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Prehydrolysis liquid (PHL) from dissolving pulp and biorefinery industries is rich in saccharides and lignin, being considered as a potential source of value-added materials and platform molecules. This study proposed an environmentally friendly and simple method to prepare morphologically controllable hollow lignin nanoparticles (LNPs) and levulinic acid (LA) from PHL. In the first step, after hydrothermal treatment of PHL with p -toluenesulfonic acid ( p -TsOH), lignin with a uniform molecular weight was obtained to prepare LNPs. The prepared LNPs have an obvious hollow structure, with an average size of 490-660 nm, and exhibit good stability during 30 days of storage. When the as-obtained LNPs were used as a sustained-release agent for amikacin sulfate, the encapsulation efficiency reached over 70% and the release efficiency within 40 h reached 69.2% in a pH 5.5 buffer. Subsequently, the remaining PHL that contains saccharides was directly used for LA production under the catalysis of p -TsOH. At 150 °C for 1.5 h, the LA yield reached 58.4% and remained at 56% after 5 cycles of p -TsOH. It is worth noting that only p -TsOH was used as a reactive reagent throughout the entire preparation process. Overall, this study provided a novel pathway for the integrated utilization of PHL and showed the immense potential of the preparation and application of LNPs.

The pre-hydrolysis liquor (PHL) produced during pulp dissolution and biomass refining is mainly composed of hemicellulose and lignin, and it is a potential source for production of value-added materials and platform chemicals; however, their utilization has been a serious challenge. In this study, we proposed a green and simple strategy to simultaneously prepare size-controlled functional lignin nanoparticles (LNPs) and levulinic acid (LA) from PHL as the raw material. The as-prepared LNPs exhibited remarkable stability thanks to the presence of saccharides with abundant oxygen-containing groups and surface charges, which prevented aggregation and maintained long-term storage stability. Trace amounts of the LNPs (≤ 0.2 wt%) could stabilize various Pickering emulsions, even with oil-to-water ratios as high as 5:5 (v/v). Subsequently, the remaining PHL was directly used to produce LA without adding a catalyst; under optimal conditions (160 °C and 1 h), the yield of LA was 56.3 % based on the dry saccharide content in the raw PHL. More importantly, p-toluenesulfonic acid (p-TsOH), the only reactive reagent used during the entire preparation process, including the two preparation steps of the LNPs and LA, was reusable, and the recovery rate was >70 % after five cycles. Overall, this green and simple strategy effectively and comprehensively utilized the PHL and showed potential for producing biobased nanomaterials and platform chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Selective fractionation of hemicelluloses is of great significance for realizing high-value application of hemicelluloses and comprehensive utilization of lignocellulosic biomass. Tetramethylammonium hydroxide (TMAH) solvent has been confirmed as a promising solvent to selectively fractionate hemicelluloses from holocellulose. Herein, TMAH solvent was adopted to pretreat poplar thermomechanical pulp (PTMP) for the selective fractionation of hemicelluloses and enhancement of enzymatic hydrolysis performance of residues. The maximal hemicelluloses yield (65.0 %) and excellent cellulose retention rate (93.3 %) were achieved after pretreatment by the 25 wt% TMAH solvent, while the delignification was only 33.9 %. The hemicelluloses fractions could be selectively fractionated with high molecular weights (109,800-118,500 g/mol), the contents of Klason lignin in them were low (3.2-5.9 %), and the dominating structure of them was 4-O-methylglucurono-β-D-xylan. Compared to the H 2 SO 4 and NaOH methods, the hemicelluloses fractionated by TMAH method exhibited higher yields, more complete structures and higher molecular weights. Furthermore, the crystalline structure of cellulose practically remained stable, and the highest yield of enzymatic hydrolysis glucose was 57.5 %, which was 3.3 times of that of PTMP. The fractionation effectiveness of TMAH solvent was not significantly reduced after repeatedly recycling. This work demonstrated TMAH solvent could selectively fractionate hemicelluloses from PTMP and efficiently promote sustainable poplar-based biorefinery., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The lignin plays one of the most important roles in plant secondary metabolism. However, it is still unclear how lignin can contribute to the impressive height of wood growth. In this study, C3'H, a rate-limiting enzyme of the lignin pathway, was used as the target gene. C3'H3 was knocked out by CRISPR/Cas9 in Populus tomentosa. Compared with wild-type popular trees, c3'h3 mutants exhibited dwarf phenotypes, collapsed xylem vessels, weakened phloem thickening, decreased hydraulic conductivity and photosynthetic efficiency, and reduced auxin content, except for reduced total lignin content and significantly increased H-subunit lignin. In the c3'h3 mutant, the flavonoid biosynthesis genes CHS, CHI, F3H, DFR, ANR, and LAR were upregulated, and flavonoid metabolite accumulations were detected, indicating that decreasing the lignin biosynthesis pathway enhanced flavonoid metabolic flux. Furthermore, flavonoid metabolites, such as naringenin and hesperetin, were largely increased, while higher hesperetin content suppressed plant cell division. Thus, studying the c3'h3 mutant allows us to deduce that lignin deficiency suppresses tree growth and leads to the dwarf phenotype due to collapsed xylem and thickened phloem, limiting material exchanges and transport., Competing Interests: Declaration of competing interest The authors declare that they have no conflicts of interest associated with this work., (Copyright © 2023. Published by Elsevier B.V.)

