Highly Bioadaptive Scaffolds with Tuned Porous Structure Templated by Xylan Nanocrystal High Internal Phase Pickering Emulsions.

Fabrication of traditional 3D cell culturing scaffolds requires synthetic polymers or additives, posing a risk of poor biocompatibility and low biodegradability. Pickering emulsions stabilized by biobased nanomaterials can be used as templates to produce scaffolds with facile tunable porous structure, excellent cytocompatibility, and biodegradability. In this study, very stable high internal phase Pickering emulsions (HIPPE) with an oil content of 80% were successfully prepared by xylan hydrate nanocrystals (XNC). The HIPPE can exist stably for more than 30 days, exhibiting a high viscosity. By adding cellulose nanofibers (CNF) and removing the oil phase, scaffolds with a tuned porous structure and enhanced cell culturing ability were successfully fabricated. In the HIPPE templated scaffolds with XNC/CNF, XNC plays a major role in stabilizing the emulsions, while CNF improves the mechanical properties of the scaffolds, both of which are vital to the successful fabrication of the scaffolds. Compared with non-HIPPE templated scaffolds, the HIPPE templated scaffold had a higher porosity and a higher median pore size. The HIPPE templated scaffold was able to maintain 80% cell activity and showed an excellent cytocompatibility. The HIPPE templated scaffolds consisting of XNC and CNF demonstrate great potential in 3D cell culturing for medical purpose.

Significantly improve film formability of acetylated xylans by structure optimization and solvent screening.

Acetylated xylans have great potential in fabricating functional film and coating materials, which need a good solubility/dispersibility and film formability in an easily evaporable solvent. However, the changes of film formability with degree of substitution by acetyls (DSAc) in different solvent systems for xylans have not been extensively studied, which limit the application of acetylated xylans in film materials. In this study, acetylated xylans with DSAc of 0-2 were prepared and the effects of acetyl groups on solubility/dispersibility, crystallinity and film formability of xylans in water and chloroform solvent systems were investigated. Due to the change of polarity, xylans with DSAc of 0-0.62 are only soluble in water solvents, while xylans with DSAc of 1.13-2 are only soluble in chloroform/ethanol (70/30 v/v) organic solvents. We have found that the film formability of acetylated xylans is highly related to their solubility and crystallization. Film formable xylans all had good solubility in the cast solvents. However, although with good solubility, xylans with DSAc of 0-0.3 and DSAc of 1.76-2 cannot form intact films, which is due to the forming of xylan hydrate crystals and xylan diacetate crystals. With the increase of DSAc, the mechanical property of xylan film increases initially at low DSAc and decreases at high DSAc. This study provides theoretical basis for applying xylans and their derivatives in advanced functional film and coating materials with great biocompatibility and biodegradability.

The molecular structure, vibrational spectra, solvation effect, non-covalent interactions investigations of psilocin.

Psilocin, or 4-HO-DMT (or 3-(2-dimethylaminoethyl)-1H-indol-4-ol), is a psychoactive alkaloid substance from the tryptamine family, isolated from Psilocybe mushrooms. This substance is being studied by various research groups because it has a clear therapeutic effect in certain dosages. In this work, the study of the structure and properties of psilocin was carried using theoretical methods: the effects of polar solvents (acetonitrile, dimethylsulfoxide, water, and tetrahydrofuran) on the structural parameters, spectroscopic properties (Raman, IR, and UV-Vis), frontier molecular orbital (FMO), molecular electrostatic potential (MEP) surface, and nonlinear optical parameters (NLO). Theoretical calculations were performed at the B3LYP/6-311++G(d,p) level by the density functional theory (DFT) method. IEFPCM was used to account for solvent effects. The types and nature of non-covalent interactions (NCI) between psilocin and solvent molecules were determined using Atoms in Molecules (AIM), the reduced density gradient method (RDG), the electron localization function (ELF), and the localization orbital locator (LOL). Experimental and calculated FT-IR, FT-Raman, and UV-Vis spectra were compared and found to be in good agreement.

