Effect of Substituents on Molecular Reactivity during Lignin Oxidation by Chlorine Dioxide: A Density Functional Theory Study.

Lignin is a polymer with a complex structure. It is widely present in lignocellulosic biomass, and it has a variety of functional group substituents and linkage forms. Especially during the oxidation reaction, the positioning effect of the different substituents of the benzene ring leads to differences in lignin reactivity. The position of the benzene ring branched chain with respect to methoxy is important. The study of the effect of benzene substituents on the oxidation reaction's activity is still an unfinished task. In this study, density functional theory (DFT) and the m062x/6-311+g (d) basis set were used. Differences in the processes of phenolic oxygen intermediates formed by phenolic lignin structures (with different substituents) with chlorine dioxide during the chlorine dioxide reaction were investigated. Six phenolic lignin model species with different structures were selected. Bond energies, electrostatic potentials, atomic charges, Fukui functions and double descriptors of lignin model substances and reaction energy barriers are compared. The effects of benzene ring branched chains and methoxy on the mechanism of chlorine dioxide oxidation of lignin were revealed systematically. The results showed that the substituents with shorter branched chains and strong electron-absorbing ability were more stable. Lignin is not easily susceptible to the effects of chlorine dioxide. The substituents with longer branched chains have a significant effect on the flow of electron clouds. The results demonstrate that chlorine dioxide can affect the electron arrangement around the molecule, which directly affects the electrophilic activity of the molecule. The electron-absorbing effect of methoxy leads to a low dissociation energy of the phenolic hydroxyl group. Electrophilic reagents are more likely to attack this reaction site. In addition, the stabilizing effect of methoxy on the molecular structure of lignin was also found.

High-Strength, High-Water-Retention Hemicellulose-Based Hydrogel and Its Application in Urea Slow Release.

The use of fertilizer is closely related to crop growth and environmental protection in agricultural production. It is of great significance to develop environmentally friendly and biodegradable bio-based slow-release fertilizers. In this work, porous hemicellulose-based hydrogels were created, which had excellent mechanical properties, water retention properties (the water retention ratio in soil was 93.8% after 5 d), antioxidant properties (76.76%), and UV resistance (92.2%). This improves the efficiency and potential of its application in soil. In addition, electrostatic interaction and coating with sodium alginate produced a stable core-shell structure. The slow release of urea was realized. The cumulative release ratio of urea after 12 h was 27.42% and 11.38%, and the release kinetic constants were 0.0973 and 0.0288, in aqueous solution and soil, respectively. The sustained release results demonstrated that urea diffusion in aqueous solution followed the Korsmeyer-Peppas model, indicating the Fick diffusion mechanism, whereas diffusion in soil adhered to the Higuchi model. The outcomes show that urea release ratio may be successfully slowed down by hemicellulose hydrogels with high water retention ability. This provides a new method for the application of lignocellulosic biomass in agricultural slow-release fertilizer.

Polydopamine-Modified Cellulose Nanofibril Composite Aerogel: An Effective Dye Adsorbent.

In this study, a new cellulose nanofibril (CNF) composite aerogel was fabricated using a green and facile mussel-inspired coating strategy. First, the CNF hydrogel was crosslinked by calcium ion followed by immersion in dopamine solution. Second, the surface of CNF was modified using polydopamine (PDA) to obtain PDA@CNF (PCNF) composite aerogel. The PCNF composite aerogels had large surface areas (368.15 m2/g) and low bulk density (27.2 mg/cm3). The composite aerogel exhibited improved mechanical properties, which were almost three times compared with those of CNF aerogel. Moreover, PCNF composite aerogel had good resilience under a wet state. The PDA functional layer remarkably enhanced the adsorption capacities of the composite aerogel for methylene blue (MB). The maximum adsorption of MB was 208 mg/g at an initial dye concentration of 50 mg/L. The adsorption isotherm and kinetic behaviors of the composite aerogel were consistent with Langmuir and pseudo-second-order models. In addition, the PCNF composite aerogels had a high adsorption capacity over a wide pH range. The reuse experiment showed that the removal efficiency of the composite aerogel remained higher than 85% after five cycles. Therefore, PCNF composite aerogels may have potential application in wastewater treatment due to its environmental sustainability and low energy consumption.

