Preparation and characterization of a novel high barrier mulching film with tunicate cellulose nanocrystals/sodium alginate/alkali lignin.

In this study, the base film (CSL) was prepared by blending tunicate cellulose nanocrystals (TCNCs) extracted from tunicate shells, with sodium alginate (SA) and alkali lignin (AL). Then, the mulching film (CSL-WK) was prepared using water-borne polyurethane (WPU) as binder to install low-energy Kaolin on the surface of CSL film. The influences of composition with different concentrations on mechanical properties were studied. The tensile strength and elongation at break of CSL-WK film could reach 86.58 MPa and 50.49 %, respectively. The mulching films were characterized by degradability test, SEM, FTIR, and TGA. TCNCs had good compatibility with SA and AL, and a rough structure was formed on the surface of the film to improve the hydrophobicity. The barrier properties, including ultraviolet resistance, water contact angle, water vapor permeability, water retention, and flame retardancy, were tested. The results showed that CSL-WK films could block 97 % of ultraviolet light, reduce about 25 % of soil water loss, and self-extinguish within 7 s of open flame ignition. Note that the secondary spraying method significantly improved the barrier property of films. This study lays a foundation for the preparation of ecologically friendly, biodegradable, and high barrier mulching film, and expands the application of marine resources.

Preparation of light-colored bio-based particles by isocyanate-modified lignins and its application for tetracycline adsorption.

A practical method for the preparation of lignin derivatives-light-colored bio-based particles (LC-BP) via the modification of hexamethylene diisocyanate (HDI) is presented in this work. In the mixed EtOH/H2O system, the change of solvent polarity induced the self-assembly of the lignosulfonate (LS) with the hydrophobic chromophores encapsulated inside the particles. The color of LS was reduced by the polymerization between the isocyanate groups (-N=C=O) of HDI and hydroxy groups of LS. Compared with the typical lignin-based adsorbent preparation process in the past, this is a simple, direct, and efficient preparation method and the synthetic LC-BP has good chemical stability and resistance to heat, acid and alkali. This effectively solves the problem that LS has high water solubility and is difficult to use directly for wastewater treatment. To investigate the properties, the synthetic LC-BP was characterized by SEM, specific surface area, L*a*b* (CIELAB) color space, FT-IR, XPS, and TGA. The results showed that the LC-BP exhibited obvious advantages in color reduction with a low CIE-L* value. The LC-BP exhibits a scale-like intercalation structure, which makes it a promising candidate for adsorbing tetracycline (TC) from wastewater. The conditions of pH, adsorbent dosages, adsorption time, and initial TC concentration were investigated, and the adsorption performance of LC-BP for TC was significantly better than that of conventional polyurethane particles (PP). The adsorption fitted the Langmuir model and there were hydrogen bonding, π-π conjugated binding, and electrostatic attraction during the absorption process. The adsorption capacity was up to 53.1 mg/g, and the removal rate was 67 %. The utilization of LC-BP, a low-cost, effective, and renewable resource derived from natural biomass, holds immense practical and economic potential in wastewater treatment.

Dual-emitting cellulose nanocrystal hybrid materials with circularly polarized luminescence for anti-counterfeiting labels.

Cellulose nanocrystal (CNC) hybrid materials with numerous optical states have great potential as anti-counterfeiting labels and information encryption materials. However, it is challenging to construct multicolor emitting materials with tunable behaviors, which can dramatically enhance anti-counterfeiting abilities. Here, free-standing composite films with vivid multi-structural colors and dual-emitting fluorescence are successfully fabricated through a host-guest coassembly strategy. The lanthanide complex and an aggregation-induced emission molecule (tetraphenylethylene derivative, TPEC) are selected as luminescent guests, which are integrated into the chiral nematic structure of CNCs. The obtained photonic films display broadband reflection across the visible spectrum, which may be attributed to the chiral nematic domains with variations in the helical pitches and helical axis orientations. Under 254 nm excitation, the film exhibits bright red emission, while blue-green emission switching occurs under 365 nm excitation. The broad reflection band of the film covers both the green and red fluorescent emission centers, and right circularly polarized luminescence emission with different dissymmetry factors is produced due to the selective reflection of the left chiral nematic structure. A large glum value up to -0.21 at 600 nm was realized. Additionally, CNC-based materials with tailored shapes are further used in anti-counterfeit tags and decorative applications.

