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We present a catalytic strategy for converting lignin into various pharmaceutical intermediates based on a highly selective lignin depolymerization method and a green benzylic oxidation method employing O2. Selective depolymerization of lignin first afforded 4-ethylphenol, which then efficiently generates several pharmaceutical intermediates with a simple 5-step process, resulting in substantial economic benefits. The study provides an innovative solution for the efficient utilization of lignin and the green acquisition of pharmaceutical intermediates.
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The contemporary production of carbon materials heavily relies on fossil fuels, contributing significantly to the greenhouse effect. Biomass is a carbon-neutral resource whose organic carbon is formed from atmospheric CO2. Employing biomass as a precursor for synthetic carbon materials can fix atmospheric CO2 into solid materials, achieving negative carbon emissions. Hydrothermal carbonization (HTC) presents an attractive method for converting biomass into carbon materials, by which biomass can be transformed into materials with favorable properties in a distinct hydrothermal environment, and these carbon materials have made extensive progress in many fields. However, the HTC of biomass is a complex and interdisciplinary problem, involving simultaneously the physical properties of the underlying biomass and sub/supercritical water, the chemical mechanisms of hydrothermal synthesis, diverse applications of resulting carbon materials, and the sustainability of the entire technological routes. This review starts with the analysis of biomass composition and distinctive characteristics of the hydrothermal environment. Then, the factors influencing the HTC of biomass, the reaction mechanism, and the properties of resulting carbon materials are discussed in depth, especially the different formation mechanisms of primary and secondary hydrochars. Furthermore, the application and sustainability of biomass-derived carbon materials are summarized, and some insights into future directions are provided.
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To comprehend the biosynthesis processes of conifers, it is essential to investigate the disparity between the cell wall shape and the interior chemical structures of polymers throughout the development of Chinese pine. In this study, branches of mature Chinese pine were separated according to their growth time (2, 4, 6, 8 and 10 years). The variation of cell wall morphology and lignin distribution was comprehensively monitored by scanning electron microscopy (SEM) and confocal Raman microscopy (CRM), respectively. Moreover, the chemical structures of lignin and alkali-extracted hemicelluloses were extensively characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The thickness of latewood cell walls increased steadily from 1.29 µm to 3.38 µm, and the structure of the cell wall components became more complicated as the growth time increased. Based on the structural analysis, it was found that the content of ß-O-4 (39.88-45.44/100 Ar), ß-ß (3.20-10.02/100 Ar) and ß-5 (8.09-15.35/100 Ar) linkages as well as the degree of polymerization of lignin increased with the growth time. The complication propensity increased significantly over 6 years before slowing to a trickle over 8 and 10 years. Furthermore, alkali-extracted hemicelluloses of Chinese pine mainly consist of galactoglucomannans and arabinoglucuronxylan, in which the relative content of galactoglucomannans increased with the growth of the pine, especially from 6 to 10 years.
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Parede Celular , Lignina , Pinus , Polissacarídeos , Lignina/química , Pinus/química , Pinus/crescimento & desenvolvimento , Polissacarídeos/química , Parede Celular/química , Parede Celular/metabolismoRESUMO
The complete utilization of all lignin depolymerization streams obtained from the reductive catalytic fractionation (RCF) of woody biomass into high-value-added compounds is a timely and challenging objective. Here, we present a catalytic methodology to transform beech lignin-derived dimers and oligomers (DO) into well-defined 1,4-cyclohexanediol and 1,4-cyclohexanediamine. The latter two compounds have vast industrial relevance as monomers for polymer synthesis as well as pharmaceutical building blocks. The proposed two-step catalytic sequence involves the use of the commercially available RANEY® Ni catalyst. Therefore, the first step involves the efficient defunctionalization of lignin-derived 2,6-dimethoxybenzoquinone (DMBQ) into 1,4-cyclohexanediol (14CHDO) in 86.5% molar yield, representing a 10.7 wt% yield calculated on a DO weight basis. The second step concerns the highly selective amination of 1,4-cyclohexanediol with ammonia to give 1,4-cyclohexanediamine (14CHDA) in near quantitative yield. The ability to use RANEY® Ni and ammonia in this process holds great potential for future industrial synthesis of 1,4-cyclohexanediamine from renewable resources.
