Lignin Model Substrates Research Articles

Oxidative cleavage of lignin model substrates with Co(salen) catalyst: an experimental study on the effect of different reaction parameters in batch and continuous flow

Continuous flow screening improved Co(salen)-catalyzed oxidative cleavage of lignin models, revealing new key parameters for robust and optimal batch operation.

Enhancing photocatalytic cleavage of C[sbnd]C bonds in lignin model substrates by ternary nanocomposite of g-C3N4/rGO/CdS using rGO as electronic mediators

Depolymerizing lignin into aromatic monomers with high yield and selectivity via photocatalysis remains a challenging task. Herein, we introduced reduced graphene oxide (rGO) nanosheets as solid electronic mediators and successfully synthesized g-C3N4/rGO/CdS ternary nanocomposites using a simple multi-step assembly strategy. The photocatalysts can efficiently break the CC bond of lignin under simulated sunlight conditions. The characterization results demonstrate that the loading of CdS effectively enhances the light absorption range and accelerates the transfer of photogenerated charge carriers. Simultaneously, the introduction of rGO inhibits the recombination of electron-hole pairs. When using the β-O-4 model substrate, a 95% conversion rate could be achieved with yields of 71% benzaldehyde and 69% phenyl formate, which are 3.09 times and 3.63 times higher than that of pure g-C3N4, respectively. Our research highlights the importance of energy band structure engineering and electronic mediator design in developing efficient photocatalysts for breaking CC bonds of lignin.

Visible-light-driven selective cleavage of C[sbnd]C bonds in lignin model substrates using carbon nitride-supported ruthenium single-atom catalyst

The selective cleavage of the CC bonds in lignin is highly pursued to obtain aromatic monomers from renewable resources but remains challenging due to their high dissociation energies and steric hindrance between bulky aromatic groups. Herein, a mesoporous carbon nitride-supported ruthenium single-atom photocatalyst (Ru1/MCN) is reported for efficient oxidative Cα-Cβ bonds scissoring towards lignin β-O-4 model compounds with high activity and selectivity under visible–light irradiation and room temperature. With this strategy, a nearly total conversion of > 99% and > 98% selectivity of CC bond cleavage can be achieved upon 2–phenoxy–1–phenylethanol. In-depth investigations verify that the Cβ-H extraction by photogenerated holes is the critical step of the transformation, which directly generates the Cβ radical intermediates and thus promotes the selective Cα-Cβ bonds breaking by coupling with superoxide radicals induced by photogenerated electrons. This work explores the potential of single-atom catalysts for photocatalytic production of aromatics from renewable biomass feedstocks.

Highly stable and tunable peptoid/hemin enzymatic mimetics with natural peroxidase-like activities

Developing tunable and stable peroxidase mimetics with high catalytic efficiency provides a promising opportunity to improve and expand enzymatic catalysis in lignin depolymerization. A class of peptoid-based peroxidase mimetics with tunable catalytic activity and high stability is developed by constructing peptoids and hemins into self-assembled crystalline nanomaterials. By varying peptoid side chain chemistry to tailor the microenvironment of active sites, these self-assembled peptoid/hemin nanomaterials (Pep/hemin) exhibit highly modulable catalytic activities toward two lignin model substrates 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) and 3,3’,5,5’-tetramethylbenzidine. Among them, a Pep/hemin complex containing the pyridyl side chain showed the best catalytic efficiency (Vmax/Km = 5.81 × 10−3 s−1). These Pep/hemin catalysts are highly stable; kinetics studies suggest that they follow a peroxidase-like mechanism. Moreover, they exhibit a high efficacy on depolymerization of a biorefinery lignin. Because Pep/hemin catalysts are highly robust and tunable, we expect that they offer tremendous opportunities for lignin valorization to high value products.

Fenton-Mediated Chlorophenol Degradation by Iron-Reducing Compounds Isolated from Endophytic Fungi in Atacama Puna Plateau Lecanicillium ATA01

Low-molecular-mass iron-reducing compounds (IRCs) were produced by entomopathogenic endophytic fungi Lecanicillium sp. ATA01 in liquid cultures. The extracellular hydrophilic extract contained three IRCs formed by peptides, iron and phenolate structures with molecular masses of 1207, 567 and 550 Da. These compounds were able to chelate and mediate the reduction of Fe+3 to Fe+2 and oxidized recalcitrant lignin-model substrates such as veratryl alcohol (VA), 2,6-dimethoxyphenol (DMP), and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid (ABTS) with or without hydrogen peroxide. Besides, IRCs can promote the degradation of chlorophenols. The maximal degradation of p-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol was conducted at optimal degradation conditions for IRCs (pH 3.5, iron 100 mM, and H2O2 10 mM). Furthermore, Fenton-like reactions using the synthetic iron chelates DTPA and EDTA and free Fe+2 and Fe+3 were also carried out in order to compare with the reaction mediated by IRCs. The ferric IRCs displayed the ability to enhance the hydroxylation of chlorophenols as a part of a degradation mechanism of the IRC-assisted Fenton reaction. The complexed iron was more efficient than free iron in the Fenton-like reaction, and between them, the fungal chelates were more efficient than the synthetic mill chelates.

