Chitin nanofibers are prepared from the exoskeletons of crabs and prawns, squid pens and mushrooms by a simple mechanical treatment after a series of purification steps. The nanofibers have fine nanofiber networks with a uniform width of approximately 10 nm. The method used for chitin-nanofiber isolation is also successfully applied to the cell walls of mushrooms. Commercial chitin and chitosan powders are also easily converted into nanofibers by mechanical treatment, since these powders consist of nanofiber aggregates. Grinders and high-pressure waterjet systems are effective for disintegrating chitin into nanofibers. Acidic conditions are the key factor to facilitate mechanical fibrillation. Surface modification is an effective way to change the surface property and to endow nanofiber surface with other properties. Several modifications to the chitin NF surface are achieved, including acetylation, deacetylation, phthaloylation, naphthaloylation, maleylation, chlorination, TEMPO-mediated oxidation, and graft polymerization. Those derivatives and their properties are characterized.

Chitin and Chitosan Nanofibers: Preparation and Chemical Modifications

Chitin, a fascinating biopolymer found in living organisms, fulfills current demands of availability, sustainability, biocompatibility, biodegradability, functionality, and renewability. A feature of chitin is its ability to structure into hierarchical assemblies, spanning the nano- and macroscales, imparting toughness and resistance (chemical, biological, among others) to multicomponent materials as well as adding adaptability, tunability, and versatility. Retaining the inherent structural characteristics of chitin and its colloidal features in dispersed media has been central to its use, considering it as a building block for the construction of emerging materials. Top-down chitin designs have been reported and differentiate from the traditional molecular-level, bottom-up synthesis and assembly for material development. Such topics are the focus of this Review, which also covers the origins and biological characteristics of chitin and their influence on the morphological and physical-chemical properties. We discuss recent achievements in the isolation, deconstruction, and fractionation of chitin nanostructures of varying axial aspects (nanofibrils and nanorods) along with methods for their modification and assembly into functional materials. We highlight the role of nanochitin in its native architecture and as a component of materials subjected to multiscale interactions, leading to highly dynamic and functional structures. We introduce the most recent advances in the applications of nanochitin-derived materials and industrialization efforts, following green manufacturing principles. Finally, we offer a critical perspective about the adoption of nanochitin in the context of advanced, sustainable materials.

Nanochitin: Chemistry, Structure, Assembly, and Applications

Comparison of nanocrystals and nanofibers produced from shrimp shell α-chitin: From energy production to material cytotoxicity and Pickering emulsion properties.

Nanochitin and nanochitosan (with random‐copolymer‐based multiscale architectures of glucosamine and N‐acetylglucosamine units) have recently attracted immense attention for the development of green, sustainable, and advanced functional materials. Nanochitin and nanochitosan are multiscale materials from small oligomers, rod‐shaped nanocrystals, longer nanofibers, to hierarchical assemblies of nanofibers. Various physical properties of chitin and chitosan depend on their molecular‐ and nanostructures; translational research has utilized them for a wide range of applications (biomedical, industrial, environmental, and so on). Instead of reviewing the entire extensive literature on chitin and chitosan, here, recent developments in multiscale‐dependent material properties and their applications are highlighted; immune, medical, reinforcing, adhesive, green electrochemical materials, biological scaffolds, and sustainable food packaging are discussed considering the size, shape, and assembly of chitin nanostructures. In summary, new perspectives for the development of sustainable advanced functional materials based on nanochitin and nanochitosan by understanding and engineering their multiscale properties are described.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/adma.202203325

Nanochitin and Nanochitosan: Chitin Nanostructure Engineering with Multiscale Properties for Biomedical and Environmental Applications

Favorable effects of superficially deacetylated chitin nanofibrils on the wound healing process.

Phthaloylation of chitin nanofiber (NF) was achieved by reaction with phthalic anhydride in aqueous media. The phthaloyl group was quantitatively introduced into an amino group of a surface-deacetylated chitin NF surface. The characteristic nanofiber network structure was maintained after phthaloylation. The NFs were dispersed homogeneously in organic solvents, and even in several aromatic solvents, due to the high solvation interactions with the phthaloyl group. In addition, the homogeneous dispersions in aromatic solvents had reversible thermo-responsive properties and exhibited a dispersive-to-precipitate phase transition response at approximately 25 °C. Due to the presence of the phthaloyl group, the NF dispersion and the nano-composite film cut harmful ultraviolet light.

Surface phthaloylation of chitin nanofiber in aqueous media to improve dispersibility in aromatic solvents and give thermo-responsive and ultraviolet protection properties

Surface N -maleylation and N -naphthaloylation of chitin nanofiber (NF) were achieved by reaction with maleic and naphthalic anhydrides in water, respectively. Maleyl and naphthaloyl groups were sufficiently introduced to an amino group on a surface-deacetylated chitin NF. The characteristic nanofiber morphology was maintained after maleylation and naphthaloylation. These NFs were homogeneously dispersed in several organic solvents. Especially, naphthaloyl chitin NF was dispersed even in aromatic solvents, owing to the high level of solvation interactions with the naphthaloyl group. The NF dispersions in those aromatic solvents exhibited a dispersive-to-precipitate transition response at approximately 29 °C. Moreover, the naphthaloyl chitin NF dispersion cut harmful ultraviolet light. The maleyl chitin NF formed a self-standing gel after cross-linking polymerization.

Surface maleylation and naphthaloylation of chitin nanofibers for property enhancement

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Surface phthaloylation of chitin nanofiber in aqueous media to improve dispersibility in aromatic solvents and give thermo-responsive and ultraviolet protection properties

Surface maleylation and naphthaloylation of chitin nanofibers for property enhancement