Study on cellulose nanofibers/aramid fibers lithium-ion battery separators by the heterogeneous preparation method.

In this study, a heat-resistant and high-wettability lithium-ion batteries separator (PI-CPM-PI) composed of cellulose nanofibers (CNF) and aramid fibers (PMIA chopped fiber/PPTA pulp) with the reinforced concrete structure was fabricated via a traditional heterogeneous paper-making process. CNF played crucial roles in optimizing the pore structure and improving the wettability of PI-CPM-PI separator. The effects of composition on separator properties were investigated and the results indicated that the optimal compositions were 0.5 wt% CNF, 0.5 wt% PMIA chopped fiber/PPTA pulp (ratio of 5:5), 0.05 wt% diatomite and 1.5 wt% polyimide. Relevant tests demonstrated that the performance advantages of PI-CPM-PI separators were exhibited at the wettability and thermal stability compared to the commercial separator (PP). Additionally, batteries assembled with PI-CPM-PI separators showed excellent electrochemical and cycling performance (ionic conductivity of 1.041 mS.cm-1, the first discharge capacity of 158.2 mAh.g-1 at 0.2C and capacity retention ratio of 99.76 % after 100 cycles).

In-situ lignin sulfonation for enhancing enzymatic hydrolysis of poplar using mild organic solvent pretreatment.

Biomass pretreatment is an essential strategy to overcome biomass recalcitrance and promote lignocellulosic bioconversion. Here, a reusable organic solvent system (formic acid-methanesulfonic acid) was explored to pretreat poplar under a mild temperature (below 100 °C). The results showed that the co-solvent system could extract basically complete hemicelluloses and part of lignin with original cellulose retained in the pretreated substrates. Meanwhile, sulfonic acid groups were introduced into lignin structure remained in the substrates. The glucose conversion yield of the substrates with a higher concentration of sulfonic acid groups (13.2 mmol/kg) reached 45.9 % by reducing the hydrophobic interaction between lignin and cellulase, showing 89.3 % improvement compared with that of the substrates treated with single formic acid. This progressive study aimed to develop a new strategy to realize sulfonation and promote enzymatic hydrolysis of substrates by using mild organic solvent pretreatment.

Bilayer Designed Paper-Based Solar Evaporator for Efficient Seawater Desalination.

Solar desalination devices utilizing sustainable solar energy and the abundant resource of seawater has great potential as a response to global freshwater scarcity. Herein, a bilayered solar evaporator was designed and fabricated utilizing a facile paper sheet forming technology, which was composed of cellulose fibers decorated with Fe3O4 nanoparticles as the top absorbent layer and the original cellulose fibers as the bottom supporting substrate. The characterization of the cellulose fibers decorated with Fe3O4 nanoparticles revealed that the in situ formed Fe3O4 nanoparticles were successfully loaded on the fiber surface and presented a unique rough surface, endowing the absorber layer with highly efficient light absorption and photothermal conversion. Moreover, due to its superhydrophilic property, the cellulose fiber-based bottom substrate conferred ultra-speed water transport capability, which could enable an adequate water supply to combat the water loss caused by continuous evaporation on the top layer. With the advantages mentioned above, our designed bilayered paper-based evaporator achieved an evaporation rate ~1.22 kg m-2 h-1 within 10 min under 1 sun irradiation, which was much higher than that of original cellulose cardboard. Based on the simple and scalable manufacture process, the bilayered paper-based evaporator may have great potential as a highly efficient photothermal conversion material for real-world desalination applications.

Sustainable and hydrophobic polysaccharide-based mulch film with thermally stable and ultraviolet resistance performance.

