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It is an interesting research topic to study the interfacial interactions between hemicellulose and cellulose, specifically how hemicellulose's structure affects its binding to cellulose nanofibers. Our research proposes that dispersion interaction play an important role in this interfacial interaction, more so than electrostatic forces when considering the adherence of cellulose to xylan. To quantify these interactions, the Atomic Force Microscope (AFM) colloidal probe technique is applied to measure the intermolecular forces between cellulose nanofibers, which are attached to the probe and xylan. These measured forces are then analyzed in relation to the length, diameter and functional groups of the nanocellulose, as well as the molecular weight and side chains of the xylan. Moreover, the predominance of dispersion forces by contrasting the adhesive forces before and after the grafting of a large nonpolar group onto xylan. This modification significantly reduces contact between the cellulose and xylan backbone, thereby markedly diminishing the dispersion interactions. Parallel to the AFM experiments, molecular dynamics (MD) simulations corroborate the experimental results and support our hypotheses. Collectively, these findings contribute to a deeper understanding of polysaccharide interactions within lignocellulose., 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 © 2024 Elsevier B.V. All rights reserved.)

The Bletilla striata polysaccharides (BSP) extracted through alkali-assisted method exhibit significant antioxidant activity, but its bioaccessibility was inadequate due to its tightly filamentous reticulation structure and high molecular weight. The anti-photoaging and anti-melanogenesis effects of degraded BSP (DBSPs) against UVB-induced oxidative stress on the skin were investigated. The molecular weights of the DBSPs were reduced to 153.94 kDa, 66.96 kDa, and 15.54 kDa from an initial value of 298.82 kDa. The degradation treatment altered the branched chain structure of the DBSPs, while the backbone structure, triple-helix structure, and crystallinity remained. DBSPs with a lower molecular weight exhibit better in vitro antioxidant activity. DBSPs did not show cytotoxicity to HSF cells but inhibited B16F10 cell proliferation. The addition of DBSPs protected HSF and B16F10 cells from oxidative stress and reduced ROS levels, B16F10 melanin content, and B16F10 tyrosinase activity after UVB damage, but DBSP-10 particles were slightly less effective due to aggregation. In contrast, DBSP-5 demonstrated effectiveness in reducing MDA levels in cells stressed by oxidative stress, increased total antioxidant capacity, and inhibited melanogenesis in B16F10, suggesting that DBSP-5 has potential as a topical therapeutic agent for the treatment of skin diseases associated with oxidative stress., 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 © 2024 Elsevier B.V. All rights reserved.)

Local drug delivery has generated considerable interest due to its controlled and sustained drug release at the target site on demand. Nanoaggregate-incorporated composite hydrogels are desirable as local drug delivery systems; however, it is difficult to achieve sustained and controlled hydrophobic drug release and superior mechanical properties in one system. Herein, a "smart" composite hydrogel was synthesized by incorporating hemicellulose-based nanoaggregates into a double network consisting of alginate/Ca 2+ and polyacrylic acid-co-dimethylaminoethyl methacrylate [P(AA-co-DMAEMA)]. Hemicellulose-based nanoaggregates were assembled from xylan-rich hemicellulose laurate methacrylate (XH-LA-MA) polymers and entrapped into the hydrogel framework via chemical fixation. Another composite hydrogel with physically embedded hemicellulose laurate (XH-LA) nanoaggregates was prepared as a comparison. Accordingly, covalently cross-linked XH-LA-MA nanoaggregates in hydrogels resulted in a denser pore structure and reinforced mechanical properties. Nanoaggregate diffusion analysis revealed that covalent bonding between the nanoaggregates and the hydrogel framework contributed to prolonged diffusion behavior. Curcumin (Cur)-loaded XH-LA-MA composite hydrogels enabled sustained Cur release in simulated body fluid and showed stimulus responsiveness toward ethylenediaminetetraacetic acid (EDTA) and/or glutathione (GSH). All the composite hydrogels were biocompatible, as verified by Cell Counting Kit-8 (CCK-8) assay against NIH/3T3 cells. These composite hydrogels hold great potential as a promising dosage form for biomedical applications., 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 © 2024 Elsevier B.V. All rights reserved.)

