Search

Mass transport of liberated lignin fragments from pits and fiber walls into black liquor is considered a determining step in the delignification process. However, our current understanding of the diffusion of lignin through cellulose and the influential parameter on this process is very limited. A comprehensive and detailed study of lignin mass transport through cellulosic materials is, therefore, of great importance. In this study, diffusion cell methodology is implemented to systematically investigate the transport of fractionated kraft lignin molecules through model cellulose membranes. Pulping is a complex process and lignin is very heterogenous material therefore to perform a more detailed study on lignin diffusion, we included an additional solvent fractionation step. One of the benefits of this method is that the setup can be adjusted to various experimental conditions allowing the complex chemical reactions occurring during pulping, which would affect the mass transfer of lignin, to be avoided. Here, the effects of the alkalinity of the aqueous solution and molecular weight of the kraft lignin molecules on their diffusion were investigated. Additionally, NMR spectroscopy, size exclusion chromatography, and UV/Vis spectroscopy were used to characterize the starting material and the molecules that passed through the membrane. Lignin molecules detected in the acceptor chamber of the diffusion cells had lower molecular weights, indicating a size fractionation between the donor and acceptor chamber. UV/Vis showed higher concentrations of ionized conjugated kraft lignin molecules in the acceptor chamber, which is a sign of chemical fractionation. This study suggests that the diffusion of lignin through small cellulose pores can be enhanced by decreasing the average molecular weight of the diffusing kraft lignin molecules and increasing alkalinity.

Although organosolv processes using high-boiling solvents have been investigated in recent decades for developing novel industrial processes, there are potential benefits of using high-boiling point solvents for traditional sulphate-based cooking processes, both from an industrial perspective and from a laboratory perspective. Using high-boiling solvents, experiments can be done under atmospheric conditions, thus making it easier to continually monitor laboratory experiments and extracting aliquots at desired intervals. Using such a system, alkaline consumption was monitored during impregnation of spruce chips in glycerol media using chemical charges of 1 M NaOH and 0.1 M NaHS, i. e., kraft pulping conditions, and compared to a similar investigation of alkaline consumption in water media using steel autoclaves. The resulting data was fitted to a first order kinetic model, with an apparent activation energy of 22 kJ mol−1 in glycerol media. Finally, a “normal quality pulp” of kappa number 28 and a viscosity of 1113 ml g−1 was successful produced using a cooking process with an impregnation step at 140 °C for 3 h and a cooking step at 160 °C for 4 h. A nuclear magnetic resonance study on the dissolved lignin produced for said experiment showed characteristics typical of other kraft lignins.

An integrated lignin biorefinery process was studied by chemometrics. A regime for structurally preserved lignins with tuneable properties was identified.

A series of different technical hardwood lignin-based resins have been successfully synthesized, characterized, and utilised to produce thiol-ene thermoset polymers. Firstly, technical lignin was fractionated and allylated, whereafter it was crosslinked with a trifunctional thiol. Structural and morphological characteristics of the lignin fractions were studied by $^{1}$H NMR, $^{31}$P NMR, SEC, FTIR, DSC, TGA, and WAXS. The hardwood lignin fractions have a high content of C5-substituted OH groups. The WAXS studies on lignin fractions revealed the presence of two π-π stacking conformations, sandwiched (4.08–4.25 Å) and T-shaped (6.52–6.91 Å). The presence of lignin superstructures with distances/sizes between 10.5 and 12.8 Å was also identified. The curing reaction of the thermosets was investigated by RT-FTIR. Almost all thermosets (excepting one fraction) reached 95% of the thiol conversion in less than 17 h, revealing the enhanced reactivity of the allylated hardwood lignin samples. The mechanical properties of the thermosets were investigated by DMA. The curing performance, as well as the final thermoset properties, have been correlated to variations in chemical composition and morphological differences of lignin fractions. The described results clearly demonstrate that technical hardwood lignins can be utilized for these applications, but also that significant differences compared to softwood lignins have to be considered for material design.

Studies have shown that the size of LNP depends on the molecular weight (Mw) of lignin.