Efficient Separation and Recovery of Petroleum Hydrocarbon from Oily Sludge by a Combination of Adsorption and Demulsification.

The treatment of oily sludge (OS) can not only effectively solve environmental pollution but also contribute to the efficient use of energy. In this study, the separation effect of OS was analyzed through sodium lignosulfonate (SL)-assisted sodium persulfate (S/D) treatment. The effects of SL concentration, pH, temperature, solid-liquid ratio, revolving speed, and time on SL adsorption solubilization were analyzed. The effects of sodium persulfate dosage, demulsification temperature, and demulsification time on sodium persulfate oxidative demulsification were analyzed. The oil removal efficiency was as high as 91.28%. The results showed that the sediment was uniformly and finely distributed in the S/D-treated OS. The contact angle of the sediment surface was 40°, and the initial apparent viscosity of the OS was 56 Pa·s. First, the saturated hydrocarbons and aromatic hydrocarbons on the sediment surface were adsorbed by the monolayer adsorption on SL. Stubborn, cohesive oil agglomerates were dissociated. Sulfate radical anion (SO4-·) with a high oxidation potential, was formed from sodium persulfate. The oxidation reaction occurred between SO4-· and polycyclic aromatic hydrocarbons. A good three-phase separation effect was attained. The oil recovery reached 89.65%. This provides theoretical support for the efficient clean separation of oily sludge.

Effects of the Preferential Oxidation of Phenolic Lignin Using Chlorine Dioxide on Pulp Bleaching Efficiency.

Chlorine dioxide is widely used for pulp bleaching because of its high delignification selectivity. However, efficient and clean chlorine dioxide bleaching is limited by the complexity of the lignin structure. Herein, the oxidation reactions of phenolic (vanillyl alcohol) and non-phenolic (veratryl alcohol) lignin model species were modulated using chlorine dioxide. The effects of chlorine dioxide concentration, reaction temperature, and reaction time on the consumption rate of the model species were also investigated. The optimal consumption rate for the phenolic species was obtained at a chlorine dioxide concentration of 30 mmol·L-1, a reaction temperature of 40 °C, and a reaction time of 10 min, resulting in the consumption of 96.3% of vanillyl alcohol. Its consumption remained essentially unchanged compared with that of traditional chlorine dioxide oxidation. However, the consumption rate of veratryl alcohol was significantly reduced from 78.0% to 17.3%. Additionally, the production of chlorobenzene via the chlorine dioxide oxidation of veratryl alcohol was inhibited. The structural changes in lignin before and after different treatments were analyzed. The overall structure of lignin remained stable during the optimization of the chlorine dioxide oxidation treatment. The signal intensities of several phenolic units were reduced. The effects of the selective oxidation of lignin by chlorine dioxide on the pulp properties were analyzed. Pulp viscosity significantly increased owing to the preferential oxidation of phenolic lignin by chlorine dioxide. The pollution load of bleached effluent was considerably reduced at similar pulp brightness levels. This study provides a new approach to chlorine dioxide bleaching. An efficient and clean bleaching process of the pulp was developed.

High-Efficiency and High-Quality Extraction of Hemicellulose of Bamboo by Freeze-Thaw Assisted Two-Step Alkali Treatment.

Hemicellulose is a major component of the complex biomass recalcitrance structure of fiber cell walls. Even though biomass recalcitrance protects plants, it affects the effective utilization of lignocellulosic biomass resources. Therefore, the separation and extraction of hemicellulose is very important. In this study, an improved two-step alkali pretreatment method was proposed to separate hemicellulose efficiently. Firstly, 16.61% hemicellulose was extracted from bamboo by the weak alkali treatment. Then, the physical freezing and the alkali treatment were carried out by freezing at -20 °C for 12.0 h and thawing at room temperature, heating to 80 °C, and treating with 5.0% sodium hydroxide for 90 min; the extraction yield of hemicellulose reached 73.93%. The total extraction yield of the two steps was 90.54%, and the molecular weight and purity reached 44,865 g·mol-1 and 89.60%, respectively. It provides a new method for breaking the biomass recalcitrance of wood fiber resources and effectively extracting hemicellulose.

Isolation, Purification, and Antioxidant Activities of Polysaccharides from Choerospondias axillaris Leaves.

