Preparation and characterization of cellulose-chitosan/ß-FeOOH composite hydrogels for adsorption and photocatalytic degradation of methyl orange.

Biopolymer-based hydrogels have received great attention in wastewater treatment due to their excellent properties, e.g., high adsorption capacity, fast kinetics, reusability and ease of operation. In the present work, cellulose-chitosan/ß-FeOOH composite hydrogels were prepared via co-dissolution and regeneration process as well as hydrothermal in situ synthesis of ß-FeOOH. Effect of ß-FeOOH loading on the properties of the composite hydrogels and the removal efficiency of methyl orange (MO) was investigated. Results showed that ß-FeOOH was uniformly loaded onto the hydrogel framework, and the nanoporous structure of composite hydrogels could increase not only the effective contact area between ß-FeOOH and the pollutants but also the active sites. Moreover, the increased ß-FeOOH loading led to the enhanced MO removal rate under light conditions. When the loading time was extended from 6 h to 9 h, the MO removal rate increased by 21%, which can be mainly due to the photocatalytic degradation. In addition, MO removal rate reached 97.75% within 40 min under optimal conditions and attained 80.81% after five repetitions. The trapping experiment and EPR results indicated that the main active species were hydrogel radicals and holes. Consequently, this work provides an effective preparation approach for cellulose-chitosan/ß-FeOOH composite hydrogel with high adsorption and photocatalytic degradation, which would hold great promise for wastewater treatment applications.

Introducing terminal alkyne groups at the reducing end of cellulose nanocrystals by aldimine condensation for further click reaction.

In recent years, click reactions with cellulose nanocrystals (CNC) participation have gradually become a research hotspot. Carboxylamine condensation is the most used method to introduce terminal alkyne groups at the reducing end of CNC as reaction sites for click reactions. However, hydroxyl groups on CNC surface would be slightly oxidized during the carboxyamine condensation process, inducing the potential positions of introduced alkynes would be not only at the reducing end but also on CNC surface. Here, aldimine condensation was proposed to introduce terminal alkyne groups just at the reducing end of CNC, and a systematic comparison analysis was conducted with carboxylamine condensation. Firstly, the selectivity and extent of alkynylation were characterized by XPS and EA. Secondly, the end aldehyde content in these CNC samples was measured by the BCA method, which quantitatively explained the grafting efficiency of aldimine condensation and further verified its feasibility. Thirdly, the clickability of the modified CNC samples was confirmed through XPS analysis of the products after a pre-designed click reaction. In sum, aldimine condensation was proven to be a simple and effective strategy for introducing terminal alkyne groups at the reducing end of CNC, which could be used as reaction sites for further click reactions.

Synthesis and characterization of polyaniline-based composites using cellulose nanocrystals as biological templates.

Polyaniline (PANI) is considered as an ideal electrode material due to its remarkable Faradaic activity, exceptional conductivity, and ease of processing. However, the agglomeration and poor cycling stability of PANI largely limit its practical utilization in energy storage devices. To address these challenges, PANI was synthesized via a facile one-pot, two-step process using cellulose nanocrystals (CNCs) as bio-templates in this work. Zeta potential and particle size measurements revealed that the CNC template could impart improved dispersion stability to the synthesized PANI, which exhibited a decrease in average particle size from 1100 nm to 300 nm as a function of 10 % CNCs. Furthermore, the effect of CNC loadings on the performance of PANI was systematically investigated. The results showed that the specific capacitance of PANI/CNC increased from 102.52 F·g-1 to 138.12 F·g-1 with the CNC loading increase from 0 to 10 wt%. Particularly, the PANI/CNC composite film with a 1:9 ratio (C-P-10 %) demonstrated a capacity retention of 84.45 % after 6000 cycles and an outstanding conductivity of 526 S·m-1. This work generally offers an effective solution for the preparation of high-performance PANI-based composites, which might hold great promise in energy storage device applications.

Network pharmacology analysis and experimental verification of the antitumor effect and molecular mechanism of isocryptomerin on HepG2 cells.