The interest in the bark and the attempt to add value to its utilization have increased over the last decade. By applying an integrated bark biorefinery approach, it is possible to investigate the recovery of compounds that can be used to develop green and sustainable alternatives to fossil-based materials. In this work, the focus is on extracting Norway spruce (

Mechanical milling of lignocellulose has been used in several studies as a key pretreatment enabling the extraction of lignin from various sources for structural analysis. It is also applied as an alternative to wet chemical methods for lignin valorization. However, the changes caused to the plant cell walls at different hierarchical scales and how they relate to the molecular events are still poorly understood. In this context, we sought to gain deeper insights into molecular heterogeneity in milled cell walls, with a primary focus on lignin. A novel fractionation protocol was developed to enable the advanced analysis (1D and 2D NMR, SEC, XRD) of molecular populations in ball milled fiber walls. The methodology was applied to follow the emergence of such populations through the milling process, and in different milling environments. Lignin heterogeneity in the ball milled fibers was found to consist of distinct populations of small and large fractions of lignin carbohydrate complexes and pure lignin fractions, both with differences in lignin inter-unit abundances. Lignin-carbohydrate bonds of benzyl ester type were unequivocally demonstrated for the first time by combination of HSQC-HMBC NMR analysis. γ-Ester LCC and phenyl glycoside LCCs were also detected. Furthermore, an important branching point in lignin, previously controversial, namely the 4-O-etherified 5-5′ substructure, is unequivocally shown here by HSQC-HMBC analysis of the milled wood isolates, and supported by biomimetic lignin (DHP) to originate from the native structure. Based on the advanced characterization, the origin of lignin heterogeneity in ball milled fibers is proposed to result from the uneven distribution of the applied mechanical energy, where synergistic effects between crystalline and amorphous states play a central role. Accordingly, a plant cell wall model is proposed and a complete mechanism of its disintegration during the milling exercise is presented. The unveiled heterogeneity model of ball milled cell walls can serve as a useful guide for future studies on mechanical fractionation and valorization of lignocellulose based polymers.

Paper grade pulp production across the globe is dominated by the kraft process using different lignocellulosic raw materials. Delignification is achieved around 90% using different chemical treatments. A bottleneck for complete delignification is the presence of residual covalent bonds that prevail between lignin and carbohydrate even after severe chemical pulping and oxygen delignification steps. Different covalent bonds are present in native wood that sustain drastic pulping conditions. In this study, 100% birch wood was used for producing paper grade pulp, and the lignin carbohydrate bonds were analyzed at different stages of the kraft cook. The lignin carbohydrate bonds that were responsible for residual lignin retention in unbleached pulp were compared and analyzed with the original lignin-carbohydrate complex (LCC) bonds in native birch wood. It was shown that lignin remaining after pulping and oxygen delignification was mainly bound to xylan, whereas the lignin bound to glucomannan was for the most part degraded.

Anisotropic carbon-rich microcapsule morphologies are of great value in many applications including catalysis, energy storage, biomedicine, and osmosis-triggered drug delivery, due to an observed s...

Plant β-mannans are complex heteropolysaccharides that represent an abundant resource from lignocellulosic biomass. The influence of the molecular motifs of plant mannans on the backbone flexibilit...

Here we investigate the relationship between thermomechanical properties and chemical structure of well-characterized lignin-based epoxy resins. For this purpose, technical lignins from eucalyptus and spruce, obtained from the Kraft process, were used. The choice of lignins was based on the expected differences in molecular structure. The lignins were then refined by solvent fractionation, and three fractions with comparable molecular weights were selected to reduce effects of molar mass on the properties of the final thermoset resins. Consequently, any differences in thermomechanical properties are expected to correlate with molecular structure differences between the lignins. Oxirane moieties were selectively introduced to the refined fractions, and the resulting lignin epoxides were subsequently cross-linked with two commercially available polyether diamines (Mn = 2000 and 400) to obtain lignin-based epoxy resins. Molecular-scale characterization of the refined lignins and their derivatives were performed by 31P NMR, 2D-NMR, and DSC methods to obtain the detailed chemical structure of original and derivatized lignins. The thermosets were studied by DSC, DMA, and tensile tests and demonstrated diverse thermomechanical properties attributed to structural components in lignin and selected amine cross-linker. An epoxy resin with a lignin content of 66% showed a Tg of 79 °C from DMA, Young's modulus of 1.7 GPa, tensile strength of 66 MPa, and strain to failure of 8%. The effect of molecular lignin structure on thermomechanical properties was analyzed, finding significant differences between the rigid guaiacyl units in spruce lignin compared with sinapyl units in eucalyptus lignin. The methodology points toward rational design of molecularly tailored lignin-based thermosets.