The extraction, characterization and antioxidant activity of polysaccharides from Choerospondias axillaris leaves were investigated in the present study. Two purified polysaccharide fractions, CALP-1 and CALP-2, were isolated from crude Choerospondias axillaris leaf polysaccharides (CALP) by DEAE-52 cellulose chromatography and Sephadex G-100 column chromatography. The characteristics of CAL-1 and CALP-2 were determined by using High-performance Gel Permeation Chromatography (HPGPC), High-Performance Anion-Exchange Chromatography, HPAEC (HPAEC-PAD) and Fourier transform infrared spectroscopy (FTIR). CALP-1 with molecular weight of 11.20 KDa was comprised of Rhamnose, Arabinose, Galactose, Glucose, Xylose, Mannose and galacturonic acid in a molar ratio of 5.16:2.31:5.50:27.18:1.00:0.76:1.07. CAL-2 with molecular weight of 8.03 KDa consisted of Rhamnose, Arabinose, Galactose, Glucose, and galacturonic acid at a ratio of 1.38:3.63:18.84:8.28:1.45. FTIR revealed that CALP-1 and CALP-2 were acidic polysaccharides. The antioxidant activity of crude CALP, CALP-1 and CALP-2 was evaluated in vitro. The fraction CALP-2 was demonstrated to be of polysaccharide nature containing a large percentage of Galactose but no Xylose and Mannose. The antioxidant activity assays showed that CALP-1 and CALP-2 exhibited antioxidant and scavenging activities on hydroxyl and DPPH radicals in vitro. Compared with pure polysaccharide, crude CALP exhibited stronger anti-oxidant activities. These results will provide a better understanding of Choerospondias axillaris leaf polysaccharide and promote the potential applications of Choerospondias axillaris leaf polysaccharide in the pharmacological field and as a natural antioxidant.

A comprehensive review of chloropropanol analytical method in the context of food safety.

Chloropropanols are among the major food contaminants, and quantifying their content in food is a key food-safety issue. In response to the demand for highly sensitive and selective analysis, the scientific community is committed to continuous innovation and optimization of various analytical techniques. This paper comprehensively reviews the latest developments in chloropropanol analysis technologies and systematically compares and analyzes the working principles, application conditions, advantages, and challenges of these methods. Gas chromatography-mass spectrometry is the preferred choice for chloropropanol analysis in complex sample matrices owing to its high resolution, sensitivity, and accuracy. Electrochemical methods provide strong support for the real-time monitoring of chloropropanols because of their high selectivity and sensitivity towards electrochemically active molecules. Other techniques offer innovative solutions for the rapid and accurate analysis of chloropropanol at different levels. Finally, innovative directions for the development of chloropropanol analysis methods for food safety are highlighted.

Differential Studies on the Structure of Lignin-Carbohydrate Complexes (LCC) in Alkali-Extracted Plant Hemicelluloses.

Hemicellulose extracted by alkali treatment is of interest because of the advantages of its intact sugar structure and high degree of polymerization. However, the hemicellulose extracted by alkali treatment contained more lignin fragments and the presence of a lignin-carbohydrate complex (LCC), which affected the isolation and purification of hemicellulose and its comprehensive utilization. Therefore, the evaluation of the LCC structure of different types of lignocellulosic resources is of great significance. In this study, the LCC structures of hardwoods and Gramineae were enriched in alkaline systems. Information on the composition, structural proportions, and connection patterns of LCC samples was discussed. The similarities and differences between the LCC structures of different units of raw materials were comparatively studied. The results indicated that the monosaccharide fractions were higher in the LCC of Gramineae compared to hardwoods. The composition of the lignin fraction was dominated by G and S units. The phenyl glycosidic (PhGlc) bond is the predominant LCC linkage under alkali-stabilized conditions. In addition, Gramineae PhGlc types are more numerous compared to hardwoods. The results of the study provide insights into the differences in the chemical composition and structural features of LCC in different plants and provide important guidance for the optimization of the process of purifying hemicellulose.

Efficient degradation of lignin by chlorine dioxide and preparation of high purity pulp fiber.