Isocryptomerin (ISO) is a flavonoid isolated from the natural medicine Selaginellae Herba, which has various pharmacological activities. This study investigated the antitumor effect and underlying molecular mechanism of ISO on hepatocellular carcinoma (HCC) HepG2 cells. The cell viability assay revealed that ISO has a considerable killing effect on HCC cell lines. The apoptosis assay showed that ISO induced mitochondria-dependent apoptosis through the Bad/cyto-c/cleaved (cle)-caspase-3/cleaved (cle)-PARP pathway. The network pharmacological analysis found 13 key target genes, and epidermal growth factor receptor (EGFR), AKT, mitogen-activated protein kinase (MAPK), and reactive oxygen species (ROS) signaling pathways were strongly associated with ISO against HCC. Further verification of the results showed that ISO induced apoptosis by increasing p-p38 and p-JNK expression and decreasing p-EGFR, p-SRC, p-ERK, and p-STAT3 expression. Furthermore, ISO induced G0/G1 phase arrest by downregulating p-AKT, Cyclin D, and CDK 4 expression and upregulating p21 and p27 expression in HepG2 cells. Moreover, ISO inhibited HepG2 cell migration by decreasing p-GSK-3ß, ß-catenin, and N-cadherin expression and increasing E-cadherin expression. Additionally, ISO promoted ROS accumulation in HepG2 cells, and ISO-induced apoptosis, arrest cell cycle, and inhibition of migration were reversed by an ROS scavenger, N-acetyl- l-cysteine. Overall, ISO induced cell apoptosis and cell cycle arrest and inhibited cell migration by ROS-mediated EGFR, AKT, and MAPK signaling pathways in HepG2 cells.

Facile dissolution of cellulose by superbase-derived ionic liquid using organic solvents as co-solvents at mild temperatures.

Dissolving cellulose at low temperatures is a key step in its efficient utilization as a renewable resource to produce high-value-added platform chemicals and high-performance materials. Here, the potential of four aprotic organic solvents was investigated for use as co-solvents with a sustainable DBU-derived ionic liquid (SIL) for the low-temperature dissolution and regeneration of cellulose. Combined experiments, density functional theory calculations, and molecular dynamic simulations were performed. The type and amount of co-solvent were found to have a significant impact on the solubility of cellulose, the dissolution process, and the structure of regenerated cellulose. The addition of organic solvents can significantly reduce the cellulose dissolution temperature and increase the solubility. Among the solvents assessed, 40 wt% DMSO exhibited the most effective synergistic interaction with SIL, where the solubility of cellulose was 14.6 wt% at 75 °C. Subsequently, the effects of the different types and amounts of co-solvents on the microscopic morphology and chemical structure of regenerated cellulose were thoroughly explored. The results showed that different types of organic solvents had different effects on the microstructure of regenerated cellulose. The results may guide the manufacturing specifications of high-performance regenerated fiber materials.

Jaceosidin induces apoptosis and inhibits migration in AGS gastric cancer cells by regulating ROS-mediated signaling pathways.

Jaceosidin (JAC) is a natural flavonoid with anti-oxidant and other pharmacological activities; however, its anti-cancer mechanism remains unclear. We investigated the mechanism of action of JAC in gastric cancer cells. Cytotoxicity and apoptosis assays showed that JAC effectively killed multiple gastric cancer cells and induced apoptosis in human gastric adenocarcinoma AGS cells via the mitochondrial pathway. Network pharmacological analysis suggested that its activity was linked to reactive oxygen species (ROS), AKT, and MAPK signaling pathways. Furthermore, JAC accumulated ROS to up-regulate p-JNK, p-p38, and IκB-α protein expressions and down-regulate the p-ERK, p-STAT3, and NF-κB protein expressions. Cell cycle assay results showed that JAC accumulated ROS to up-regulate p21 and p27 protein expressions and down-regulate p-AKT, CDK2, CDK4, CDK6, Cyclin D1, and Cyclin E protein expressions to induce G0/G1 phase arrest. Cell migration assay results showed JAC accumulated ROS to down-regulate Wnt-3a, p-GSK-3ß, N-cadherin, and ß-catenin protein expressions and up-regulate E-cadherin protein expression to inhibit migration. Furthermore, N-acetyl cysteine pre-treatment prevented the change of these protein expressions. In summary, JAC induced apoptosis and G0/G1 phase arrest and inhibited migration through ROS-mediated signaling pathways in AGS cells.