Correction for ‘Protected lignin biorefining through cyclic extraction: gaining fundamental insights into the tuneable properties of lignin by chemometrics’ by Maria Karlsson et al., Green Chem., 2022, 24, 1211–1223, DOI: 10.1039/D1GC04171A.

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 h...

High temperature aqueous treatment of wood is the preferred technology for deconstructing lignocellulosics. Many studies have been carried out on the kinetics and mechanism of hot-water extraction. ...

Transforming biomass derived components to materials with controlled and predictable properties is a major challenge. Current work describes the controlled synthesis of starcopolymers with functional and degradable arms from the Lignoboost® process. Macromolecular control is achieved by combining lignin fractionation and characterization with ring-opening copolymerization (ROCP). The cyclic monomers used are e-caprolactone (eCL) and a functional carbonate monomer, 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC). The synthesis is performed at ambient temperature, under bulk conditions, in an open flask, and the graft composition and allyl functionality distribution are controlled by the copolymerization kinetics. Emphasis is placed on understanding the initiation efficiency, structural changes to the lignin backbone and the final macromolecular architecture. The present approach provides a green, scalable and cost effective protocol to create well-defined functional macromolecules from technical lignins.

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 complex (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 a valuable bio-resource in the manufacturing of carbon-based functional materials, because of its large carbon content (~60%), various phenolic structural units, abundancy and sustainability. Here, we explored its use in photocatalytic and self-propelling applications. First, hydroxyl-abundant lignin-based carbon precursor particles, HCLSs, were produced by hydrothermal carbonization of lignin-based microcapsules (LCs). Then, by heating urea coated HCLSs, carbon spheres with a layer of graphitic carbon nitride (g-C3N4) were produced. The presence of surface available -OH groups on the HCLSs, were critical in the formation mechanism. Under visible-light irradiation, the photocatalytic spheres exhibited enhanced activity (49% of the model pollutant remained after 60 min, at 100 mW cm−2) and possessed a three times higher average removal rate constant compared to that of g-C3N4 powder. The g-C3N4 powder was obtained when heating urea only. Additionally, by introducing a Pt/Pd coating on only one side of the composite spheres, the spheres were made self-propelling in the presence of a fuel (H2O2). This work provides new insights into the preparation principles of lignin-based photocatalytic spheres for effective solar photocatalysis applications.

Lignin has gained interest in academia as a raw material for advanced materials such as thermosets. Attractive features include its natural and technical abundances, its structural compositions, distribution of functionalities and most importantly its origin from renewable sources, i.e. lignocellulosic biomass. In this chapter, we will focus on lignin-based thermosets, specifically reviewing the recent strategies for such applications in polyurethanes, phenol-formaldehyde resins and epoxy thermosets. In these contexts, the advantages and competitiveness of lignin over conventional petrol-based will be discussed based on comparisons with benchmark properties. The chapter emphasizes the unique polymer chemistries adopted by different researchers, the effects of the chemical and physical properties of lignin on both reactivities during synthesis and thermomechanical properties of materials. Furthermore, the direct use of lignin in the unmodified state is contrasted with the use of selectively modified lignins in these polymer systems. The use of multifunctional lignin oligomers as raw material is also contrasted with the use of lignin platform monomers obtained through de-polymerization approaches. Finally, the challenges of lignin or monomers thereof, as a raw material in these applications are discussed to direct the future outlook of this research area.

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 ligni ...

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., Powers of consolidation: A consolidated green processing approach has been developed to obtain high yields of hemicelluloses and lignin with a close to native molecular structure, by subcritical water extraction of hemicelluloses followed by organosolv lignin extraction. A static cycle process is developed as a physical protection strategy for lignin with advanced NMR analysis to monitor any structural changes in the lignin.

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. ...

Galactoglucomannan (GGM) from sprucewas studied with respect to the degradation behavior inalkaline solution. Three reference systems includinggalactomannan from locust bean gum, glucomannanfrom ko ...

In a recent study, it was suggested that there could be direct associations between cellulose and lignin in mild alkaline cooked pulps. The observation was based on studies showing that the molecul ...

