Rambutan peel: An unconventional source of lignin and its potential applications in polymer science

This study aimed to evaluate the properties of soda lignin obtained from an unconventional and abundant waste - the rambutan peel - since lignin has been shown as the most promising natural organic feedstock alternative to petroleum for polymer science. FTIR analysis and pH measurements have confirmed the acidic form of lignin, which has shown solubility in a wide range of polarities and so many solvents, making its insertion easy on polymeric matrices. While the ability to absorb UV-light was higher than commercial lignin tested as reference, the morphology and size distribution at microscopic level were less regular than that. When added to a starch-based film, the lignin decreases its natural affinity for water, improving the barrier properties, as well as increasing its thermal resistance. Microorganisms could be developed easily on starch-based films containing this kind of lignin. This material, still underreported for technological applications, points towards as promisor to be a component or additive in polymeric matrices.

Odor and Constituent Odorants of HDPE–Lignin Blends of Different Lignin Origin

The still-rising global demand for plastics warrants the substitution of non-renewable mineral oil-based resources with natural products as a decisive step towards sustainability. Lignin is one of the most abundant natural polymers and represents an ideal but hitherto highly underutilized raw material to replace petroleum-based resources. In particular, the use of lignin composites, especially polyolefin–lignin blends, is currently on the rise. In addition to specific mechanical property requirements, a challenge of implementing these alternative polymers is their heavy odor load. This is especially relevant for lignin, which exhibits an intrinsic odor that limits its use as an ingredient in blends intended for high quality applications. The present study addressed this issue by undertaking a systematic evaluation of the odor properties and constituent odorants of commercially available lignins and related high-density polyethylene (HDPE) blends. The potent odors of the investigated samples could be attributed to the presence of 71 individual odorous constituents that originated primarily from the structurally complex lignin. The majority of them was assignable to six main substance classes: carboxylic acids, aldehydes, phenols, furan compounds, alkylated 2-cyclopenten-1-ones, and sulfur compounds. The odors were strongly related to both the lignin raw materials and the different processes of their extraction, while the production of the blends had a lower but also significant influence. Especially the investigated soda lignin with hay- and honey-like odors was highly different in its odorant composition compared to lignins resulting from the sulfurous kraft process predominantly characterized by smoky and burnt odors. These observations highlight the importance of sufficient purification of the lignin raw material and the need for odor abatement procedures during the compounding process. The molecular elucidation of the odorants causing the strong odor represents an important procedure to develop odor reduction strategies.

Lignin Phenol Formaldehyde Resins Synthesised Using South African Spent Pulping Liquor

Purpose The current study investigated to which extent phenol could be replaced by lignins to produce lignin phenol formaldehyde (LPF) resins, utilising soda lignin and sodium lignosulphonate as by-products from the South African pulping industry.Method The lignins were characterised and soda lignin indicated the highest reactivity. It was therefore utilised to produce LPF resins at 60%, 80%, and 100% phenol substitution, using central composite designs to maximise the adhesive strength. A one-pot method allowing direct transition from phenolation to resin synthesis was used for the first time with a pulping lignin at 60% and 80% substitution.Results Plywood made with LPF60, LPF80, and LPF100 resins attained their highest shear strengths of 0.786, 1.09, and 0.987 MPa, respectively, which adhered to the GB/T 14732-2013 standard (≥ 0.7 MPa). A substitution level of 68% produced the highest shear strength of 1.11 MPa. High-density particleboard made with this LPF68 resin gave a MOR and MOE of 40 and 3209 MPa, respectively, adhering to the ANSI A208.1 requirements. Thickness swelling and water absorption was 13.5% and 37.2%, respectively.Conclusion The soda-lignin isolated by precipitation from sugarcane bagasse pulping liquor is the first industrial lignin shown to produce LPF100 resins adhering to standard requirements, without modification or additives.

A Putative Lignin Copper Oxidase from Trichoderma reesei

The ability of Trichoderma reesei, a fungus widely used for the commercial production of hemicellulases and cellulases, to grow and modify technical soda lignin was investigated. By quantifying fungal genomic DNA, T. reesei showed growth and sporulation in solid and liquid cultures containing lignin alone. The analysis of released soluble lignin and residual insoluble lignin was indicative of enzymatic oxidative conversion of phenolic lignin side chains and the modification of lignin structure by cleaving the β-O-4 linkages. The results also showed that polymerization reactions were taking place. A proteomic analysis conducted to investigate secreted proteins at days 3, 7, and 14 of growth revealed the presence of five auxiliary activity (AA) enzymes in the secretome: AA6, AA9, two AA3 enzymes), and the only copper radical oxidase encoded in the genome of T. reesei. This enzyme was heterologously produced and characterized, and its activity on lignin-derived molecules was investigated. Phylogenetic characterization demonstrated that this enzyme belonged to the AA5_1 family, which includes characterized glyoxal oxidases. However, the enzyme displayed overlapping physicochemical and catalytic properties across the AA5 family. The enzyme was remarkably stable at high pH and oxidized both, alcohols and aldehydes with preference to the alcohol group. It was also active on lignin-derived phenolic molecules as well as simple carbohydrates. HPSEC and LC-MS analyses on the reactions of the produced protein on lignin dimers (SS ββ, SS βO4 and GG β5) uncovered the polymerizing activity of this enzyme, which was accordingly named lignin copper oxidase (TrLOx). Polymers of up 10 units were formed by hydroxy group oxidation and radical formation. The activations of lignin molecules by TrLOx along with the co-secretion of this enzyme with reductases and FAD flavoproteins oxidoreductases during growth on lignin suggest a synergistic mechanism for lignin breakdown.

