The Synergetic Reduction of the Condensation Degree of Dissolved Lignin (DL) during the Refining Process of Wheat Straw Biomass Based on the MA/O3 System.

Lignin, a natural pol2ymer with a complex structure that is difficult to separate, is prone to C-C bond condensation during the separation process. To reduce the condensation of lignin, here, a novel method is proposed for separating the components by using a combination of maleic acid (MA)/ozone (O3) to co-treat wheat straw. The removal of lignin, glucan, and xylan was 38.07 ± 0.2%, 31.44 ± 0.1%, and 71.98 ± 0.1%, respectively, under the conditions of ball-milling of wheat straw for 6 h, reaction temperature of 60 °C, and O3 holding time of 9 min. Lignin-rich solutions were collected to extract the dissolved lignin (DL) after washing the treated samples. The DL obtained under MA/O3 conditions had a carboxyl group (-COOH) content of 2.96 mmol/g. The carboxyl group of MA underwent esterification with the hydroxyl group (-OH) at the γ position of lignin and O3 reacted on the positions of the lignin side chain or the phenolic ring, resulting in a break in the side chain and the opening of the phenolic ring to introduce the carboxyl group. The 2D-HSQC-NMR results revealed that the phenolic ring-opening reaction of lignin in the presence of O3 was essentially free of ß-ß and ß-5 condensation bonds.

Heat-sealable, transparent, and degradable arabinogalactan/polyvinyl alcohol films with UV-shielding, antibacterial, and antioxidant properties.

Petroleum-based packaging materials are nondegradable and unsustainable and thus are harmful to the environment. Renewable packaging films prepared from bio-based raw materials are promising alternatives to petroleum-based packaging materials. In this study, colorless and transparent bio-based films were successfully cast using a solution containing a mixture of arabinogalactan (AG) and poly (vinyl alcohol) (PVA). Vanillin was incorporated into the mixture to endow the films with UV-shielding, antioxidant, and antibacterial properties. The morphological, physical, antioxidant, and antibacterial properties of the blend films were then characterized. At an AG:PVA weight ratio of 1:3, and the vanillin content was 0.15 %, the tensile strength of the AG/PVA/Vanillin (APV) films reached ~28 MPa, while their elongation at break reached ~475 %. The addition of vanillin significantly affected the antioxidant and antibacterial properties of the blend films, which exhibited superb UV barrier capacity. The APV films exhibited extremely low oxygen transmittance, delaying the onset of mold/rot in strawberries and reducing their weight loss. Because of the heat sealability of the blend films, they can be used for encapsulating various substances, such as concentrated laundry liquid. Moreover, the blend films were recyclable and biodegradable. Thus, these films have great potential for applications that require sustainable packaging.

Green, recyclable, mechanically robust, wet-adhesive and ionically conductive cellulose-based bioplastics enabled by supramolecular covalent hydrophobic eutectic networks.

The development of novel cellulose-based bioplastics (CBPs) is highly desirable because CBPs are green, rationally use resources, and lead to a reduction in environmental pollution compared to alternative materials. However, incorporating high transparency, water resistance, mechanical robustness, wet-adhesion, ionic conductivity and recyclability into CBP remains a challenge. In this paper, novel CBPs with supramolecular covalent networks are fabricated by introducing polymerizable hydrophobic deep eutectic solvents (HDES) into ethylcellulose (EC) networks through in situ plasticization followed by a rapid photopolymerization process. The excellent molecular interfacial compatibility enables EC to be loaded with a high content of poly(HDES), while allowing high transparency (more than 90 %) of the prepared CBPs. Multiple intermolecular interactions provide CBPs with mechanical robustness, water resistance, and underwater adhesion, and CBPs can be readily recovered by the solvent in a closed loop. Moreover, CBPs possess inherent ionic conductivities, and using them as green substrates, personalized electroluminescent devices can be successfully constructed. The method proposed in this paper provides a new strategy for the preparation of multifunctional CBPs, which will greatly enrich their applications in self-adhesive materials, green flexible electronics and other package materials.