Efficient one-pot synthesis of 5-chloromethylfurfural (CMF) from carbohydrates in mild biphasic systems.

5-Halomethylfurfurals can be considered as platform chemicals of high reactivity making them useful for the preparation of a variety of important compounds. In this study, a one-pot route for the conversion of carbohydrates into 5-chloromethylfurfural (CMF) in a simple and efficient (HCl-H3PO4/CHCl3) biphasic system has been investigated. Monosaccharides such as D-fructose, D-glucose and sorbose, disaccharides such as sucrose and cellobiose and polysaccharides such as cellulose were successfully converted into CMF in satisfactory yields under mild conditions. Our data shows that when using D-fructose the optimum yield of CMF was about 47%. This understanding allowed us to extent our work to biomaterials, such as wood powder and wood pulps with yields of CMF obtained being comparable to those seen with some of the enumerated mono and disaccharides. Overall, the proposed (HCl-H3PO4/CHCl3) optimized biphasic system provides a simple, mild, and cost-effective means to prepare CMF from renewable resources.

Structural elucidation of hemicelluloses from oil-tea camellia fruit shell.

Oil-tea camellia fruit shell (CFS) is a very abundant waste lignocellulosic resource. The current treatments of CFS, i.e. composting and burning, pose a severe threat on environment. Up to 50 % of the dry mass of CFS is composed of hemicelluloses. However, chemical structures of the hemicelluloses in CFS have not been extensively studied, which limits their high-value utilization. In this study, different types of hemicelluloses were isolated from CFS through alkali fractionation with the assistance of Ba(OH)2 and H3BO3. Xylan, galacto-glucomannan and xyloglucan were found to be the major hemicelluloses in CFS. Through methylation, HSQC and HMBC analyses, we have found that the xylan in CFS is composed of →4)-ß-D-Xylp-(1→ and →3,4)-ß-D-Xylp-(1→ linked by (1→4)-ß glycosidic bond as the main chain; the side chains are α-L-Fucp-(1→, →5)-α-L-Araf-(1→, ß-D-Xylp-(1→, α-L-Rhap-(1→ and 4-O-Me-α-D-GlcpA-(1→, connected to the main chain through (1→3) glycosidic bond. The main chain of galacto-glucomannan in CFS consists of →6)-ß-D-Glcp-(1→, →4)-ß-D-Glcp-(1→, →4,6)-ß-D-Glcp-(1→ and →4)-ß-D-Manp-(1→; the side chains are ß-D-Glcp-(1→, →2)-ß-D-Galp-(1→, ß-D-Manp-(1→ and →6)-ß-D-Galp-(1→ connected to the main chain through (1→6) glycosidic bonds. Moreover, galactose residues are connected by α-L-Fucp-(1→. The main chain of xyloglucan is composed of →4)-ß-D-Glcp-(1→, →4,6)-ß-D-Glcp-(1→ and →6)-ß-D-Glcp-(1→; the side groups, i.e. ß-D-Xylp-(1→ and →4)-ß-D-Xylp-(1→, are connected to the main chain by (1→6) glycosidic bond; →2)-ß-D-Galp-(1→ and α-L-Fucp-(1→ can also connect to →4)-ß-D-Xylp-(1→ forming di- or trisaccharide side chains.

Characterization of hemicellulose in Cunninghamia lanceolata stem during xylogenesis.

