Harnessing Atomically Dispersed Cobalt for the Reductive Catalytic Fractionation of Lignocellulose.

The reductive catalytic fractionation (RCF) of lignocellulose, considering lignin valorization at design time, has demonstrated the entire utilization of all lignocellulose components; however, such processes always require catalysts based on precious metals or high-loaded nonprecious metals. Herein, the study develops an ultra-low loaded, atomically dispersed cobalt catalyst, which displays an exceptional performance in the RCF of lignocellulose. An approximately theoretical maximum yield of phenolic monomers (48.3 wt.%) from lignin is realized, rivaling precious metal catalysts. High selectivity toward 4-propyl-substituted guaiacol/syringol facilitates their purification and follows syntheses of highly adhesive polyesters. Lignin nanoparticles (LNPs) are generated by simple treatment of the obtained phenolic dimers and oligomers. RCF-resulted carbohydrate pulp are more obedient to enzymatic hydrolysis. Experimental studies on lignin model compounds reveal the concerted cleavage of Cα-O and Cß-O pathway for the rupture of ß-O-4 structure. Overall, the approach involves valorizing products derived from lignin biopolymer, providing the opportunity for the comprehensive utilization of all components within lignocellulose.

Manipulating microRNA miR408 enhances both biomass yield and saccharification efficiency in poplar.

The conversion of lignocellulosic feedstocks to fermentable sugar for biofuel production is inefficient, and most strategies to enhance efficiency directly target lignin biosynthesis, with associated negative growth impacts. Here we demonstrate, for both laboratory- and field-grown plants, that expression of Pag-miR408 in poplar (Populus alba × P. glandulosa) significantly enhances saccharification, with no requirement for acid-pretreatment, while promoting plant growth. The overexpression plants show increased accessibility of cell walls to cellulase and scaffoldin cellulose-binding modules. Conversely, Pag-miR408 loss-of-function poplar shows decreased cell wall accessibility. Overexpression of Pag-miR408 targets three Pag-LACCASES, delays lignification, and modestly reduces lignin content, S/G ratio and degree of lignin polymerization. Meanwhile, the LACCASE loss of function mutants exhibit significantly increased growth and cell wall accessibility in xylem. Our study shows how Pag-miR408 regulates lignification and secondary growth, and suggest an effective approach towards enhancing biomass yield and saccharification efficiency in a major bioenergy crop.

Discovery, disassembly, depolymerization and derivatization of catechyl lignin in Chinese tallow seed coats.

The search for feedstock of catechyl lignin (C-lignin) is great interest and importance, as C-lignin featuring homogeneity and linearity is considered as an "ideal lignin" archetype for valorization and exits in only a few plant seed coats. In this study, naturally occurring C-lignin is first discovered in the seed coats of Chinese tallow, which has the highest content of C-lignin (15.4 wt%) as compared with other known feedstocks. An optimized extraction procedure by ternary deep eutectic solvents (DESs) enables the complete disassembly of C-lignin and G/S-lignin coexisted in Chinese tallow seed coats, and characterizations revealed that the as-separated C-lignin sample is abundant in benzodioxane units with no observation of ß-O-4 structures from G/S-lignin. Catalytic depolymerization of C-lignin results in a simplex catechol product in 129 mg per gram seed coats, being higher than other reported feedstocks. Derivatizing the "black" C-lignin via the nucleophilic isocyanation of benzodioxane γ-OH leads to a "whitened C-lignin" with uniform laminar structure and excellent crystallization ability, being conducive to fabricating functional materials. Overall, this contribution showed that Chinses tallow seed coats are suitable feedstock for acquiring C-lignin biopolymer.

Rational highly dispersed ruthenium for reductive catalytic fractionation of lignocellulose.

Producing monomeric phenols from lignin biopolymer depolymerization in a detachable and efficient manner comes under the spotlight on the fullest utilization of sustainable lignocellulosic biomass. Here, we report a low-loaded and highly dispersed Ru anchored on a chitosan-derived N-doped carbon catalyst (RuN/ZnO/C), which exhibits outstanding performance in the reductive catalytic fractionation of lignocellulose. Nearly theoretical maximum yields of phenolic monomers from lignin are achieved, corresponding to TON as 431 molphenols molRu-1, 20 times higher than that from commercial Ru/C catalyst; high selectivity toward propyl end-chained guaiacol and syringol allow them to be readily purified. The RCF leave high retention of (hemi)cellulose amenable to enzymatic hydrolysis due to the successful breakdown of biomass recalcitrance. The RuN/ZnO/C catalyst shows good stability in recycling experiments as well as after a harsh hydrothermal treatment, benefiting from the coordination of Ru species with N atoms. Characterizations of the RuN/ZnO/C imply a transformation from Ru single atoms to nanoclusters under current reaction conditions. Time-course experiment, as well as reactivity screening of a series of lignin model compounds, offer insight into the mechanism of current RCF over RuN/ZnO/C. This work opens a new opportunity for achieving the valuable aromatic products from lignin and promoting the industrial economic feasibility of lignocellulosic biomass.

Sustainable Production of Bioactive Molecules from C-Lignin-Derived Propenylcatechol.

