Deconstruction and Reassembly of Renewable Polymers and Biocolloids into Next Generation Structured Materials

Abstract

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.

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

“…Three major approaches are considered, as represented in Figure 1 : (i) the exploitation of natural polymers to generate novel materials, (ii) the possibility of producing commodity polymers, which are traditionally prepared from fossil resources, using monomers derived from renewable counterparts, and (iii) the use of a variety of monomers and macromonomers derived from renewable resources to prepare original macromolecular structures with unique properties and potential applications in different industrial sectors. As this monograph is intended to give perspectives on the topic, the reader is encouraged to gather detailed information on the specific chemistry and other fundamental aspects in very rich contributions published by experts in the last decade [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 ].…”

Recent Advances on Lignocellulosic-Based Nanopesticides for Agricultural Applications

“…In addition, they observed high adhesion of nanocellulose towards hydrophilic surfaces has led to the development of biogenic nanohybrids containing biogenic silica and cellulose nanofibers for the encapsulation of various molecules including a biopesticide (thymol) (Mattos and Magalhães, 2016;Mattos et al, 2018). The difficulty of promoting dissolution of cellulose, in parallel with the current regulation on bioplastics that defines cellulose derivatives as plastics, will accelerate the development of nanocarriers from cellulose colloids, such as cellulose nanofibers, which have unique physicochemical properties such as higher surface area, nanodimension, hightemperature resistance, and biocompatibility (Shahi et al, 2021;Tardy et al, 2021). Cellulose nanofibers (CNFs) have been reported as potential high performers in nanoformulations of fertilization (do Nascimento et al, 2021), as well as cellulose nanocrystals (CNC) with chitosan to control tomato bacterial speck disease (Schiavi et al, 2021), among others (Table 1).…”

“…Nonetheless, the application of lignocellulosics in nano-enabled agriculture is currently related to the controlled delivery and release of pesticides and nutrients (Worrall et al, 2018;Papadopoulos et al, 2019;Chen et al, 2020a;Teo and Wahab., 2020). However, lignocellulosic nanomaterials could potentially stabilize emulsions (such as those used in oil borne pesticides) instead conventional surfactants in multiphase systems (Tardy et al, 2021). In this review we summarize and discuss the recent advances in lignocellulosic nanocarriers for agricultural applications; in addition, we offer a critical discussion regarding the future challenges of lignocellulosic nano-enabled materials for sustainable agricultural development.…”

Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase

“…A longer-term goal is the use of paper-grade pulp (Ma et al 2018;Kuura 2021) and perhaps even lower purity and recycled cellulosics in regenerated fibre production (Haslinger et al 2019). The topic of nanocelluloses also has significant long-term interest -as substrates for materials applications (Trache et al 2020), mainly based on the high aspect-ratio that nanocellulose provides in the formation of high-strength composites and colloids (Tardy et al 2021). However, there are also more interesting intrinsic properties, such as, nanocelluloses axial chirality (Usov et al 2015) and the potential for asymmetric chemical modification (Heise et al 2021), that allow for the preparation of novel materials.…”

“…A new dimension to develop the intrinsic qualities of celluloses is controllable surface chemical modification, where the crystallinity and morphology of the native materials can be maintained (Tardy et al 2021). This not only can be used to introduce functional chemical moieties but also for modification of surface properties, for physiochemical interaction with different media, e.g., in nanocomposites and dispersions (Beaumont et al 2021b;Yang et al 2021;Tardy et al 2021). Thus, understanding and controlling the surface chemistry of these materials is critical.…”