Visible-Light-Induced Selective C–C Bond Cleavage Reactions of Dimeric β-O-4 and β-1 Lignin Model Substrates Utilizing Amine-Functionalized Fullerene

Finding a selective and efficient fragmentation process under ambient conditions is pivotal for the generation of fuels and chemical feedstocks from lignoceullosic biomass. In the present study, visible-light and amine-functionalized fullerene-based photocatalyst-promoted photodegradation reactions of dimeric β-O-4 and β-1 lignin model compounds, containing varying numbers of methoxy substituents on the arene ring, were explored to find and develop mild, eco-friendly photochemical techniques for efficient delignification. The results showed that, in contrast to well-known organic photoredox catalysts, amine-functionalized fullerene photocatalyst promoted photochemical reactions of lignin model compounds could lead to more efficient lignin fragmentation reactions through a pathway involving a selective Cα-Cβ bond cleavage process, and in addition, Cα-hydroxyl moiety in lignin model compounds played a significant role in the success of the Cα-Cβ bond cleavage reaction of lignin model substrates.

High Triplet Energy Iridium(III) Isocyanoborato Complex for Photochemical Upconversion, Photoredox and Energy Transfer Catalysis.

Cyclometalated Ir(III) complexes are often chosen as catalysts for challenging photoredox and triplet-triplet-energy-transfer (TTET) catalyzed reactions, and they are of interest for upconversion into the ultraviolet spectral range. However, the triplet energies of commonly employed Ir(III) photosensitizers are typically limited to values around 2.5-2.75 eV. Here, we report on a new Ir(III) luminophore, with an unusually high triplet energy near 3.0 eV owing to the modification of a previously reported Ir(III) complex with isocyanoborato ligands. Compared to a nonborylated cyanido precursor complex, the introduction of B(C6F5)3 units in the second coordination sphere results in substantially improved photophysical properties, in particular a high luminescence quantum yield (0.87) and a long excited-state lifetime (13.0 μs), in addition to the high triplet energy. These favorable properties (including good long-term photostability) facilitate exceptionally challenging organic triplet photoreactions and (sensitized) triplet-triplet annihilation upconversion to a fluorescent singlet excited state beyond 4 eV, unusually deep in the ultraviolet region. The new Ir(III) complex photocatalyzes a sigmatropic shift and [2 + 2] cycloaddition reactions that are unattainable with common transition metal-based photosensitizers. In the presence of a sacrificial electron donor, it furthermore is applicable to demanding photoreductions, including dehalogenations, detosylations, and the degradation of a lignin model substrate. Our study demonstrates how rational ligand design of transition-metal complexes (including underexplored second coordination sphere effects) can be used to enhance their photophysical properties and thereby broaden their application potential in solar energy conversion and synthetic photochemistry.

Organophotoredox-Catalyzed Reductive Cleavage of Oxidized Lignin Model Substrates

Key words reductive lignin cleavage - C−O bond cleavage - photoredox catalysis

Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions.

SummaryHydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role in organic synthesis. However, the direct cleavage of Csp3-O bond in alcohols with high selectivity and efficiency, especially without the assistance of metal catalyst, has been a formidable challenge because of its strong bond dissociation energy and unfavorable thermodynamics. Herein, an efficient metal-free strategy that enables direct deoxygenation of alcohols has been developed for the first time, with hydrazine as the reductant induced by light. This protocol features mild reaction conditions, excellent functional group tolerance, and abundant and easily available starting materials, rendering selective deoxygenation of a variety of 1° and 2° alcohols, vicinal diols, and β-1 and even β-O-4 models of natural wood lignin. This strategy is also highlighted by its “traceless” and non-toxic by-products N2 and H2, as readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being a key intermediate in this transformation.