Several different methods for the extraction, separation, and purification of wood constituents were combined in this work as a unified process with the purpose of achieving a high overall efficiency of material extraction and utilization. This study aimed to present a laboratory-scale demonstrator biorefinery that illustrated how the different wood constituents could be separated from the wood matrix for later use in the production of new bio-based materials and chemicals by combining several approaches. This study builds on several publications and ongoing activities within the Wallenberg Wood Science Center (WWSC) in Sweden on the theme “From wood to material components.” Combining the approaches developed in these WWSC projects – including mild steam explosion, membrane and chromatographic separation, enzymatic treatment and leaching, ionic liquid extraction, and fractionation together with Kraft pulping – formed an outline for a complete materials-biorefinery. The process steps involved were tested as integral steps in a linked process. The scale of operations ranged from the kilogram-scale to the gram-scale. The feasibility and efficiency of these process steps in a biorefinery system were assessed, based on the data, beginning with whole wood.

Hydrothermal extraction of hemicelluloses from lignocellulosic biomass for conversion to renewable materials or fuels has captured attention. The extraction is however partial and some lignin is codissolved. Herein, we investigated the role of molecular structure in the recalcitrance. Wood meal of Spruce and Birch were subjected to pressurized hydrothermal extraction at 160 °C for 2 h, which extracted 68–75% of the hemicelluloses. 2D heteronuclear single quantum coherence (HSQC) NMR, HSQC-TOCSY, and 13C NMR were applied for structural studies of both extracts and residues. Subsequent to the known partial hydrolysis of native carbon-2 and carbon-3 acetates in hemicellulose, some acetylation of primary alcohols on hemicelluloses and lignin was observed. Lignin carbohydrate complexes (LCC) were detected in both the extracts and residues. In Spruce extracts, only the phenyl glycoside-type of LCC was detected. Birch extracts contained both the phenyl glycoside and benzyl ether-types. In the hydrothermal wood r...

The covalent connectivity between lignin and polysaccharides forming the so-called lignin–carbohydrate complexes (LCCs) is important to obtain fundamental knowledge on wood formation and may shed light on molecular aspects of wood processing. Although widely studied, unequivocal proofs of their existence in native-state biomass are still lacking, mainly because of harsh preanalytical fractionation conditions that could cause artifacts. In the present study, we applied a mild protocol for quantitative fractionation of LCCs and performed detailed structural studies using 2D HSQC NMR spectroscopy, 31P NMR spectroscopy, and thioacidolysis in combination with GC–MS and GC with flame ionization detection. The detailed structural analysis of LCCs, including both lignin and the carbohydrate skeleton, unveiled insights into the role of molecular structure of xylan on the type of lignin–carbohydrate (LC) bonds formed. More specifically, it is shown that xylan LCCs differ in the degree of substitution of hydroxyl fu...

Wood is not fully soluble in current non-derivatising direct-dissolution solvents, contrary to the many reports in the literature quoting wood 'dissolution' in ionic liquids. Herein, we demonstrate that the application of autohydrolysis, as a green and economical wood pre-treatment method, allows for a massive increase in solubility compared to untreated wood. This is demonstrated by the application of two derivitising methods (phosphitylation and acetylation), followed by NMR analysis, in the cellulose-dissolving ionic liquids 1-allyl-3-methylimidazolium chloride ([amim]Cl) and 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]. In addition, the non-derivitising tetrabutylphosphonium acetate ([P-4444][OAc]) : DMSO-d6 electrolyte also allowed for dissolution of the autohydrolysed wood samples. By combination of different particle sizes and P-factors (autohydrolysis intensity), it has been clearly demonstrated that the solubility of even wood chips can be drastically increased by application of autohydrolysis. The physiochemical factors affecting wood solubility after autohydrolysis are also discussed.

Lignin is the most abundant renewable source of phenolic compounds with great application potential in renewable materials, biofuels and platform chemicals. The current technology for producing cellulose-rich fibers co-produces heterogeneous lignin, which includes an untapped source of monomeric phenolics. One such monomer also happens 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 the quinone methide intermediate of lignin polymerization. The solvent system applied was 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 characterization was 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 a high functionalization degree were noted. The structure of lignin was tailored through the solvent system choice, with 50% aqueous acetone producing a skeletal structure favorable for a high degree of functionalization. Finally, material concepts are demonstrated using classical thiol–ene- and Diels–Alder-chemistries to show the potential for the thermoset and thermoplastic concepts, respectively. The functionalization concept presents unprecedented opportunities for the 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 (QC 20180509