Evaluation of Soda Lignin from Wheat Straw/Sarkanda Grass as a Potential Future Consolidant for Archaeological Wood

This work is part of a larger study, which aims to use soda lignin from straw as the starting point for a non-aqueous consolidant for highly degraded archaeological wood from the Oseberg collection. This wood was treated with alum salts in the early 1900s, is actively degrading and exists in varying states of preservation. Non-aqueous consolidants are an option to stabilize this wood mechanically in cases where it is too deteriorated to undergo aqueous-based retreatments, for example using polyethylene glycol. The aim of this study was to compare the extent of penetration of two soda lignin preparations in low- to medium-degraded archaeological pine. The soda lignins were dissolved in ethyl acetate and had two molecular weight groups: P1000 (molecular weight Mw of~3 kDa) and the ethyl acetate fraction FB01 (Mw of ~1 kDa). Penetration after immersion was evaluated by infrared spectroscopy and analytical pyrolysis. Treated specimens were also evaluated using weight and dimensional change and scanning electron microscopy. Both lignins penetrated into sample cores, but P1000 did not penetrate as well as FB01. This may be due to differences in their molecular weights, but also differences in polarity due to the presence of different functional groups.

Phenolic Hydroxyl Groups in the Lignin Polymer Affect the Formation of Lignin Nanoparticles

Alkaline soda lignin (AL) was sequentially fractionated into six fractions of different molecular size by means of solvent extraction and their phenolic hydroxyl groups were chemoselectively methylated to determine their effect on nanoparticle formation of lignin polymers. The effect of the lignin structure on the physical properties of nanoparticles was also clarified in this study. Nanoparticles were obtained from neat alkaline soda lignin (ALNP), solvent-extracted fractions (FALNPs, i.d. 414–1214 nm), and methylated lignins (MALNPs, i.d. 516–721 nm) via the nanoprecipitation method. Specifically, the size properties of MALNPs showed a high negative correlation (R2 = 0.95) with the phenolic hydroxyl group amount. This indicates that the phenolic hydroxyl groups in lignin could be influenced on the nucleation or condensation during the nanoprecipitation process. Lignin nanoparticles exhibited high colloidal stability, and most of them also showed good in vitro cell viability. This study presents a possible way to control nanoparticle size by blocking specific functional groups and decreasing the interaction between hydroxyl groups of lignin.

Ecofriendly wood adhesives from date palm fronds lignin for plywood

Utilization of lignin phenol glyoxal (LPG) resins was studied as a potential alternative for phenol formaldehyde (PF) resins. Lignin was extracted by alkaline pulping processes (kraft and soda) from date palm fronds (DPF) and was used as an alternative for phenol in LPG resins. The isolated lignin samples were characterized using complementary analyses that included Fourier transform infrared (FTIR) spectroscopy, 13C nuclear magnetic resonance (NMR) spectroscopy, thermal stability, thermogravi-metric analysis (TGA), and differential scanning calorimetry (DSC). Kraft lignin phenol glyoxal (KLPG) and soda lignin phenol glyoxal (SLPG) resins also were characterized in terms of solid content, viscosity, and gel time. Finally, physico-mechanical tests were performed on plywood panels that were treated with different molar ratios of LPG resins. The results revealed that 50% (w/w) KLPG resin resulted in higher tensile strength (65.3 MPa) than PF resin (58.57 MPa), which was potentially attributed to the higher amount of phenolic groups compared to soda lignin. Therefore, the substitution of DPF lignin in LPG resins enhanced the adhesive in terms of its chemical and mechanical properties, enabling it to produce a more environmentally friendly wood adhesive.

Lignin-containing adhesion enhancer for wood-plastic composites

A lignin-containing adhesion enhancer, a water-soluble polyelectrolyte complex (LPEC) composed of soda hardwood lignin (HASL) and polyethylenimine (PEI), and the effect of the treatment of hydrolyzed and ammoxidized aspen sawdust with the LPEC nanoparticles were studied relative to the properties of wood-plastic composites (WPCs) based on recycled polypropylene (rPP). The presence of the excess of free amine groups and salt bonds between PEI and soda lignin, forming hydrophobic sites in the LPEC structure, caused the enhanced surface activity of the LPEC. The treatment with the LPEC nanoparticles increased the content of the fixed nitrogen in the modified sawdust samples and was accompanied by decreasing their water sorption and increasing contact angles that favored the decrease in the polar part of their surface free energy. The decreasing wetting ability enhanced the mechanical and water sorption properties of the obtained WPC samples. The improvement of the interfacial adhesion between the nitrogen-containing groups of the treated sawdust and the oxygen-containing groups of rPP was explained by the formation of both covalent and physicochemical bonds.