Closed-loop recyclability of a biomass-derived epoxy-amine thermoset by methanolysis.

Epoxy resin thermosets (ERTs) are an important class of polymeric materials. However, owing to their highly cross-linked nature, they suffer from poor recyclability, which contributes to an unacceptable level of environmental pollution. There is a clear need for the design of inherently recyclable ERTs that are based on renewable resources. We present the synthesis and closed-loop recycling of a fully lignocellulose-derivable epoxy resin (DGF/MBCA), prepared from dimethyl ester of 2,5-furandicarboxylic acid (DMFD), 4,4'-methylenebis(cyclohexylamine) (MBCA), and glycidol, which displays excellent thermomechanical properties (a glass transition temperature of 170°C, and a storage modulus at 25°C of 1.2 gigapascals). Notably, the material undergoes methanolysis in the absence of any catalyst, regenerating 90% of the original DMFD. The diamine MBCA and glycidol can subsequently be reformed by acetolysis. Application and recycling of DGF/MBCA in glass and plant fiber composites are demonstrated.

Clean Synthetic Strategies to Biologically Active Molecules from Lignin: A Green Path to Drug Discovery.

Deriving active pharmaceutical agents from renewable resources is crucial to increasing the economic feasibility of modern biorefineries and promises to alleviate critical supply-chain dependencies in pharma manufacturing. Our multidisciplinary approach combines research in lignin-first biorefining, sustainable catalysis, and alternative solvents with bioactivity screening, an in vivo efficacy study, and a structural-similarity search. The resulting sustainable path to novel anti-infective, anti-inflammatory, and anticancer molecules enabled the rapid identification of frontrunners for key therapeutic indications, including an anti-infective against the priority pathogen Streptococcus pneumoniae with efficacy in vivo and promising plasma and metabolic stability. Our catalytic methods provided straightforward access, inspired by the innate structural features of lignin, to synthetically challenging biologically active molecules with the core structure of dopamine, namely, tetrahydroisoquinolines, quinazolinones, 3-arylindoles and the natural product tetrahydropapaveroline. Our diverse array of atom-economic transformations produces only harmless side products and uses benign reaction media, such as tunable deep eutectic solvents for modulating reactivity in challenging cyclization steps.

Deriving high value products from depolymerized lignin oil, aided by (bio)catalytic funneling strategies.

Lignin holds tremendous and versatile possibilities to produce value-added chemicals and high performing polymeric materials. Over the years, different cutting-edge lignin depolymerization methodologies have been developed, mainly focusing on achieving excellent yields of mono-phenolic products, some even approaching the theoretical maximum. However, due to lignin's inherent heterogeneity and recalcitrance, its depolymerization leads to relatively complex product streams, also containing dimers, and higher molecular weight fragments in substantial quantities. The subsequent chemo-catalytic valorization of these higher molecular weight streams, containing difficult-to-break, mainly C-C covalent bonds, is tremendously challenging, and has consequently received much less attention. In this minireview, we present an overview of recent advances on the development of sustainable biorefinery strategies aimed at the production of well-defined chemicals and polymeric materials, the prime focus being on depolymerized lignin oils, containing high molecular weight fractions. The key central unit operation to achieve this is (bio)catalytic funneling, which holds great potential to overcome separation and purification challenges.

High-Performance Thermoplastics from a Unique Bicyclic Lignin-Derived Diol.

Polyesters are an important class of thermoplastic polymers, and there is a clear demand to find high-performing, recyclable, and renewable alternatives. In this contribution, we describe a range of fully bio-based polyesters obtained upon the polycondensation of the lignin-derived bicyclic diol 4,4'-methylenebiscyclohexanol (MBC) with various cellulose-derived diesters. Interestingly, the use of MBC in combination with either dimethyl terephthalate (DMTA) or dimethyl furan-2,5-dicarboxylate (DMFD) resulted in polymers with industrially relevant glass transition temperatures in the 103-142 °C range and high decomposition temperatures (261-365 °C range). Since MBC is obtained as a mixture of three distinct isomers, in-depth NMR-based structural characterization of the MBC isomers and thereof derived polymers is provided. Moreover, a practical method for the separation of all MBC isomers is presented. Interestingly, clear effects on the glass transition, melting, and decomposition temperatures, as well as polymer solubility, were evidenced with the use of isomerically pure MBC. Importantly, the polyesters can be efficiently depolymerized by methanolysis with an MBC diol recovery yield of up to 90%. The catalytic hydrodeoxygenation of the recovered MBC into two high-performance specific jet fuel additives was demonstrated as an attractive end-of-life option.

Novel stereoisomeric lignin-derived polycarbonates: towards the creation of bisphenol polycarbonate mimics.

In this work, we have described a family of bio-based polycarbonates (PC-MBC) based on the unique lignin-derived aliphatic diol 4,4'-methylenebiscyclohexanol (MBC) that was sustainably sourced from lignin oxidation mixture. The detailed structure analysis of these polycarbonates has been confirmed by a series of 2D NMR (HSQC and COSY) characterizations. Depending on the stereoisomerism of MBC, the PC-MBC displayed a wide achievable T g range of 117-174 °C and high T d5% of >310 °C by variation of the ratio of the stereoisomers of MBC, offering great substitution perspectives towards a bisphenol-containing polycarbonates. Nonetheless, the most here presented PC-MBC polycarbonates were film-forming and transparent.

