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Herbaceous plants-derived hydroxycinnamic units can serve as unique monomers to construct recyclable and controllable copolyesters via biomass RCF, one-pot derivatization, and copolymerization.

Scandium, titanium and vanadium dialkyl complexes bearing PCP-type pincer ligands have been synthesized, characterized, and explored for styrene polymerization.

Bio-oils are an important part of the future energy composition. This review primarily focuses on model compounds, catalysts, and equipment involved in the hydrodeoxygenation (HDO) of bio-oils. Initially, this article reviews the basic physicochemical properties of bio-oils and introduces different upgrading methods. Among them, HDO can effectively facilitate calorific value and improve the acidity and viscosity of bio-oils. Secondly, the basic HDO reaction pathways and proposed catalytic mechanism of various model compounds are summarized to understand the catalytic behavior and structure–performance relationship of the HDO reaction. Subsequently, we review different catalysts used in actual HDO of bio-oils, some of which lead to excellent stability and improved HDO reactivity. Finally, progress in the development of HDO equipment, including fixed bed and ebullated bed reactors in the pilot stage, is reviewed. This review aims to summarize progress in the utilization of the HDO process and provides useful insights for the efficient practical application of bio-oils.

The excessive use of petroleum-based non-biodegradable plastic products has resulted in severe environmental pollution and ecological problems, which has stimulated the development of biodegradable and renewable alternative materials. Lignin, as the most abundant aromatic polymer with great biodegradability and biocompatibility, exhibits enormous potential for preparing various functional and sustainable materials as alternatives to plastics. Recently, lignin-derived biodegradable films have received extensive attention in both fundamental research and practical applications, and many significant achievements have been made in this field. Herein, the latest progress in the preparation and advanced applications of lignin-derived biodegradable film materials is summarized from a sustainability point of view. An introduction to the structural and chemical characteristics of lignin is presented first, and then the designs and advances of construction systems are reviewed based on the building matrixes, including lignocellulose, natural macromolecules, biodegradable synthetic copolymers, and other cutting-edge materials. In this review, the tailored applications of these film materials are mainly focused on sensors and responsive materials, energy storage systems, packaging, and biomedical materials. Finally, the main challenges of lignin-derived biodegradable film materials are presented, and potential development directions for sustainable and eco-friendly lignin-derived film materials are also proposed.

The search for efficient and selective routes for the disassembly of C-lignin and G/S lignin coexisting in Euphorbiaceae seed coats is of great interest and importance, because a plentiful supply of C-lignin can serve as a green carbon feedstock for the production of catechols in a selective manner. Herein, we investigated a series of pretreatment methods for the disassembly of C and G/S lignins in Jatropha seed coats, and extraction by dilute HCl in dioxane was established as the optimized process. This protocol enabled the almost complete segregation of the two types of lignins in Jatropha seeds, and can be generalized to other Euphorbiaceae plants (candlenut, tung, and castor) containing both C and G/S lignins. Characterization by NMR spectroscopic analyses revealed that the isolated lignin samples were mostly composed of benzodioxane units. The disassembled C-lignin samples can produce a single catechylpropanol product (selectivity up to 97%) through Pd/C-catalyzed hydrogenolysis, and are superior to the feedstocks containing C and G/S lignins in terms of catalytic activity and selectivity.

Gaining more insight into the lignin hydrogenolysis mechanism is of great importance for developing next-generation catalysts and regulating product distribution because lignin is the only renewabl...

Remote C-H functionalization at C5 is the most sparingly observed selectivity in the functionalization of indole templates. Herein, we reported that the combination of a AgSbF6 catalyst and phenyliodine diacetate oxidation enabled the C-H selenylation at the C5 position of indole scaffolds in a selective version, thus leading to the formation of a wide scope of 5-selenylated indole derivatives, which are otherwise difficult to prepare. Mechanistic studies indicated that current transformation follows a radical process, and the tethered C3 pivaloyl group on indole scaffolds plays roles in both blocking the active C3 position and manipulating the electronic affinity of the arenes.

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, β-modification, β,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.

