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Bottom-up synthesis of β-glucans such as callose, fungal β-(1,3)(1,6)-glucan and cellulose, can create the defined compounds that are needed to perform fundamental studies on glucan properties and develop applications. With the importance of β-glucans and cellulose in high-profile fields such as nutrition, renewables-based biotechnology and materials science, the enzymatic synthesis of such relevant carbohydrates and their derivatives has attracted much attention. Here we review recent developments in enzymatic synthesis of β-glucans and cellulose, with a focus on progress made over the last five years. We cover the different types of biocatalysts employed, their incorporation in cascades, the exploitation of enzyme promiscuity and their engineering, and reaction conditions affecting the production as well as in situ self-assembly of (non)functionalised glucans. The recent achievements in the application of glycosyl transferases and β-1,4- and β-1,3-glucan phosphorylases demonstrate the high potential and versatility of these biocatalysts in glucan synthesis in both industrial and academic contexts., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The design of new functional materials and devices substantially relies on self-assembly of hierarchical structures. Formation of 2D platelets is known in the enzymatic synthesis of cellulose-like polymers. Here we demonstrate the feasibility of postsynthesis assembly of novel fluorinated cellodextrins. Highly ordered 2D structures of large lateral dimensions, unattainable in the polymerization process, can be formed because of postsynthesis assembly of the cellodextrins. These cellodextrins were also involved in coassembly with cellulose nanocrystals (CNCs) leading to hybrid systems. The hybrid architectures obtained depend on the content of fluorine atoms in the fluorinated cellodextrins. Monofluorinated cellodextrins coassemble with CNCs into a nanoweb, while multifluorinated cellodextrins assemble around the CNCs.

Cellulose modification often employs chemical processes to tailor its properties and functionalities to fit the demands of a wide range of applications, maximizing its potential as a versatile and sustainable material. From both synthetic and environmental standpoints, one of the ultimate goals is to achieve significant modifications to enhance the end properties of the cellulose while minimizing the number of modified building blocks. The current study demonstrates that a synthetic glucose derivative, 6‐deoxy‐6‐fluoro‐glucose (6F‐Glc), fed into the fertilized cotton ovules, resulted in the accumulation of fluorine inside the cotton fibers with no apparent alteration to their morphology or development. These fibers exhibited a degree of substitution of 0.006, which is 170 times lower than that reported for chemical methods for cellulose modification. However, the physical characterization of the modified fibers showed a surprisingly large impact of this low‐level modification on the cellulose structure (e.g., hydrogen bonding network rearrangement) and a modest increase in the mechanical properties of the fibers. The obtained results exemplify the use of biological systems to introduce low quantities of new functionalities while maximizing the impact on fiber properties. [ABSTRACT FROM AUTHOR]