High-purity pulp fibers can be obtained by using chlorine dioxide to oxidize lignin. However, organic halogen compounds (AOX) are generated from chlorination side reactions during the lignin oxidation process. In this study, phenolic lignin model compounds with different substituents were selected. The effects of substituent position on the production of free radicals and oxidative ring opening in benzene rings were analyzed. It was found that the structural transformation of lignin and the reaction consumption of ClO2 were significantly changed under high concentration of ClO2. The molar consumption ratio of compound to ClO2 was increased from 1:2 to 1:3. Quinone, an intermediate product that promotes the formation of phenoxy radicals, was found to be stabilized in the reaction. This is attributed to that the benzene ring of lignin is activated through long-range electrostatic interactions. The formation of free radicals and the oxidative ring-opening reaction of benzene rings were facilitated. The efficient oxidation of lignin by ClO2 was fulfilled. Chlorination reactions of lignin were suppressed at elevated oxidation efficiency. The pollution load of wastewater was significantly reduced. AOX generation was reduced by 69.27 %. This provides a new method for efficient oxidative degradation of lignin and preparation of high purity pulp fiber.

Unveiling the Dissolution Regularities of the Lignin-Carbohydrate Complex in Bamboo Cell Walls during Alkali Pretreatment.

Bamboo is a promising biomass resource. However, the complex multilayered structure and chemical composition of bamboo cell walls create a unique anti-depolymerization barrier, which increases the difficulty of separation and utilization of bamboo. In this study, the relationship between the connections of lignin-carbohydrate complexes (LCCs) within bamboo cell walls and their multilayered structural compositions was investigated. The chemical composition, structural properties, dissolution processes, and migration mechanisms of LCCs were analyzed. Alkali-stabilized LCC bonds were found to be predominantly characterized by phenyl glycoside (PhGlc) bonds along with numerous p-coumaric acid (PCA) linkage structures. As demonstrated by the NMR and CLSM results, the dissolution of the LCC during the alkaline pretreatment process was observed to migrate from the inner secondary wall (S-layer) of the bamboo fiber cell walls to the cell corner middle lamella (CCML) and compound middle lamella (CML), ultimately leading to its release from the bamboo. Furthermore, the presence of H-type lignin-FA-arabinoxylan linkage structures within the bamboo LCC was identified with their primary dissolution observed in the S-layer of the bamboo fiber cell walls. The study results provided a clear target for breaking down the anti-depolymerization barrier in bamboo, signifying a major advancement in achieving the comprehensive separation of bamboo components.

Anaerobic biotransformation of hexachlorocyclohexane isomers in aqueous condition: Dual CCl isotope fractionation and impact on microbial community compositions.

Hexachlorocyclohexane (HCH) isomers are persistent organic pollutants (POPs) with high toxicity, lipid solubility, chemical stability. Despite the current ban on usage of Lindane, residual contamination cannot be ignored, and HCH are frequently detected in groundwater and threaten human health. Cultures capable of degrading α-HCH, ß-HCH, γ-HCH, and δ-HCH individually have been enriched in anoxic aqueous conditions. Compound-Specific Isotope Analysis (CSIA) was applied to examine the transformation mechanisms of different HCH isomers by the four enrichment cultures. 16S rRNA sequencing techniques were employed to examine the community composition of the enrichment cultures and detect changes in these communities resulting from adding individual HCH isomers. The results indicated that the ability of the enrichment cultures for dichloroelimination of HCH isomers was inconsistent. During dichloroelimination, different bond cleavage mode of ß- and δ-HCH led to distinct isotopic effects. HCH isomers had significant impact on the microbial community, while different microbial communities showed comparable isotopic effects during the transformation of a specific HCH isomer. In addition, bacteria in the phyla Proteobacteria and Firmicutes were proposed as the dominant dechlorinators. This study provides a novel perspective on the mode of bond cleavage during HCH dichloroelimination and the effect of HCH on microbial communities, which could potentially support the evaluation of HCH transformation by CSIA and their effects on the microecosystems of groundwater.

A facile strategy to fabricate antibacterial hydrophobic, high-barrier, cellulose papersheets for food packaging.

