过氧化氢调控藜芦醇介导木素过氧化物酶催化氧化邻苯三酚红研究

木素过氧化物酶(LiP)催化H₂O₂氧化邻苯三酚红(PR)反应的氧化产物受H₂O₂与PR的摩尔比控制, H₂O₂与PR的摩尔比不同, 所得降解产物不一样. 分析表明, H₂O₂在LiP催化氧化PR过程中的双重作用(即低浓度的H₂O₂是LiP的激活剂, 高浓度的H₂O₂是LiP的抑制剂)是导致上述现象的根本原因. 藜芦醇(VA)对LiP催化氧化PR的反应有促进作用, 尤其是当H₂O₂与PR的摩尔比较高时这种促进作用更为明显; 然而PR对LiP催化氧化VA的反应却有抑制作用. 后者可以用来解释为什么在用白腐菌降解染料时在培养液中常常检测不到LiP的藜芦醇活力. 分析表明, VA的存在不但促进了LiP酶中间体LiP(II)和/或LiP(III)向LiP的转化, 使LiP的催化循环加速, VA生成的VA^＋·也间接氧化了染料PR, 从而使PR的氧化速率提高.     

Preparation and Performance of Lignin-Based Multifunctional Superhydrophobic Coating

Superhydrophobic coatings have drawn much attention in recent years for their widespread potential applications. However, there are challenges to find a simple and cost-effective approach to prepare superhydrophobic materials and coatings using natural polymer. Herein, we prepared a kraft lignin-based superhydrophobic powder via modifying kraft lignin through 1H, 1H, 2H, 2H-perfluorodecyl-triethoxysilane (PFDTES) substitution reaction, and constructed superhydrophobic coatings by direct spraying the suspended PFDTES-Lignin powder on different substrates, including glass, wood, metal and paper. The prepared lignin-based coatings have excellent repellency to water, with a water contact angle of 164.7°, as well as good friction resistance, acid resistance, alkali resistance, salt resistance properties and quite good self-cleaning performance. After 30 cycles of sand friction or being stayed in 2 mol/L HCl, 0.25 mol/L NaOH and 2 mol/L NaCl solution for 30 min, the coatings still retain super hydrophobic capability, with contact angles higher than 150°. The superhydrophobic performance of PFDTES-Lignin coatings is mainly attributed to the constructed high surface roughness and the low surface energy afforded by modified lignin. This lignin-based polymer coating is low-cost, scalable, and has huge potential application in different fields, providing a simple way for the value-added utilization of kraft lignin.     

Conversion of Phenol and Lignin as Components of Renewable Raw Materials on Pt and Ru-Supported Catalysts

Hydrogenation of phenol in aqueous solutions on Pt-Ni/SiO₂, Pt-Ni-Cr/Al₂O₃, Pt/C, and Ru/C catalysts was studied at temperatures of 150–250 °C and pressures of 40–80 bar. The possibility of hydrogenation of hydrolysis lignin in an aqueous medium in the presence of a Ru/C catalyst is shown. The conversion of hydrolysis lignin and water-soluble sodium lignosulfonate occurs with the formation of a complex mixture of monomeric products: a number of phenols, products of their catalytic hydrogenation (cyclohexanol and cyclohexanone), and hydrogenolysis products (cyclic and aliphatic C₂–C₇ hydrocarbons).     

Conversion of Cellulose and Lignin Residues into Transparent UV-Blocking Composite Films

The valorization of cellulose and lignin residues in an integrated biorefinery is of great significance to improve the overall economics but has been challenged by their structural recalcitrance, especially for lignin residue. In this work, a facile chemical conversion route to fabricating functional UV-blocking cellulose/lignin composite films through a facile dissolution–regeneration process using these biomass residues was proposed. Three representative lignin residues, i.e., aspen and poplar wood lignin, and corn stover (CS) lignin were assessed for their feasibility for the film fabrication. The UV-blocking performance of the composite films were comparatively investigated. Results showed that all these three lignin residues could enhance the UV-blocking property of the composite films, corresponding to the reduction in the optical energy band gap from 4.31 to 3.72 eV, while poplar lignin had a considerable content of chromophores and showed the best UV-blocking enhancement among these three assessing lignins. The enhancement of UV-blocking property was achieved without compromising the visible-light transparency, mechanical strength and thermal stability of the composite films even at 4% lignin loading. This work showed the high promise of integrating biomass residue conversion into lignocellulose biorefinery for a multi-production purpose.     