Selective fractionation of hemicelluloses is of great significance for realizing high-value application of hemicelluloses and comprehensive utilization of lignocellulosic biomass. Tetramethylammonium hydroxide (TMAH) solvent has been confirmed as a promising solvent to selectively fractionate hemicelluloses from holocellulose. Herein, TMAH solvent was adopted to pretreat poplar thermomechanical pulp (PTMP) for the selective fractionation of hemicelluloses and enhancement of enzymatic hydrolysis performance of residues. The maximal hemicelluloses yield (65.0 %) and excellent cellulose retention rate (93.3 %) were achieved after pretreatment by the 25 wt% TMAH solvent, while the delignification was only 33.9 %. The hemicelluloses fractions could be selectively fractionated with high molecular weights (109,800-118,500 g/mol), the contents of Klason lignin in them were low (3.2-5.9 %), and the dominating structure of them was 4-O-methylglucurono-β-D-xylan. Compared to the H 2 SO 4 and NaOH methods, the hemicelluloses fractionated by TMAH method exhibited higher yields, more complete structures and higher molecular weights. Furthermore, the crystalline structure of cellulose practically remained stable, and the highest yield of enzymatic hydrolysis glucose was 57.5 %, which was 3.3 times of that of PTMP. The fractionation effectiveness of TMAH solvent was not significantly reduced after repeatedly recycling. This work demonstrated TMAH solvent could selectively fractionate hemicelluloses from PTMP and efficiently promote sustainable poplar-based biorefinery., 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 © 2023 Elsevier B.V. All rights reserved.)

It is believed that hemicellulose plays a crucial role in binding cellulose and lignin in plant cells. It may provide significant implications through figuring out the interaction between hemicellulose and microfibers and gaining insights how the structure of hemicellulose affects its association with cellulose nanofibers. Herein, the hemicellulose and nanocellulose fractions from pulps obtained by controlling the H-factors of kraft pulping process were quantitatively evaluated for their adsorption behavior using QCM-D. The results showed that harsher cooking (corresponding to high H-factor) significantly affected the chemical composition of hemicellulose, leading to a decrease of its molecular weight and gradually turning it into a linear structure. Hemicellulose possesses a strong natural affinity for CNC-coated sensors. The hemicellulose from the pulp cooked by high H-factor process decreases its ability to adsorb onto nanocellulose, the adsorption rate also slows down, and the conformation of the adsorbed layer changes which makes the binding weak and reversible. In conclusion, the pulping process in high H-factor significantly changed the structure of hemicellulose, leading to a variation in the strength of its interaction with nanocellulose., 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 © 2024 Elsevier B.V. All rights reserved.)

In this work, we investigate a multicomponent synthetic method for combining saccharides with cellulose to produce saccharide branched cellulose (b-Cel). First, cellulose is modified conventionally using carboxymethyl to create carboxyl functional groups for multicomponent reactions. The Passerini three-component reaction (Passerini-3CR) is then used to synthesize the saccharide b-Cel, with particular attention paid to the scope of the substrate and reaction process optimization. The structure of saccharide b-Cel is regulated by modifying the carboxyl group of cellulose molecules, the kind of saccharide molecules (including glucose, galactose, lactose, cellobiose, and cellulose), and the degree of branching. The branched structure of saccharide b-Cel greatly influenced its rheological characteristics and solubility. This work presents a practical method for the synthesis of artificial branching polysaccharides and is crucial for the development of innovative materials based on biomass., 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 © 2023 Elsevier B.V. All rights reserved.)