Construction of Poly(hydrophobic deep eutectic solvent)/Ethylcellulose Composite Films for Green Recyclable Tapes.

Constructing green recyclable cellulose-based tapes with high transparency, mechanical robustness, and strong wet adhesion using natural components is highly desirable but challenging. Herein, novel cellulose-based self-adhesive tapes were reported by coating a polymerizable hydrophobic deep eutectic solvent (DES) on ethylcellulose followed by photopolymerization. The prepared ethylcellulose-based self-adhesive tape (ECSAT) exhibited an optical transmittance of up to ∼88% and could provide strong adhesion by interfacial intermolecular interactions without obstructing information. Due to the hydrophobic nature of the overall structure, ECSAT does not exhibit significant adhesive strength and mechanical degradation under water, acid, and alkali environments. Notably, ECSAT can be completely dissolved in the resultant DES and furthermore reused as a self-adhesive coating. The recycled ECSAT still maintained good optical transparency, mechanical strength, and wet adhesion. We believe that ECSATs with all-around performances have a wide range of applications in packaging and other engineering fields.

Self-adhesive, ionic-conductive, mechanically robust cellulose-based organogels with anti-freezing and rapid recovery properties for flexible sensors.

Cellulose-based functional gels have received considerable attention because of their good mechanical properties, biocompatibility, and low cost. However, the preparation of cellulose gels with self-adhesion, mechanical robustness, ionic conductivity, anti-freezing ability, and environmental stability remains a challenge. Here, gallic acid esterified microcrystalline cellulose (MCC-GA) was obtained by grafting gallic acid (GA) onto the macromolecular chains of microcrystalline cellulose (MCC) through a one-step esterification method. Then the prepared MCC-GA was dissolved in Lithium chloride/dimethyl sulfoxide (LiCl/DMSO) system and polymerized with acrylic acid (AA) to prepare a multi-functional cellulose-based organogel. The prepared MCC-GA/polyacrylic acid (PAA) organogels exhibited enhanced interfacial adhesion through hydrogen bonding, π-π interactions, and electrostatic interactions. Additionally, the MCC-GA/PAA organogels could withstand 95 % of the compressive deformation and rapidly self-recover owing to chemical cross-linking and dynamic non-covalent interactions. The organogels also exhibited excellent anti-freezing properties (up to -80 °C), solvent retention, and ionic conductivity. Considering its excellent overall performance, the MCC-GA/PAA organogel was used as an effective flexible sensor for human motion detection and is expected to play an important role in the future development of flexible bioelectronics.

Recyclable, UV-shielding, and biodegradable chitosan-based cardanol glycidyl ether as excellent water and oil resistance as well as gas barrier coating for paper.

Developing a feasible and low-cost approach to fabricate recyclable, UV-shielding, biodegradable as well as water- and oil-resistant coating for paper substance is still a challenge. Herein, novel full-biobased chitosan-derived cardanol glycidyl ether (CS-xCGE, x = 1/8, 1/4, 1/2, and 1) coatings with different contents of cardanol glycidyl ether (CGE) were developed for paper substance via the ethoxylation of cardanol and sequent addition with chitosan in a one-pot process. Benefiting from the hydrophobicity and ultraviolet resistance of CGE, the resultant CS-CGE (x = 1) coated paper exhibited not only remarkable oil resistance (kit rating value of 11/12), but also water resistance (Cobb 60 value of 5.78 g/m2), UV shielding and excellent recyclability. Compared with the uncoated paper, the mechanical properties of CS-CGE coated paper including tensile strength, folding strength, and resistance of water vapor permeability were improved 25 %, 63 %, and 73.4 %, respectively, which could be ascribed to the flexible long-alkyl chain in the structure of CS-CGE and the continuous and homogeneous CS-CGE derived film covered in paper substance. Most importantly, CS-CGE film is biodegradable when it is only buried in soil. This study affords a feasible and sustainable strategy for large-scale fabrication of full-biobased, recyclable, UV-shielding, water and oil resistant, as well as biodegradable coating for green paper-derived packaging.