In this study, hemicellulose was isolated from the apical, middle and basal segments of C. lanceolata stem to investigate the dynamic change of its structure during xylogenesis. Results showed that the C. lanceolata hemicellulose is mainly consisted of O-acetylgalactoglucomannan (GGM) which backbone is alternately linked by ß-d-mannopyranosyl (Manp) and ß-d-glucopyranosyl (Glcp) via (1 â†’ 4)-glycosidic bond, while the side chains are α-d-galactopyranosyl (Galp) and acetyl. In addition, 4-O-methylglucuronoarabinoxylan (GAX) is another dominant structure of C. lanceolata hemicellulose which contains a linear backbone of (1 â†’ 4)-ß-d-xylopyranosyl (Xylp) and side chains of 4-O-Me-α-d-glucuronic acid (MeGlcpA) and α-L-arabinofuranose (Araf). The thickness of the cell wall, the ratio of GGM/GAX and the molecular weight of hemicellulose were increased as the extension of growth time. The degree of glycosyl substitutions of xylan and mannan was decreased from 10.34 % (apical) to 8.38 % (basal) and from 15.63 % (apical) to 10.49 % (basal), respectively. However, the total degree of acetylation was enhanced from 0.28 (apical) to 0.37 (basal). Transcriptome analysis showed that genes (CSLA9, IRX9H1, IRX10L, IRX15L, GMGT1, TBL19, TBL25, GUX2, GUX3, GXM1, F8H1 and F8H2) related to hemicellulose biosynthesis are mainly expressed in mature part. This study is of great significance for genetic breeding and high-value utilization of C. lanceolata.

Advances in green materials derived from wood for detecting and removing mercury ions in water.

The issue of mercury pollution in environmental remediation has garnered significant attention due to its severe health hazards to humans. Various strategies have been devised to mitigate the impact of toxic mercury ions, including coagulation, ion exchange, adsorption, membrane technology, and electrochemical treatment. Among these approaches, adsorption has emerged as an efficient and widely employed method for the uptake of low concentrations of mercury ions. It offers convenient operation, high removal efficiency, and facile regeneration of the adsorbent. Wood, being the most abundant renewable and sustainable bioresource, has garnered attention as a promising material for treating heavy metal wastewater. This is attributed to its unique physical and chemical characteristics, encompassing hierarchical pores, aligned channels, active functional groups, biodegradability, and cost-effectiveness. However, a comprehensive examination of the cutting-edge applications of wood and wood-derived biopolymers in the detection and removal of mercury ions from wastewater has yet to be undertaken. Consequently, this article presents a chronological overview of recent advancements in materials and structures derived from bulk wood and its constituents, including cellulose, lignin, hemicellulose, and tannin, with a specific focus on their utility in detecting and eliminating mercury from water sources. Subsequently, the most promising techniques and strategies involving wood and wood-derived biopolymers in addressing the predicament of mercury pollution are explored. Furthermore, this piece offers insights into the existing challenges and future prospects concerning environmentally friendly materials derived from wood, aiming to foster the development of cost-effective mercury adsorbents and detection devices.

Influence of formic acid esterified cellulose nanofibrils on compressive strength, resilience and thermal stability of polyvinyl alcohol-xylan hydrogel.

Having competitive compressive strength and resilience as well as biocompatibility simultaneously still remains a challenge for composite hydrogels, which is critical if they are aimed for use as functional biomaterials. In the present work, a facile and green method was designed for producing a composite hydrogel based on polyvinyl alcohol (PVA) and xylan with sodium tri-metaphosphate (STMP) as cross-linker, aiming to specially enhance its compressive properties with the aid of eco-friendly produced formic acid esterified cellulose nanofibrils (CNFs). The CNF addition caused a compressive strength decrease of the hydrogels, although the values (2.34-4.57 MPa at a compressive strain of 70 %) were still at a high level among the reported PVA (or polysaccharide) based hydrogels so far. However, the compressive resilience of the hydrogels was enhanced significantly by the CNF addition, with maximal compressive strength retention of 88.49 % and 99.67 % in height recovery after 1000 compression cycles at a strain of 30 %, which reflects the significant influence of CNFs on the compressive recovery ability of the hydrogel. All materials used in the present work are naturally non-toxic with good biocompatible, which makes the synthesized hydrogels with great potential in biomedical applications, e.g., soft-tissue engineering.