Optically transparent wood, combining optical and mechanical performance, is an emerging new material for light-transmitting structures in buildings with the aim of reducing energy consumption. One of the main obstacles for transparent wood fabrication is delignification, where around 30wt% of wood tissue is removed to reduce light absorption and refractive index mismatch. This step is time consuming and not environmentally benign. Moreover, lignin removal weakens the wood structure, limiting the fabrication of large structures. A green and industrially feasible method has now been developed to prepare transparent wood. Up to 80wt% of lignin is preserved, leading to a stronger wood template compared to the delignified alternative. After polymer infiltration, a high-lignin-content transparent wood with transmittance of 83%, haze of 75%, thermal conductivity of 0.23WmK(-1), and work-tofracture of 1.2MJm(-3) (a magnitude higher than glass) was obtained. This transparent wood preparation method is efficient and applicable to various wood species. The transparent wood obtained shows potential for application in energy-saving buildings. QC 20171024

Aromatic material constituents derived from renewable resources are attractive for new biobased polymer systems. Lignin, derived from lignocellulosic biomass, is the most abundant natural source of such structures. Technical lignins are, however, heterogeneous in both structure and polydispersity and require a refining to obtain a more reproducible material. In this paper the ethanol-soluble fraction of Lignoboost Kraft lignin is selectively allylated using allyl chloride by means of a mild and industrially scalable procedure. Analysis using1H-,31P-, and 2D HSQC NMR give a detailed structural description of lignin, providing evidence of its functionalization and that the suggested procedure is selective toward phenols with a conversion of at least 95%. The selectively modified lignin is subsequently cross-linked using thermally induced thiol-ene chemistry. FT-IR is utilized to confirm the cross-linking reaction, and DSC measurements determined the Tgof the thermosets to be 45-65 °C depending on reactive group stoichiometry. The potential of lignin as a constituent in a thermoset application is demonstrated and discussed.

Background Lignocellulose from fast growing hardwood species is a preferred source of polysaccharides for advanced biofuels and “green” chemicals. However, the extensive acetylation of hardwood xylan hinders lignocellulose saccharification by obstructing enzymatic xylan hydrolysis and causing inhibitory acetic acid concentrations during microbial sugar fermentation. To optimize lignocellulose for cost-effective saccharification and biofuel production, an acetyl xylan esterase AnAXE1 from Aspergillus niger was introduced into aspen and targeted to cell walls. Results AnAXE1-expressing plants exhibited reduced xylan acetylation and grew normally. Without pretreatment, their lignocellulose yielded over 25% more glucose per unit mass of wood (dry weight) than wild-type plants. Glucose yields were less improved (+7%) after acid pretreatment, which hydrolyses xylan. The results indicate that AnAXE1 expression also reduced the molecular weight of xylan, and xylan–lignin complexes and/or lignin co-extracted with xylan, increased cellulose crystallinity, altered the lignin composition, reducing its syringyl to guaiacyl ratio, and increased lignin solubility in dioxane and hot water. Lignin-associated carbohydrates became enriched in xylose residues, indicating a higher content of xylo-oligosaccharides. Conclusions This work revealed several changes in plant cell walls caused by deacetylation of xylan. We propose that deacetylated xylan is partially hydrolyzed in the cell walls, liberating xylo-oligosaccharides and their associated lignin oligomers from the cell wall network. Deacetylating xylan thus not only increases its susceptibility to hydrolytic enzymes during saccharification but also changes the cell wall architecture, increasing the extractability of lignin and xylan and facilitating saccharification. Electronic supplementary material The online version of this article (doi:10.1186/s13068-017-0782-4) contains supplementary material, which is available to authorized users.

Next to cellulose, lignin is the second most abundant biopolymer, and the main source of aromatic structures on earth. It is a phenolic macromolecule, with a complex structure which considerably varies depending on the plant species and the isolation process. Lignin has long been obtained as a by-product of cellulose in the paper pulp production, but had rather low added-value applications. Changes in the paper market have however stimulated the need to focus on other applications for lignins. In addition, the emergence of biorefinery projects to develop biofuels, bio-based materials and chemicals from carbohydrate polymers should also generate large amounts of lignin with the potential for value addition. These developments have brought about renewed interest in the last decade for lignin and its potential use in polymer materials. This review covers both the topics of the direct use of lignin in polymer applications, and of the chemical modifications of lignin, in a polymer chemistry perspective. The future trend toward micro- and nanostructured lignin-based materials is then addressed.