Hemicellulose extracted from ecalyptus APMP pulping waste liquor and undergoes etherification modification to produce carboxymethyl hemicellulose (CMHC). Subsequently, CMHC undergoes esterification reaction with p-hydroxybenzoic acid to synthesize a novel polysaccharide-based preservative known as carboxymethyl hemicellulose p-hydroxybenzoate (P-CMHC). The synthesis conditions of P-CMHC were optimized using the response surface methodology, resulting in an optimal esterification condition that achieved a degree of substitution of 0.232. P-CMHC exhibits excellent antioxidant activity, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radical scavenging activities. Additionally, it demonstrates favorable hygroscopic and moisturizing properties. Thiazole blue (MTT) experiments evaluating cell proliferation rate indicate that P-CMHC possesses negligible cytotoxicity, making it a promising, safe, and healthy preservative. Consequently, it can be considered as a new material for applications in the fields of biomedicine, food, and cosmetics., Competing Interests: Declaration of competing interest We wish to draw the attention of the Editor to the following facts which may be considered as potential conflicts of interest and to significant financial contributions to this work. We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us. We confirm that we have given due consideration to the protection of intellectual property associated with this work and that there are no impediments to publication, including the timing of publication, with respect to intellectual property. In so doing we confirm that we have followed the regulations of our institutions concerning intellectual property., (Copyright © 2023. Published by Elsevier Ltd.)

Polysaccharides, due to their remarkable features, have gained significant prominence in the sustainable production of nanoparticles (NPs). High market demand and minimal production cost, compared to the chemically synthesised NPs, demonstrate a drive towards polysaccharide-based nanoparticles (PSNPs) benign to environment. Various approaches are used for the synthesis of PSNPs including cross-linking, polyelectrolyte complexation, and self-assembly. PSNPs have the potential to replace a wide diversity of chemical-based agents within the food, health, medical and pharmacy sectors. Nevertheless, the considerable challenges associated with optimising the characteristics of PSNPs to meet specific targeting applications are of utmost importance. This review provides a detailed compilation of recent accomplishments in the synthesis of PSNPs, the fundamental principles and critical factors that govern their rational fabrication, as well as various characterisation techniques. Noteworthy, the multiple use of PSNPs in different disciplines such as biomedical, cosmetics agrochemicals, energy storage, water detoxification, and food-related realms, is accounted in detail. Insights into the toxicological impacts of the PSNPs and their possible risks to human health are addressed, and efforts made in terms of PSNPs development and optimising strategies that allow for enhanced delivery are highlighted. Finally, limitations, potential drawbacks, market diffusion, economic viability and future possibilities for PSNPs to achieve widespread commercial use are also discussed., 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 © 2023 Elsevier B.V. All rights reserved.)

The anisotropic features play indispensable roles in regulating various life activities in different organisms. Increasing efforts have been made to learn and mimic various tissues' intrinsic anisotropic structure or functionality for broad applications in different areas, especially in biomedicine and pharmacy. This paper discusses the strategies for fabricating biomaterials using biopolymers for biomedical applications with the case study analysis. Biopolymers, including different polysaccharides, proteins, and their derivates, that have been confirmed with sound biocompatibility for different biomedical applications are summarized, with a special focus on nanocellulose. Advanced analytical techniques for understanding and characterizing the biopolymer-based anisotropic structures for various biomedical applications are also summarized. Challenges still exist in precisely constructing biopolymers-based biomaterials with anisotropic structures from molecular to macroscopic levels and fitting the dynamic processes in native tissue. It is foreseeable that with the advancement of biopolymers' molecular functionalization, biopolymer building block orientation manipulation strategies, and structural characterization techniques, developing anisotropic biopolymer-based biomaterials for different biomedical applications would significantly contribute to a friendly disease-curing and healthcare experience., 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 © 2023 Elsevier Ltd. All rights reserved.)

