Recent years have seen the development of technically feasible methods to retrieve kraft lignin from the black liquor as solids or liquids. This opens enormous opportunities to position kraft lignin as a renewable aromatic polymer precursor. However, the heterogeneity of kraft lignin is one major hurdle and manifests in its largely unknown molecular structure, which in recent years has drawn further attention. In this context, we herein studied the detailed structure of Eucalyptus kraft lignin with special emphasis on identifying new linkages signatory to retro-aldol and subsequent radical coupling reactions, which we recently showed to be a key reaction sequence contributing to the structure of spruce kraft lignin. In combination with novel model studies, we unequivocally identified new structures by advanced 2D NMR characterization of Eucalyptus kraft lignin, i.e., 3,5-tetramethoxy-para-diphenol, 3-dimethoxy-para-diphenol and small amounts of 3,5-dimethoxy-benzoquinone. These structures are signatory to retro-aldol followed by radical coupling reactions. The two diphenol structures were further quantified by 1D C-13 NMR at 9% of the interunit linkages in Eucalyptus kraft lignin, which was comparable to the amounts we previously identified in softwood kraft lignin (10%). Radical condensation of kraft lignin to form carbon-carbon bonds therefore does not discriminate between syringyl lignin and guaiacyl lignin units. We rationalize such indiscrimination to emanate from possibilities for radical couplings at unsubstituted C-1 in the formed syringol and guaiacol lignin as a result of the retro-aldol reaction.

As part of the continuing efforts in lignin-first biorefinery concepts, this study concerns a consolidated green processing approach to obtain high yields of hemicelluloses and lignin with a close to native molecular structure, leaving a fiber fraction enriched in crystalline cellulose. This is done by subcritical water extraction of hemicelluloses followed by organosolv lignin extraction. This initial report focuses on a detailed characterization of the lignin component, with the aim of unravelling processing strategies for the preservation of the native linkages while still obtaining good yields and high purity. To this effect, a static cycle process is developed as a physical protection strategy for lignin, and advanced NMR analysis is applied to study structural changes in lignin. Chemical protection mechanisms in the cyclic method are also reported and contrasted with the mechanisms in a reference batch extraction process where the role of homolytic cleavage in subsequent repolymerization reactions is elucidated.

The kraft process is the main process used for the production of chemical pulps. In this process, an efficient delignification is achieved, yielding bleachable grade pulps. In recent years, there has been interest in valorization of the dissolved lignins, prompted by the development of technically feasible processes to retrieve it from the black liquor. However, the structural-, functional-, and size-related heterogeneities of lignin present both analytical challenges and challenges in developing new applications. Hence, refining of the crude product is essential. Herein, advanced NMR characterization (¹³C NMR, APT/DEPT NMR, ³¹P NMR, HSQC, HMBC, HSQC-TOCSY) was applied to profile the detailed molecular structures of refined kraft lignins and unravel mechanistic insights on important lignin reactions during kraft pulping. From this structural analysis of the lignins, a model oligomer was synthesized and analyzed to provide support to the effect that a retro-aldol reaction in combination with radical recombination reactions play a significant role in the formation of the reconstituted fraction of kraft lignin. In this regard, a new type of linkage accounting for approximately 10% of the interunits in kraft lignin is reported.

The question of whether lignin is covalently linked to carbohydrates in native wood, forming what is referred to as lignin–carbohydrate complexes (LCCs), still lacks unequivocal proof. This is mainly due to the need to isolate lignin from woody materials prior to analysis, under conditions leading to partial chemical modification of the native wood polymers. Thus, the correlation between the structure of the isolated LCCs and LCCs in situ remains open. As a way to circumvent the problematic isolation, biomimicking lignin polymerization in vivo and in vitro is an interesting option. Herein, we report the detection of lignin–carbohydrate bonds in the extracellular lignin formed by tissue-cultured Norway spruce cells, and in modified biomimetic lignin synthesis (dehydrogenation polymers). Semi-quantitative 2D heteronuclear singular quantum coherence (HSQC)-, ³¹P -, and ¹³C-NMR spectroscopy were applied as analytical tools. Combining results from these systems, four types of lignin–carbohydrate bonds were detected; benzyl ether, benzyl ester, γ-ester, and phenyl glycoside linkages, providing direct evidence of lignin–carbohydrate bond formation in biomimicked lignin polymerization. Based on our findings, we propose a sequence for lignin–carbohydrate bond formation in plant cell walls.

Replacing fossil-based resources with renewable alternatives is generally acknowledged as a critical component to address several of today's environmental concerns. In this context, lignocellulosic biomass is an attractive, sustainable resource. However, the constitutional biopolymers of interest are locked in the structural complexity of the plant cell walls, which defines their properties and contributes to fractionation recalcitrance. One of the key suspects restricting fractionation of the biopolymers in high yield is the presence of lignin-carbohydrate bonds forming a matrix referred to as Lignin-Carbohydrate Complexes (LCC). Nevertheless, covalent bonds between lignin and carbohydrates, remain one of the most controversial topics in lignocellulose chemistry. This challenge can be attributed to the slow progress made in their research, which also forms the basis for this review. Herein, we will critically discuss the literature with a particular focus on the latest characterization and analytical techniques. Discussions on existing techniques and, importantly the drawbacks with them should be compelling to researchers in the area, especially at this time when crucial issues surrounding the realization of biorefineries need to be addressed.

