Lignin Domains Research Articles

Enhancing the mechanical performance of lignin based hydrogel via lignin acetylation

Kraft lignin (KL) is an industrial byproduct of pulp preparation from woody biomass and is mainly burned for energy recovery. To explore value-added applications of KL, it was first acetylated, and acetylated lignin (AcL) was combined with poly(N,N-dimethylacrylamide) to prepare tough lignin hydrogels crosslinked by hydrophobic lignin domains via a simple solvent exchange method. The AcL hydrogels (AcLGs) with optimum mechanical properties have a high tensile strength of 1.7 MPa, large Young's modulus of 1 MPa, and super high fracture energy of ∼47600 J m−2. The Young's modulus and tensile strength of AcLG are 60 and 6 times higher than those of the pristine KL based hydrogel, respectively. AcLG had a weak inhibitory effect on Chinese hamster lung cell proliferation. Owing to its good mechanical properties and noncytotoxicity, AcLG has excellent potential as a biomedical material.

Mechanically Robust, Self-Repairable, Shape Memory and Recyclable Ionomeric Elastomer Composites with Renewable Lignin via Interfacial Metal-Ligand Interactions.

Lignin, the most abundant aromatic polymer in nature, is one of the most promising renewable feedstocks for value-added polymer products. However, it is challenging to prepare high-performance and multifunctional polymer materials with renewable lignin because of its poor compatibility with the elastomer matrix. In fact, lignin often requires solvent fractionation, chemical modification, or prohibitively expensive additives. This work develops a cost-effective strategy to prepare ionomeric elastomer composites based on a commercial carboxyl elastomer and a high content of lignin without purification or chemical modification. The compatibility between the elastomer and lignin is improved by the incorporation of zinc oxide which creates metal-ligand coordination at the interfaces between the carboxyl groups of the elastomer and the oxygen-bearing groups of the lignin. This results in fine dispersion of the lignin in the elastomer matrix, even when its content reaches 50 wt %. The lignin/elastomer composites show excellent mechanical properties, which are attributed to the reinforcing effect of the lignin domains and the presence of abundant sacrificial coordination bonds. Moreover, ionic bonds and ionic aggregates created by the neutralization of the zinc ions with the carboxyl groups of the elastomer behave as physical crosslinks which endow the composites with excellent recyclability; namely, their mechanical properties are retained or even improved after multiple reprocessing cycles. They also show good self-repairability and shape memory. Hence, this work may open up new avenues to utilize lignin as a renewable alternative to petroleum derivatives for designing and fabricating high-performance and multifunctional elastomer materials.

Xylan adsorption on cellulose: Preferred alignment and local surface immobilizing effect

Interaction between xylan and cellulose microfibrils is required to maintain the integrity of secondary cell walls. However, the mechanisms governing their assembly and the effects on cellulose surface polymers are not fully clear. Here, molecular dynamics simulations are used to study xylan adsorption onto hydrated cellulose fibrils. Based on multiple spontaneous adsorption simulations it is shown that an antiparallel orientation is thermodynamically preferred over a parallel one, and that adsorption is accompanied by the formation of regular but orientation-dependent hydrogen bond patterns. Furthermore, xylan adsorption restricts the local dynamics of the adjacent glucose residues in the surface layer to a level of the crystalline core, which is manifested as a three-fold increase in their 13C NMR T1 relaxation time. These results suggest that xylan forms a rigid and ordered layer around the cellulose fibril that functions as a transition phase to more flexible and disordered polysaccharide and lignin domains.

Co-curing of epoxy resins with aminated lignins: insights into the role of lignin homo crosslinking during lignin amination on the elastic properties

Abstract To improve the reactivity of lignin for incorporation into high value polymers, the introduction of amines via Mannich reaction is a commonly used strategy. During this functionalization reaction, intra- as well as intermolecular lignin–lignin crosslinking occurs, which can vastly change the elastic properties of the lignin, and therefore, the properties of the resulting polymer. Therefore, the molecular structure of the amine that is used for such a lignin functionalization may be of great importance. However, the relationship between the molecular structure of the amine and the elastic properties of the lignin-based polymer that is generated thereof, has not been fully understood. Herein, this relationship was investigated in detail and it was observed that the molecular flexibility of the amines plays a predominant role: The use of more flexible amines results in an increase in elasticity and the use of less flexible amines yields more rigid resin material. In addition to the macroscopic 3-point bending flexural tests, the elastic modules of the resins were determined on the nanometer scale by using atomic force microscopy (AFM) in the PeakForce tapping modus. Thus, it could be demonstrated that the intrinsic elasticities of the lignin domains are the main reason for the observed tendency.