Water-insensitive self-adhesive elastomers derived from hydrophobic deep eutectic polymers.

Water-insensitive self-adhesive elastomers derived from hydrophobic deep eutectic polymers (HDEPs) are reported. With the help of hydrophobic π-π interactions and dynamic hydrogen bonding networks, the HDEPs performed excellent self-adhesive properties on various materials, even in aqueous environments.

Biomass-based indole derived composited with cotton cellulose fiber integrated as sensitive fluorescence platform for NH3 detection and monitoring of seafood spoilage.

Herein, an indole-derived water-soluble fluorescence nanomaterial and biomass-based cellulose filter paper integrated as solid-state fluorescence platform (H2-FP) for seafood spoilage detection was prepared. H2 exhibits high fluorescence stability and good biocompatibility with green beans, onion tissues, blood and zebrafish, which proving that H2 has a wide range of application scenarios. Further, H2-FP with effective, solid-state fluorescence, portable, and reusable characteristics is nanoengineered for NH3 quantitative and qualitative detection (DOL = 2.6 ppm). Then, H2-FP has been successfully used to monitor NH3 release in the seafood spoilage process at various storage time (4 °C and 25 °C). More importantly, fluorescence color of H2-FP is integrated smartphone are converted to digital values through RGB channels and successfully used to visualize semi-quantitative recognition of NH3. This sensing fluorescence platform integrated with smartphone furnishes an effective fabrication strategy and broad prospects for explore various biomass-based materials for sensing NH3 change in biological and environmental samples.

A biomass-derived Schiff base material composited with polylactic acid nanofiber membrane as selective fluorescent 'turn off/on' platform for Pb2+ quantitative detection and characterization.

Herein, a biomass-derived compound Z1 is synthesized via 'one pot' method for detection Pb2+ using fluorescence and visual dual-mode in aqueous solution. Z1 shows good response to Pb2+ with a limit of detection (LOD) of 13.4 nM. Importantly, the coordination mode of Z1 with Pb2+ is further evaluated by UV-vis and NMR spectroscopy and a 1:1 stoichiometry is identified. Furthermore, Z1 can be applied to detection Pb2+ in practical samples with satisfactory recoveries in range of 96.0 %-112.0 % in real samples. Besides, Z1 is added into polylactic acid (PLA) solution and made as portable fluorescence nanofiber membrane for Pb2+ detection. Further, Z1 responds to Pb2+ with high selectivity and sensitivity and has been applied for tracking Pb2+ changes in soil samples, zebrafish, and plant tissues. These results indicated that Z1 had great application potential in accurate detection Pb2+.

Enhancement of the antioxidant abilities of lignin and lignin-carbohydrate complex from wheat straw by moderate depolymerization via LiCl/DMSO solvent catalysis.

A facile and environmentally-friendly strategy for increasing antioxidant activity is a crucial issue for value-added lignin and lignin-carbohydrate complex (LCC) as alternative antioxidants. However, the antioxidant activities of lignin and LCC by the traditional solid-liquid extraction (SLE) methods were restricted by the relatively lower solubility induced from high molecular weight (Mw), and the less functional groups including, phenolic hydroxyl and carboxyl. To improve the antioxidantion of lignin and LCC, lithium chloride/dimethyl sulfoxide (LiCl/DMSO) solvent fractionation (LDSF) was conducted to increase the functional groups and reduce Mw, in which LiCl/DMSO acted triple roles as solvent, acid, and metal chloride catalyst for the depolymerization reaction synchronously. The ß-O-4' linkages were cleaved to release the phenolic hydroxyl, resulting in decreasing Mw; the hydroxyl of the side-chain of lignin was oxidized into carboxyl. Thus, the lignin (LD-RL) and LCC (LD-LCC) samples from LDSF had a higher syringyl (S)/guaiacyl (G) ratio, phenolic hydroxyl, and carboxyl contents, but less Mw than control groups from SLE. Consequently, they presented more excellent scavenging rates toward DPPH and ABTS radicals, up to 90%. This work provided panoramic perspectives and basics of the green and convenient approach to isolate and modify lignin and LCC for great antioxidantion with LDSF.