This work aimed to construct a polysaccharide-based mulch film with good performance for replacing plastic mulch by coating the glutaraldehyde crosslinking chitosan and humic acid/urea complexes (GCS) into cellulose/humic acid (HA/CE) film. By flow-coating with GCS to construct hierarchical networks, GCS-HA/CE film is endowed with the improved property. The influences of composition with different concentrations on mechanical properties were studied, and the optimum concentration was determined. The tensile strength and elongation of GCS-HA/CE film could reach 53.97 MPa and 12.86 % in dry state, respectively. Results suggest that glutaraldehyde crosslinking reduces moisture content, water solubility, and water vapor permeability, but increases contact angle (94.025°). Meanwhile, the thermostability and ultraviolet resistance were improved. The infrared spectroscopy and X-ray diffractometry demonstrated the successfully crosslinked by glutaraldehyde. Morphological analyses present film has excellent compatibility. In addition, GCS-HA/CE film shows good heat preservation, aging resistance, and biodegradability, indicating certain guiding significance for polysaccharide-based mulch film.

A facile approach to cellulose/multi-walled carbon nanotube gels-Structure, formation process and adsorption to methylene blue.

In view of the deficiencies in the preparation of cellulose gels, such as, cumbersome process, harsh conditions, high consumption of chemicals, secondary pollution caused by side reactions, this work reports a facile approach to make cellulose/multi-walled carbon nanotube (MWCNTs) hydrogels and aerogels via mixing cellulose with N,N'-methylene bisacrylamide (MBA) and MWCNTs in NaOH/urea/H2O aqueous solution. The gels were revealed to be formed by an addition reaction between the double bonds of MBA and the hydroxyl groups of cellulose and the intermolecular interactions between cellulose and MWCNTs. The preparation process can be realized at room temperature and atmospheric pressure without the intervention of ultrasonic dispersion, catalyst and initiator. The gelation time, puncture strength and water retention ability of the hydrogels were investigated. Results showed that, compared with pure cellulose hydrogel, cellulose/MWNCTs hydrogels have obviously shorter sol-gel transition time (124-129.2 min), higher puncture strength (29.6022-34.2854 KPa) and water retention ability (274.2619-301.7291 g/g). Cellulose/MWCNTs aerogels possessed three dimensional network with macroporous structure (about 500 µm), low density (0.00546-0.00557 g/cm3), high porosity (99.6360-99.6426 %), good thermal stability (242 °C) and certain absorbency to methylene blue (233.2901-242.1122 mg/g).

Iridescent chiral nematic papers based on cellulose nanocrystals with multiple optical responses for patterned coatings.

Chiral nematic papers (CNPs) with mesopores structure based on cellulose nanocrystals (CNCs) were fabricated successfully via a swelling and freeze-drying method. The order of the original chiral nematic cellulose nanocrystals film was preserved in CNPs, which was proved by scanning electron microscopy (SEM), polarized optical microscopy (POM) measurements and circular dichroism (CD) spectra. The CNPs exhibited excellent optical responsive properties to different solvents. Inspired by this feature, a colorable ink containing amounts of gel particles was prepared by pulverizing CNPs/water mixture into a suspension. Patterns written in suspension ink with various colors can be formed when soaked with different solvents. Moreover, CNPs displayed an irreversible color response to compression. Additionally, the hydrophilicity of CNPs was tuned by polyethyleneimine. Modified CNPs exhibited different colors under the identical solvent environment when compared to the original one. Aqueous PEI can be used as an ink to depict responsive photonic patterns on CNPs.

Starch-Based Composite Films with Enhanced Hydrophobicity, Thermal Stability, and UV-Shielding Efficacy Induced by Lignin Nanoparticles.