To comprehend the biosynthesis processes of conifers, it is essential to investigate the disparity between the cell wall shape and the interior chemical structures of polymers throughout the development of Chinese pine. In this study, branches of mature Chinese pine were separated according to their growth time (2, 4, 6, 8 and 10 years). The variation of cell wall morphology and lignin distribution was comprehensively monitored by scanning electron microscopy (SEM) and confocal Raman microscopy (CRM), respectively. Moreover, the chemical structures of lignin and alkali-extracted hemicelluloses were extensively characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The thickness of latewood cell walls increased steadily from 1.29 μm to 3.38 μm, and the structure of the cell wall components became more complicated as the growth time increased. Based on the structural analysis, it was found that the content of β-O-4 (39.88-45.44/100 Ar), β-β (3.20-10.02/100 Ar) and β-5 (8.09-15.35/100 Ar) linkages as well as the degree of polymerization of lignin increased with the growth time. The complication propensity increased significantly over 6 years before slowing to a trickle over 8 and 10 years. Furthermore, alkali-extracted hemicelluloses of Chinese pine mainly consist of galactoglucomannans and arabinoglucuronxylan, in which the relative content of galactoglucomannans increased with the growth of the pine, especially from 6 to 10 years., 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 © 2023 Elsevier B.V. All rights reserved.)

Modifying natural polymers with silicones gives new possibilities for packaging products and waste management. In this study, the innovative papers produced were altered following the reaction of polysaccharides and organosilicon compounds. The susceptibility of the studied material to biodegradation caused by a brown-rot fungus was assessed. Strength properties by tensile strength and dynamic mechanical analysis and hydrophobic properties by water uptake test and water contact angle analysis were evaluated. Moreover, elemental analysis by ICP method was controlled. The durability against fungi and the hydrophobic properties were increased by the modification. The fungal decay resistance of the silanized paper was reduced by water storage, which allows for managing paper waste. Cellulose-based paper treated with starch-modified methyltrimethoxysilane showed potential as a packaging material due to its reduced water uptake. Possible application areas could be corrugated boxes, cellulose thermoformed products for electronics, and food packaging. However, the water-repellent effect is limited to short-term exposure in humid conditions., 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 © 2023 Elsevier Ltd. All rights reserved.)

MXene-based structural materials with high mechanical robustness and excellent electrical conductivity are highly desirable for multifunctional applications. The incorporation of macromolecular polymers has been verified to be beneficial to alleviate the mechanical brittleness of pristine MXene films. However, the intercalation of a large amount of insulating macromolecules inevitably compromises their electrical conductivity. Inspired by wood, short-chained hemicellulose (xylo-oligosaccharide) acts as a molecular binder to bind adjacent MXene nanosheets together; this work shows that this can significantly enhance the mechanical properties without introducing a large number of insulating phases. As a result, MXene-hemicellulose films can integrate a high electrical conductivity (64,300 S m -1 ) and a high mechanical strength (125 MPa) simultaneously, making them capable of being high-performance electrode materials for supercapacitors and humidity sensors. This work proposes an alternative method to manufacture robust MXene-based structural materials for multifunctional applications.

Super adsorbents exhibit great potential to remove pollutants from media or store considerable amounts of water, which may undermine the pressure triggered by environmental pollution and shortage of water resources. Super adsorbents made from biopolymers have been an attractive topic because of biodegradability, renewability and outstanding adsorption capacity. Hemicelluloses are a type of biopolymers very abundant in agricultural, forestry and pulping industrial wastes. Hemicellulose-based bio-adsorbents are thriving because the inherent chemical structures and physical properties of hemicelluloses make themselves easy to be processed into matrix materials applicable in super adsorbents. This review summarizes recent studies in hemicellulose-based bio-adsorbents, i.e. hydrogels and activated carbons, from the perspectives of types, applications, fabrication methods, the elements affecting the adsorption performance and the kinetics of adsorption process, which thus helps to further improve the properties of hemicellulose-based bio-adsorbents and to promote the industrial production and utilization of hemicelluloses and hemicellulose-based bio-adsorbents., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In this work, we study interactions of five different hemicellulose models, i.e. Galactoglucomannan, O-Acetyl-Galactoglucomannan, Fuco-Galacto-Xyloglucan, 4-O-Methylglucuronoxylan, and 4-O-Methylglucuronoarabinoxylan, and their respective binding strength to cellulose nanocrystals by molecular dynamics simulations. Glucuronoarabinoxylan showed the highest free energy of binding, whereas Xyloglucan had the lowest interaction energies amongst the five models. We further performed simulated shear tests and concluded that failure mostly happens at the inter-molecular interaction level within the hemicellulose fraction, rather than at the interface with cellulose. The presence of water molecules seems to have a weakening effect on the interactions of hemicellulose and cellulose, taking up the available hydroxyl groups on the surface of the cellulose for hydrogen bonding. We believe that these studies can shed light on better understanding of plant cell walls, as well as providing evidence on variability of the structures of different plant sources for extractions, purification, and operation of biorefineries., (Copyright © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