High yield production of 1,4-cyclohexanediol and 1,4-cyclohexanediamine from high molecular-weight lignin oil.

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.

Primary amines from lignocellulose by direct amination of alcohol intermediates, catalyzed by RANEY® Ni.

Primary amines are crucially important building blocks for the synthesis of a wide range of industrially relevant products. Our comprehensive catalytic strategy presented here allows diverse primary amines from lignocellulosic biomass to be sourced in a straightforward manner and with minimal purification effort. The core of the methodology is the efficient RANEY® Ni-catalyzed hydrogen-borrowing amination (with ammonia) of the alcohol intermediates, namely alkyl-phenol derivatives as well as aliphatic alcohols, obtained through the two-stage LignoFlex process. Hereby the first stage entails the copper-doped porous metal oxide (Cu20PMO) catalyzed reductive catalytic fractionation (RCF) of pine lignocellulose into a crude bio-oil, rich in dihydroconiferyl alcohol (1G), which could be converted into dihydroconiferyl amine (1G amine) in high selectivity using ammonia gas, by applying our selective amination protocol. Notably also, the crude RCF-oil directly afforded 1G amine in a high 4.6 wt% isolated yield (based on lignin content). Finally it was also shown that the here developed Ni-catalysed heterogeneous catalytic procedure was equally capable of transforming a range of aliphatic linear/cyclic primary/secondary alcohols - available from the second stage of the LignoFlex procedure - into their respective primary amines.

One-Pot Catalytic Conversion of Lignin-Derivable Guaiacols and Syringols to Cyclohexylamines.

Cyclic primary amines are elementary building blocks to many fine chemicals, pharmaceuticals, and polymers. Here, a powerful one-pot Raney Ni-based catalytic strategy was developed to transform guaiacol into cyclohexylamine using NH3 (7 bar) and H2 (10 bar) in up to 94 % yield. The methodology was extendable to the conversion of a wider range of guaiacols and syringols into their corresponding cyclohexylamines. Notably, a crude bio-oil originating from the reductive catalytic fractionation of birch lignocellulose was transformed into a product mixture rich in 4-propylcyclohexylamine, constituting an interesting case of catalytic funneling. The isolated yield of the desired 4-propylcyclohexylamine reached as high as 7 wt % (on lignin basis). Preliminary mechanistic studies pointed at the consecutive occurrence of three key catalytic transformations, namely, demethoxylation, hydrogenation, and amination.

Fully lignocellulose-based PET analogues for the circular economy.

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.

A Diamine-Oriented Biorefinery Concept Using Ammonia and Raney Ni as a Multifaceted Catalyst.

Diamines are important industrial chemicals. In this paper we outline the feasibility of lignocellulose as a source of diol-containing molecules. We also illustrate the possibility of turning these diols into their diamines in good to excellent yields. Central to these transformations is the use of commercially available Raney Ni. For diol formation, the Raney Ni engages in hydrogenation and often also demethoxylation, that way funneling multiple components to one single molecule. For diamine formation, Raney Ni catalyzes hydrogen-borrowing mediated diamination in the presence of NH3.

Catalytic Upgrading of Ethanol to n-Butanol: Progress in Catalyst Development.

Because n-butanol as a fuel additive has more advantageous physicochemical properties than those of ethanol, ethanol valorization to n-butanol through homo- or heterogeneous catalysis has received much attention in recent decades in both scientific and industrial fields. Recent progress in catalyst development for upgrading ethanol to n-butanol, which involves homogeneous catalysts, such as iridium and ruthenium complexes, and heterogeneous catalysts, including metal oxides, hydroxyapatite (HAP), and, in particular, supported metal catalysts, is reviewed herein. The structure-activity relationships of catalysts and underlying reaction mechanisms are critically examined, and future research directions on the design and improvement of catalysts are also proposed.

Continuous catalytic upgrading of ethanol to n-butanol over Cu-CeO2/AC catalysts.

Cu-CeO2/AC catalysts exhibited extraordinary catalytic performance in the upgradation of ethanol to n-butanol. To the best of our knowledge, this is the first report that the highest n-butanol yields of 21.6% and nearly 20% could be achieved over heterogeneous catalysts under mild reaction conditions in batch and fixed-bed reactors, respectively. The high catalytic activity, selectivity and stability of these catalysts could be ascribed to the synergy of Cu, CeO2 and the activated carbon support.

Quantitative effects of magnesium chloride stress on aggregation of Sup35p in [psi-] yeast cells.

[PSI(+)] phenotype can be transiently induced when Magnesium chloride (MgCl(2)) was the selective pressure in SUP35 repeat-expansion mutant [psi(-)] yeast strains. We further investigated [PSI(+)] phenotype change under different MgCl(2) conditions with native Sup35p and quantified the Sup35p status changes with fluorescence recovery after photobleaching (FRAP) and semi-denaturing detergent-agarose gel electrophoresis (SDD-AGE) analysis. It was found that the [PSI(+)] phenotype presented a dose-dependent relationship with the concentrations of MgCl(2). Furthermore, Sup35p aggregated in MgCl(2) treated cells but did not form large aggregates as it does in [PSI(+)] cells, and the size of Sup35p aggregates showed a time-dependent relationship with the MgCl(2) application. The aggregation of Sup35p strictly depended on the presence of MgCl(2) stress in our strains.