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Polyethylene terephthalate is one of the most abundantly used polymers, but also a significant pollutant in oceans. Due to growing environmental concerns, polyethylene terephthalate alternatives are highly sought after. Here we present readily recyclable polyethylene terephthalate analogues, made entirely from woody biomass. Central to the concept is a two-step noble metal free catalytic sequence (Cu20-PMO catalyzed reductive catalytic fractionation and Raney Ni mediated catalytic funneling) that allows for obtaining a single aliphatic diol 4-(3-hydroxypropyl) cyclohexan-1-ol in high isolated yield (11.7 wt% on lignin basis), as well as other product streams that are converted to fuels, achieving a total carbon yield of 29.5%. The diol 4-(3-hydroxypropyl) cyclohexan-1-ol is co-polymerized with methyl esters of terephthalic acid and furan dicarboxylic acid, both of which can be derived from the cellulose residues, to obtain polyesters with competitive Mw and thermal properties (Tg of 70-90 °C). The polymers show excellent chemical recyclability in methanol and are thus promising candidates for the circular economy.
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Lignina , Polietilenotereftalatos , Biomassa , Lignina/química , PolímerosRESUMO
The temperature and pressure of the hydrothermal process occurring in a batch reactor are typically coupled. Herein, we develop a decoupled temperature and pressure hydrothermal system that can heat the cellulose at a constant pressure, thus lowering the degradation temperature of cellulose significantly and enabling the fast production of carbon sub-micron spheres. Carbon sub-micron spheres can be produced without any isothermal time, much faster compared to the conventional hydrothermal process. High-pressure water can help to cleave the hydrogen bonds in cellulose and facilitate dehydration reactions, thus promoting cellulose carbonization at low temperatures. A life cycle assessment based on a conceptual biorefinery design reveals that this technology leads to a substantial reduction in carbon emissions when hydrochar replacing fuel or used for soil amendment. Overall, the decoupled temperature and pressure hydrothermal treatment in this study provides a promising method to produce sustainable carbon materials from cellulose with a carbon-negative effect.
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Carbono , Celulose , Carbono/química , Temperatura Alta , Solo , TemperaturaRESUMO
Deep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.
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Eucalyptus , Lignina , Biomassa , Solventes Eutéticos Profundos , Hidrólise , Lignina/química , Solventes/químicaRESUMO
Understanding of the morphological changes at different growth stages and lignin accumulation pattern for pine biomass plays the key role in facilitating the further development of value-added utilization and downstream conversion processes. This work systematically revealed the morphological change and lignin accumulation pattern in Chinese pine branches cell walls via confocal Raman microscopy (CRM) technology. Meanwhile, the structural characteristics of isolated lignin samples from different growth stages were synthetically characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques. The results indicated that the content of pith in adult pine new branch was bigger than juvenile trees. With the increase of physiological age, the branches in adult pine could accumulate more lignin both in overall content and the concentration of cell corner middle layer. Moreover, the significantly increases of molecular weights and the ß-O-4, ß-ß linkages content revealed that the lignin macromolecule of pine would polymerize faster in the adult stage (14, 35 years). The panorama generated from the structural and chemical features of pine native lignin not only benefited to understand the biosynthetic pathways and lignin macromolecules structural variation in plant cell walls from different growth stages but also contributed to the valorization and deconstruction of biomass.
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Lignina , Pinus , Biomassa , Parede Celular/química , China , Lignina/químicaRESUMO
In recent years, visualization and characterization of lignocellulose at different scales elucidate the modifications of its ultrastructural and chemical features during hydrothermal pretreatment which include degradation and dissolving of hemicelluloses, swelling and partial hydrolysis of cellulose, melting and redepositing a part of lignin in the surface. As a result, cell walls are swollen, deformed and de-laminated from the adjacent layer, lead to a range of revealed droplets that appear on and within cell walls. Moreover, the certain extent morphological changes significantly promote the downstream processing steps, especially for enzymatic hydrolysis and anaerobic fermentation to bioethanol by increasing the contact area with enzymes. However, the formation of pseudo-lignin hinders the accessibility of cellulase to cellulose, which decreases the efficiency of enzymatic hydrolysis. This review is intended to bridge the gap between the microstructure studies and value-added applications of lignocellulose while inspiring more research prospects to enhance the hydrothermal pretreatment process.
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Celulose , Lignina , Biomassa , HidróliseRESUMO
The lignin-first strategy has emerged as one of the most powerful approaches for generating novel platform chemicals from lignin by efficient depolymerization of native lignin. Because of the emergence of this novel depolymerization method and the definition of viable platform chemicals, future focus will soon shift towards innovative downstream processing strategies. Very recently, many interesting approaches have emerged that describe the production of valuable products across the whole value chain, including bulk and fine chemical building blocks, and several concrete examples have been developed for the production of polymers, pharmaceutically relevant compounds, or fuels. This Minireview provides an overview of these recent advances. After a short summary of catalytic systems for obtaining aromatic monomers, a comprehensive discussion on their separation and applications is given. This Minireview will fill the gap in biorefinery between deriving high yields of lignin monomers and tapping into their potential for making valuable consumer products.