Cellulose dissolution and regeneration behavior via DBU-levulinic acid solvents.

Most organic solvents are unable to dissolve carbohydrates due to the lack of hydrogen bonding ability. The development of solvent systems for dissolving cellulose is of great importance for its utilization and conversion. In this study, four new cellulose solvents were designed using inexpensive levulinic acid (LevA) and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) as raw materials. The results showed that the prepared DBU-LevA-2 solvent was able to dissolve up to 7 wt% of bamboo cellulose (DP = 860) and 16 wt% of microcrystalline cellulose (DP = 280) at 100 °C and regenerated without derivatization. Also, the molar ratio of each component of this solvent has a significant effect on the dissolution properties of cellulose. The regenerated cellulose had the typical crystalline characteristics of cellulose II. Subsequently, the interactions and microscopic behaviors of solvent and cellulose during the dissolution process were thoroughly investigated by using NMR spectroscopy combined with density functional theory. The systematic study showed that the hydrogen bond-forming ability provided by DBU, a superbase, plays an indispensable role in the overall solvent system.

Synthesis of bifunctional thermal response promoters for improved high-solids enzymatic hydrolysis of corncob residues.

The enzymatic hydrolysis cost of lignocellulose can be reduced by improving enzymatic hydrolysis and recycling cellulase by adding additives. A series of copolymers P(SSS-co-SPE) (PSSPs) were synthesized using sodium p-styrene sulfonate (SSS) and sulfobetaine (SPE) as monomers. PSSP exhibited upper critical solution temperature response. PSSP with high molar ratio of SSS displayed more significant improved hydrolysis performance. When 10.0 g/L PSSP5 was added to the hydrolysis system of corncob residues, and substrate enzymatic digestibility at 72 h (SED@72 h) increased by 1.4 times. PSSP with high molecular weight and moderate molar ratio of SSS, had significant temperature response, enhanced hydrolysis, and recovering cellulase properties. For high-solids hydrolysis of corncob residues, SED@48 h increased by 1.2 times with adding 4.0 g/L of PSSP3. Meanwhile, 50% of cellulase amount was saved at the room temperature. This work provides a new idea for reducing the hydrolysis cost of lignocellulose-based sugar platform technology.

Conductive and antibacterial films by loading reduced graphene oxide/silver nanoparticles on cellulose nanofiber films.

The development of sustainable high-performance materials based on nanocellulose has received great attention in recent years. Herein, nanocellulose based composite films with highly electro-conductive and antibacterial properties have been developed by loading reduced graphene oxide (rGO)/silver nanoparticles (AgNPs) on cellulose nanofiber films via vacuum filtration process. The reduction effect of gallic acid on the chemical structure and electrical conductivity of rGO/AgNP composites was studied. Due to the strong reducibility of gallic acid, the obtained rGO/AgNPs exhibited a high electrical conductivity of 1549.2 S·m-1. Furthermore, the electrical conductivity, mechanical properties and antibacterial properties of the prepared rGO/AgNP-cellulose nanofiber films as a function of various proportions were investigated. The prepared composite film with a specific ratio of rGO/AgNPs to cellulose nanofibers as 7:3 exhibited the superior tensile strength of 28.0 MPa and the electrical conductivity of 1199.3 S·m-1. Meanwhile, compared with pure cellulose nanofiber films, rGO/AgNP-cellulose nanofiber films displayed strong antibacterial effect against Escherichia coli and Staphylococcus aureus. Therefore, this work demonstrated an effective approach for imparting structural and functional properties to cellulose nanofiber based films, which could hold great application prospects for flexible and wearable electronics.

Lignin-grafted quaternary ammonium phosphate with temperature and pH responsive behavior for improved enzymatic hydrolysis and cellulase recovery.