Efficient isolation of organosolv lignin-carbohydrate complexes (LCC) with high antioxidative activity via introducing LiCl/DMSO dissolving.

Lignin-carbohydrate complexes (LCC) have shown great potential as biocompatible antioxidants. But it is difficult to isolate LCC efficiently from lignocellulose by traditional Solid-Liquid Extraction method (SLE), which is blamed to the innate bioimpedance caused by the complex supramolecular structure of the lignocellulose, and a great mass transferring resistance between the extracting solution and solid lignocellulose. To release these restrictions above and improve the efficiency of LCC isolation, a modified isolating method named Liquid-Liquid Extraction (LLE) was proposed, in which ball-milled wheat stalk was dissolved in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) solution, then regenerated by dioxane aqueous to extract LL-LCCs. The effect of the LLE on the LCC isolating was evaluated and results showed that both the total yield and antioxidant activity of LL-LCCs were higher than that of control group. It proved the dissolution of wheat stalk in LiCl/DMSO solution could reduce the mass transfer resistance during the extraction. Due to the catalyzation of LiCl as Lewis acid, LL-LCCs had lower molecular weight but more phenolic hydroxyl groups and higher S/G ratios. These factors of LL-LCCs resulted in greater free-radical scavenging ability than control sample. The modified isolation protocol could facilitate the isolation and utilization of LCCs as a free-radical scavenger.

Structural characterization and antioxidant activity of water-soluble lignin-carbohydrate complexes (LCCs) isolated from wheat straw.

Lignin-carbohydrate complex (LCC) was proven to possess antioxidant activities. To understand structures and antioxidant activities of LCC, water-soluble LCC-stalk, LCC-sheath and LCC-leaf were isolated from ball-milled wheat straw stalk, sheath and leaf by successive dissolution in LiCl/DMSO solvent, water extraction and purification. LCCs were later structurally characterized by wet chemistry, chromatography and spectroscopy respectively. Their antioxidant activities were evaluated by ferric reducing antioxidant power (FRAP) and DPPH radical scavenging assays. The results showed that three LCCs were carbohydrate-rich (≈70%) and presented relatively narrow molecular weight distribution (PI < 2.0). The lignin moieties of LCCs were mainly connected with ß-O-4' structures, and phenyl glycoside and γ-ester linkages were main LCC linkages in LCCs. However, guaiacyl units were the predominant lignin units in LCC-stalk and LCC-sheath, while syringyl units were predominant in LCC-leaf. Intermolecular cross-linkages were mainly pCA-bridges in LCC-stalk and FA-bridges in LCC-sheath and LCC-leaf. Besides, LCC-sheath featured higher polysaccharide content exhibited higher molecular weight, fewer LCC linkages and better antioxidant activities (DPPH radical scavenging rate up to 74.91%) than both LCC-stalk (74.55%) and LCC-leaf (64.52%). This work helped to know LCCs in wheat straw well and inspire the application of LCC as potential antioxidants.

Fabrication of thermo-sensitive lignocellulose hydrogels with switchable hydrophilicity and hydrophobicity through an SIPN strategy.

