Molecular Structure Of Lignin Research Articles

Hard carbon anodes for sodium-ion batteries: Dependence of the microstructure and performance on the molecular structure of lignin

Hard carbon is currently believed to be the most promising anode material for commercial sodium-ion batteries. However, the sodium-ion storage mechanism of hard carbons remains ambiguous due to the unclear relationship between their microstructures and sodium-ion storage performance. This work reports several hard carbons with different pore structures by the carbonization of different lignin precursors, and further studies the relationship between their microstructures and sodium-ion storage performance. Corn cob lignin, pine lignin, and acetylated pine lignin with different molecular structures were selected as the precursors for the preparation of hard carbons. It is found that hard carbon prepared by corn cob lignin has the highest closed pore volume, resulting in the highest plateau capacity. The formation of closed pores is due to the formation of micropores at low pyrolysis temperatures. The micropores then transform into closed pores at high carbonization temperatures. N2 adsorption/desorption, CO2 adsorption/desorption, and small-angle X-ray scattering are used to analyze the pore architectures of the obtained hard carbons, and a method for calculating the closed pore volume is proposed. It is found that the plateau capacity is positively correlated with the closed pore volume.

Effect of Substituents on Molecular Reactivity during Lignin Oxidation by Chlorine Dioxide: A Density Functional Theory Study.

Lignin is a polymer with a complex structure. It is widely present in lignocellulosic biomass, and it has a variety of functional group substituents and linkage forms. Especially during the oxidation reaction, the positioning effect of the different substituents of the benzene ring leads to differences in lignin reactivity. The position of the benzene ring branched chain with respect to methoxy is important. The study of the effect of benzene substituents on the oxidation reaction's activity is still an unfinished task. In this study, density functional theory (DFT) and the m062x/6-311+g (d) basis set were used. Differences in the processes of phenolic oxygen intermediates formed by phenolic lignin structures (with different substituents) with chlorine dioxide during the chlorine dioxide reaction were investigated. Six phenolic lignin model species with different structures were selected. Bond energies, electrostatic potentials, atomic charges, Fukui functions and double descriptors of lignin model substances and reaction energy barriers are compared. The effects of benzene ring branched chains and methoxy on the mechanism of chlorine dioxide oxidation of lignin were revealed systematically. The results showed that the substituents with shorter branched chains and strong electron-absorbing ability were more stable. Lignin is not easily susceptible to the effects of chlorine dioxide. The substituents with longer branched chains have a significant effect on the flow of electron clouds. The results demonstrate that chlorine dioxide can affect the electron arrangement around the molecule, which directly affects the electrophilic activity of the molecule. The electron-absorbing effect of methoxy leads to a low dissociation energy of the phenolic hydroxyl group. Electrophilic reagents are more likely to attack this reaction site. In addition, the stabilizing effect of methoxy on the molecular structure of lignin was also found.

Polylactic Acid/Lignin Composites: A Review

With the gradual depletion of petroleum resources and the increasing global awareness of environmental protection, biodegradable plastics are receiving more and more attention as a green substitute for traditional petroleum-based plastics. Poly (lactic acid) is considered to be the most promising biodegradable material because of its excellent biodegradability, biocompatibility, and good processability. However, the brittleness and high cost limit its application in more fields. Lignin, as the second largest renewable biopolymer in nature after cellulose, is not only rich in reserves and low in cost, but it also has an excellent UV barrier, antioxidant activity, and rigidity. The molecular structure of lignin contains a large number of functional groups, which are easy to endow with new functions by chemical modification. Currently, lignin is mostly treated as waste in industry, and the value-added utilization is insufficient. The combination of lignin and poly (lactic acid) can on the one hand solve the problems of the high cost of PLA and less efficient utilization of lignin; on the other hand, the utilization of lignocellulosic biomass in compounding with biodegradable synthetic polymers is expected to afford high-performance wholly green polymer composites. This mini-review summarizes the latest research achievements of poly (lactic acid)/lignin composites. Emphasis was put on the influence of lignin on the mechanical properties of its composite with poly (lactic acid), as well as the compatibility of the two components. Future research on these green composites is also prospected.

Lignin-based materials for electrochemical energy storage devices

Lignin is the most abundant aromatic polymer in nature, which is rich in a large number of benzene ring structures and active functional groups. The molecular structure of lignin has unique designability and controllability, and is a class of functional materials with great application prospects in energy storage and conversion. Here, this review firstly focuses on the concept, classification, and physicochemical property of lignin. Then, the application research of lignin in the field of electrochemical storage materials and devices are summarized, such as lignin-carbon materials and lignin-carbon composites in supercapacitors and secondary batteries. Finally, this review points out the bottlenecks that need to be solved urgently and the prospects for future research priorities.