As a traditionally used packaging material, natural cellulose-based paper has poor barrier properties to water and oxygen, which severely limits its wide application in food packaging. In this study, we report a new sustainable approach to producing hydrophobic, high-barrier, and antibacterial packaging materials from cellulose paper. In this process, commercially available microcrystalline cellulose was first modified by long-chain stearic acid to form hydrophobic microcrystalline cellulose ester and then mixed with stearic acid as filler in the subsequent surface coating of bagasse fibre paper. The microcrystalline cellulose ester/stearic acid-coated paper (MSP) exhibited good water repellency and oxygen barrier activity due to a continuous hydrophobic film that formed, which completely covered the pores of the original bagasse fibre paper. The coated MSP sample also showed excellent dimensional stability in water and a good wet tensile strength of 16 MPa. In addition, poly(hexamethylene guanidine) (PHMG) was chemically grafted onto the free carboxyl groups of the MSP surface layer, and the resulting MSP-g-PHMG samples exhibited excellent antibacterial activity against Escherichia coli and Listeria monocytogenes. The biodegradable cellulose-based MSP-g-PHMG sample significantly delayed the decay of raspberry during storage, indicating its potential application in food packaging.

Distinct microplastics abundance variation in root-associated sediments revealed the underestimation of mangrove microplastics pollution.

Mangrove sediment is acknowledged as the critical sink of microplastics (MPs). However, the potential effect of mangrove root systems on the MPs migration in sediment remains largely unknown. Here, our study characterized the spatial distribution of MPs trapped in root hair, rhizosphere, and non-rhizosphere zones, and analyzed their correlations with physicochemical properties of sediments. The significantly increased MPs abundances toward root systems shed light on the distinct effect on the migration of MPs exerted by mangrove root systems. Partial least squares path modeling (PLS-PM) analysis revealed that pore water content and pH influenced the abundances of different MP characteristics (shape, color, size, and type) and further promoted the accumulation of MPs toward the root systems. In different mangrove areas from landward to seaward, other sediment properties (median grain size, clay content, and salinity) also controlled MP distribution. Additionally, smaller-sized MPs (<1000 µm) were more easily transported to the root systems. Our study emphasizes the importance of considering root systems effect when investigating the mechanisms of MPs distribution and migration in mangrove sediments.

A facile strategy to fabricate high-barrier, water- and oil-repellent paper with carboxymethyl cellulose/collagen fiber/modified polyvinyl alcohol.

Due to the increasingly serious environmental and human health hazards brought by traditional food packaging materials, paper-based packaging materials have become increasingly popular among consumers in recent years. Currently, the fabrication of fluorine-free degradable water- and oil-repellent paper using low-cost bio-based polymers by a simple method is a hot subject in the field of food packaging. In this work, we used carboxymethyl cellulose (CMC), collagen fiber (CF), and modified polyvinyl alcohol (MPVA) to create coatings that were impervious to water and oil. The homogeneous mixture of CMC and CF generated electrostatic adsorption to impart excellent oil repellency to the paper. PVA was chemically modified by sodium tetraborate decahydrate, and the MPVA coating imparted excellent water-repellent properties to the paper. Finally, the water- and oil-proof paper showed excellent water repellency (Cobb value: 1.12 g/m2), oil repellency (kit rating: 12/12), low air permeability (0.3 µm/Pa·s), and stronger mechanical properties (4.19 kN/m). This non-fluorinated degradable water- and oil-repellent paper with high barrier properties prepared by a convenient method is expected to be in widespread use in the food packaging field.

High-performance arabinoglucuronoxylan-based biosurfactants for oily sludge separation.

Arabinoglucuronoxylan (AGX), an important carbohydrate polymer in lignocellulosic biomass, contains many functional groups. It has excellent amphiphilic modification properties and has potential application in the separation of oily sludge. In this study, a simple strategy for producing high-performance AGX-based biosurfactants was studied and the raw AGX was extracted from bamboo by hydrothermal treatment. AGX-based biosurfactants with amphiphilic structure were produced by AGX and dodecanal succinic anhydride (DDSA) using rapid homogeneous esterification reactions in deep eutectic solvents (DES). This resulted in a significant reduction in the surface tension of the water from 72.32 to 29.76 mN·m-1. These parameters are similar to those achieved using sodium dodecyl sulfate (SDS), a widely employed synthetic surfactant. Other physicochemical properties, including foamability, emulsification activity, stability, solubilization, and detergency were significantly improved compared to the unmodified AGX, demonstrate that AGX-based biosurfactants are promising detergents for oily sludge remediation and oil recovery. The results provide a new pathway for high value utilization of arabinoglucuronoxylan.

Simultaneous achievement of efficient hemicellulose separation and inhibition of lignin repolymerization using pyruvic acid treatment.