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Biodegradable materials are increasingly imperative in modern society owing to their eco-friendly character, but their high cost and limited properties restrict their applications. In this study, lignin-based (30–50 wt%) biodegradable composites with superior performances were successfully prepared by incorporating lignin into the poly(butylene adipate-co-terephthalate) (PBAT) matrix. In order to improve the compatibility, lignin was efficiently modified by a green esterification reaction under microwave-assisted solvent-free conditions. Comprehensive characterization revealed that modified lignin had fewer inter-unit linkages, increased molecular weights, lower Tg and enhanced hydrophobicity. Moreover, the prepared modified lignin/PBAT composites reinforced with maleic anhydride (MAH) exhibited controllable improvements in mechanical properties and exhibited excellent UV-shielding properties, and their elongation at break, even with 40 wt% lignin, increased by 500% compared to that of unmodified counterparts. The ideal dispersion and compatibility of the modified lignin in the matrix facilitated the mechanical properties of composites, as revealed by morphological and thermal analysis. Importantly, molecular dynamics (MD) simulation unprecedentedly confirmed that the modification of lignin distinctly strengthened molecular interaction and compatibility of the matrices, enhancing the mechanical performance of the composites. This work presents a green and feasible route to produce cost-efficient biodegradable materials with controlled mechanical and UV-shielding properties for packaging application.

Poplar is not only an important woody plant, but also a model species for molecular plant studies. We identified PagGRF11 (pAxG07Gg0005700), a homolog of the Arabidopsis AtGRF1 (AT4G37740) and AtGRF2 (AT2G22840) gene. We transformed the poplar clone “84K” with PagGRF11, and the transgenic overexpressed plants (PagGRF11-OE) showed plant height reduction (dwarfing), stem diameter increase, internode shortening, and larger leaf area. The Arabidopsis overexpression line grf-oe (Overexpression of PagGRF11 in Arabidopsis), mutant line atgrf (a loss-of-function mutant of the AtGRF1 gene of Arabidopsis thaliana), and mutant trans-complementary line atgrf+oe (overexpression of PagGRF11 in mutant plants (atgrf)) also showed different leaf size phenotypes. Further, tissue sections revealed that increased xylem production was the main cause of stem thickening. Transcriptome differential expression analysis of PagGRF11 overexpressed and control plants showed that PagGRF11 promoted CCCH39(C3H39) expression. The expression profile of CCCH39 in different tissues showed that it was highly expressed in xylem. Yeast single hybrid and instantaneous double luciferase assay results showed that PagGRF11 directly transcribed and activated CCCH39 expression through interaction with cis-acting element GARE (TCTGTTG), thus promoting xylem development. This is the first finding that GRF positively regulates xylem development through CCCH39 expression activation and further suggests that PagGRF11 is a potential target for increasing wood yield.

Lignin, which can be recycled from bioethanol and paper production wastes, is the second largest renewable resource. However, studies and applications on sustainable upgrading of lignin are extremely limited and most of them only focus on its combustion to obtain energy. The abundance of reactive groups in lignin makes it a potential feedstock for the production of sustainable low carbon footprint value-added materials. Among them, the preparation of flocculants from lignin has attracted much attention. This paper systematically reviews recent progress of low carbon footprint lignin-based flocculants. The modification methods for the production of lignin-based flocculants, Mannich, sulfonation, carboxylation, crosslinking and graft copolymerization, and the flocculation mechanisms in wastewater treatment are discussed emphatically. Moreover, the factors affecting the flocculation performance of lignin-based flocculants, including internal factors, such as charge density, molecular weight, conformation, and external factors, such as dosage, treatment time, wastewater pH, and temperature are discussed in detail, which are conducive to design, production and application of lignin-based flocculants for lower carbon footprint. Furthermore, we critically point out the current deficiencies of the lignin-based flocculants and the challenges facing commercialization, then we propose the corresponding possible solutions. The production and application of high-efficiency lignin-based flocculants are of great significance for resource conservation, low carbon footprint, and wastewater reuse.

Substantial attention has been given to depolymerization of lignin into monomeric phenols in recent years because lignin is a renewable and CO2-netural aromatic resource. Recent results indicated t...

Lignin, which is biosynthesized through oxidative radical polymerization from primary monolignols during plant growth, represents the most abundant source of renewable aromatic resources. The searc...