Synthesis and Characterization of Novel Phyto-Mediated Catalyst, and Its Application for a Selective Oxidation of (VAL) into Vanillin under Visible Light

Here, we report an efficient and highly selective oxidation of lignin model substrate using phyto-mediated ZnFe2O4 nanoparticle using Boswellia carterii extract. The nanocatalyst with an average size of 8 nm showed excellent photocatalytic activity of the synthesized carbonyl containing products under visible light irradiation. The catalytic activity and selectivity towards oxidation of vanillyl alcohol to vanillin with selectivity up to 99% at conversion over 98% and turn-over frequency values up to 1600 h−1 were obtained in the presence of H2O2 and base. The cubic spinel nano-ZnFe2O4 catalyst was characterized by powder-XRD, FESEM, HR-TEM and Mössbauer analysis. The demonstrated catalyst was robust and stable under the reaction conditions. Furthermore, it was easy to be separated from the reaction mixture and be reused for subsequent reactions up to 5 times without significant reactivity or selectivity loss.

Photocatalytic Cleavage of β-O-4 Ether Bonds in Lignin over Ni/TiO2

It is of great importance to explore the selective hydrogenolysis of β-O-4 linkages, which account for 45–60% of all linkages in native lignin, to produce valued-added chemicals and fuels from biomass employing UV light as catalyst. TiO2 exhibited satisfactory catalytic performances in various photochemical reactions, due to its versatile advantages involving high catalytic activity, low cost and non-toxicity. In this work, 20 wt.% Ni/TiO2 and oxidant PCC (Pyridinium chlorochromate) were employed to promote the cleavage of β-O-4 alcohol to obtain high value chemicals under UV irradiation at room temperature. The Ni/TiO2 photocatalyst can be magnetically recovered and efficiently reused in the following four consecutive recycling tests in the cleavage of β-O-4 ether bond in lignin. Mechanism studies suggested that the oxidation of β-O-4 alcohol to β-O-4 ketone by oxidant PCC first occurred during the reaction, and was followed by the photocatalysis of the obtained β-O-4 ketone to corresponding acetophenone and phenol derivates. Furthermore, the system was tested on a variety of lignin model substrates containing β-O-4 linkage for the generation of fragmentation products in good to excellent results.

The reaction of lignin model compounds during enzymatic bleaching with a Curvularia verruculosa haloperoxidase: impact on chlorination

AbstractRecent developments in enzymatic bleaching processes have led to replacement strategies of harsh chemicals by haloperoxidases. For this purpose, it is important to control the haloperoxidase-mediated formation of adsorbable organic halides (AOX). In this study, we studied the chlorination of monomeric and dimeric lignin model substrates. Guaiacol, acetovanillone, veratryl alcohol, pinoresinol and adlerol were treated with Curvularia verruculosa haloperoxidase and compared to a sodium hypochlorite treatment. High-performance liquid chromatography-diode array detection-mass spectrometry (HPLC-DAD-MS) analysis was employed for the characterization of the reaction products. Our results show that while treatment with haloperoxidases in the presence of sodium chloride and hydrogen peroxide leads to no improvement in AOX formation compared to chemical treatment with NaOCl, addition of ammonium chloride substantially lessens chlorination and promotes β-O-4 ether bond cleavage. The use of ammonium chloride in conjunction with enzymatic haloperoxidase-based bleaching could be a route to minimize lignin chlorination.

Reactivity of Re2O7 in aromatic solvents – Cleavage of a β-O-4 lignin model substrate by Lewis-acidic rhenium oxide nanoparticles

The nature of the active species in a dehydration reaction using the “catalyst” Re2O7 is investigated. During studies on the cleavage of the β-O-4 bond of a lignin model substrate, apparent “TOFs” of 240 h−1 and good selectivities of up to 73% for the sensitive product phenylacetaldehyde (compared to other applied (Lewis) acids) are observed. However, divergent kinetic data during the studies led to an in-depth investigation on the activation mechanism of Re2O7 in the applied apolar, aprotic medium. Here, it is shown, that, in fact, Re2O7 itself is completely inactive in the dehydration reaction, but forms even at low temperatures mixed valence rhenium nanoparticles, which promote the desired reaction. The nanoparticles are characterized by XPS, DLS and TEM. In order to discriminate whether either dissolved rhenium compounds or nanoparticles are the active species, 17O NMR studies and kinetic experiments are performed. An activation mechanism of rhenium heptoxide is suggested based on a careful analysis of byproducts under catalytic conditions and application of selected potential catalysts. Furthermore, an outlook is given, as these nanoparticles might participate in numerous other catalytic reactions.

Photolytic C–O Bond Cleavage with Quantum Dots

Quantum dots are used as photoredox catalysts to drive bond cleavage in lignin model substrates. Cadmium selenide quantum dots selectively cleave C–O bonds with yields comparable to the best transi...