Thehighly efficient utilization of lignin is of great importance for the development of the biorefinery industry. Herein, a novel "core-shell" lignin nanoparticle (LNP) with a diameter of around 135 nm was prepared, after the lignin was isolated from the effluent of formic acid fractionation via dialysis. In an attempt to endow composite materials with vital functionalities, the LNP was added to the starch film and the starch/polyvinyl alcohol (PVA) or starch/polyethylene oxide (PEO) composite film. The results showed that the hydrophobicity performance of the synthesized films was enhanced significantly. Specifically, the dynamic water contact angle value of the starch/PVA composite film with 1% (wt) addition of LNPs could be maintained as high as 122° for 180 s; the starch/PEO composite film also achieved an excellent water contact angle above 120°. The addition of LNPs promoted the formation of some rough structures on the film surface, as shown by the scanning electron microscopy images, which could repel the water molecules efficiently and are closely related to the enhanced hydrophobicity of the starch film. What is more, the as-prepared LNP conferred strengthened thermal stability and ultraviolet blocking properties on the starch composite film. The structural combination of the polymer film with LNPs holds the promise for providing advanced functionalities to the composite material with wide applications.

Efficient removal of surface-deposited pseudo-lignin and lignin droplets by isothermal phase separation during hydrolysis.

During the traditional autohydrolysis, formation and deposition of "pseudo-lignin" and lignin droplets on the surface of biomass had a detrimental effect on the subsequent biomass conversion. In this study, isothermal phase separation was introduced into autohydrolysis, and the effects of isothermal phase separation on the dissolution of components and enzymatic hydrolysis of bamboo were studied. The research showed that isothermal phase separation after autohydrolysis without cooling had an effective reduction in the deposition of "pseudo-lignin" and lignin droplets on the residues surface. After isothermal phase separation, the contents of sugar (14.05 g/L) and lignin (6.16 g/L) in pre-hydrolysates increased by 20% and 19% compared with control, respectively. Moreover, the efficient removal of "pseudo-lignin" and lignin droplets from cell wall surface could further promote the biological conversion of pretreated biomass (22% higher than that of control) during the subsequent enzymatic hydrolysis.

Laccase-Catalyzed Grafting of Lauryl Gallate on Chitosan To Improve Its Antioxidant and Hydrophobic Properties.

Biografting is a promising and ecofriendly approach to meet various application requirements of products. Herein, a popular green enzyme, laccase, was adopted to graft a hydrophobic phenolic compound (lauryl gallate, LG) onto chitosan (CTS). The resultant chitosan derivate (Lac/LG-CTS) was systematically analyzed by Fourier transform infrared (FTIR), grafting efficiency, scanning probe microscopy (SPM), and X-ray diffraction (XRD). This grafting technique produced a multifunctional chitosan copolymer with remarkably enhanced antioxidant property, hydrophobicity, and moisture barrier property. Furthermore, the swelling capacity and acid solubility of the copolymer film decreased significantly, although the tensile strength and elongation were slightly weakened as compared to those of native chitosan. These results suggest that the Lac/LG-CTS holds great potential as a food-packaging material, preservative agent, or edible coating material.

Modification of the aspen lignin structure during integrated fractionation process of autohydrolysis and formic acid delignification.

Integrated fractionation process based on autohydrolysis (H) and subsequent formic acid delignification (FAD) has been considered as an effective strategy to separate the main lignocellulosic components in view of the biorefinery. For the better understanding of the structural changes of the lignin during the integrated process, the fractionated aspen lignins were thoroughly characterized by Fourier transform infrared (FT IR), 13C, two-dimensional heteronuclear single quantum coherence (2D-HSQC) and 31P nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Compared to the milled wood lignin (MWL), the fractionated lignins had higher amounts of phenolic OH groups as due to the cleavage of ß-O-4 linkages and less alcoholic OH groups mainly due to the esterification of the aliphatic OH groups by formic acid. Demethylation action of the lignin was not significant during the FAD process. More syringyl-propane (S) units were extracted during the H-FAD process than guaiacyl-propane (G) units resulting in a higher S/G ratio and more OCH3 in the fractionated lignins. Furthermore, autohydrolysis of aspen at higher temperature led to more condensation of the fractionated lignins which exhibited higher molecular weight and more ß-5 and ß-ß linkages. The fractionated lignins exhibited high purities due to the breakage of the lignin-carbohydrate bonds.