Lignin is the most abundant renewable source of phenolic compound with great application potential in renewable materials, biofuels and platform chemicals. Current technology for producing cellulose-rich fibers co-produces heterogeneous lignin, which includes an untapped source of monomeric phenolics. One such monomer also happen to be the main monomer in soft wood lignin biosynthesis, namely coniferyl alcohol. Herein, we investigate the potential of coniferyl alcohol as a platform monomer for the biomimetic production of tailored functionalized oligolignols with desirable properties for material synthesis. Accordingly, a bifunctional molecule with at least one carboxyl-ended functionality is included with coniferyl alcohol in biomimetic lignin synthesis to, in one-pot, produce a functionalized lignin. The functionalization mechanism is a nucleophilic addition reaction to quinone methide intermediate of lignin polymerization. The solvent systems applied were pure water or 50% aqueous acetone. Several bi-functional molecules differing in the second functionality were successfully inserted in the lignin demonstrating the platform component of this work. Detailed characterizations were performed by a combination of NMR techniques which include 1H NMR, COSY-90, 31P NMR, 13C NMR, 13C APT, HSQC, HMBC and HSQC TOCSY. Excellent selectivity towards benzylic carbon and high functionalization degree were noted. The structure of lignin was tailored through solvent system choice, with the 50% aqeuous acetone producing a skeletal structure favorable for high functionalization degrees. Finally, material concepts are demonstrated using classical Thiol-ene- and Diels Alder- chemistries to show potential for thermoset- and thermoplastic- concepts, respectively. The functionalization concept presents unprecedentent opportunities for green production of lignin-based recyclable biomaterials.

Hardwoods constitute an essential renewable resource for the production of platform chemicals and bio-based materials. A method for the sequential extraction of hemicelluloses and lignin from hardwoods is proposed using subcritical water in buffered conditions without prior delignification. This allows the cascade isolation of mannan, xylan and lignin-carbohydrate complexes based on their extractability and recalcitrance in birch lignocellulose. The time evolution of the extraction was monitored in terms of composition, oligomeric mass profiling and sequencing of the hemicelluloses, and molecular structure of the lignin and lignin-carbohydrate complexes (LCCs) by heteronuclear single quantum coherence nuclear magnetic resonance (2D HSQC NMR). The minor mannan and pectin populations are easily extractable at short times (<5 min), whereas the major glucuronoxylan (GX) becomes enriched at moderate extraction times. Longer extraction times results in major hydrolysis exhibiting GX fractions with tighter glucuronation spacing and lignin enrichment. The pattern of acetylation and glucuronation in GX is correlated with extractability and with connectivity with lignin through LCCs. This interconnected molecular heterogeneity of hemicelluloses and lignin has important implications for their supramolecular assembly and therefore determines the recalcitrance of hardwood lignocellulosic biomass.

The presence of covalent bonds between lignin and polysaccharides was investigated in dissolving pulps made with one-stage and two-stage acidic sulfite pulping for 100% pine heartwood raw material. The covalent bonds between lignin and pulp polysaccharides occurred mainly to xylan and glucomannan and were of the phenyl glycosides and γ–esters types. The α-ethers that are common in wood were missing in the studied pulp samples. Based on these findings and known lignin reactions during sulfite pulping, a mechanism explaining the absence of the α-ethers is discussed. It is suggested that the lignin carbohydrate bonds may play a vital role in lignin recalcitrance.

Lignin extracted from trees is one of the most abundant biopolymers on Earth. Quinone, a sub-structure in lignin, can be used for energy storage via reversible redox reactions through absorbing and releasing electrons and protons. However, these efforts have encountered hindrances, such as short life cycle, low cycling efficiency, and a high self-discharge rate. All of these issues are related to electrode dissolution by electrolyte solvents and the insulating nature of lignin. Addressing these critical challenges, for the first time we use a reconfigurable and hierarchical graphene cage to capture the lignin by mimicking the prey-trapping of venus flytraps. The reconfigurable graphene confines the lignin within the electrode to prevent its dissolution, while acting as a three-dimensional current collector to provide efficient electron transport pathways during the electrochemical reactions. This bioinspired design enables the best cycling performance of lignin reported so far at 88% capacitance retention for 15000 cycles and 211 F g-1 capacitance at a current density of 1.0 A g-1. This study demonstrates a feasible and effective strategy for solving the long-term cycling difficulties of lignin-based electrochemically active species, and makes it possible to utilize lignin as an efficient, cheap, and renewable energy storage material.