Freeze-casting production of thermal insulating and fire-retardant lightweight aerogels based on nanocellulose and boron nitride.

Cellulose aerogels exhibit biocompatibility and biodegradability, rendering them promising candidate for application in building energy conservation and insulation materials. However, the intrinsic inflammability of pristine cellulose aerogel causes unneglectable safety concerns, hindering their application in energy-efficient buildings. Herein, a thermal insulating, fire-retardant, strong, and lightweight aerogel was produced via freeze-casting suspensions of cellulose nanofibril (CNF) and l-glutamine functionalized boron nitride nanosheets (BNNS-g). The aerogel with a BNNS-g:CNF concentration ratio of 15:5 exhibited outstanding mechanical strength owing to the strong interaction between BNNS-g and CNF as well as satisfactory thermal insulating performance (0.052 W/m·K). Particularly, this aerogel showed excellent fire-retardant and self-extinguishing capabilities in the vertical burning test, which remained unscathed after over 60 s of burning in a butane flame. Further, the limit oxygen index (LOI) of this aerogel was 36.0 %, which was better than the LOIs of traditional petrochemical-based insulating materials. This study provides a promising strategy for producing aerogels with excellent properties using cellulose and other inorganic nano-fillers.

Fabrications and applications of hemicellulose-based bio-adsorbents.

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.

An environment-friendly dip-catalyst with xylan-based catalytic paper coatings.

Replacing catalyst supports with sustainable and degradable materials is an urgent task. Xylan is a type of abundant natural polymers with potential applications in dispersing, anchoring, and coating materials, but its material values have always been underestimated. In this study, polyethyleneimine modified dialdehyde xylan (DAX-PEI) was used as a dispersing and anchoring agent to bind Pd nanoparticles onto paper surface to produce a DAX-PEI-Pd coated paper, which was used to catalyze Suzuki-Miyaura reactions. The catalytic coated paper exhibited a good catalytic activity with a yield of 91% and a high turnover frequency (TOF) of 3300 h-1. Besides, it showed an excellent recyclability with the same catalytic coated paper being used 15 times and still having a yield of nearly 90%. This environment-friendly catalytic coated paper owns its great prospect in organic synthesis.

Supercritical CO2 Assisted TiO2 Preparation to Improve the UV Resistance Properties of Cotton Fiber.

Cotton fiber is favored by people because of its good moisture absorption, heat preservation, soft feel, comfortable wearing and other excellent performance. In recent years, due to the destruction of the ozone layer, the intensity of ultraviolet radiation at ground level has increased. Cotton fiber will degrade under long time ultraviolet irradiation, which limits the outdoor application of cotton fiber. In this study, titanium dioxide (TiO2) particles were prepared on the surface of cotton fibers with the help of supercritical carbon dioxide (SCCO2) to improve the UV resistance of cotton fibers. The effects of SCCO2 treatment on the morphology, surface composition, thermal stability, photostability and mechanical properties of TiO2 were studied by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, thermogravimetric analysis, UV-VIS spectroscopy, and single fiber test. The results showed that TiO2 particles were generated on the fiber surface, which reduced the photo-degradation rate of cotton fiber. This is because TiO2 can absorb UV rays and reduce the absorption of UV rays by the cotton fiber itself. The synthesis process of SCCO2 is simple and environmentally friendly, which provides a promising technology for the synthesis of metal nitrogen dioxide on natural plant fibers.

Conductive Hydrogels Based on Industrial Lignin: Opportunities and Challenges.

