Effect of molecular weight of PEI on the strength and hydrophobic performance of fiber-based papers via PEI-KH560 surface sizing.

In recent years, researchers have put much attention on the improvements and upgrades of novel wet strength agent in the papermaking fields, especially in the usage of household paper. Herein, PEIM-KH560 by polyethyleneimine (PEI) and γ-glycidyl ether propyl trimethoxysilane (KH560) was synthesized with five molecular weights (Mw) of PEI at 600, 1800, 10,000, 70,000 and 750,000. Results showed that the molecular weight greatly influenced the physicochemical properties of PEI-KH560, such as the size and thermal stability. The intrinsic cationic charge of PEI-KH560 provided the bonding sites with the paper fibers, forming strengthened fiber-fiber joints. It was shown that the dry, wet strength and hydrophobicity of cellulosic paper sheets were obviously improved. When the m (PEI):m(KH560) is 1:2, the strength of papers after sizing by Mw of PEI at 600 and 1800 is the most obvious, with the dry strength increased by 227.9 % and 187.5 %, and the wet strength increased by 183.8 % and 207.8 %, respectively. The maximum hydrophobicity was found at the PEI1800-KH560 with the contact angle value of 130.6°. The resultant environmental-friendly agent (PEI-KH560) obtained in this work provides valuable significance for the preparation of household and food packaging paper.

Synthesis and Properties of Photocurable Polymers Derived from the Polyesters of Glycerol and Aliphatic Dicarboxylic Acids.

The rapid development of 3D printing technology and the emerging applications of shape memory elastomer have greatly stimulated the research of photocurable polymers. In this work, glycerol (Gly) was polycondensed with sebacic, dodecanedioic, or tetradecanedioic acids to provide precursor polyesters with hydroxyl or carboxyl terminal groups, which were further chemically functionalized by acryloyl chloride to introduce sufficient, photocurable, and unsaturated double bonds. The chemical structures of the acrylated polyesters were characterized by FT IR and NMR spectroscopies. The photoinitiated crosslinking behavior of the acrylated polyesters under ultraviolet irradiation without the addition of any photoinitiator was investigated. The results showed that the precursor polyesters that had a greater number of terminated hydroxyls and a less branched structure obtained a relatively high acetylation degree. A longer chain of aliphatic dicarboxylic acids (ADCAs) and higher ADCA proportion lead to a relatively lower photopolymerization rate of acrylated polyesters. However, the photocured elastomers with a higher ADCA proportion or longer-chain ADCAs resulted in better mechanical properties and a lower degradation rate. The glass transition temperature (Tg) of the elastomer increased with the alkyl chain length of the ADCAs, and a higher Gly proportion resulted in a lower Tg of the elastomer due to its higher crosslinking density. Thermal gravimetric analysis (TGA) showed that the chain length of the ADCAs and the molar ratio of Gly to ADCAs had less of an effect on the thermal stability of the elastomer. As the physicochemical properties can be adjusted by choosing the alkyl chain length of the ADCAs, as well as changing the ratio of Gly:ADCA, the photocurable polyesters are expected to be applied in multiple fields.

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.

Production of Cellulose Pulp and Lignin from High-Density Apple Wood Waste by Preimpregnation-Assisted Soda Cooking.

Apple wood waste (AWW), mainly tree trucks, is collectible lignocellulosic biomass from orchard rotation. The biorefinery of AWW is challenging because of the hard and dense structure. In the present work, chemical composition determination and microstructure observation was performed for the first time on AWW. Alkali-preimpregnation-assisted soda cooking (APSC) was developed to separate cellulose a pulp and lignin from AWW. APSC attained pulp yield of 34.2% at 23% NaOH, showing a 13.2% improvement compared to conventional soda cooking (SC). Fiber length analysis showed APSC-AWW pulp consisted mainly of medium and short fibers, which means blending with long-fibered pulp to enhance the physical strength of pulp sheets. A blend of APSC-AWW pulp and long-fibered pulp in the proportion of 80:20 attained comparable physical strength to hardwood kraft pulp. ASPC-AWW lignin was separated from spent liquor by acidification and then purified by dialysis desalination. The purified ASPC-AWW lignin showed a weight-average molecular weight of 4462 g/mol, similar to softwood kraft lignin but more uniform. Structural analysis revealed that ASPC-AWW lignin was composed of a syringyl unit (S), guaiacyl unit(G), and p-hydroxyphenyl unit (H), and an S unit was dominant with an S/G/H ratio of 74.5:18.2:7.3. It is believed the utilization of fruit tree wood waste as the feedstock of biorefinery is attractive to countries without sufficient forestry resources. Furthermore, the developed APSC is based on conventional SC, which ensures the feasibility of an industrial application.

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.

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.

Cellulosic paper with high antioxidative and barrier properties obtained through incorporation of tannin into kraft pulp fibers.