Enhancement of lignin removal from pre-hydrolysis liquor for saccharide recovery via horseradish peroxidase treatment in the presence of Ca2.

The removal of lignin is important to the recovery of saccharides from the pre-hydrolysis liquor (PHL) in kraft-based dissolved pulp production. A one-step process for lignin removal from PHL via treatment with horseradish peroxidase (HRP) in the presence of Ca2+ was proposed, and its principle was studied. The results demonstrated synergy between HRP and Ca2+ in lignin removal from PHL, whereas NH4+ had little effect on lignin removal. HRP treatment in the presence of 60 mmol/L of Ca2+ resulted in a lignin removal of 64.8% accompanied by a saccharide loss of 14.2%. HRP catalyzed both the polymerization and depolymerization of the lignin in the PHL. The HRP-catalyzed lignin polymerization rendered some lignin insoluble enabling it to be directly removed. The HRP-catalyzed depolymerization of lignin decreased its molecular weight with an evident increase in its carboxyl content. The insoluble complexes formed between the lignin with carboxyl and the Ca2+ facilitated the removal of the depolymerized lignin.

Short-Time Hydrothermal Treatment of Poplar Wood for the Production of a Lignin-Derived Polyphenol Antioxidant.

Artificial antioxidants are synthesized from fossil sources and are now widely used in the polymer, food, and cosmetics industries. The gradual depletion of fossil resources makes it practically significant and necessary to produce green antioxidants from renewable lignocellulosic resources. Herein, short-time hydrothermal (STH) treatment was developed for production of lignin-derived polyphenol antioxidants (LPAs) from poplar wood under conditions of high temperature and high pressure. LPA yields from 21.5 to 37.6 % on the basis of lignin in untreated wood were obtained by STH treatments as result of lignin depolymerization at 190-200 °C and 10 MPa in 5-8 min. Depolymerization reactions were confirmed by the much lower molecular weight of LPA (1076 g mol-1 ) than that of native lignin (4094 g mol-1 ). NMR spectroscopy revealed the structural features of lignin in the isolated LPA, namely syringyl and guaiacyl units with well-preserved interunit linkages. A Folin-Ciocalteu assay indicated that each LPA molecule contained 5.4 phenolic hydroxyl groups on average, much more than other technical lignins. The remarkable antioxidant ability of LPA was verified by the radical-scavenging index of 53.5-67.3, much higher than 0.2-11.1 of the commercial antioxidants butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). STH treatment only requires water and heat for production of high-value antioxidant, which provides a green and sustainable method for the utilization of lignocelluloses.

Responsive and patterned cellulose nanocrystal films modified by N-methylmorpholine-N-oxide.

A type of cellulose solvent, i.e., aqueous N-methylmorpholine- N-O xide (NMMO) solutions, was used to modify cellulose nanocrystal (CNC) photonic films. CNC films can be swollen by NMMO, resulting in red-shifted reflected colors. The swelling effect is supposed to come from NMMO permeation into the crystalline regions of individual CNCs and intercalating in between CNC particles. When NMMO was removed, the reflected colors of CNC films blue shifted because of the reduced helical pitches. NMMO-treated CNC films display reversible responsive colors to humidity changes in several minutes. Increasing NMMO content allows CNC films to enlarge the responsive color range. Aqueous NMMO can be used as an ink to depict responsive photonic patterns on CNC films. This post-treatment approach to producing responsive colors and photonic patterns in CNC films may be applied to the areas of sensor, anti-counterfeiting, and decoration.

Photonic actuators with predefined shapes.