Reductive catalytic fractionation (RCF) of lignocellulosic biomass, that is depolymerization of the native lignin component into well-defined monomeric phenols in the first step, offers an opportunity to utilize entire biomass components. Herein, we report that Ni@ZIF-8 can serve as a chemodivergent catalyst in RCF of eucalyptus sawdust, thus selectively producing phenolic compounds having either a propyl or propanol end-chain under different reaction conditions. In both cases, high yields of lignin monomers and a high degree of delignification were achieved, next to well-preserved carbohydrate pulp suitable for further processing. A mechanistic study using model compounds indicated that the dehydroxylation at the γ-position of the β-O-4 structure may be involved in the selectivity-controlling step.

Lignin is the most abundant renewable resource for production of bio-aromatic chemicals. However, the catalytic depolymerisation of lignin into phenolic monomers is still challenging due to its intrinsic heterogeneity. Herein, we report that Ni/AC can serve as an efficient and stable catalyst in the hydrogenolysis of biorefinery corncob lignin into low-molecular-weight aromatics. This catalyst showed high activity towards reductive fragmentation of hydroxycinnamic esters and β-O-4 linkages through scission by reaction with hydrogen to cleave C–O bonds. Under optimal conditions, this catalytic system produced 31% selectivity towards unsaturated substituents containing coumarate and ferulate derivatives, which afforded mono-aromatic phenols (up to 12.1 wt%) derived from hydroxycinnamic acid moieties (8.1 wt%) and β-O-4 units (2.7 wt%), respectively. The use of non-precious metals to develop highly efficient heterogeneous catalysts makes this approach of great interest in the production of aromatic phenols for the valorisation of industrial lignin.

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.

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.

The search for nonprecious-metal-based catalysts for the synthesis of γ-valerolactone (GVL) through hydrogenation of levulinic acid and its derivatives in an efficient fashion is of great interest and importance, as GVL is an important a sustainable liquid. We herein report a pincer iron complex that can efficiently catalyze the hydrogenation of levulinic acid and methyl levulinate into GVL, achieving a turnover number of up to 23 000 and a turnover frequency of 1917 h-1 . This iron-based catalyst also enabled the formation of GVL from various biomass-derived carbohydrates in aqueous solution, thus paving a new way toward a renewable chemical industry.

The recently discovered catechyl lignin (C-lignin) represents an ideal lignin platform for depolymerization because of its exclusive benzodioxane linkages between caffeyl alcohol monolignols. In this report, we described catalytic hydrogenolysis of castor seed coats by using deep eutectic solvents, where naturally grown C-lignin was extracted from endocarp matrix and depolymerized into monomeric catechols. The production efficiency of catechols from present one-pot manner was comparable to that from a two-step approach. High selectivity towards 4-propyl catechol was observed in DESs reactions, which was complementary to previous reports. This study offered a step-efficient protocol for producing a single, valuable catechol compound from bulk sustainable castor seed coats.

Lignin represents the most abundant source of renewable aromatic resources, and the depolymerization of lignin has been identified as a prominent challenge to produce low-molecular-mass aromatic chemicals. Herein, we report a nanostructured MoOx/CNT, which can serve as an efficient catalyst in hydrogenolysis of enzymatic mild acidolysis lignins (EMALs) derived from various lignocellulosic biomass, thus giving monomeric phenols in high yields (up to 47 wt %). This catalyst showed high selectivity toward phenolic compounds having an unsaturated substituent, because the cleavage of C–O bonds in β-O-4 units is prior to reduction of double bonds by MoOx/CNT under a H2 atmosphere, which was confirmed by examination of lignin model compound reactions. The effects of some key parameters such as the influence of solvent, temperature, reaction time, and catalyst recyclability were also examined in view of monomer yields and average molecular weight. This method constitutes an economically responsible pathway for li...

Additional file 1: Table S1. The chemical composition of Eucalyptus sawdust and carbohydrate pulp. Table S2. Reductive catalytic fractionation of Eucalyptus under different temperature. Table S3. Reductive catalytic fractionation of Eucalyptus under different temperature, time, and solvent. Fig. S1. Schematic representation of Pd/C-catalyzed RCF of Eucalyptus sawdust. Fig. S2. Gas chromatograms and peak identification of the lignin monomers from catalytic hydrogenolysis of Eucalyptus sawdust using Pd/C catalyst. Fig. S3. 1H NMR spectra of 4-propanol syringol. Fig. S4. 13C NMR spectra of 4-propanol syringol. Fig. S5. 1H NMR spectra of 4-propanol guaiacol. Fig. S6. 13C NMR spectra of 4-propanol guaiacol. Fig. S7. The X-ray diffraction patterns of Eucalyptus sawdust and solid residue obtained from the RCF.