The development of green materials, especially the preparation of high-performance conductive hydrogels from biodegradable biomass materials, is of great importance and has received worldwide attention. As an aromatic polymer found in many natural biomass resources, lignin has the advantage of being renewable, biodegradable, non-toxic, widely available, and inexpensive. The unique physicochemical properties of lignin, such as the presence of hydroxyl, carboxyl, and sulfonate groups, make it promising for use in composite conductive hydrogels. In this review, the source, structure, and reaction characteristics of industrial lignin are provided. Description of the preparation method (physical and chemical strategies) of lignin-based conductive hydrogel is elaborated along with their several important properties, such as electrical conductivity, mechanical properties, and porous structure. Furthermore, we provide insights into the latest research advances in industrial lignin conductive hydrogels, including biosensors, strain sensors, flexible energy storage devices, and other emerging applications. Finally, the prospects and challenges for the development of lignin-conductive hydrogels are presented.

A xylan assisted surface-enhanced Raman scattering substrate for rapid food safety detection.

Cellulose fiber/paper-based surface-enhanced Raman scattering (SERS) is considered as a promising food safety detection technology due to its non-toxicity, low cost, flexibility, and hygroscopicity for possible rapid on-site agricultural product contaminant detection. However, it faces the problems of poor noble metal adhesion and toxic noble metal reducing agent. In this study, a natural macromolecule-xylan was used as both a reducing agent and a stabilizing agent to prepare stable Au-Ag bimetal nanoparticles, which were anchored on the paper surface by xylans in order to fabricate a paper-based Au-Ag bimetallic SERS substrate. The results show that the SERS substrate has a high Raman enhancement performance and reproductively. The substrate can effectively detect trace pesticide, i.e., thiram, and the limit of detection is as low as 1 × 10-6 mol/L (0.24 ppm). In addition, the paper-based SERS substrate can be used for direct detection of pesticide residues on the surface of fruit. The paper-based SERS substrate developed in this study has great potential in applications for rapid food safety detection.

Emulsifying properties of naturally acetylated xylans and their application in lutein delivery emulsion.

Xylans play an important role in dispersing and lubricating cellulose fibrils in lignocellulosic plant cell walls. However, the effect of acetylation on the dispersing and emulsifying properties of xylan is still unclear. In this study, we show that the natural degree of acetylation is vital to ensure xylan an excellent water solubility and emulsifying ability. Alkali extracted xylans were artificially acetylated to degree of substitution (DSAc) between 0.12 and 2.00, while the DMSO extracted originally acetylated xylan (OAX) shows a DSAc of 0.18. Artificially acetylated xylans (AX) with DSAc value similar to OAX shows water solubility and emulsifying ability similar to those of OAX and the best among all the AX samples with different DSAc. They demonstrate excellent emulsifying properties with an emulsifying activity of ~1.3 and an emulsion cream index of ~5 %. AX with the natural DSAc value also demonstrates strong barrier effects in preparing lutein delivery emulsions.

Characterization of hemicellulose during xylogenesis in rare tree species Castanopsis hystrix.

Hemicellulose is an important component of the plant cell wall which vary in structure and composition between plant species. The research of hemicellulose structures is primarily focused on fast-growing plants during xylogenesis, with slow-growing and rare trees receiving the least attention. Here, hemicellulose structure of the rare species Castanopsis hystrix during xylogenesis was analyzed. Acetyl methyl glucuronide xylan was the most common type of hemicellulose in C. hystrix, with a unique tetrasaccharide structure at the reducing end. Hemicellulose type, structure, molecular weight, thermal stability, biosynthesis and acetyl substitution content and pattern remained stable during the xylogenesis in C. hystrix, which could be attributed to its slow growth. The stable polymer type, low side chain modification and high acetyl substitution of hemicellulose throughout the stems are among the reasons for the hardness and corrosion resistance properties of C. hystrix wood. Genetic modification can be used to improve these properties.

Sulfation of Wheat Straw Soda Lignin with Sulfamic Acid over Solid Catalysts.

