl substituent ratios exhibit thermoplasticity.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Thermoplastic Mixed Chitin Esters

Shigenobu,

Nakashima,

Kadokawa

2023

Biomacromolecules

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“…The reduction in particle size was more uniform, leading to increased heat-exposed area and earlier mass loss . Ionic liquids, such as [EMIM][OAc], containing carboxylate anions, act as effective solvents for structural polysaccharides like chitin and can dissolve it to a certain concentration …”

Section: Resultsmentioning

confidence: 99%

“…34 Ionic liquids, such as [EMIM][OAc], containing carboxylate anions, act as effective solvents for structural polysaccharides like chitin and can dissolve it to a certain concentration. 35 Optimization of the Immobilized Enzyme ChNF-chiA1 and Optical Reaction Conditions. Phospholipase D is a phospholipid hydrolase that can break the phosphodiester bonds in phospholipid molecules and participates in phospholipid acyl transfer reactions, leading to the synthesis of novel phospholipids with diverse functional headgroups.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…Influence of Temperature and pH on the Activity of Immobilized ChNF-chiA1. To assess the impact of temperature on free PLD-chiA1 and immobilized ChNF-chiA1, enzymatic hydrolysis assays were conducted in the same reaction system at different temperature conditions (25,30,35 Subsequently, optimal pH conditions were determined, and the reactions were performed in the pH range of 3.0 to 10.0, utilizing various buffering solutions. Each reaction was repeated three times to calculate the relative activity.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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High-Yield Synthesis of Phosphatidylserine in a Well-Designed Mixed Micellar System

Yin,

Sun,

Guo

et al. 2023

J. Agric. Food Chem.

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A sustainable enzymatic system is essential for efficient phosphatidylserine (PS) synthesis in industrial production. Conventional biphasic systems face challenges such as excessive organic solvent usage, enzyme-intensive processes, and increased costs. This study introduces a novel approach using chitin nanofibrils (ChNFs) as an immobilization material for phospholipase D (PLD) in a mixed micellar system stabilized by the food-grade emulsifier sodium deoxycholate (SDC). The immobilized enzyme, ChNF-chiA1, was quickly prepared in a one-step process, eliminating the need for purification. By optimizing the reaction conditions, including L-Ser concentration (1.0 M), SDC concentration (10 mM), reaction time (8 h), and enzyme dosage (1.0 U), a remarkable PS yield of 96.74% was achieved in the solvent-free mixed micellar system. The catalytic efficiency of ChNF-chiA1 surpassed that of the free PLD-chiA1 biphasic system by 6.0-fold. This innovative and green biocatalytic technology offers a reusable solution for the high-value enzymatic synthesis of phospholipids, providing a promising avenue for industrial applications.

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“…Recently, the construction of controlled polymeric assemblies at the nanoscale (e.g., nanofibers, nanocrystals, and nanowhiskers) has been found to be an efficient approach for the functionalization of chitin [ 12 , 13 , 14 ], owing to the remarkable properties of bio-based nanomaterials, such as their lightweight character, nanosheet formability, high tensile strength, low thermal expansion coefficient, and biocompatibility [ 15 , 16 , 17 , 18 , 19 , 20 , 21 ]. Previously, two types of approaches for providing such nanochitins have been developed: a top-down approach, where natural chitin sources break down to the nanoscale [ 12 , 13 , 14 ], and a bottom-up approach, where chitin chains self-assemble regeneratively at the nanoscale [ 22 , 23 , 24 ]. Moreover, nanochitins have been employed in biomedical applications, such as wound healing and bone regenerative engineering [ 25 , 26 , 27 , 28 ].…”

Section: Introductionmentioning

confidence: 99%

Hydrogelation from Self-Assembled and Scaled-Down Chitin Nanofibers by the Modification of Highly Polar Substituents

Kadokawa

2023

Gels

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Chitin nanofibers (ChNFs) with a bundle structure were fabricated via regenerative self-assembly at the nanoscale from a chitin ion gel with an ionic liquid using methanol. Furthermore, the bundles were disentangled by partial deacetylation under alkaline conditions, followed by cationization and electrostatic repulsion in aqueous acetic acid to obtain thinner nanofibers called scaled-down ChNFs. This review presents a method for hydrogelation from self-assembled and scaled-down ChNFs by modifying the highly polar substituents on ChNFs. The modification was carried out by the reaction of amino groups on ChNFs, which were generated by partial deacetylation, with reactive substituent candidates such as poly(2-oxazoline)s with electrophilic living propagating ends and mono- and oligosaccharides with hemiacetallic reducing ends. The substituents contributed to the formation of network structures from ChNFs in highly polar dispersed media, such as water, to produce hydrogels. Moreover, after the modification of the maltooligosaccharide primers on ChNFs, glucan phosphorylase-catalyzed enzymatic polymerization was performed from the primer chain ends to elongate the amylosic graft chains on ChNFs. The amylosic graft chains formed double helices between ChNFs, which acted as physical crosslinking points to construct network structures, giving rise to hydrogels.

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Application of ionic liquids for the functional materialization of chitin

Abstract: Ionic liquids (ILs) have been shown to efficiently dissolve substrates with poor solubility. In particular, they act as powerful solvents for structural polysaccharides, which are difficult to dissolve using conventional...

Cited by 18 publications

References 121 publications

Synthesis of Thermoplastic Mixed Chitin Esters

Synthesis of Thermoplastic Mixed Chitin Esters

High-Yield Synthesis of Phosphatidylserine in a Well-Designed Mixed Micellar System

Hydrogelation from Self-Assembled and Scaled-Down Chitin Nanofibers by the Modification of Highly Polar Substituents

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