Background Lignocellulosic biomass, which is composed of cellulose, hemicellulose and lignin, represents the most abundant renewable carbon source with significant potential for the production of sustainable chemicals and fuels. Current biorefineries focus on cellulose and hemicellulose valorization, whereas lignin is treated as a waste product and is burned to supply energy to the biorefineries. The depolymerization of lignin into well-defined mono-aromatic chemicals suitable for downstream processing is recognized increasingly as an important starting point for lignin valorization. In this study, conversion of all three components of Eucalyptus grandis into the corresponding monomeric chemicals was investigated using solid and acidic catalyst in sequence. Results Lignin was depolymerized into well-defined monomeric phenols in the first step using a Pd/C catalyst. The maximum phenolic monomers yield of 49.8 wt% was achieved at 240 °C for 4 h under 30 atm H2. In the monomers, 4-propanol guaiacol (12.9 wt%) and 4-propanol syringol (31.9 wt%) were identified as the two major phenolic products with 90% selectivity. High retention of cellulose and hemicellulose pulp was also obtained, which was treated with FeCl3 catalyst to attain 5-hydroxymethylfurfural, levulinic acid and furfural simultaneously. The optimal reaction condition for the co-conversion of hemicellulose and cellulose was established as 190 °C and 100 min, from which furfural and levulinic acid were obtained in 55.9% and 73.6% yields, respectively. Ultimately, 54% of Eucalyptus sawdust can be converted into well-defined chemicals under such an integrated biorefinery method. Conclusions A two-step process (reductive catalytic fractionation followed by FeCl3 catalysis) allows the fractionation of all the three biopolymers (cellulose, hemicellulose, and lignin) in Eucalyptus biomass, which provides a promising strategy to make high-value chemicals from sustainable biomass.

The asymmetric C–H annulation of O-pivaloyl 1-indolehydroxamic acid with donor/acceptor diazo compounds has been achieved for the first time, to the best of our knowledge, by using a rhodium catalyst embedded in a chiral binaphthyl backbone. This protocol constitutes a straightforward route for the synthesis of a new family of 1,2-dihydro-3H-imidazo[1,5-a]indol-3-one derivatives having a quaternary carbon stereocenter in high yields and excellent enantioselectivity (up to 98:2 er).

A fundamental understanding of lignin solubilization offers structural information that would benefit a variety of value added applications. Small angle neutron scattering (SANS) and nuclear magnetic resonance (NMR) spectroscopy were used to study correlations between the functional groups/substructures and solution structures of lignin in DMSO-d6 and 0.1 N NaOD. Three types of alkaline lignins (Sigma-Aldrich kraft lignin, poplar wood kraft lignin, and corncob soda lignin), exhibiting different degrees of aggregation in 0.4 wt% solutions, were investigated to identify the major intermolecular interactions that cause lignin aggregation. Intermolecular hydrogen bonding, non-covalent π–π interactions between phenyl rings, lignin chain conformation and the degree of branching were discussed. Different operating forces for lignin solubilization and aggregation were found in DMSO-d6 and NaOD solutions.

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.

The high value utilization of lignin is facing sheer challenge, and the use of lignin as a raw material to prepare flocculants is of tremendous significance for wastewater treatment. In this study, lignin-based flocculants (LBFs) with tunable performances were prepared by mild copolymerization of lignosulfonate and [2-(Methacryloyloxy) ethyl] trimethylammonium chloride solution (METAC) under short-wavelength ultraviolet light. The effect of preparation conditions on the product performances was investigated, and two classes of LBFs were obtained in the same system by adjusting the preparation conditions. As compared with the preparation of LBFs suitable for simulated dye wastewater, higher monomer dose and lower pH were required for the preparation of LBFs suitable for kaolin and E. coli suspensions. Among them, LBF-1 could remove more than 95 % dye, and LBF-2 had 99.2 % and 97.5 % turbidity and bacterial removal rates, respectively. Moreover, the effects of external factors such as the LBF-1 dose, initial concentration of dye and wastewater pH on the decolorization efficiency were also explored. In addition, the sterilization function of LBF was studied, and LBF-2 experienced a process of first flocculation followed by sterilization. Furthermore, the flocculation mechanisms of LBFs in treating three kinds of wastewaters were discussed in detail.