Developing actuators with multi-responsibility, large deformation, and predefined shapes is critical for the application of actuators in the field of artificial intelligence. Herein, we report the preparation of a new type of unimorph actuators containing phenol-formaldelyde resin (PFR) and graphene oxide (GO) using the chiral nematic structure of cellulose nanocrystals (CNCs) as the template. The so-obtained PFR/GO films have a unimorph structure with an asymmetric distribution of GO across the film. They exhibit synchronous responses of both photonic properties and actuation to humidifying/dehumidifying. Moreover, PFR/GO films can be forged into desired shapes by aldehyde treatment, and thereby are able to produce complex movements. In addition, the objects with predetermined shapes show good shape recovery capability upon many wetting-drying cycles, especially through the treatment with formaldehyde. A mechanism model for shape predetermination by aldehyde treatment is suggested based on experimental details. By further designing the predetermined shapes and patterns, such PFR/GO actuators may hold great promise for smart actuation devices of highly complex movements.

Rapid Nondestructive Fractionation of Biomass (≤15†min) by using Flow-Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin.

Whole valorization of carbohydrate and lignin from biomass was achieved by rapid flow-through fractionation (RFF) within 15 min. Wheat straw was effectively deconstructed into its principle components without degradation by using easily recyclable aqueous formic acid (72 wt %) at 130 °C. The obtained cellulose-rich solid showed a nearly complete glucan recovery and 73.8 % glucose conversion after enzymatic hydrolysis. Xylan also reached full recovery with negligible furfural formation with a sum of 80 % of oligo/mono xylose in spent liquor and 20 % of xylan remaining in the solid. Up to 75.4 % lignin was dissolved in the spent liquor and further fractionated into water-insoluble (WIL) and water-soluble lignin (WSL) by dilution with water. WIL showed a non-condensed and well-preserved structure with 84.5 % ß-O-4 remaining, which is believed to be beneficial for catalytic conversion into low-molecular-weight chemicals and fuels. The concentration of employed formic acid was below the formic acid/water azeotrope, and therefore the reaction medium could be restored through simple distillation. Together with the joint valorization of lignin and carbohydrates, the presented RFF is a promising process for sustainable biorefinery.

Mild and efficient extraction of hardwood hemicellulose using recyclable formic acid/water binary solvent.

Formic acid/water binary solvent extraction with formic acid fraction lower than 77.5% (w/w) of azeotrope was used to extract hemicellulose-derived saccharides from poplar wood at various levels of severity. The highest xylose yield of 77.8% and arabinose yield of 93.5% were obtained at 120 °C and 1 h. To reduce cellulose hydrolysis and facilitate downstream xylose crystallization, mild conditions at 90 °C and 4 h was chosen as optimum severity, which led to the highest xylose fraction of 81.7% in all saccharides extracted, with a remarkable xylose yield of 73.1%. Mass balance analysis showed that 5.84% of xylan was degraded, but only 0.25% of xylan ended up as furfural at optimum severity. The proposed extraction process has high feasibility for industrial application since the low formic acid fraction in solvent allows simple recovery and concentration of used solvent.

Recycling of pre-hydrolysis liquor to improve the concentrations of hemicellulosic saccharides during water pre-hydrolysis of aspen woodchips.

In this study, the pre-hydrolysis liquor (PHL) was recycled during aspen chip water pre-hydrolysis, and the effects of PHL recycling on the extraction and accumulation of the hemicellulosic saccharides especially that with high molecular weight in the PHL were studied. The results showed that the concentration of hemicellulose saccharides in PHL depended on the pre-hydrolysis temperature and PHL recycling times. Compared to the unrecycled PHL, the concentration of hemicellulosic saccharides in PHL increased significantly when recycling PHL once or twice at 170°C. Furthermore, the amount of high-molecular-weight hemicelluloses (HMHs) in PHL recycled once at 170°C increased from 2.58g/L (unrecycled) to 6.18g/L, but the corresponding average molecular weight of HMHs decreased from 9.2kDa to 7.6kDa. The concentration of hemicellulosic saccharides in PHL decreased with PHL recycling time at 180°C, accompanied by the formation of a significant amount of furfural.