An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber.

An ionomeric, leathery thermoplastic with high mechanical strength is prepared by a new thermal processing method from a soft, melt-processable rubber. Compositions made by incorporation of equal-mass lignin, a renewable oligomeric feedstock, in an acrylonitrile-butadiene rubber often yield weak rubbers with large lignin domains (1-2 µm). The addition of zinc chloride (ZnCl2 ) in such a composition based on sinapyl alcohol-rich lignin during a solvent-free synthesis induces a strong interfacial crosslinking between lignin and rubber phases. This compositional modification results in finely interspersed lignin domains (<100 nm) that essentially reinforce the rubbery matrix with a 10-22 °C rise in the glassy-to-rubbery transition temperature. The ion-modified polymer blends also show improved materials properties, like a 100% increase in ultimate tensile strength and an order of magnitude rise in Young's modulus. Coarse-grained molecular dynamics (MD) simulations verify the morphology and dynamics of the ionomeric material. The computed result also confirms that the ionomers have glassy characteristics.

Structural Redesigning Arabidopsis Lignins into Alkali-Soluble Lignins through the Expression of p-Coumaroyl-CoA:Monolignol Transferase PMT.

Grass lignins can contain up to 10% to 15% by weight of p-coumaric esters. This acylation is performed on monolignols under the catalysis of p-coumaroyl-coenzyme A monolignol transferase (PMT). To study the impact of p-coumaroylation on lignification, we first introduced the Brachypodium distachyon Bradi2g36910 (BdPMT1) gene into Arabidopsis (Arabidopsis thaliana) under the control of the constitutive maize (Zea mays) ubiquitin promoter. The resulting p-coumaroylation was far lower than that of lignins from mature grass stems and had no impact on stem lignin content. By contrast, introducing either the BdPMT1 or the Bradi1g36980 (BdPMT2) gene into Arabidopsis under the control of the Arabidopsis cinnamate-4-hydroxylase promoter boosted the p-coumaroylation of mature stems up to the grass lignin level (8% to 9% by weight), without any impact on plant development. The analysis of purified lignin fractions and the identification of diagnostic products confirmed that p-coumaric acid was associated with lignins. BdPMT1-driven p-coumaroylation was also obtained in the fah1 (deficient for ferulate 5-hydroxylase) and ccr1g (deficient for cinnamoyl-coenzyme A reductase) lines, albeit to a lower extent. Lignins from BdPMT1-expressing ccr1g lines were also found to be feruloylated. In Arabidopsis mature stems, substantial p-coumaroylation of lignins was achieved at the expense of lignin content and induced lignin structural alterations, with an unexpected increase of lignin units with free phenolic groups. This higher frequency of free phenolic groups in Arabidopsis lignins doubled their solubility in alkali at room temperature. These findings suggest that the formation of alkali-leachable lignin domains rich in free phenolic groups is favored when p-coumaroylated monolignols participate in lignification in a grass in a similar manner.

Soil Organic Matter in Its Native State: Unravelling the Most Complex Biomaterial on Earth.

Since the isolation of soil organic matter in 1786, tens of thousands of publications have searched for its structure. Nuclear magnetic resonance (NMR) spectroscopy has played a critical role in defining soil organic matter but traditional approaches remove key information such as the distribution of components at the soil-water interface and conformational information. Here a novel form of NMR with capabilities to study all physical phases termed Comprehensive Multiphase NMR, is applied to analyze soil in its natural swollen-state. The key structural components in soil organic matter are identified to be largely composed of macromolecular inputs from degrading biomass. Polar lipid heads and carbohydrates dominate the soil-water interface while lignin and microbes are arranged in a more hydrophobic interior. Lignin domains cannot be penetrated by aqueous solvents even at extreme pH indicating they are the most hydrophobic environment in soil and are ideal for sequestering hydrophobic contaminants. Here, for the first time, a complete range of physical states of a whole soil can be studied. This provides a more detailed understanding of soil organic matter at the molecular level itself key to develop the most efficient soil remediation and agricultural techniques, and better predict carbon sequestration and climate change.

