Characterization of Lignin Compounds at the Molecular Level: Mass Spectrometry Analysis and Raw Data Processing

Lignin is the second most abundant natural biopolymer, which is a potential alternative to conventional fossil fuels. It is also a promising material for the recovery of valuable chemicals such as aromatic compounds as well as an important biomarker for terrestrial organic matter. Lignin is currently produced in large quantities as a by-product of chemical pulping and cellulosic ethanol processes. Consequently, analytical methods are required to assess the content of valuable chemicals contained in these complex lignin wastes. This review is devoted to the application of mass spectrometry, including data analysis strategies, for the elemental and structural elucidation of lignin products. We describe and critically evaluate how these methods have contributed to progress and trends in the utilization of lignin in chemical synthesis, materials, energy, and geochemistry.     

Facile Tailoring of Structures for Controlled Release of Paracetamol from Sustainable Lignin Derived Platforms

Nowadays, sustainable materials are receiving significant attention due to the fact that they will be crucial for the development of the next generation of products and devices. In the present work, hydrogels have been successfully synthesized using lignin which is non-valorized biopolymer from the paper industry. Hydrogels were prepared via crosslinking with Poly(ethylene) glycol diglycidyl ether (PEGDGE). Different crosslinker ratios were used to determine their influence on the structural and chemical properties of the resulting hydrogels. It has been found that pore size was reduced by increasing crosslinker amount. The greater crosslinking density increased the swelling capacity of the hydrogels due to the presence of more hydrophilic groups in the hydrogel network. Paracetamol release test showed higher drug diffusion for hydrogels produced with a ratio lignin:PEGDGE 1:1. The obtained results demonstrate that the proposed approach is a promising route to utilize lignocellulose waste for producing porous materials for advanced biomedical applications in the pharmacy industry.     

Sulfuryl Fluoride Mediated Synthesis of Amides and Amidines from Ketoximes via Beckmann Rearrangement

A metal-free and redox-neutral method for Beckmann rearrangement employing inexpensive and readily available SO₂F₂ gas is described. The reported transformation proceeds at ambient temperature and is compatible with a wide range of sterically and electronically diverse aromatic, heteroaromatic, aliphatic and lignin-like oximes providing amides in good to excellent yields. The reaction proceeds through the formation of an imidoyl fluoride intermediate that can also be used for the synthesis of amidines.     

Copper-Mediated Conversion of Complex Ethers to Esters: Enabling Biopolymer Depolymerisation under Mild Conditions

Selective processing of the β-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O₂ system, a protocol was developed that gave the desired β-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.     

Experimental and molecular simulating study on promoting electrolyte-immersed mechanical properties of cellulose/lignin separator for lithium-ion battery

Lithium-ion batteries have been developing intensively and earn an unprecedented reputation, yet advanced performance and safety issue still require considerable investigation. Separator is vital to comprehensive properties of batteries, where the mechanical properties are key to breaking through of new-type separator. Unfortunately, electrolyte submersion has caused damage to strength of cellulose separator. Whereupon, in this work, cellulose separator is optimized by introducing lignin particles to promote electrolyte-immersed mechanical strength. Experiments are conducted concerning surface morphology, contact angle, porosity, electrolyte uptake, mechanical properties and electrochemical performance. Molecular simulation is implemented to explore the mechanism of tensile behavior of cellulose and lignin subjected to electrolyte solvents. Experimental results confirm positive effect of lignin addition in improving mechanical properties and simultaneously maintaining impressive electrochemical performance of the cellulose/lignin composites separators. Besides, lignin addition amount of 2.5% and 5% is recommended to achieve promising overall properties. Molecular simulation has successfully unveiled that weakening of cellulose separator submerged in electrolyte is resulted by the deformed cellulose amorphous region and the promoting effect of adding lignin is contributed from the new hydrogen bonds generated between cellulose and lignin molecules. Hopefully, this work provides novel insight on preparing remarkable separator and mechanism of materials behavior.     

Lignin,a biomass crosslinker,in a shape memory polycaprolactone network

This work reports a new direction of natural lignin valorization, which utilizes lignin to produce crosslinked polycaprolactone (PCL) via a straightforward synthesis. Lignin's hydroxyl groups of its multibranched phenolic structure allow lignin to serve as crosslinkers, whereas the aromatic groups serve as hard segments. The modified natural lignin containing alkene terminals is crosslinked with a thiol‐terminal PCL via Ru‐catalyzed photoredox thiol‐ene reaction. The high rate of gel contents measured for all crosslinked polymers, with the least being 84% of gel content, indicates efficient crosslinking. The prepared flat rectangular shape lignin‐crosslinked PCL sample demonstrates rapid thermal responsive shape memory behavior at 10 °C and 80 °C showing interconversion between a permanent and temporary shape. The melting temperature of the lignin‐crosslinked PCL is tunable by varying the percent weight of lignin. The 11, 21, and 30 wt % lignin demonstrated T_m of 42 °C, 35 °C, and 26 °C, respectively. The role of lignin as a crosslinker presented in this work suggests that lignin can serve as an efficient biomass‐based functional additive to polymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2121–2130     

Lignin and Lignin-Derived Compounds for Wood Applications—A Review

Improving the environmental performance of resins in wood treatment by using renewable chemicals has been a topic of interest for a long time. At the same time, lignin, the second most abundant biomass on earth, is produced in large scale as a side product and mainly used energetically. The use of lignin in wood adhesives or for wood modification has received a lot of scientific attention. Despite this, there are only few lignin-derived wood products commercially available. This review provides a summary of the research on lignin application in wood adhesives, as well as for wood modification. The research on the use of uncleaved lignin and of cleavage products of lignin is reviewed. Finally, the current state of the art of commercialization of lignin-derived wood products is presented.     

木质素热解生物油组成成分与分子尺寸分布特性分析

选用脱碱木质素作为原料,以热裂解气质联用技术(Py-GC/MS)研究木质素在350～600℃下热解产物成分和含量,并利用Joback法、 Lijie法和Tahami法3种基团贡献法计算了生物油各组成成分的临界参数和动力学直径,对木质素热解油产物的分子动力学直径分布特性进行计算.结果显示,愈创木基结构、紫丁香基结构、苯酚类、邻苯二酚类和芳烃类等5种芳香族化合物是350～600℃下木质素热解生物油的主要组成成分,其中愈创木基结构化合物的平均峰面积百分比达到70.7%.随着反应温度从350提高到600℃,分子动力学直径在0.560～0.610 nm区间内的木质素热解油组分含量从14.6%增加至31.3%.木质素热解生物油主要产物的动力学直径在0.560～0.710nm,表明一些孔径尺寸在此范围内的分子筛如SSZ-20、 ZSM-5和Beta可作为木质素裂解制备高品质芳烃燃料的催化剂.     

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5–2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.