Interaction of lignin and xylan in the hydrothermal synthesis of lignocellulose-based carbon quantum dots and their application in in-vivo bioimaging.

The complex interaction of lignin, cellulose, and hemicellulose in the hydrothermal degradation progress of lignocellulose, has led to uncertainty in the hydrothermal synthesis of lignocellulose-based CQDs (LC-CQDs). This makes it difficult to identify the specific formation mechanism of LC-CQDs. To simplify the reaction system and comprehensively describe the formation of LC-CQDs, both lignin and hemicellulose, the main hydrothermal degradation products of lignocellulose, were used as precursor to simulate and explore the synthesis of LC-CQDs at different time intervals (2-12 h). First, different lignin models were employed for preparing CQDs to determine the key lignin structure that govern CQDs formation. G-type lignin-model based CQDs were shown to have higher fluorescence intensity than H- and S-type. Then, G-type lignin model and hemicellulose model (xylan) were used simultaneously hydrothermal to prepare LC-CQDs. The analysis shows that the carbon nucleus preferentially formed by the lignin provides growth sites for small molecules degraded from hemicellulose, which gradually grow around the carbon core over time, thus forming a "sunflower" structure of CQDs. The presence of a lignin model could effectively guide the small molecules toward CQDs formation instead of carbonization. Additionally, the CQDs exhibit good in-vivo imaging performance.

Revealing the relationship between molecular weight of lignin and its color, UV-protecting property.

Lignin has great potential as a natural, green, and sustainable broad-spectrum sunscreen active ingredient. However, the coexistence of dark color and sunscreen properties hinders its application in cosmetics. In this study, we focus on the effects of the molecular weight of lignin on tis UV-protecting property and color in order to prepare lignin-based sunscreen with high performance. A prepared sunscreen containing low molecular weight lignin (F5, <1000 g/mol) exhibits good UV-protecting property (sun protection factor (SPF) = 7.14) and light color advantages (ΔE = 46.2). Moreover, a strong synergistic effect on UV-protecting property exists between low molecular weight lignin and ethylhexyl methoxycinnamate (EHMC), resulting in high SPF of F5@EHMC-based sunscreen (55.56). Additionally, added TiO2 can efficiently mitigate the dark color of lignin-based sunscreens due to prominent covering power of TiO2. Moreover, lignin-based sunscreens have good biocompatibility with HaCaT cells. This work is useful for understanding the mechanism of the UV-protecting property and dark color of lignin, and for designing an efficient and safe lignin-based sunscreen.

Preparation, Properties, and Application of Lignocellulosic-Based Fluorescent Carbon Dots.

Carbon dots (CDs) are a relatively new type of fluorescent carbon material with excellent performance and widespread application. As the most readily available and widely distributed biomass resource, lignocellulosics are a renewable bioresource with great potential. Research into the preparation of CDs with lignocellulose (LC-CDs) has become the focus of numerous researchers. Compared with other carbon sources, lignocellulose is low cost, rich in structural variety, exhibits excellent biocompatibility,[1] and the structures of CDs prepared by lignin, cellulose, and hemicellulose are similar. This Review summarized research progress in the preparation of CDs from lignocellulosics in recent years and reviewed traditional and new preparation methods, physical and chemical properties, optical properties, and applications of LC-CDs, providing guidance for the formation and improvement of LC-CDs. In addition, the challenges of synthesizing LC-CDs were also highlighted, including the interaction of different lignocellulose components on the formation of LC-CDs and the nucleation and growth mechanism of LC-CDs; from this, current trends and opportunities of LC-CDs were examined, and some research methods for future research were put forward.

Enhancing thermal conductivity and toughness of cellulose nanofibril/boron nitride nanosheet composites.

Generally, the thermal conductivity (TC) of composite based on cellulose nanofibrils (CNF) is improved by adding thermal conductive filler, which inevitably leads to the loss of its mechanical properties. In this work, it is the first to simultaneously improve the toughness and TC of CNF/boron nitride nanosheets (BNNS) composite from the perspective of thermal conductive filler addition and CNF crystal change. The hydrophilic-modified BNNSs were successfully prepared by xylose-assisted ball-milling prior to adding into CNF. Compared with that of CNF film (1.34 W/(m·K)), the in-plane TC of CNF/BNNS composite (12.68 W/(m·K)) increased significantly by 846 % with loading 30 % BNNS. Afterwards, both toughness (8.0 MJ·m-3, increased ~250 %) and TC (14.7 W/(m·K), increased ~16 %) of CNF/BNNS composite were further enhanced significantly by mercerization with 12.5 % NaOH solution. The simultaneously improvement of toughness and TC is unprecedented in related studies, which contributes to the effective preparation of thermal management materials.

Utilization of guaiacol-based deep eutectic solvent for achieving a sustainable biorefinery.

