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Here, biomimetic dual esterification strategy was proposed on natural polysaccharides cellulose nanocrystals (CNCs) and galactomannan (GM) in combination with tartaric acid (TA) and benzoic anhydride (BA) respectively. Evaporation-induced self-assembly (EISA) formed the oriented quasinematic structure of the nanocomposites membranes. The CNCs crystallites were modified by TA and intercalated by amorphous polysaccharides, building a complex supramolecular network. Thus, it presents excellent light scattering property with the optical haze of ~90%, which was rarely reported previously. TA and BA simultaneously contributed to satisfying UV adsorption capability for the membranes, showing almost whole-spectra UVA/UVB blocking. Super high mechanical strength (>150 MPa) and toughness (~8 kJ/m 3 ) were revealed by the membranes with high addition amount of BA, together with the efficient antibacterial capability on both Gram-positive and negative bacteria. The diverse optical, mechanical and biological functions displayed by the polysaccharides membranes, propose new horizons on application for packaging, optoelectronic and biomonitoring sensors., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Deep eutectic solvents (DESs) have received considerable interests as pretreatment solvents for biorefinery. In the present work, five kinds of dicarboxylic acids based DESs were introduced to pretreatments on moso bamboo (MB) with microwave irradiation assistance. Factors influencing the enzymatic conversion of MB cellulose to glucose were determined. With the fast heating, pretreated samples all present significant delignification and hemicelluloses matrix removal, thus improving the enzymatic conversion yield from 15% of MB to ~60%. For the DESs, hydrogen donors with less carbon atoms (oxalic acid) and more hydroxyl groups (tartaric acid) displayed higher efficiency due to separation of aggregated cellulose microfibrils. The microwave assisted DESs (MW-DESs) pretreatments also contributed to cellulose crystal variations including decrystallization and more exposure of hydrophobic surfaces, which are beneficial for followed cellulase adsorption and hydrolysis. The exploration of fast MW-DESs pretreatments may expand the potentials of lignocellulose biomass on effective and applicable biorefinery., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Discovering green solvents and their inner mechanisms for efficient deconstruction of lignocellulosic biomass recalcitrance are receiving growing interests. In this work, eco-friendly levulinic acid (LA) based deep eutectic solvents (DES) were proposed for pretreatment on moso bamboo by combining acetamide (Am), betaine (Ba) and choline chloride (ChCl) as hydrogen bonding acceptors. LA/ChCl pretreated materials showed optimal enzymatic accessibility with the highest glucose yield (79.07%) because of its higher lignin removal, morphological disruption and decreased crystallinity. Moreover, the microvoids (averagely 30 nm) and cracks were observed for cellulose microfibrils in anisotropic directions, which resulted in shorter microfibrils and crystallites facilitating the enzymatic hydrolysis. The studies on recyclability revealed that LA/Ba DES had better recycling performance due to its maintaining capability of lignin extraction. Series of supramolecular changes on oriented crystalline cellulose were determined in this work by novel LA based DES, which may provide new alternatives for biomass pretreatments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Nanocellulose has functionalities suitable for efficient sensor transducer surface design including crystallinity, biocompatible and high specific surface area. Here we explore two forms of nanocellulose as transducer surfaces to enable colorimetric detection of human neutrophil elastase (HNE), and a wide range of inflammatory diseases. A deep eutectic solvent (DES) was utilized to mediate formation of cotton cellulose nanocrystals (DCNCs) employed to prepare a peptide-cellulose conjugate as a protease sensor of HNE. The tetrapeptide-cellulose analog on DCNC is contrasted with an analogous derivative of TEMPO-oxidized wood cellulose nanofibrils (WCNFs). DCNCs showed greater degree of substitution of HNE tetrapeptide and sensitivity to the elastase than WCNFs, despite the smaller surface area and pore sizes. XRD models revealed the higher crystallinity and larger crystallite sizes of DCNCs, indicating the well-arranged cellulose chains for immobilization of the tetrapeptide on (110) lattice reflections of cellulose crystals. The sensitivity of DCNCs-based colorimetric sensor was less than 0.005 U/mL, which would provide a convenient, sensitive sensor applicable for improved colorimetric point of care protease biomarker detection., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The insufficient resolution of conventional methods has long limited the structural elucidation of cellulose and its derivatives, especially for those with relatively low crystallinities or in native cell walls. Recent 2D/3D solid-state NMR studies of 13 C uniformly labeled plant biomaterials have initiated a re-investigation of our existing knowledge in cellulose structure and its interactions with matrix polymers but for unlabeled materials, this spectroscopic method becomes impractical due to limitations in sensitivity. Here, we investigate the molecular structure of unlabeled cotton cellulose by combining natural abundance 13 C- 13 C 2D correlation solid-state NMR spectroscopy, as enabled by the sensitivity-enhancing technique of dynamic nuclear polarization (DNP), with statistical analysis of the observed and literature-reported chemical shifts. The atomic resolution allows us to monitor the loss of Iα and Iβ allomorphs and the generation of a novel structure during ball-milling, which reveals the importance of large crystallite size for maintaining the Iα and Iβ model structures. Partial order has been identified in the "disordered" domains, as evidenced by a discrete distribution of well-resolved peaks. This study not only provides heretofore unavailable high-resolution insights into cotton cellulose but also presents a widely applicable strategy for analyzing the structure of cellulose-rich materials without isotope-labeling. This work was part of a multi-technique study of ball-milled cotton described in the previous article in the same issue.

The study aimed to explore the crystallinity and crystalline structure of alkaline pretreated cellulose. The enzymatic hydrolysis followed by pretreatment was conducted for measuring the efficiency of sugar conversion. For cellulose Iβ dominated samples, alkaline pretreatment (<8wt%) caused increased cellulose crystallinity and depolymerized hemicelluloses, that were superimposed to affect the enzymatic conversion to glucose. Varying crystallite sizes and lattice spacings indicated the separation of cellulose crystals during mercerization (8-12wt% NaOH). Completion of mercerization was proved under higher alkaline concentration (14-18wt% NaOH), leading to distortion of crystalline cellulose to some extent. Cellulose II crystallinity showed a stimulative impact on enzymatic hydrolysis due to the weakened hydrophobic interactions within cellulose chains. The current study may provide innovative explanations for enhanced enzymatic digestibility of alkaline pretreated lignocellulosic materials., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Deconstruction of lignocellulosic plant cell walls to fermentable sugars by biochemical means is impeded by several poorly understood ultrastructural and chemical barriers. Pretreatment is an essential step by altering the morphological and compositional characteristics of biomass to enhance the sugar release during enzymatic hydrolysis. Therefore, getting insight into this field is necessary to improve the conversion of biomass into biofuels. In this review, we highlight our recent understanding on the impact of various promising pretreatments on biomass, with emphasis on the topochemical and ultrastructural changes of plant cell walls that are related to the reduction of recalcitrance and the consequence of saccharification. It will lend support to the scientific research and development with respect to biomass conversion.