Whole-cell cascade for the preparation of enantiopure β-O-4 aryl ether compounds with glutathione recycling

Bacterial β-etherases and glutathione lyases are glutathione-dependent enzymes that catalyze the selective cleavage of β-O-4 aryl ether bonds found in lignin. Their glutathione (GSH) dependence is regarded as major limitation for their application in the production of aromatics from lignin polymer and oligomers, as stoichiometric glutathione amounts are required. Thus, recycling of the GSH cofactor by a NAD(P)H-dependent glutathione reductase was proposed previously. Herein, the use of a whole-cell catalyst was studied for efficient β-O-4 aryl ether bond cleavage with intracellular GSH supply and recycling. After optimization of the whole-cell catalyst as well as reaction conditions, up to 5 mM lignin model substrate 2,6-methoxyphenoxy-α-veratrylglycerone (2,6-MP-VG) were efficiently converted into 2,6-methoxyphenol (2,6-MP) and veratryl glycerone (VG) without addition of external GSH. Unexpectedly, no glucose supply was required for glutathione recycling within the cells up to this substrate concentration. To demonstrate the applicability of this whole-cell approach, a whole-cell cascade combining a stereoselective β-etherase (either LigE from Sphingobium sp. SYK-6 or LigF-NA from Novosphingobium aromaticivorans) and a glutathione lyase (LigG-TD from Thiobacillus denitrificans) was employed in the kinetic resolution of racemic 2,6-MP-VG. This way, enantiopure (S)- and (R)-2,6-MP-VG were obtained on semi-preparative scale without the need for external GSH supply.

Copper-catalyzed synthesis of benzanilides from lignin model substrates 2-phenoxyacetophenones under an air atmosphere

A novel approach for the synthesis of benzanilides is presented via the Cu-catalyzed reaction of 2-phenoxyacetophenones with anilines under an air atmosphere, and a series of benzanilides can be obtained in high yields.

Heterologous expression of a Streptomyces cyaneus laccase for biomass modification applications

Laccases are used for the conversion of biomass into fermentable sugars but it is difficult to produce high yields of active laccases in heterologous expression systems. We overcame this challenge by expressing Streptomyces cyaneus CECT 3335 laccase in Escherichia coli (ScLac) and we achieved a yield of up to 104 mg L−1 following purification by one-step affinity chromatography. Stability and activity assays using simple lignin model substrates showed that the purified enzyme preparation was active over a broad pH range and at high temperatures, suggesting it would be suitable for biomass degradation. The reusability of ScLac was also demonstrated by immobilizing the enzyme on agarose beads with a binding yield of 33%, and by the synthesis of cross-linked enzyme aggregates with an initial activity recovery of 72%.

Photocatalytic Oxidation of Lignin Model Systems by Merging Visible-Light Photoredox and Palladium Catalysis.

Lignin valorization has long been recognized as a sustainable solution for the renewable production of aromatic compounds. Two-step oxidation/reduction strategies, whereby the first oxidation step is required to "activate" lignin systems for controlled fragmentation reactions, have recently emerged as viable routes toward this goal. Herein we describe a catalytic protocol for oxidation of lignin model systems by combining photoredox and Pd catalysis. The developed dual catalytic protocol allowed the efficient oxidation of lignin model substrates at room temperature to afford the oxidized products in good to excellent yields.

Peroxidative Oxidation of Lignin and a Lignin Model Compound by a Manganese SALEN Derivative

The manganese catalyst, (1R,2R)-(−)-[1,2-cyclohexanediamino-N,N′-bis(3,5-di-t-butylsalicylidene)]manganese(III) chloride, was used to activate H2O2 to oxidize organosolv lignin and a lignin model compound. Oxidation of the β-O-4 lignin model substrate 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (320.3 m/z) and poplar organosolv lignin resulted in both fragmentation and polymerization processes, likely via phenoxy radical formation. Matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS) of the reaction products from the β-O-4 model substrate showed oligomers of the substrate with masses of 661.192, 979.355, and 1297.466 m/z that correspond to a dimer, trimer, and tetramer of the β-O-4 model substrate, respectively. Nuclear magnetic resonance (NMR) shows the formation of 5–5 diphenyl and 4-O-5 linkages in the β-O-4 model substrate oxidation products. Gel permeation chromatography (GPC) detected three peaks, corresponding to the β-O-4 model subs...

Ruthenium‐Catalyzed CC Bond Cleavage in Lignin Model Substrates

AbstractRuthenium–triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox‐neutral CC bond cleavage of the β‐O‐4 lignin linkage of 1,3‐dilignol model compounds. A mechanistic pathway involving a dehydrogenation‐initiated retro‐aldol reaction for the CC bond cleavage was proposed in line with experimental data and DFT calculations.