γ-Valerolactone (GVL), a biomass-derived green chemical, offers an environmentally responsible solvent for conversion of lignocellulose to high value-added chemicals. Herein, we report a two-step process for directly producing cellulosic residual, furfural and lignin from Miscanthus × giganteus (M. × giganteus) bypassing the isolation of xylose, which exhibits promising advantage in energy reduction. The optimized pretreatment (100 mM FeCl 3 at 160 °C for 60 min) induced significant xylan removal (98.4%), resulting in rugged fibre surface, thus leading to the peak cellulose conversion of 99.3%. Furfural yield in the second step reached to 76.6% after 100 mM FeCl 3 catalyzed GVL/H 2 O treatment at 180 °C for 10 min without addition of any chemical. The extracted lignin showed representative structure (such as β-O-4', β-β' linkages) and medium molecular weight (4275.5 g/mol). 79.6% of furfural can be recovered by distillation. This study proposes a systematic and energy efficient approach for maximizing biomass utilization., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The transformation of modern industries towards enhanced sustainability is facilitated by green technologies that rely extensively on rare earth elements (REEs) such as cerium (Ce), neodymium (Nd), terbium (Tb), and lanthanum (La). The occurrence of productive mining sites, e.g., is limited, and production is often costly and environmentally harmful. As a consequence of increased utilization, REEs enter our ecosystem as industrial process water or wastewater and become highly diluted. Once diluted, they can hardly be recovered by conventional techniques, but using cyanobacterial biomass in a biosorption-based process is a promising eco-friendly approach. Cyanobacteria can produce extracellular polymeric substances (EPS) that show high affinity to metal cations. However, the adsorption of REEs by EPS has not been part of extensive research. Thus, we evaluated the role of EPS in the biosorption of Ce, Nd, Tb, and La for three terrestrial, heterocystous cyanobacterial strains. We cultivated them under N-limited and non-limited conditions and extracted their EPS for compositional analyses. Subsequently, we investigated the metal uptake of a) the extracted EPS, b) the biomass extracted from EPS, and c) the intact biomass with EPS by comparing the amount of sorbed REEs. Maximum adsorption capacities for the tested REEs of extracted EPS were 123.9–138.2 mg g−1 for Komarekiella sp. 89.12, 133.1–137.4 mg g−1 for Desmonostoc muscorum 90.03, and 103.5–129.3 mg g−1 for Nostoc sp. 20.02. A comparison of extracted biomass with intact biomass showed that 16% (Komarekiella sp. 89.12), 28% (Desmonostoc muscorum 90.03), and 41% (Nostoc sp. 20.02) of REE adsorption was due to the biosorption of the extracellular EPS. The glucose- rich EPS (15%–43% relative concentration) of all three strains grown under nitrogen-limited conditions showed significantly higher biosorption rates for all REEs. We also found a significantly higher maximum adsorption capacity of all REEs for the extracted EPS compared to cells without EPS and untreated biomass, highlighting the important role of the EPS as a binding site for REEs in the biosorption process. EPS from cyanobacteria could thus be used as efficient biosorbents in future applications for REE recycling, e.g., industrial process water and wastewater streams.