Soda lignin is a by-product of the soda process for producing cellulose from grassy raw materials. Since a method for the industrial processing of lignin of this type is still lacking, several research teams have been working on solving this problem. We first propose a modification of soda lignin with sulfamic acid over solid catalysts. As solid catalysts for lignin sulfation, modified carbon catalysts (with acid sites) and titanium and aluminum oxides have been used. In the elemental analysis, it is shown that the maximum sulfur content (16.5 wt%) was obtained with the Sibunit-4® catalyst oxidized at 400 °C. The incorporation of a sulfate group has been proven by the elemental analysis and Fourier-transform infrared spectroscopy. The molecular weight distribution has been examined by gel permeation chromatography. It has been demonstrated that the solid catalysts used in the sulfation process causes hydrolysis reactions and reduces the molecular weight and polydispersity index. It has been established by the thermal analysis that sulfated lignin is thermally stabile at temperatures of up to 200 °C. According to the atomic force microscopy data, the surface of the investigated film consists of particles with an average size of 50 nm. The characteristics of the initial and sulfated ß-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

Highly Stable Pickering Emulsions with Xylan Hydrate Nanocrystals.

Xylan is a highly abundant plant-based biopolymer. Original xylans in plants are in an amorphous state, but deacetylated and low-branched xylan can form a crystalline structure with water molecules. The utilizations of xylan have been limited to bulk applications either with inconsistency and uncertainty or with extensive chemical derivatization due to the insufficient studies on its crystallization. The applications of xylan could be greatly broadened in advanced green materials if xylan crystals are effectively utilized. In this paper, we show a completely green production of nano-sized xylan crystals and propose their application in forming Pickering emulsions. The branches of xylan were regulated during the separation step to controllably induce the formation of xylan hydrate crystals. Xylan hydrate nanocrystals (XNCs) with a uniform size were successfully produced solely by a mild ultrasonic treatment. XNCs can be adsorbed onto oil-water interfaces at a high density to form highly stable Pickering emulsions. The emulsifying properties of XNCs were comparable to some synthetic emulsifiers and better than some other common biopolymer nanocrystals, demonstrating that XNCs have great potential in industrial emulsification.

Characterization of hemicellulose in Cassava (Manihot esculenta Crantz) stem during xylogenesis.

Cassava is one of the three major potato crops due to the high starch content in its tubers. Unlike most current studies on the utilization of cassava tubers, our research is mainly focused on the stem of cassava plant. Through nuclear magnetic resonance (NMR), fourier transform infrared spectrometer (FTIR) and other methods, we found that cassava stalk hemicellulose consists of ß-1,4 glycosidic bond-linked xylan backbone with a tetrasaccharide reducing end and decorated with methylated glucuronic acid, acetyl groups and a high degree of arabinose substitutions. Hemicellulose content gradually increased from the upper to the lower parts of the stem. The apical part of cassava stalk contained more branched and heterogeneous glycans than the middle and basal parts, and the molecular weight of hemicellulose increased from top to bottom. Our findings will be helpful in understanding of structural variations of cassava hemicellulose during xylogenesis, as well as in better utilization of cassava plant waste in industry.

Effective photocatalytic degradation and physical adsorption of methylene blue using cellulose/GO/TiO2 hydrogels.

Environmentally friendly cellulose/GO/TiO2 hydrogel photocatalyst has been successfully fabricated via a green, simple, and one-step method and evaluated as the photocatalyst and adsorbent for the removal of methylene blue (MB). The XRD and FTIR analysis suggested the strong interaction among cellulose, GO and TiO2, resulting from the formation of hydrogen bonds. Due to the unique porous structure of cellulose hydrogel and introduction of GO, the cellulose/GO/TiO2 hydrogel showed superior (degradation ratio ∼ 93%) and reproducible (no significant change during the ten consecutive cycles) performance in the removal of MB under UV light. Consequently, the prepared cellulose/GO/TiO2 hydrogel can be applied as an eco-friendly, high-performance, reproducible, and stable photocatalyst and adsorbent for the removal of MB. This green hydrogel is a promising candidate for dye wastewater treatment. Moreover, this work is expected to extend the scope of bio-templated synthesis of other nanomaterials for various applications.