Lignocellulose-based polymers are presently being investigated for potential as raw materials for polymer industry. However, covalent bonds between carbohydrates and lignin, so called lignin carbohydrate complexes (LCCs) present one of the factors impeding clean fractionation of the polymers. Understanding the chemical structure of LCCs in relation to the cell wall ultra-structure therefore provides relevant insight for technical fractionation. In the present work, new mild analytical protocols for LCCs were developed and fractions thereof subjected to detailed structural/ultra-structural characterization. When combined with size exclusion chromatography, the application of mono-component ploysaccharidases proved to be crucial for the identification of LCC moieties and provided indirect evidence for existence of lignin-carbohydrate bonds. The carbohydrate composition of the LCC moieties was essential to determination of the ultra-structural origin of the LCC types. Analytical 31P NMR of the LCCs and of their thioacidolysis products was useful in unveiling lignin structure in LCCs. A complete structure/ultra-structure relationship of LCCs in softwood was determined.

The Glucuronoyl esterases (GE) have been proposed to target lignin-carbohydrate (LC) ester bonds between lignin moieties and glucuronic acid side groups of xylan, but to date, no direct observations of enzymatic cleavage on native LC ester bonds have been demonstrated. In the present investigation, LCC fractions from spruce and birch were treated with a recombinantly produced GE originating from Acremonium alcalophilum (AaGE1). A combination of size exclusion chromatography and (31) P NMR analyses of phosphitylated LCC samples, before and after AaGE1 treatment provided the first evidence for cleavage of the LC ester linkages existing in wood.

The macromolecular conformation of the constituent polysaccharides in lignocellulosic biomass influences their supramolecular interactions, and therefore their function in plants and their performance in technical products. The flexibility of glycosidic linkages from the backbone of hemicelluloses was studied by evaluating the conformational freedom of the φ and ψ dihedral angles using molecular dynamic simulations, additionally selected molecules were correlated with experimental data by nuclear magnetic resonance spectroscopy. Three types of β-(1→4) glycosidic linkages involving the monosaccharides (Glcp, Xylp and Manp) present in the backbone of hemicelluloses were defined. Different di- and tetrasaccharides with combinations of such sugar monomers from hemicelluloses were simulated, and free energy maps of the φ - ψ space and hydrogen-bonding patterns were obtained. The glycosidic linkage between Glc-Glc or Glc-Man (C-type) was the stiffest with mainly one probable conformation; the linkage from Man-Man or Man-Glc (M-type) was similar but with an increased probability for an alternative conformation making it more flexible, and the linkage between two Xyl-units (X-type) was the most flexible with two almost equally populated conformations. Glycosidic linkages of the same type showed essentially the same conformational space in both disaccharides and in the central region of tetrasaccharides. Different probabilities of glycosidic linkage conformations in the backbone of hemicelluloses can be directly estimated from the free energy maps, which to a large degree affect the overall macromolecular conformations of these polymers. The information gained contributes to an increased understanding of the function of hemicelluloses both in the cell wall and in technical products.

A simplified method for sequentially dissolving and fractionating ball milled hard wood polymers in high yield is presented. The complete dissolution of the whole ball milled wood, and the fractions recovered from it by applying the sequential fractionation, was accomplished in lithium chloride/dimethylacetamide solvent system enabling size exclusion chromatography studies. The chromatography applied a four detector system; an Ultraviolet-Visible spectroscopy-, Intrinsic Viscosity-Differential Pressure-, Right Angle Laser Light Scattering- and Refractive Index detectors, a combination hereby proposed to enable interpretation of the complex elution profiles with emphasis on chemical interactions. Indirect evidence of the presence of lignin carbohydrate complexes in hardwoods is provided. It is also proposed that cellulose is severely degraded from a degree of polymerization of 10,000 in wood, down to a value of approximately 400 by either the applied ball milling condition or in subsequent solubil...

The fungus Phoma herbarum isolated from soil showed growth on highly pure lignin extracted from spruce wood and on synthetic lignin (DHP). The lignin remaining after cultivation was shown to have a lower molecular weight. The reduction in the numbers of ether linkages of the extracted lignins was also observed by derivatization followed by reductive cleavage (DFRC) in combination with 31P NMR studies. The fungal strain showed an ability to degrade synthetic lignin by extracellular catalysts. GC–MS was applied to study the evolution of low molar mass adducts, e.g., monolignols and it was shown that a reduced coniferyl alcohol product was produced from DHP in a cell-free environment. The work has demonstrated the ability of soil microbes to grow on lignin as sole carbon source. The potential impact is in the production of low molar mass renewable phenols for material application.