Lignin Distribution on Cell Wall Micro-Morphological Regions of Fibre in Developmental Phyllostachys pubescens Culms.

Bamboo is a natural fibre reinforced composite with excellent performance which is, to a certain extent, an alternative to the shortage of wood resources. The heterogeneous distribution and molecular structure of lignin is one of the factors that determines its performance, and it is the key and most difficult component in the basic research into the chemistry of bamboo and in bamboo processing and utilization. In this study, the distribution of lignin components and lignin content in micro-morphological regions were measured in semi-quantitative level by age and radial location by means of visible-light microspectrophotometry (VLMS) coupled with the Wiesner and Maule reaction. There as guaiacyl lignin and syringyl lignin in the cell wall of the fibre. Lignin content of the secondary cell wall and cell corner increased at about 10 days, reached a maximum at 1 year, and then decreased gradually. From 17 days to 4 years, the lignin content of the secondary cell wall in the outer part of bamboo is higher than that in the middle part (which is, in turn, higher than that in the inner part of the bamboo). VLSM results of the micro-morphological regions showed that bamboo lignification developed by aging. Guaiacyl and syringl lignin units can be found in the cell wall of the fibre, parenchyma, and vessel. There was a difference in lignin content among different ages, different radial location, and different micro-morphological regions of the cell wall. The fibre walls were rich in guaiacyl lignin in the early stage of lignification and rich in syringyl units in the later stage of lignification. The guaiacyl and syringyl lignin deposition of bamboo green was earlier than that of the middle part of bamboo culm, and that of the middle part of bamboo culm was earlier than that of bamboo yellow. The single molecule lignin content of the thin layer is higher than that of thick layers, while the primary wall is higher than the secondary cell wall, showing that lignin deposition is consistent with the rules of cell wall formation. The obtained cytological information is helpful to understand the origin of the anisotropic, physical, mechanical, chemical, and machining properties of bamboo.

Influence of hydrocracking and ionic liquid pretreatments on composition and properties of Arabidopsis thaliana wild type and CAD mutant lignins

Lignin is the primary contributor to the high cost of biofuel-production from lignocellulosic biomass. In order to study lignin removal and the release of aromatic monomers, we applied hydrocracking and ionic liquid pretreatments on Arabidopsis thaliana biomass from both wild type (WT) and a mutant (CAD cxd) defective in two cinnamyl alcohol dehydrogenase genes involved in the lignin biosynthetic pathway. For Arabidopsis WT, our results highlight that pretreatments reduce average molecular weight of lignin by about 65% and decrease the content of β-O-4 linkages between lignin monomers. For Arabidopsis CAD mutant, an opposite effect is evidenced. Fewer differences were observed on depolymerization and molecular structure of lignin, which indicates that (8-O-4), (8-5), and (8-8) linkages observed in CAD mutant make lignin more resilient to pretreatment than wild-type lignin. Finally, our study shows the potential of hydrocracking pretreatment technology for extracting valuable aldehyde monomers such as vanillin and syringaldehyde from biomass.

Revealing the Topochemistry and Structural Features of Lignin during the Growth of Eucalyptus grandis × Eucalyptus urophylla

The heterogeneity of the topochemistry and molecular structure of lignin have impeded the potential application of lignocellulosic biomass. In this study, confocal Raman microscopy (CRM), 2D heteronuclear single-quantum coherence (2D HSQC), and phosphorus magnetic resonance spectroscopy (31P NMR) were used to elucidate the topochemistry and structural variations of Eucalyptus lignin during the growth. CRM results confirmed that the lignin concentration was in the following order: cell corner middle lamella (CCML) > compound middle lamella (CML) > S2 regions in cell walls. The growth rate of lignin concentration in CCML decreased from 1 to 4 years old, which was contrary to the tendency in S2 regions. Swollen residue enzyme lignin (SREL) was isolated as a representative sample to be used in the characterization of the structural features of lignin. High yield (83.9–94.2%) and low carbohydrate content (5.11–6.25%) were observed in SRELs. An alteration in predominant monosaccharide content in the lignin samp...

Solubility of Organosolv Lignin in γ-Valerolactone/Water Binary Mixtures.