Herein, thermo-sensitive lignocellulose hydrogels with varying lignin contents were fabricated with N-isopropylacrylamide (NIPAAm) by a semi-interpenetrating polymer network (SIPN) strategy using a LiCl/DMSO solvent system. Soda lignin mixed with the lignocellulose/LiCl/DMSO solution was also used to prepare the composite hydrogels, and the influence of the existential state of lignin on the hydrogel properties was analyzed objectively. The SIPN hydrogels exhibited more favorable mechanical properties due to the physical entanglement of poly-NIPAAm and lignocellulose. The presence of externally added lignin in the composite hydrogels is beneficial for mechanical improvement. Both the mechanical properties and the morphologies of the SIPN hydrogels can be tuned by varying the existential state and content of lignin. Furthermore, the prepared SIPN hydrogels showed rapid conversion from being hydrophilic at 20 °C to being hydrophobic at 45 °C. All SIPN hydrogels exhibited obvious oil absorbency in an oil/water mixture at 45 °C. Moreover, the different lignin existential states in the hydrogels resulted in different lower critical solution temperatures (LCST). This study provides a feasible route to produce reinforced thermo-sensitive hydrogels and develops a method for tailoring the morphology and the absorption properties of hydrogels by controlling the existential state and content of lignin.

Synthesis of new 4-anilinoquinazoline analogues and evaluation of their EGFR inhibitor activity.

Thirteen of 4-anilinoquinazoline derivatives with imine groups at position 6 of quinazoline ring were synthesized and their antitumor activities were evaluated by MTT assay and Western blotting analysis. Among these compounds, 13a-131 were reported first time. The MTT assay was carried out on three human cancer cell lines (A549, HepG2 and SMMC7721) with EGFR highly expressed. Among the tested compounds, 13i and 13j exhibited notable inhibition potency and their IC50 values on three cell lines were equivalent to or less than those of gefitinib. Compound 14, without imine group substituted, displayed excellent inhibitor potency only on A549 cell line. Compounds 14 and 13j were chosen to perform Western blotting analysis on A549. The results showed that both of the compounds could inhibit the expression level of phosphorylated EGFR remarkably. It was concluded that the inhibitor potency of compound 14 was almost equivalent to that of gefitinib and the inhibitor potency of 13j was better than that of gefitinib.

Distribution study of tryptanthrin in rat tissues by HPLC and its relationship with meridian tropism of indigo naturalis in traditional Chinese medicine.

The aim of the present study is to characterize the distribution of tryptanthrin (TRYP) in rat tissues following oral administration at a dose of 100 mg/kg and its relationship with meridian tropism (MT) of indigo naturalis (IN) in traditional Chinese medicine (TCM). For quantitative analysis in biological samples, a sensitive, inexpensive and accurate high-performance liquid chromatographic method was developed and validated with 2-hydroxy acetophenone as internal standard, a Shimadzu C18 column and water-acetonitrile (55:45, v/v) as mobile phase. Acceptable intra-day and inter-day precision at high, medium and low concentration was acquired with RSD ranging from 0.87 to 5.22% and from 1.25 to 6.47%, respectively. Good assay and extraction recoveries were obtained with a single and relatively fast step to precipitate protein. The extraction recovery of TRYP ranged from 87.5 to 94.5 %. TRYP concentration was highest in the liver and remained for a much longer time than in other tissues. It could also be detected in kidney, lung, heart and spleen, but not in brain under the experimental conditions. The results confirmed the traditional knowledge of TCM that MT of IN belongs to the liver meridians and demonstrated that TRYP is one of the active constituents of the MT of IN.

[Study on the chemical changes of whole constituents in the preparing process of kansui root].

OBJECTIVE: To study the chemical changes of whole constituents in the preparing process of kansui root in order to uncover the mechanism of detoxication in preparing process. METHODS: The raw and prepared kansui were extracted with water and methanol and analyzed with HPLC respectively. RESULTS: Seven constituents disappeared in the prepared kansui and four new consitituents were produced in the water extracts. The concentration of four other constituents decreased. In the methoanol extract, two constituents disappeared and one constituent produced during preparing process. The concentration of six other constituents increased in the methanol extracts. CONCLUSION: The mechanism of detoxication of kansui root preparing process is may be that the toxic constituents decomposing or water solubility reducing.