The cost of lignocellulosic enzymatic hydrolysis was reduced by enhancing enzymatic hydrolysis and recycling cellulase. Lignin-grafted quaternary ammonium phosphate (LQAP) with sensitive temperature and pH response, was obtained by grafting quaternary ammonium phosphate (QAP) onto enzymatic hydrolysis lignin (EHL). LQAP dissolved under the hydrolysis condition (pH 5.0, 50 °C) and enhanced the hydrolysis. After hydrolysis, LQAP and cellulase co-precipitated by the hydrophobic binding and electrostatic attraction, when lowering pH to 3.2, and cooling to 25 °C. LQAP had significant performances of pH-UCST response, enzymatic hydrolysis enhancement and cellulase recovery at the same time. When 3.0 g/L LQAP-100 was added to the system of corncob residue, SED@48 h increased from 62.6 % to 84.4 %, and 50 % of amount of cellulase was saved. Precipitation of LQAP at low temperature was mainly attributed to the salt formation of positive and negative ions in QAP; LQAP enhanced the hydrolysis for its ability to decrease the ineffective adsorption of cellulase by forming a hydration film on lignin and through the electrostatic repulsion. In this work, a lignin amphoteric surfactant with temperature response, was used to enhance hydrolysis and recover cellulase. This work will provide a new idea for reducing the cost of lignocellulose-based sugar platform technology, and high-value utilization of industrial lignin.

Nanocellulose-based electrodes and separator toward sustainable and flexible all-solid-state supercapacitor.

Nanocellulose, as the most abundant natural nanomaterial with sustainability, biodegradability, and excellent mechanical properties, has been widely applied in modern electronic systems, particularly, in the flexible electrochemical energy storage devices. Herein, a reduced graphene oxide (RGO)/cellulose nanocrystal/cellulose nanofiber (RCC) composite membrane was prepared by using a one-pot method. Compared to the pure RGO membranes, the RCC composite membranes exhibited better mechanical properties and hydrophilicity. Furthermore, due to the synergistic effect of nanocellulose and RGO sheets, the RCC composite membrane exhibited a specific capacitance as high as 171.3 F·cm-3. Consequently, a nanocellulose-based symmetric flexible all-solid-state supercapacitor (FASC) was constructed, in which two RCC composite membranes served as electrodes and a porous cellulose nanofiber membrane acted as separator. This fabricated FASC demonstrated a high volumetric specific capacitance of 164.3 F·cm-3 and a satisfactory energy density of 3.7 mW·h·cm-3, which exceeded that of many other FASCs ever reported. This work may open a new avenue in design of next-generation nanocellulose based, sustainable and flexible energy storage device.

Flotation de-inking for recycling paper: contrasting the effects of three mineral oil-free offset printing inks on its efficiency.

Paper for recycling has become a promising raw material for the pulp and paper industry due to its low cost and because it is conducive to sustainable development. Unfortunately, recycled paper contains a high volume of printed paper that is difficult to deink, which restricts its applications. Flotation deinking plays an essential role in the product quality and process cost of wastepaper recycling. This study was performed to evaluate the deinkability of environmentally friendly offset inks by flotation deinking. For this purpose, three mineral oil free series of four-color inks, namely, hybrid light emitting diode ultraviolet (LED-UV), LED-UV, and vegetable oil-based inks, were printed on white lightweight coated papers under laboratory conditions. The deinking methodology involves repulping, deinking agent treatment, flotation, hand sheet making, and evaluation of the produced hand sheets. The obtained results indicated that the hybrid LED-UV prints had the best deinkability. After flotation deinking, the deinking efficiency and the whiteness of the hybrid LED-UV ink increased by 58.1% and 47.6%, respectively. LED-UV ink had a 46.9% increase in the deinking efficiency and a 37.0% increase in the whiteness of the hand sheet. The deinking efficiency of the vegetable oil-based ink was the lowest, at 42.1%, and the whiteness of the hand sheet increased only by 23.8%. The particle size distribution analysis demonstrated that the hybrid LED-UV four-color ink exhibited a larger value of the average particle size than the two other. Scanning electron microscopy revealed that the hybrid LED-UV ink particles on the surface of the fibers were the least abundant after deinking. The physical strength properties of the hand sheets, including tensile index, folding resistance, and interlayer bonding strength of the hybrid LED-UV, LED-UV inks, and vegetable oil-based inks, increased.

Ultrafast improvement of cellulose accessibility via non-dissolving pretreatment with LiBr·3H2O under room temperature.