This study proposed a renewable deep eutectic solvent (DES) pretreatment using lignin-derived guaiacol as the hydrogen bond donor. The DES showed excellent biomass fractionation efficiency after the incorporation of trace AlCl3 as the reinforcer, which removed 79.1 % lignin while preserving more than 90 % glucan. The pretreated bamboo exhibited 96.2 % glucan enzymatic hydrolysis yield at only 110 °C. The physicochemical properties of the pretreated solids were comprehensively investigated to explain how the DES fractionation overcame the biomass recalcitrance. The regenerated lignin from the DES pretreatment was also analyzed, which revealed that lignin ß-O-4 bond was significantly cleaved. This guaiacol-based DES could greatly contribute to establish a closed-loop biorefinery sequence with high lignin fractionation efficiency and great solvent recyclability.

Fluorescence Enhancement of Lignin-Based Carbon Quantum Dots by Concentration-Dependent and Electron-Donating Substituent Synergy and Their Cell Imaging Applications.

Black liquor is an important pollutant in the pulp industry, but it also has the potential for high-value utilization. In this study, lignin extracted from black liquor was hydrothermally prepared into lignin-based carbon quantum dots (L-CQDs) using a one-pot method. Physicochemical characterization suggested that the L-CQDs exhibited a lamellar core-shell multilayered graphene structure surrounded by oxygen-containing functional groups. The fluorescence intensity of the L-CQDs was strengthened depending on their own concentration dependence and the doping of external groups. The fluorescence intensity of L-CQDs varied between 89.09 and 183.66 under different concentrations, and the most intense fluorescence (183.66) was obtained at 0.1 mg mL-1. At hydroxyl and amino adsorption capacities of 11.08 and 0.98 mmol g-1, the hydroxylated RL-CQDs-5 and aminated NL-CQDs-3 exhibited the highest fluorescence intensities at 689.22 and 605.39, respectively. Moreover, when pristine L-CQDs were sequentially aminated and hydroxylated, the NRL-CQDs' fluorescence intensity reached 1224.92. Cell imaging experiments proved that cells cultivated with NRL-CQDs have brighter fluorescence compared with L-CQDs. The results will render L-CQDs more suitable for practical applications.

A hydrothermal-carbonization process for simultaneously production of sugars, graphene quantum dots, and porous carbon from sugarcane bagasse.

A green and facile approach was proposed to simultaneously produce fermentative sugar (FS), graphene quantum dots (GQDs), and hierarchical porous carbon (HPC) from sugarcane bagasse through the hydrothermal-carbonization process. In this work, the maximum yields of FS were 35.77%, 30.54%, 1.23%, 28.52%, and 41.85% for xylose, mannose, glucose, galactose, and arabinose, respectively. The GQDs, with bright blue fluorescence, had an average diameter at 2.26 nm, and exhibited a well-defined spherical shape and graphene structure. The formation mechanism of GQDs was further investigated, and the GQDs mainly derived from the dissolved lignin and polysaccharides. Moreover, the HPC presented a much higher surface area and controllable oxygen content than non-hydrothermal pretreatment porous carbon, whose unique pore structure was mainly resulted from the dissolution of FS. The green and facile approach provides a novel pathway to produce high value-added materials from sugarcane bagasse, developing a foundation for the preparation of better biomass materials.

Surface characterization and chemical analysis of bamboo substrates pretreated by alkali hydrogen peroxide.

The surface characterization and chemical analysis of bamboo substrates by alkali hydrogen peroxide pretreatment (AHPP) were investigated in this study. The results tended to manifest that AHPP prior to enzymatic and chemical treatment was potential for improving accessibility and reactivity of bamboo substrates. The inorganic components, organic solvent extractives and acid-soluble lignin were effectively removed by AHPP. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface of bamboo chips had less lignin but more carbohydrate after pre-treatment. Fiber surfaces became etched and collapsed, and more pores and debris on the substrate surface were observed with Scanning Electron Microscopy (SEM). Brenauer-Emmett-Teller (BET) results showed that both of pore volume and surface area were increased after AHPP. Although XRD analysis showed that AHPP led to relatively higher crystallinity, pre-extraction could overall enhance the accessibility of enzymes and chemicals into the bamboo structure.

Removal of hexenuronic acid by xylanase to reduce adsorbable organic halides formation in chlorine dioxide bleaching of bagasse pulp.

Xylanase-aided chlorine dioxide bleaching of bagasse pulp was investigated. The pulp was pretreated with xylanase and followed a chlorine dioxide bleaching stage. The ATR-FTIR and XPS were employed to determine the surface chemistry of the control pulp, xylanase treated and chlorine dioxide treated pulps. The hexenuronic acid (HexA) could obviously be reduced after xylanase pretreatment, and the adsorbable organic halides (AOX) were reduced after chlorine dioxide bleaching. Compared to the control pulp, AOX could be reduced by 21.4-26.6% with xylanase treatment. Chlorine dioxide demand could be reduced by 12.5-22% to achieve the same brightness. The ATR-FTIR and XPS results showed that lignin and hemicellulose (mainly HexA) were the main source for AOX formation. Xylanase pretreatment could remove HexA and expose more lignin, which decreased the chlorine dioxide demand and thus reduced formation of AOX.