The solubility of lignin in a mixture of γ‐valerolactone (GVL) and water at different weight ratios was measured using the Hildebrand solubility parameters. Based on the molecular structure of lignin, its solubility parameter (δ‐value) was calculated as 25.5 MPa1/2. The δ‐value for aqueous GVL solvent increased from 23.1 MPa1/2 for pure GVL to 45.6 MPa1/2 for pure water. Therefore, the lignin solubility was predicted to increase with increasing GVL concentration in the aqueous mixture up to approximately 92–96 wt % of GVL. A ternary diagram describing the phase behavior of water–GVL–lignin mixtures at room temperature was constructed based on the experimental results. The three‐component system exhibited a complex behavior with a liquid–liquid and solid–liquid–liquid phase split. The efficiency of the selected fractionation trials in a previous work was validated using the ternary solubility diagram. A promising recovery pathway and lignin isolation method were deduced from the results of this work.

Influence of RANEY Nickel on the Formation of Intermediates in the Degradation of Lignin

Lignin forms an important part of lignocellulosic biomass and is an abundantly available residue. It is a potential renewable source of phenol. Liquefaction of enzymatic hydrolysis lignin as well as catalytical hydrodeoxygenation of the main intermediates in the degradation of lignin, that is, catechol and guaiacol, was studied. The cleavage of the ether bonds, which are abundant in the molecular structure of lignin, can be realised in near-critical water (573 to 673 K, 20 to 30 MPa). Hydrothermal treatment in this context provides high selectivity in respect to hydroxybenzenes, especially catechol. RANEY Nickel was found to be an adequate catalyst for hydrodeoxygenation. Although it does not influence the cleavage of ether bonds, RANEY Nickel favours the production of phenol from both lignin and catechol. The main product from hydrodeoxygenation of guaiacol with RANEY Nickel was cyclohexanol. Reaction mechanism and kinetics of the degradation of guaiacol were explored.

Catalytic hydrogenolysis of ethanol organosolv lignin

Abstract The production of ethanol based on lignocellulosic materials will bring about the coproduction of significant amounts of under-utilized lignin. This study examines the potential of conventional heterogeneous and novel homogeneous catalysts for the selective cleavage of the aryl-O-aryl and aryl-O-aliphatic linkages of ethanol organosolv lignin to convert it from a low grade fuel to potential fuel precursors or other value added chemicals. The development of hydrogenolysis conditions that effectively increase the solubility of lignin were initially examined with Ru(Cl)2(PPh3)3 and demonstrated the ability to decrease the molecular weight and enhance the solubility of the lignin polymer. Later studies examined several heterogeneous and homogeneous hydrogenation catalysts at optimized reaction conditions resulting in 96.4% solubility with Ru(Cl)2(PPh3)3, increase in H/C ratio with Raney-Ni, Pt/C and extensive monomer formation with NaBH4/I2. The changes in molecular structure of lignin were followed by size exclusion chromatography, qualitative and quantitative NMR spectroscopy and elemental analysis. These studies demonstrated that aryl-O-aryl and aryl-O-aliphatic linkages could be cleaved and the hydrogenated lignin had a decrease in oxygen functionality and the formation of products with lower oxygen content.

Mass spectrometry in the biosynthetic and structural investigation of lignins.

Lignin, a resistant cell-wall constituent of all vascular plants that consists of ether and carbon-linked methoxyphenols, is still far from being structurally described in detail. The main problem in its structural elucidation is the difficulty of isolating lignin from other wood components without damaging lignin itself. Furthermore, the high number and variegated forms of linkages that occur between the monomeric units and the chemical resistance of certain ether bonds limit the extent to which analytical and degradation procedures can be used to elucidate the lignin structure. Most of our present knowledge about the molecular structure of lignin is based on the analysis of monomers, dimers or, at the most, tetramers of degraded isolated lignins. Mass spectrometry (MS), which offers advantages in terms of speed, specificity, and sensitivity, has revealed to be a very powerful technique in the structural elucidation of lignins, in combination with the great number of chemical and thermal degradation methods available in the study of lignin. Moreover, the recent development of new ionization techniques in MS-electrospray ionization (ESI)-MS and matrix-assisted laser desorption/ionization (MALDI)-MS-has provided new possibilities to also analyze the undegraded lignin macromolecule.

Alterations in the biosynthesis of lignin in transgenic plants with chimeric genes for 4-coumarate: coenzyme A ligase.

The introduction of chimeric sense and antisense gene constructs for 4-coumarate:coenzyme A ligase into tobacco plants caused the reduction of the 4CL activity in the transgenic plants. In the transgenic plants, the cell walls of the xylem tissue in stems were brown and the molecular structure of lignin in the colored cell walls was dramatically different from that in the control plants. Analysis with different types of stain revealed that levels of cinnamyl aldehyde residues and syringyl units in lignin were depressed in the brownish cell walls. Furthermore, the lignin content in colored tissue was lower than that in the normal tissue. Our results indicate that 4CL has important roles in the determination of the composition and the amount of lignin in tobacco plants.