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Inherently complex, lignin-derived aromatic monomers comprising valuable structural moieties present in many pharmaceuticals would serve as ideal substrates for the construction of biologically active molecules. Here, we describe a strategy that incorporates all intrinsic functional groups present in platform chemicals obtained by lignin depolymerization into value-added amines, using sustainable catalytic methods and benign solvents. Our strikingly efficient protocol provides access to libraries of aminoalkyl-phenol derivatives and seven-membered N-heterocycles directly from wood in two, respectively three, waste-free steps. Several molecules in these libraries have shown promising antibacterial or anticancer activities, emphasizing the advantage of this modular synthetic strategy and the potential for drug discovery. The sustainable catalytic pathways presented here can lead to significant benefits for the pharmaceutical industry where reduction of hazardous waste is a prime concern, and the described strategies that lead to high-value products from non-edible biomass waste streams also markedly increase the economic feasibility of lignocellulosic biorefineries.
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Primary benzylamines are highly important building blocks in the pharmaceutical and polymer industry. An attractive catalytic approach to access these compounds is the direct coupling of benzyl alcohols with ammonia via the borrowing hydrogen methodology. However, this approach is usually hampered by a series of side-reactions, one of the most prominent being the overalkylation of the formed primary amine. Herein, we describe a robust catalytic methodology, which utilizes commercially available heterogeneous Ni catalysts and easy-to-handle ammonia sources, such as aqueous ammonia or ammonium salts, for the formation of primary benzylamines with good selectivity and scope. Notably, our method enables the conversion of potentially lignin-derived vanillyl alcohol to vanillylamine, which can be used to produce emerging biobased polymers or as pharma building blocks. Important sugar derived platform alcohols as well as long chain aliphatic primary alcohols can be successfully aminated. Moreover, we provide an alternative, sustainable route to p-xylylenediamine and m-xylylenediamine, important components of heat resistant polyamides such as Kevlar.
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Direct conversion of lignocellulose to alkanes is challenged by the complex and recalcitrant nature of the starting material. Generally, alkanes are obtained from one of the main lignocellulose constituents (cellulose, hemicellulose or lignin) after their separation, and platform chemicals derived therein. Here we describe a two-step methodology, which uses unprocessed lignocellulose directly, targeting a mixture of alkanes. The first step involves the near-complete conversion of lignocellulose to alcohols, using a copper doped porous metal oxide (Cu-PMO) catalyst in supercritical methanol. The second step comprises a novel solvent exchange procedure and the exhaustive hydrodeoxygenation (HDO) of the complex mixture of aliphatic alcohols, obtained upon depolymerization, to C2-C10 alkanes by either HZSM-5 or Nafion at 180 °C in conjunction with Pd/C in dodecane. This describes an unprecedented two-step process from lignocellulose to hydrocarbons, with an overall carbon yield of 50%.
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The structural complexity of lignocellulose offers unique opportunities for the development of entirely new, energy efficient and waste-free pathways in order to obtain valuable bio-based building blocks. Such sustainable catalytic methods - specifically tailored to address the efficient conversion of abundant renewable starting materials - are necessary to successfully compete, in the future, with fossil-based multi-step processes. In this contribution we give a summary of recent developments in this field and describe our "cleave and couple" strategy, where "cleave" refers to the catalytic deconstruction of lignocellulose to aromatic and aliphatic alcohol intermediates, and "couple" involves the development of novel, sustainable transformations for the formation of C-C and C-N bonds in order to obtain a range of attractive products from lignocellulose.
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Lignin, a major component of lignocellulose, is the largest source of aromatic building blocks on the planet and harbors great potential to serve as starting material for the production of biobased products. Despite the initial challenges associated with the robust and irregular structure of lignin, the valorization of this intriguing aromatic biopolymer has come a long way: recently, many creative strategies emerged that deliver defined products via catalytic or biocatalytic depolymerization in good yields. The purpose of this review is to provide insight into these novel approaches and the potential application of such emerging new structures for the synthesis of biobased polymers or pharmacologically active molecules. Existing strategies for functionalization or defunctionalization of lignin-based compounds are also summarized. Following the whole value chain from raw lignocellulose through depolymerization to application whenever possible, specific lignin-based compounds emerge that could be in the future considered as potential lignin-derived platform chemicals.
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The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (ß-O-4)-(ß-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected ß-O-4, ß-5, and ß-ß structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.