Layered serpentine Ni

The efficient and selective ortho-alkylation of N,N-dimethyl anilines via C–H addition to alkenes was achieved for the first time using a cationic half-sandwich yttrium catalyst. This protocol constitutes a straightforward and atom-economical route for the synthesis of a new family of tertiary aniline derivatives with branched alkyl substituents, which are otherwise difficult to obtain. DFT calculation studies suggest that the interaction between the yttrium atom and the NMe2 group plays an important role and the intramolecular C–H activation through a σ-bond metathesis pathway is the rate-determining step, which is consistent with the experimental KIE observations.

The possibility of developing new methods for the efficient construction of organic molecules via disconnections other than traditional functional group transformations has driven the interest in direct functionalization of C-H bonds. The ubiquity of C-H bonds makes such transformations attractive, but they also pose several challenges. The first is the reactivity and selectivity of C-H bonds. To achieve this, directing groups (DGs) are often installed that can enhance the effective concentration of the catalyst, leading to thermodynamically stable metallacyclic intermediates. However, the presence of a pendant directing group in the product is often undesirable and unnecessary. This may account for the limitation of applications of C-H functionalization reactions in more common and general uses. Thus, the development of removable or functionalizable directing groups is desirable. Another key problem is that the reactivity of the resulting M-C bond can be low, which may limit the scope of the coupling partners and hence limit the reaction patterns of C-H activation reactions. While the first Cp*Rh(III)-catalyzed C-H activation of arenes was reported only 7 years ago, significant progress has been made in this area in the past few years. We began our studies in this area in 2010, and we and others have demonstrated that diversified catalytic functionalization of arenes can be realized using Cp*Rh(III) complexes with high reactivity, stability, and functional group compatibility. This Account describes our efforts to solve some of these challenges using Rh(III) catalysis. We fulfilled our design and activation of the arene substrates by taking advantage of the nucleophilicity, electrophilicity, oxidizing potential, and properties of a participating ligand of the directing groups when the arenes are coupled with relatively reactive unsaturated partners such as alkenes and alkynes. These in situ funtionalizable roles of the DG allowed extensive chemical manipulation of the initial coupled product, especially in the construction of a diverse array of heterocycles. In the coupling of arenes with polar coupling partners, the polar Rh(III)-C(aryl) bond showed higher reactivity as both an organometallic reagent and a nucleophilic aryl source. The polar coupling partners were accordingly activated by virtue of umpolung, ring strain, and rearomatization. All of these transformations have been made possible by integration of the higher reactivity, stability, and compatibility of Rh(III)-C bonds into catalytic systems. We have demonstrated that to date some of these transformations can be achieved only under rhodium catalysis. In addition, by means of stoichiometric reactions, we have gained mechanistic insights into the interactions between the Rh-C bond and the other coupling partners, which have opened new avenues in future direct C-H functionalization reactions.

A Rh(III)-catalyzed site-selective C–H activation of C(3)-functionalized indoles in a coupling with diazo esters has been realized with carbonyl as a weakly coordinating group. The coupling selectivity is dictated by the temperature and additives, affording either C4-alkylated indoles or C2-annulated lactones in moderate to excellent efficiency.

Heteroatoms enhance polymerization and copolymerization of functional olefins., Heteroatom-functionalized polyolefins are of fundamental interest and practical importance. This has spurred investigations of the copolymerization of polar and nonpolar olefins. We report the first syndiospecific polymerization of a series of heteroatom-containing α-olefins and their copolymerization with ethylene catalyzed by half-sandwich rare-earth complexes. We have found that the interaction between a heteroatom in a functional α-olefin monomer and a rare-earth metal catalyst can significantly raise the olefin polymerization activity and thereby promote its copolymerization with ethylene. By using this heteroatom-assisted olefin polymerization (HOP) strategy, we have successfully synthesized a series of heteroatom (O, S, Se, N, and P)–functionalized polyolefins with high molecular weights and controllable functional monomer contents. The mechanistic aspect of the HOP process has been elucidated by computational studies. We expect that our findings will guide the design of new catalyst systems for the synthesis of various desired functional polyolefins.