The development of sustainable and effective pretreatment methods to improve the accessibility of cellulose is of vital importance for its utilization. Herein, a novel high-efficiency pretreatment method based on lithium bromide trihydrate (LBTH) was established, which realized the fast improvement of cellulose accessibility under ambient conditions without dissolution of cellulose. The cellulose I structure of microcrystalline cellulose (MCC) was transformed into amorphous structure just within 5 min of LBTH pretreatment, and the crystallinity was reduced from 79.1 to 19.9%. After pretreatment for 30 min, the BET surface area of MCC increased from 2.1 to 125.9 m2/g. Particularly, the pretreated cellulose could be near-completely saccharified to glucose (98.3%) with ultra-low enzyme dosage (2.5 mg protein/g-glucan) just within 24 h, while the conversion of untreated MCC under the same conditions was only 16.7%. Additionally, this non-dissolving pretreatment is beneficial to the separation and recycling of LBTH, guaranteeing a clean and sustainable process.

Reduced graphene oxide/cellulose nanocrystal composite films with high specific capacitance and tensile strength.

Due to the environmental degradation and energy depletion, the strategy for fabricating high-performance supercapacitor electrode materials based on graphene and nanocellulose has received great attention. Herein, an environmentally friendly reduced graphene oxide (RGO)/cellulose nanocrystal (CNC) composite conductive film was prepared using L-ascorbic acid (L-AA) as the reductant of graphene oxide (GO). Based on chemical structure analysis, L-AA was proved to be an effective reductant to remove oxygen containing groups of GO. Through microstructure observation, a unique stacking structure of CNC and RGO was observed, which could be largely attributed to the hydrogen bond interaction. Furthermore, the effect of CNC amount on the performance of RGO/CNC composite films was also systematically investigated. Particularly, the addition of CNC was found to exert a positive effect on the tensile strength, which might be mainly due to a mass of hydrogen bonds between the CNCs. Meanwhile, the RGO/CNC composite conductive film featured ideal electrical double-layer capacitive (EDLC) behavior, exhibiting a gravity specific capacitance of 222.5 F/g and tensile strength of 32.17 MPa at 20 wt% CNC content. Therefore, the RGO/CNC composite conductive films may hold great promise for environmentally friendly electrode materials of supercapacitors and flexible electrical devices.

Cellulose nanofibril as a crosslinker to reinforce the sodium alginate/chitosan hydrogels.

Hydrogels derived from natural polymers have received great attention, but their practical applications are severely hindered by the relatively poor mechanical properties. In this work, cellulose nanofibril (CNF) was used as a crosslinker to reinforce the sodium alginate (SA)/chitosan (CS) hydrogels for drug sustained release. The CNF was prepared via a combined process of ball milling and deep eutectic solvents (DESs) pretreatment and characterized using SEM, FT-IR, and XRD. Furthermore, the microstructure, mechanical/biological properties and swelling performance of SA/CS/CNF hydrogels were investigated. Results showed that 1.0 wt% CNF addition led to the increases of 23.6% in storage modulus and 54.4% in loss modulus for the SA/CS/CNF hydrogels, indicating that CNF addition was effective in reinforcing the three-dimensional entangled networks of the hydrogels. Moreover, the presence of CNF was found to weaken the swelling performance of SA/CS/CNF hydrogels. When the synthesized SA/CS/CNF hydrogel with 1.0 wt% CNF was applied as a carrier for drug release, 50.8% reduction in the release rate in simulated gastric juice was achieved, demonstrating its outstanding sustained release properties. This work suggested that CNF might be conducive to enhancing the properties of SA/CS hydrogels, which can serve as an ideal polymeric carrier for drug release.

Hypoxia preconditioning improves structure and function of astrocytes mitochondria via PGC-1α/HIF signal.

