The molecular weight of lignin is a fundamental property that influences the recalcitrance of biomass and the valorization of lignin. The determination of the molecular weight of lignin in native biomass is dependent on the bioresources used and the isolation and purification procedures employed. The three most commonly employed isolation methods are milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL). Common characterization techniques for determining the molecular weight of lignin will be addressed, with an emphasis on gel permeation chromatography (GPC). This review also examines the mechanisms behind several biological, physical, and chemical pre‐treatments and their impact on the molecular weight of lignin. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (D) all vary in magnitude depending on the biomass source, pre‐treatment conditions, and isolation method. Additionally, there is a growing body of literature that supports changes in the molecular weight of lignin in response to genetic modifications in the lignin biosynthetic pathways. This review summarizes different procedures for obtaining the molecular weight of lignin that have been used in recent years and highlight future opportunities for applications of lignin. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd

Low-molecular-weight poly(allylamine) is prepared via free-radical polymerization, and the resulting polymer is impregnated into mesocellular silica foams at different amine loadings. The resulting poly(allylamine)–silica composites are demonstrated as effective adsorbents for the extraction of carbon dioxide from dilute (simulated flue gas) and ultradilute (simulated ambient air) gas streams. The composite adsorbents are shown to have comparable adsorption capacities to more-conventional poly(ethyleneimine)–silica adsorbents. Potential advantages of poly(allylamine)-derived adsorbents are discussed.

Lignins from various poplar genotypes were isolated by using organosolv fractionation and subjected to rheological treatment at various temperatures. Physicochemical characterization of the lignin variants shows a broad distribution of glass transition temperatures, melt viscosity, and pyrolysis char residues.Rheological treatment at 170°C induces lignin repolymerization accompanied with an increase in condensed linkages, molecular weights, and viscosities. In contrast, rheology testing at 190°C results in the decrease in lignin aliphatic and phenolic hydroxyl groups, β-O-aryl ether linkages, molecular weights, and viscosity values. Lignin under air cooling generates more oxygenated and condensed compounds, but lower amounts of ether linkages than lignin cooled under nitrogen. Lignin with a lower syringyl/guaiacyl ratio tends to form more cross-linkages along with higher viscosity values, higher molecular weight and larger amounts of condensed bonds.

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The recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose, a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.