Poly(ethylene oxide)-Assisted Macromolecular Self-Assembly of Lignin in ABS Matrix for Sustainable Composite Applications

In this effort, we report the compatibilization of biomass-derived lignin polymer in acrylonitrile butadiene styrene (ABS) thermoplastic matrix without loss of mechanical properties via poly(ethylene oxide) (PEO)-mediated macromolecular self-assembly. ABS was blended with lignin in different concentrations, and blends with 10 wt % PEO (relative to lignin) were prepared. The relative tensile strength improved slightly at low lignin content but diminished rapidly as the lignin content was increased. However, the inclusion of PEO as an interfacial adhesion promoter helped avoid deleterious effects. Dynamic mechanical analysis showed that PEO plasticized the hard phase and thus lowered the activation energy (Ea) for its relaxation but caused stiffening of the soft phase and increased its Ea. Microscopy revealed that incorporating lignin in ABS led to the statistical dispersion of discrete lignin domains (300–1000 nm) which, after PEO addition, were reduced to smaller interconnected particles (200–500 nm). The...

Mapping the lignin distribution in pretreated sugarcane bagasse by confocal and fluorescence lifetime imaging microscopy

BackgroundDelignification pretreatments of biomass and methods to assess their efficacy are crucial for biomass-to-biofuels research and technology. Here, we applied confocal and fluorescence lifetime imaging microscopy (FLIM) using one- and two-photon excitation to map the lignin distribution within bagasse fibers pretreated with acid and alkali. The evaluated spectra and decay times are correlated with previously calculated lignin fractions. We have also investigated the influence of the pretreatment on the lignin distribution in the cell wall by analyzing the changes in the fluorescence characteristics using two-photon excitation. Eucalyptus fibers were also analyzed for comparison.ResultsFluorescence spectra and variations of the decay time correlate well with the delignification yield and the lignin distribution. The decay dependences are considered two-exponential, one with a rapid (τ1) and the other with a slow (τ2) decay time. The fastest decay is associated to concentrated lignin in the bagasse and has a low sensitivity to the treatment. The fluorescence decay time became longer with the increase of the alkali concentration used in the treatment, which corresponds to lignin emission in a less concentrated environment. In addition, the two-photon fluorescence spectrum is very sensitive to lignin content and accumulation in the cell wall, broadening with the acid pretreatment and narrowing with the alkali one. Heterogeneity of the pretreated cell wall was observed.ConclusionsOur results reveal lignin domains with different concentration levels. The acid pretreatment caused a disorder in the arrangement of lignin and its accumulation in the external border of the cell wall. The alkali pretreatment efficiently removed lignin from the middle of the bagasse fibers, but was less effective in its removal from their surfaces. Our results evidenced a strong correlation between the decay times of the lignin fluorescence and its distribution within the cell wall. A new variety of lignin fluorescence states were accessed by two-photon excitation, which allowed an even broader, but complementary, optical characterization of lignocellulosic materials. These results suggest that the lignin arrangement in untreated bagasse fiber is based on a well-organized nanoenvironment that favors a very low level of interaction between the molecules.

Bicomponent Lignocellulose Thin Films to Study the Role of Surface Lignin in Cellulolytic Reactions

Ultrathin bicomponent films of cellulose and lignin derivatives were deposited on silica supports by spin coating, and after conversion into the respective polymer precursor, they were used as a model system to investigate interfacial phenomena relevant to lignocellulose biocatalysis. Film morphology, surface chemical composition, and wettability were determined by atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle, respectively. Phase separation of cellulose and lignin produced structures that resembled the cell wall of fibers and were used to monitor enzyme binding and cellulolytic reactions via quartz crystal microgravimetry. The rate and extent of hydrolysis was quantified by using kinetic models that indicated the role of the surface lignin domains in enzyme inhibition. Hydrophobic interactions between cellulases and the substrates and their critical role on irreversible adsorption were elucidated by using acetylated lignin films with different degrees of substitution. Overall, it is concluded that sensors based on the proposed ultrathin films of lignocellulose can facilitate a better understanding of the complex events that occur during bioconversion of cellulosic biomass.

