Blaise L. Tardy

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.

Significant progress in lignins valorization and development of high-performance sustainable materials have been achieved in recent years. Reports related to lignin utilization indicate excellent prospects considering green chemistry, chemical engineering, energy, materials and polymer science, physical chemistry, biochemistry, among others. To fully realize such potential, one of the most promising routes involves lignin uses in nanocomposites and nanohybrid assemblies, where synergistic interactions are highly beneficial. This review first discusses the interfacial assembly of lignins with polysaccharides, proteins and other biopolymers, for instance, in the synthesis of nanocomposites. To give a wide perspective, we consider the subject of hybridization with metal and metal oxide nanoparticles, as well as uses as precursor of carbon materials and the assembly with other biobased nanoparticles, for instance to form nanohybrids. We provide cues to understand the fundamental aspects related to lignins, their self-assembly and supramolecular organization, all of which are critical in nanocomposites and nanohybrids. We highlight the possibilities of lignin in the fields of flame retardancy, food packaging, plant protection, electroactive materials, energy storage and health sciences. The most recent outcomes are evaluated given the importance of lignin extraction, within established and emerging biorefineries. We consider the benefit of lignin compared to synthetic counterparts. Bridging the gap between fundamental and application-driven research, this account offers critical insights as far as the potential of lignin as one of the frontrunners in the uptake of bioeconomy concepts and its application in value-added products.

Recent developments in the area of plant-based hydrogels are introduced, especially those derived from wood as a widely available, multiscale, and hierarchical source of nanomaterials, as well as other cell wall elements. With water being fundamental in a hydrogel, water interactions, hydration, and swelling, all critically important in designing, processing, and achieving the desired properties of sustainable and functional hydrogels, are highlighted. A plant, by itself, is a form of a hydrogel, at least at given states of development, and for this reason phenomena such as fluid transport, diffusion, capillarity, and ionic effects are examined. These aspects are highly relevant not only to plants, especially lignified tissues, but also to the porous structures produced after removal of water (foams, sponges, cryogels, xerogels, and aerogels). Thus, a useful source of critical and comprehensive information is provided regarding the synthesis of hydrogels from plant materials (and especially wood nanostructures), and about the role of water, not only for processing but for developing hydrogel properties and uses.

This review considers the most recent developments in supramolecular and supraparticle structures obtained from natural, renewable biopolymers as well as their disassembly and reassembly into engineered materials. We introduce the main interactions that control bottom-up synthesis and top-down design at different length scales, highlighting the promise of natural biopolymers and associated building blocks. The latter have become main actors in the recent surge of the scientific and patent literature related to the subject. Such developments make prominent use of multicomponent and hierarchical polymeric assemblies and structures that contain polysaccharides (cellulose, chitin, and others), polyphenols (lignins, tannins), and proteins (soy, whey, silk, and other proteins). We offer a comprehensive discussion about the interactions that exist in their native architectures (including multicomponent and composite forms), the chemical modification of polysaccharides and their deconstruction into high axial aspect nanofibers and nanorods. We reflect on the availability and suitability of the latter types of building blocks to enable superstructures and colloidal associations. As far as processing, we describe the most relevant transitions, from the solution to the gel state and the routes that can be used to arrive to consolidated materials with prescribed properties. We highlight the implementation of supramolecular and superstructures in different technological fields that exploit the synergies exhibited by renewable polymers and biocolloids integrated in structured materials.