The efficiency of organic acid treatment in the conversion of lignocellulosic biomass fractions has been widely recognized. In this study, a novel green pyruvic acid (PA) treatment is proposed. The higher separation efficiency of eucalyptus hemicellulose was obtained at 4.0% PA and 150 °C. The hemicellulose separation yield was increased from 71.71 to 88.09% compared to glycolic acid (GA) treatment. In addition, the treatment time was significantly reduced from 180 to 40 min. The proportion of cellulose in the solid increased after PA treatment. However, the accompanying separation of lignin was not effectively controlled. Fortunately, a six-membered ring structure was formed on the diol structure of the lignin ß-O-4 side chain. Fewer lignin-condensed structures were observed. High-value lignin rich in phenol hydroxyl groups were obtained. It provides a green path for the simultaneous achievement of efficient hemicellulose separation and inhibition of lignin repolymerization using organic acid treatment.

Rapid and mild fractionation of hemicellulose through recyclable mandelic acid pretreatment.

The development of organic acid pretreatments from biological sources is essential to facilitate the progress of green and sustainable chemistry. In this study, the effectiveness of mandelic acid pretreatment (MAP) was analyzed for eucalyptus hemicellulose separation. 83.66% of xylose was separated under optimal conditions (temperature: 150 °C; concentration: 6.0 wt%; time: 80 min). The hemicellulose separation selectivity is higher than acetic acid pretreatment (AAP). The stable and effective separation efficiency (56.55%) is observed even after six reuses of the hydrolysate. Higher thermal stability, larger crystallinity index and optimized surface element distribution in the samples were demonstrated by MAP. Lignin condensation is effectively inhibited through MAP, as determined from the structural of different lignin. In particular, the demethoxylation of lignin by MA was found. These results open up a new way to construct a novel organic acid pretreatment for separating hemicellulose with high efficiency.

Pretreatment of poplar with eco-friendly levulinic acid to achieve efficient utilization of biomass.

Organic acid pretreatment is an effective method for green separation of lignocellulosic biomass. However, repolymerization of lignin seriously affects the dissolution of hemicellulose and the conversion of cellulose during organic acid pretreatment. Therefore, a new organic acid pretreatment, levulinic acid (Lev) pretreatment, was studied for the deconstruction of lignocellulosic biomass without adding additional additives. The preferred separation of hemicellulose was realized at Lev concentration 7.0%, temperature 170 °C, and time 100 min. The separation of hemicellulose increased from 58.38% to 82.05% compared with acetic acid pretreatment. It was found that the repolymerization of lignin was effectively inhibited in the efficient separation of hemicellulose. This was attributed to the fact that γ-valerolactone (GVL) is a good green scavenger of lignin fragments. The lignin fragments in the hydrolysate were effectively dissolved. The results provided theoretical support for creating green and efficient organic acid pretreatment and effectively inhibiting lignin repolymerization.

Polydopamine-Reinforced Hemicellulose-Based Multifunctional Flexible Hydrogels for Human Movement Sensing and Self-Powered Transdermal Drug Delivery.

The preparation of bio-based hydrogels with excellent mechanical properties, stable electrochemical properties, and self-adhesive properties remains a challenge. In this study, nano-polydopamine-reinforced hemicellulose-based hydrogels with typical multistage pore structures were prepared. The nanocomposite hydrogels exhibit stable mechanical properties and show no significant crushing phenomenon after 1000 cycles of cyclic compression. Its ultimate tensile strain was 101%, which is significantly higher than that of native skin. The shear adhesion strength of the hydrogel to skin tissue reaches 7.52 kPa, which is better than fibrin glue (Greenplast) (5 kPa), and the excellent adhesion property prolongs the service time of the hydrogel in biomedicine applications. The impedance of the hydrogel was reduced and the electrical conductivity was increased with the addition of nano-polydopamine. The prepared nanocomposite hydrogel can detect various body movements (even throat vibrations) in real time as a motion sensor while being able to rapidly load cationic drugs and facilitate transdermal introduction of electrically stimulated drug ions as a drug patch. It provides theoretical support for the fabrication of hemicellulose-based hydrogels with excellent properties through molecular design and nanoparticle reinforcement. This has important implications for the development of next-generation flexible materials suitable for health monitoring and self-administration.