This work aimed to study an integrated pretreatment technology employing p-toluenesulfonic acid (TsOH)-catalyzed liquid hot water (LHW) and short-time ball milling for the complete conversion of poplar biomass to xylooligosaccharides (XOS), glucose, and native-like lignin. The optimized TsOH-catalyzed LHW pretreatment solubilized 98.5% of hemicellulose at 160 °C for 40 min, releasing 49.8% XOS. Moreover, subsequent ball milling (20 min) maximized the enzymatic hydrolysis of cellulose from 65.8% to 96.5%, owing to the reduced particle sizes and cellulose crystallinity index. The combined pretreatment reduced the crystallinity by 70.9% while enlarging the average pore size and pore volume of the substrate by 29.5% and 52.4%, respectively. The residual lignin after enzymatic hydrolysis was rich in β-O-4 linkages (55.7/100 Ar) with less condensed structures. This lignin exhibited excellent antioxidant activity (RSI of 66.22) and ultraviolet absorbance. Thus, this research suggested a sustainable waste-free biorefinery for the holistic valorization of biomass through two-step biomass fractionation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Pure deep eutectic solvents (DESs) system of choline chloride (ChCl)/Lactic acid (Lac) were demonstrated to be an effective strategy for extraction of lignin. In this study, two kinds of different promising solid acid (SA) with DESs were designed to promote the pretreatment of lignocellulose. The SA of phosphotungstic acid (H 3 O 40 PW 12 ) and iron bromide (FeBr 3 ) were introduced into DESs to extract poplar wood lignin and evaluate the antioxidant activity. It was found that 82.2% and 80.9% of lignin were obtained from poplar wood under H 3 O 40 PW 12 -ChCl/Lac acid and FeBr 3 -choline ChCl/Lac system with 4 h and 8 h, respectively. The lignin fractions with a high purity (>89%), low molecular weight (Mw 1800-2000 g/mol). Besides, the antioxidant activities of lignin fractions were better than butyl hydroxyanisole (BHA). Therefore, DES lignin has prominent antioxidant activity and could developed a potential natural cosmetics and food packaging., (Copyright © 2021 Elsevier B.V. All rights reserved.)

An integration of different pretreatments is important to overcome recalcitrance and realize efficient bioconversion of lignocellulosic biomass. This study aims at the effects of combination of hydrothermal pretreatment and different chemi-mechanical pretreatments on enzymatic hydrolysis, and understanding the enzymes adsorption mechanism. The combination of hydrothermal and chemi-mechanical pretreatments effectively improved the enzymatic hydrolysis of poplar substrates, in which the enzymatic hydrolysis of substrates pretreated by hydrothermal pretreatment + Fenton pretreatment + mechanical refining (HFM) was the highest (92.39% of glucose conversion yield, and 20.88 g/L of glucose concentration). The substrates' main characteristics were obviously changed after combined pretreatments, such as swelling ability and specific surface area of substrates were increased. The Langmuir adsorption model (R 2  > 0.98) and pseudo second-order adsorption kinetic model (R 2 ≈1) were well suitable to describe the adsorption of enzymes on substrates, meanwhile the adsorption mechanism was summarized., (Copyright © 2021 Elsevier Ltd. All rights reserved.)