近红外光谱法快速测定毛竹Klason木质素的含量

研究了用近红外漫反射光谱法对毛竹Klason木质素含量的快速预测。选取了代表不同竹龄、不同高度和横向不同位置的54个竹材粉末样品,用常规实验室方法测定了54个样品的Klason木质素含量,用近红外光谱仪漫反射方式在350～2500 nm范围内采集相应样品的光谱,利用多变量统计分析软件建立样品木质素含量和光谱数据之间的相关性模型。结果表明,对原始光谱进行二阶导数预处理后,选择1 011～1675 nm和1930～2488 nm波长区间,用偏最小二乘法(PLS1)和完全交互验证方式建立了的校正模型和预测模型的相关系数分别为0.99,和0.97,校正标准误差SEC＝0.36％,预测标准误差SEP=0.59％,说明毛竹Klason木质素含量和近红外光谱之间存在非常好的相关性,用近红外光谱技术可以实现对竹材样品中Klason木质素含量的快速预测。     

Nucleation,Crystallization, and Thermal Fractionation of Poly (ε‐Caprolactone)‐Grafted‐Lignin: Effects of Grafted Chains Length and Lignin Content

Poly(ε‐caprolactone)‐grafted‐lignin (PCL‐g‐lignin) copolymers with 2 to 37 wt % lignin are employed to study the effect of lignin on the morphology, nucleation, and crystallization kinetics of PCL. Lignin displays a nucleating action on PCL chains originating an intersecting lamellar morphology. Lignin is an excellent nucleating agent for PCL at low contents (2–5 wt %) with nucleation efficiency values that are close to or >100%. This nucleating effect increases the crystallization and melting temperature of PCL under nonisothermal conditions and accelerates the overall isothermal crystallization rate of PCL. At lignin contents >18 wt %, antinucleation effects appear, that decrease crystallization and melting temperatures, reduce crystallinity degree, hinder annealing during thermal fractionation and significantly retard isothermal crystallization kinetics. The results can be explained by a competition between nucleating effects and intermolecular interactions caused by hydrogen bonding between PCL and lignin building blocks. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1736–1750     

Upgrading poly(butylene succinate)/wood fiber composites by esterified lignin

Aliphatic chains were introduced into the macromolecule of kraft lignin using aliphatic chlorides as esterification reagents. The hydrophobicity of esterified lignin (EL) was enhanced as compared to the original lignin. EL was further used as a macromolecular coupling agent in poly(butylene succinate)/chemi-thermomechanical pulp fiber composites. As a result, the composites with enhanced mechanical performance were obtained, and the tensile strength, impact strength, and bending strength were increased by 25.1, 22.4, and 19.3%, respectively, under 2 wt% EL-treatment (synthesized by palmitoyl chloride, –COCl/–OH = 1.5:1) in comparison with those of the specimen without any coupling agent treatment. Furthermore, the composite prepared with EL-treated fibers shows significant lower water absorption ratio than that of untreated one. A significant increase in storage modulus (E′) was observed upon the incorporation of treated fibers. Furthermore, the improved interfacial bonding between treated fibers and matrix was verified by SEM images. The shear viscosity of composite was increased by the incorporation of EL, but in general, the rheological behaviors of composites are not significantly changed.     

Lignin‐Containing Self‐Nanoemulsifying Drug Delivery System for Enhance Stability and Oral Absorption of trans‐Resveratrol

Self‐nanoemulsifying drug delivery system (SNEDDS) is recently studied for enhancing the bioavailability of hydrophobic drugs, such as resveratrol (RSV). However, the functional design of SNEDDS for the drug structural protection is not studied yet. Here, this paper presents an efficient approach by adding lignin (a kind of abundant biomass resource) to enhance the stability of trans‐RSV and meantime improve its oral bioavailability. Higher stability of trans‐RSV (just decreased 2% to cis‐RSV after 1 h under direct sunlight) is observed after loaded by lignin‐containing SNEDDS (RSV/SLS SNEDDS). Low toxicity, high transfer efficiency (apparent permeability coefficient >1 × 10⁻⁷ cm s⁻¹), and bioavailability (1.371%) of RSV/SLS SNEDDS is successfully demonstrated in Caco‐2 cells and rat model, respectively. This study serves to illustrate a simple, versatile, environmental, and economic sustainability approach to the development of nanodelivery systems for light instability drugs.