The protective effect of astrocytes on nerves was demonstrated by mitochondrial transfer. The neuroprotective effect of hypoxic pretreatment is widely accepted. The aim of this research is to investigate the role of hypoxic preconditioning on astrocytes mitochondria. Rat neuronal cells and astrocytes were isolated and cultured. A hypoxic preconditioned astrocyte and oxygen glucose deprivation (OGD) neuronal cell co-culture experiment was used to detect the effect of hypoxic preconditioning (HP) on nerve damage. The silencing of proliferatoractivated receptor γ coactivator-1α (PGC-1α) with siRNA was used to explore the role of HP in the repair of nerve damage and biogenesis of mitochondria. HP increased astrocyte viability and promoted neuroprotective factor secretion. The expression levels of antioxidant enzymes, PGC-1α and uncoupling protein2 (UCP2) were up-regulated by HP. In addition, HP improved mitochondrial function and reduced oxidative stress induced by OGD. It was found that HP astrocytes had a greater neuroprotective effect than normal astrocytes cells. Neuronal apoptosis and reactive oxygen species levels were down-regulated by cell co-culture. The PGC-1α siRNA experiment showed that hypoxia treatment promotes mitochondrial biogenesis and plays a neuroprotective role. HP significantly enhanced the efficacy of astrocytes in the treatment of neuronal injury.

Nanofibrillated cellulose as coating agent for food packaging paper.

Nanofibrillated cellulose (NFC), a promising bio-based nanomaterial, has received much attention in the field of coating preparation due to its unique properties. Herein, NFC was prepared from microcrystalline cellulose (MCC) via high-pressure homogenization process and deliberately employed as coating agent to enhance the properties of paper coatings and coated paper. The results demonstrated that the obtained paper coatings exhibited strong NFC concentration dependence on rheological behavior and displayed decreased water retention value with the increased NFC addition. Meanwhile, NFC addition was found to lead to the reduced Cobb value, improved air resistance, and enhanced tensile strength of coated paper. Under an optimized NFC addition of 0.30-0.40%, the properties of coated paper generally reached the optimum state. Moreover, SEM observation further confirmed that NFC addition imparted a relatively uniform surface structure to coated paper. Hence, NFC could be defined as an effective coating agent for developing high-performance coated paper for food packaging applications.

Polylactic acid based biocomposite films reinforced with silanized nanocrystalline cellulose.

Polylactic acid (PLA) and nanocrystalline cellulose (NCC) are promising biodegradable materials that have shown great potential in a wide range of healthcare and packaging applications. In the present work, PLA and NCC were compounded at various ratios to form biocomposite films via solution casting process. In order to improve the compatibility of PLA/NCC blends, the NCC was deliberately subjected to graft modification by 3-aminopropyltriethoxysilane (KH-550). The as-prepared PLA/NCC composite films were further characterized by using SEM, FTIR, X-ray diffraction, UV-visible spectra analysis, thermal analysis, air permeability and mechanical measurements. Results showed that silanized NCC (SNCC) addition had an important effect on the overall properties of PLA based composite films. The increased SNCC was found to impart improvement in air permeability, light resistance, thermal stability and mechanical properties to the PLA based composite films. Particularly, in comparison to the controlled sample, the obtained PLA based composite films with 0.5 wt % SNCC showed increases of 53.87%, 61.46% in the tensile strength and elongation at break, respectively. Moreover, PLA/SNCC composite films exhibited a decrease of 87.9% in air permeability compared with pure PLA film. Therefore, this work may offer an effective route for reinforcing PLA based composite films.

Exopolysaccharide Produced by Lactobacillus casei Promotes the Differentiation of CD4+ T Cells into Th17 Cells in BALB/c Mouse Peyer's Patches in Vivo and in Vitro.

The immunomodulatory activity of a few Lactobacillus exopolysaccharides (EPS) has been reported. However, whether Lactobacillus EPS can promote the differentiation of CD4 T lymphocytes (CD4+T) cells into T-helper 17 cells (Th17 cells) in the Peyer's Patches (PPs) of mice has not been addressed. In this study, we found the molecular weight (Mw) of the purified EPS from L. casei ranged from 2.7 × 106 Da to 1.7 × 107 Da, and the average Mw was approximately 8.4 × 106 Da. In healthy BALB/c mice, EPS elevated the numbers of Th17 cells and levels of Th17-related cytokines. In vitro, EPS induced BMDCs to stimulate the differentiation of CD4+T cells of PPs into Th17 cells and the related cytokine secretions. Results suggest that L. casei EPS can effectively induce and promote the differentiation of CD4+T cells of PPs into Th17 cells in healthy mice and has the potential ability to improve intestinal mucosa immunity.