Bonding wood with uncondensed lignins as adhesives.

Plywood is widely used in construction, such as for flooring and interior walls, as well as in the manufacture of household items such as furniture and cabinets. Such items are made of wood veneers that are bonded together with adhesives such as urea-formaldehyde and phenol-formaldehyde resins1,2. Researchers in academia and industry have long aimed to synthesize lignin-phenol-formaldehyde resin adhesives using biomass-derived lignin, a phenolic polymer that can be used to substitute the petroleum-derived phenol3-6. However, lignin-phenol-formaldehyde resin adhesives are less attractive to plywood manufacturers than urea-formaldehyde and phenol-formaldehyde resins owing to their appearance and cost. Here we report a simple and practical strategy for preparing lignin-based wood adhesives from lignocellulosic biomass. Our strategy involves separation of uncondensed or slightly condensed lignins from biomass followed by direct application of a suspension of the lignin and water as an adhesive on wood veneers. Plywood products with superior performances could be prepared with such lignin adhesives at a wide range of hot-pressing temperatures, enabling the use of these adhesives as promising alternatives to traditional wood adhesives in different market segments. Mechanistic studies indicate that the adhesion mechanism of such lignin adhesives may involve softening of lignin by water, filling of vessels with softened lignin and crosslinking of lignins in adhesives with those in the cell wall.

Revisiting alkaline cupric oxide oxidation method for lignin structural analysis.

Lignin structural analysis is important for the comprehensive utilization of lignin as well as delignification and bleaching during pulping while it is difficult to completely elucidate lignin structure due to its structural complexity and heterogeneity. Depolymerization of lignin into simple monomers via alkaline cupric oxide oxidation (OxCuO) followed by chromatographic analysis of the monomers is an effective method for lignin structural analysis. Here we revisited the OxCuO of lignin model compounds (monomers and dimers) and three representative lignocelluloses (i.e., Eucalyptus, Masson pine, and corn stover) to understand the effects of reaction conditions and lignin sub-structures on oxidation product yields and distributions. The improved OxCuO was found to be effective in oxidatively breaking the robust interunit C-C bonds in the ß-ß' and ß-5' moieties of lignin other than ß-O-4' linkages at an elevated temperature (210°C). Further degradation of the monomeric oxidation products could also occur to reduce the monomer yields under a severe condition (i.e., high temperature and long reaction time). In addition, O2 inputs could reduce the monomer yields via nonselective overoxidation, thus having negative effects on accurate structural analysis of lignin. The O2 removal via ultrasonication combined with N2 flushing prior to the oxidation reaction could improve the monomer yield about 1.2 times (compared to that without O2 removal) at a low biomass loading of 5 wt%. By using the improved method of OxCuO, a monomer yield of 71.9% could be achieved from Eucalyptus (hardwood) lignin, which was much higher than conventional nitrobenzene oxidation (59.8%) and reductive depolymerization (51.9%). Considering the low cost, high availability, and low toxicity of CuO, the improved OxCuO could be a convenient and economic method for more accurate lignin structural analysis.

Using poly(N-Vinylcaprolactam) to Improve the Enzymatic Hydrolysis Efficiency of Phenylsulfonic Acid-Pretreated Bamboo.

Chemical pretreatment followed by enzymatic hydrolysis has been regarded as a viable way to produce fermentable sugars. Phenylsulfonic acid (PSA) pretreatment could efficiently fractionate the non-cellulosic components (hemicelluloses and lignin) from bamboo and result in increased cellulose accessibility that was 10 times that of untreated bamboo. However, deposited lignin could trigger non-productive adsorption to enzymes, which therefore significantly decreased the enzymatic hydrolysis efficiency of PSA-pretreated bamboo substrates. Herein, poly(N-vinylcaprolactam) (PNVCL), a non-ionic surfactant, was developed as a novel additive for overcoming the non-productive adsorption of lignin during enzymatic hydrolysis. PNVCL was found to be not only more effective than those of commonly used lignosulfonate and polyvinyl alcohol for overcoming the negative effect of lignin, but also comparable to the robust Tween 20 and bovine serum albumin additives. A PNVCL loading at 1.2 g/L during enzymatic hydrolysis of PSA pretreated bamboo substrate could achieve an 80% cellulosic enzymatic conversion and meanwhile reduce the cellulase loading by three times as compared to that without additive. Mechanistic investigations indicated that PNVCL could block lignin residues through hydrophobic interactions and the resultant PNVCL coating resisted the adsorption of cellulase via electrostatic repulsion and/or hydration. This practical method can improve the lignocellulosic enzymatic hydrolysis efficiency and thereby increase the productivity and profitability of biorefinery.

Nanomechanics of Lignin-Cellulase Interactions in Aqueous Solutions.