Acoustic emission analysis and experiments with physical model systems reveal a peculiar nature of the xylem tension

Advanced acoustic emission analysis, special microscopic examinations and experiments with physical model systems give reasons for the assumption that the tension in the water conducting system of vascular plants is caused by countless minute gas bubbles strongly adhering to the hydrophobic lignin domains of the xylem vessel walls. We ascertained these bubbles for several species of temperate deciduous trees and conifers. It is our hypothesis that the coherent bubble system of the xylem conduits operates as a force-transmitting medium that is capable of transporting water in traveling peristaltic waves. By virtue of the high elasticity of the gas bubbles, the hydro-pneumatic bubble system is capable of cyclic storing and releasing of energy. We consider the abrupt regrouping of the wall adherent bubble system to be the origin of acoustic emissions from plants. For Ulmus glabra, we recorded violent acoustic activity during both transpiration and re-hydration. The frequency spectrum and the waveforms of the detected acoustic emissions contradict traditional assumptions according to which acoustic emissions are caused by cavitation disruption of the stressed water column. We consider negative pressure in terms of the cohesion theory to be mimicked by the tension of the wall adherent bubble system.

Signatures of cinnamyl alcohol dehydrogenase deficiency in poplar lignins

A series of transgenic poplars down-regulated for cinnamyl alcohol dehydrogenase (CAD) was analyzed by thioacidolysis. Among the lignin-derived monomers, the indene compounds that were recently shown to originate from sinapaldehyde incorporated into lignins through 8–O–4-cross-coupling, were found to increase as a function of CAD deficiency level. While these syringyl markers were recovered in substantial amounts in the most severely depressed lines, the markers for coniferaldehyde incorporation were recovered in only low amounts. In conjunction with these additional sinapaldehyde units and relative to the control samples, lignins in CAD-deficient poplar lines had less conventional syringyl-units and β–O–4-bonds and more free phenolic groups. We found that almost half of the polymers in the most deficient lines could be solubilized in alkali and at room temperature. This unusual behavior suggests that lignins in CAD-deficient poplars occur as small, alkali-leachable lignin domains. That mainly sinapaldehyde incorporates into the lignins of CAD-deficient poplars suggests that the recently identified sinapyl alcohol dehydrogenase (SAD), which is structurally distinct from the CAD enzyme targeted herein, does not play any substantial role in constitutive lignification in poplar.

Macromolecular lignin replication: A mechanistic working hypothesis

At the time of the first realization that the last step in lignin biosynthesis involves lignol radical coupling, it was difficult to envisage how such a process could be regiospecifically controlled. It was thus natural to expect that lignin macromolecules should have random primary structures. This has now been the prevailing assumption for almost fifty years, but of its correctness there has been no clear proof. Rather there have been occasional but insistent indications that lignins cannot just be products of random monolignol dehydropolymerization. Thus the present article seeks to apprehend the mechanistic implications of a situation where lignin primary structure would be determined by the sequence of interunit linkages along each biopolymer chain. The ramifications of a simple working hypothesis, that macromolecular lignin replication might occur directly through a template polymerization mechanism, are explored in detail. The manner in which the fidelity of the process could be maintained, through specific π-orbital interactions between the lignol radical precursors and characteristic substructures in the pre-existing lignin macromolecules, is explicitly described. The consequences of template polymerization are shown to be consistent with the absence of both optical activity and crystallinity in macromolecular lignin domains. It is proposed that the inherent primary structures of lignins are encoded in contiguous ‘dirigent’ arrays of lignol radical coupling sites distributed along individual polypeptide chains within lignifying plant cell walls.

Structural changes of cellulose, wood, and paper under shear deformation and high pressure

AbstractStructural changes of wood and its components have been studied after shear deformation under high pressure (SDHP) at up to 6 GPa. Cellulose amorphization and chain depolymerization was observed. Approximately 30% of microcrystalline cellulose was soluble in water after a 360‐degree twist of the Bridgman anvils. The water‐insoluble part was re‐crystallized into cellulose II lattice. Repeated treatment applied to the nondissolved part of the sample, the so‐called cascade experiment, permits the dissolving of about 30% of the residual nondissolved material once again. Extraction with water, followed by 10% sodium hydroxide, allows almost complete dissolving of microcrystalline cellulose (98%). Water‐soluble saccharides were studied by HPLC and 13C NMR. It was found that destruction of the wood lignin network needs more severe treatment conditions than cellulose destruction does. Lignin domains in wood act as “grinding stones” during cellulose destruction. Long‐living lignin free radicals have been detected with EPR after SDHP. 13C NMR CP/MAS spin diffusion studies showed that SDHP leads to separation of wood components into different biopolymer domains, which turns the system toward thermo‐dynamic equilibrium. SDHP does not permit achievement of initial compulsary compatibility of components in native wood. SDHP technique appears as a promising method for wood delignification and carbohydrate saccharification in the solid state without using harmful chemical reagents of solvents, which is important for technological safety and ecology. © 1994 John Wiley &amp; Sons, Inc.