In this work, we prepared novel cellulosic paper by incorporating tannin into the kraft pulp for potential application in active food packaging. The kraft pulp fibers were firstly periodate oxidized to obtain the dialdehyde cellulosic fibers, and then reacted with varied dosages of tannin to incorporate them into the fibers by covalent bondings between aldehyde groups on cellulose and active hydrogen on tannin. Handsheets were prepared using the tannin incorporated fibers through papermaking process and the properties were characterized. The percentage of tannin in the paper increased with the increase of the tannin dosage. FT-IR spectra confirmed the successful incorporation of tannin into the cellulosic fibers. It was found that paper after incorporation of tannin turned to be surface hydrophobic with contact angles higher than 90°, which may probably due to the covalent bonds between tannin and cellulose. The handsheets show high antioxidative and UV-shielding properties, which both increased with the increase of the tannin percentage in the paper. Water vapor transmission rate (WVTR) decreased after the incorporation of tannin, and this could facilitate its application in food packaging. The breaking length of tannin incorporated paper decreased insignificantly, less than 10% with the tannin percentage as high as 45%.

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.

Improvements on activated sludge settling and flocculation using biomass-based fly ash as activator.

Biomass-based fly ash and wastewater are undesired products of the pulping industry. Recently, the use of biomass-based fly ash as an adsorbent (i.e., a valued material) for constituents of wastewater effluents was reported. In this work, the settling performance and properties of activated sludge were studied in the presence of fly ash. Upon mixing, fly ash increased the zeta potential of the sludge from -31 mV to -28 mV, which was due to the release of cationic ions from fly ash in the sludge suspension. The sludge settling and its flocculation affinity were improved through the complexation of flocs and released cation ions from fly ash. The relationships between the protein/polysaccharide (PN/PS) ratio and the content of extracellular polymeric substances (EPS) as well as the ratio and the properties of the sludge flocs were determined. A correlation between the total loosely bound-EPS (LB-EPS) content and the effluent suspended solids (ESS) (Pearson's coefficient, rp = 0.83) was observed. The performance of sludge flocculation and settling were much more closely correlated with LB-EPS than with tightly bound EPS (TB-EPS). Scanning electron microscopy (SEM) analysis of sludge flocs before and after EPS extraction showed that the sludge flocs contained a large number of microorganisms, mainly Bacillus and Cocci. The amount of LB-EPS had an adverse influence on bioflocculation, effluent clarification and sludge settling affinity. The sludge properties had a moderate relationship with the PN/PS ratio of LB-EPS. Also, no correlation could be established between the ratio and the TB-EPS content.

Poplar Hot Water Extract Enhances Barrier and Antioxidant Properties of Chitosan/Bentonite Composite Film for Packaging Applications.

Herein, the chitosan-based (CS) composite film was fabricated via a simple and efficient blending approach by adding poplar hot water extract (HWE), bentonite (BT) and chitosan. The addition of HWE largely improved the UV blocking ability and antioxidant properties of the resultant composite film, and simultaneously a tortuous path was constructed within the chitosan matrix to enhance the water vapor and oxygen barriers after the addition of BT. Specially, the content of HWE at 10 wt % gave a greatly decreased UV light transmittance at 280 nm to the CS-BT-HWE composite film that was 99.36% lower than that of CS-BT film, and the oxidation resistance was 9.65 times higher than that of CS-BT. The mechanical properties and surface morphological observation evaluated by scanning electron microscopy (SEM) and scanning probe microscope (SPM) confirmed the film had a denser structure. The internal chemical structure analyzed using solid state NMR, FTIR and X-ray spectra exhibited the resultant Maillard structure and strong hydrogen bonding that contributed to the improved mechanical properties. Overall, the as-prepared composite film has great potential as food packaging materials, and also provides a high-efficient utilization pathway for HWE.

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.

Fabrication of Cellulose Nanocrystal/Chitosan Hydrogel for Controlled Drug Release.

In this work, a novel nanocomposite hydrogel based on cellulose nanocrystal (CNC) and chitosan (CS) was fabricated and applied as a carrier for the controlled delivery of theophylline. CNC was firstly periodate-oxidized to obtain dialdehyde nanocellulose (DACNC). Then, chitosan was crosslinked using DACNC as both the matrix and crosslinker in different weight ratios, to fabricate CNC/CS composites. The prepared composites were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), zeta potential measurement and swelling ratio tests. FT-IR results confirmed the successful reaction between the free amino groups on chitosan and the aldehyde groups on DACNC. With the increase of chitosan percentage in the hydrogel, the isoelectric point was shifted towards an alkaline pH, which was probably caused by the higher content of free amino groups. The swelling ratio of the composite also increased, which may have been due to the decrease of crosslinking density. Because the swelling ratio of the drug-loaded hydrogels differed under varied pH values, the cumulative drug release percentage of the composite hydrogel was achieved to approximately 85% and 23% in the gastric (pH 1.5) and intestinal (pH 7.4) fluids, respectively. Therefore, CNC/CS hydrogel has application potential as a theophylline carrier.