Efficient enzymatic hydrolysis of cellulose in lignocellulose to glucose is one of the most critical steps for the production of biofuels. The nonproductive adsorption of lignin to expensive cellulase highly impedes the development of biorefinery. Understanding the lignin-cellulase interaction mechanism serves as a vital basis for reducing such nonproductive adsorption in their practical applications. Yet, limited report is available on the direct characterization of the lignin-cellulase interactions. Herein, for the first time, the nanomechanics of the biomacromolecules including lignin, cellulase, and cellulose were systematically investigated by using a surface force apparatus (SFA) at the nanoscale in aqueous solutions. Interestingly, a cation-π interaction was discovered and demonstrated between lignin and cellulase molecules through SFA measurements with the addition of different cations (Na+, K+, etc.). The complementary adsorption tests and theoretical calculations further confirmed the validity of the force measurement results. This finding further inspired the investigation of the interaction between lignin and other noncatalytic-hydrolysis protein (i.e., soy protein). Soy protein was demonstrated as an effective, biocompatible, and inexpensive lignin-blocker based on the molecular force measurements through the combined effects of electrostatic, cation-π, and hydrophobic interactions, which significantly improved the enzymatic hydrolysis efficiencies of cellulose in pretreated lignocellulosic substrates. Our results offer quantitative information on the fundamental understanding of the lignin-cellulase interaction mechanism. Such unraveled nanomechanics provides new insights into the development of advanced biotechnologies for addressing the nonproductive adsorption of lignin to cellulase, with great implications on improving the economics of lignocellulosic biorefinery.

Understanding the promoting effect of non-catalytic protein on enzymatic hydrolysis efficiency of lignocelluloses.

Lignin deposits formed on the surface of pretreated lignocellulosic substrates during acidic pretreatments can non-productively adsorb costly enzymes and thereby influence the enzymatic hydrolysis efficiency of cellulose. In this article, peanut protein (PP), a biocompatible non-catalytic protein, was separated from defatted peanut flour (DPF) as a lignin blocking additive to overcome this adverse effect. With the addition of 2.5 g/L PP in enzymatic hydrolysis medium, the glucose yield of the bamboo substrate pretreated by phenylsulfonic acid (PSA) significantly increased from 38 to 94% at a low cellulase loading of 5 FPU/g glucan while achieving a similar glucose yield required a cellulase loading of 17.5 FPU/g glucan without PP addition. Similar promotion effects were also observed on the n-pentanol-pretreated bamboo and PSA-pretreated eucalyptus substrates. The promoting effect of PP on enzymatic hydrolysis was ascribed to blocking lignin deposits via hydrophobic and/or hydrogen-bonding interactions, which significantly reduced the non-productive adsorption of cellulase onto PSA lignin. Meanwhile, PP extraction also facilitated the utilization of residual DPF as the adhesive for producing plywood as compared to that without protein pre-extraction. This scheme provides a sustainable and viable way to improve the value of woody and agriculture biomass. Peanut protein, a biocompatible non-catalytic protein, can block lignin, improve enzymatic hydrolysis efficiency and thereby facilitate the economics of biorefinery.

Integrating Benzenesulfonic Acid Pretreatment and Bio-Based Lignin-Shielding Agent for Robust Enzymatic Conversion of Cellulose in Bamboo.

A hydrotrope-based pretreatment, benzenesulfonic acid (BA) pretreatment, was used to fractionate bamboo in this work. With optimized content (80 wt %) of BA in pretreatment liquor, about 90% of lignin and hemicellulose could be removed from bamboo under mild conditions (95 °C, 30 min or 80 °C, 60 min). The potential accessibility of BA pretreated substrate to cellulase was thus significantly improved and was also found to be much higher than those of acidic ethanol and dilute acid pretreatments. But the deposition of lignin on the surface of solid substrates, especially the BA pretreated substrate, was also observed, which showed a negative effect on the enzymatic hydrolysis efficiency. The addition of inexpensive soy protein, a bio-based lignin-shielding agent, could readily overcome this negative effect, leading the increase of enzymatic conversion of cellulose in BA pretreated substrate from 37% to 92% at a low cellulase loading of 4 FPU/g glucan. As compared to acidic ethanol and dilute acid pretreatments, the combination of BA pretreatment and soy protein could not only stably improve the efficiency of non-cellulose components removal, but also could significantly reduce the loading of cellulase.

Novel Kinetic Models of Xylan Dissolution and Degradation during Ethanol Based Auto-Catalyzed Organosolv Pretreatment of Bamboo.

Due to the invalidity of traditional models, pretreatment conditions dependent parameter of susceptible dissolution degree of xylan (dX) was introduced into the kinetic models. After the introduction of dX, the dissolution of xylan, and the formation of xylo-oligosaccharides and xylose during ethanol based auto-catalyzed organosolv (EACO) pretreatments of bamboo were well predicted by the pseudo first-order kinetic models (R² > 97%). The parameter of dX was verified to be a variable dependent of EACO pretreatment conditions (such as solvent content in pretreatment liquor and pretreatment temperature). Based on the established kinetic models of xylan dissolution, the dissolution of glucan and the formation of degradation products (furfural and acetic acid) could also be empirically modeled (R² > 97%). In addition, the relationship between xylan and lignin removal can provide guidance for alleviating the depositions of lignin or pseudo-lignin. The parameter of dX derived novel kinetic models can not only be used to reveal the multi-step reaction mechanisms of xylan, but also control the final removal of main components in bamboo during EACO pretreatments, indicating scientific and practical significance for governing the biorefinery of woody biomass.