Catechyl lignin (C-lignin) is a naturally occurring linear homogeneous biopolymer composed solely of caffeyl alcohol subunits with cleavable benzodioxane linkages. The inherent structural features of propenylcatechol, a direct depolymerized product of castor seed coats C-lignin, render it a sustainable and promising platform for the synthesis of bioactive molecules. Herein, diversified transformations of propenylcatechol, including C=C bond difunctionalization, ß-modification, ß,γ-rearrangement, and γ-methyl derivatization, were reported based on known or developed methods. A series of functional molecular skeletons involved in the current synthetic routes for the preparation of pharmaceuticals and bioactive molecules were obtained. Starting from castor seed coats, annuloline (natural product) and CC-5079 (antitumor) were synthesized using facile and inexpensive reagents in only four- and five-sequence reactions, respectively, thereby demonstrating a superior step-efficiency to that of reported synthetic routes. Almost all atoms in the C-lignin biopolymer were incorporated into the final products owing to the intrinsic structures of naturally occurring C-lignin. Bioactive molecules produced from C-lignin integrate a low-carbon footprint with high-quality and economical manufacture of pharmaceuticals.

Lignin-First Depolymerization of Lignocellulose into Monophenols over Carbon Nanotube-Supported Ruthenium: Impact of Lignin Sources.

Lignin-first depolymerization of lignocellulosic biomass into aromatics is of great significance to sustainable biorefinery. However, it remains a challenge, owing to the variance between lignin sources and structures. In this study, ruthenium supported on carbon nanotubes (Ru/CNT) exhibits efficient catalytic activity toward lignin hydrogenolysis to exclusively afford monophenols in high yields. Catalytic tests indicate that the yields of aromatic monomers are related to lignin sources and decrease in the order: hardwoods > herbaceous plants > softwoods. Experimental results demonstrate that the scission of C-O bonds and the high selectivity to monomeric aromatic compounds over the Ru/CNT catalyst are enhanced by avoiding side condensation. Furthermore, the fabricated Ru/CNT shows good reusability and recyclability, applicability, and biomass feedstock compatibility, rendering it a promising candidate for lignin valorization. These findings pave the way for rational design of highly active and stable catalysts to potentially address challenges in lignin chemistry.

Selective hydrogenolysis of catechyl lignin into propenylcatechol over an atomically dispersed ruthenium catalyst.

C-lignin is a homo-biopolymer, being made up of caffeyl alcohol exclusively. There is significant interest in developing efficient and selective catalyst for depolymerization of C-lignin, as it represents an ideal feedstock for producing catechol derivatives. Here we report an atomically dispersed Ru catalyst, which can serve as an efficient catalyst for the hydrogenolysis of C-lignin via the cleavage of C-O bonds in benzodioxane linkages, giving catechols in high yields with TONs up to 345. A unique selectivity to propenylcatechol (77%) is obtained, which is otherwise hard to achieve, because this catalyst is capable of hydrogenolysis rather than hydrogenation. This catalyst also demonstrates good reusability in C-lignin depolymerization. Detailed investigations by model compounds concluded that the pathways involving dehydration and/or dehydrogenation reactions are incompatible routes; we deduced that caffeyl alcohol generated via concurrent C-O bonds cleavage of benzodioxane unit may act as an intermediate in the C-lignin hydrogenolysis. Current demonstration validates that atomically dispersed metals can not only catalyze small molecules reactions, but also drive the transformation of abundant and renewable biopolymer.

Unlocking Structure-Reactivity Relationships for Catalytic Hydrogenolysis of Lignin into Phenolic Monomers.

Lignin depolymerization into aromatic monomers with high yields and selectivity is essential for the economic feasibility of biorefinery. However, the relationship between lignin structure and its reactivity for upgradeability is still poorly understood, in large part owing to the difficulty in quantitative characterization of lignin structural properties. To overcome these shortcomings, advanced NMR technologies [2D HSQC (heteronuclear single quantum coherence) and 31 P] were used to accurately quantify lignin functionalities. Diverse lignin samples prepared from Eucalyptus grandis with varying ß-O-4 linkages were subjected to Pd/C-catalyzed hydrogenolysis for efficient C-O bond cleavage to achieve theoretical monomer yields. Strong correlations were observed between the yield of monomeric aromatic compounds and the structural features of lignin, including the contents of ß-O-4 linkages and phenolic hydroxyl groups. Notably, a combined yield of up to 44.1 wt % was obtained from ß-aryl ether rich in native lignin, whereas much lower yields were obtained from technical lignins low in ß-aryl ether content. This work quantitatively demonstrates that the lignin reactivity for acquiring aromatic monomer yields varies depending on the lignin fractionation processes.

Selective Fragmentation of Biorefinery Corncob Lignin into p-Hydroxycinnamic Esters with a Supported Zinc Molybdate Catalyst.

Lignin is the largest renewable resource of bioaromatics, and the catalytic fragmentation of lignin into phenolic monomers is increasingly recognized as an important starting point for lignin valorization. Herein, we report that ZnMoO4 supported on MCM-41 can catalyze the fragmentation of biorefinery technical lignin, enzymatic mild acidolysis lignin, and native lignin derived from corncob to yield lignin oily products that contain 15-37.8 wt % phenolic monomers, in which the high selectivities towards methyl coumarate (1) and methyl ferulate (2) were obtained (up to 78 %). The effects of some key parameters such as the influence of the solvent, reaction temperature, time, H2 pressure, and catalyst dosage were examined in view of activity and selectivity. The loss of Zn from the catalyst is discussed as the primary cause of deactivation, and the catalytic activity and selectivity can be well preserved in at least six runs by thermal calcination. The high selectivity to 1 and 2 leads to their easy separation and purification from lignin oily product to provide sustainable monomers for the preparation of functional polyether esters and polyesters.

Acceptorless dehydrogenation and dehydrogenative coupling of alcohols catalysed by protic NHC ruthenium complexes.

A new family of protic NHC Ru complexes ligated with a phosphine-tethered imidazole moiety were prepared, which can act as excellent catalysts for acceptorless dehydrogenation of secondary alcohols and dehydrogenative coupling of primary and secondary alcohols, thus leading to the formation of a variety of carbonyl compounds with release of H2.