Development of a microwave-assisted extraction method for the recovery of bioactive inositols from lettuce (Lactuca sativa) byproducts

A microwave-assisted extraction (MAE) method was developed for the extraction of bioactive inositols (D-chiro- and myo-inositols) from lettuce (Lactuca sativa) leaves as a strategy for the revalorization of these agrofood residues. Gas chromatography-mass spectrometry was selected for the simultaneous determination of inositols and sugars (glucose, fructose, and sucrose) in these samples. A Box–Behnken experimental design was used to maximize the extraction of inositols based on the results of single factor tests. Optimal conditions of the extraction process were as follows: liquid-to-solid ratio of 100:1 v/w, 40°C, 30 min extraction time, 20:80 ethanol:water (v/v), and one extraction cycle. When compared with conventional solid-liquid extraction (SLE), MAE was found to be more effective for the extraction of target bioactive carbohydrates (MAE 5.42 mg/g dry sample versus SLE 4.01 mg/g dry sample). Then, MAE methodology was applied to the extraction of inositols from L. sativa leaves of different varieties (var. longifolia, var. capitata and var. crispa). D-chiro- and myo-inositol contents varied between 0.57–7.15 and 0.83–3.48 mg/g dry sample, respectively. Interfering sugars were removed from the extracts using a biotechnological procedure based on the use of Saccharomyces cerevisiae for 24 h. The developed methodology was a good alternative to classical procedures to obtain extracts enriched in inositols from lettuce residues, which could be of interest for the agrofood industry.     

CsPbBr3 Quantum Dots Promoted Depolymerization of Oxidized Lignin via Photocatalytic Semi-Hydrogenation/Reduction Strategy

Due to the demanding depolymerization conditions and limited catalytic efficiency, enhancing lignin valorization remains challenging. Therefore, lowering the bond dissociation energy (BDE) has emerged as a viable strategy for achieving mild yet highly effective cleavage of bonds. In this study, a photocatalytic semi-hydrogenation/reduction strategy utilizing CsPbBr₃ quantum dots (CPB-QDs) and Hantzsch ester (HEH₂) as a synergistic catalytic system was introduced to reduce the BDE of C_β−O−Ar, achieving effective cleavage of the C_β−O−Ar bond. This strategy offers a wide substrate scope encompassing various β-O-4 model lignin dimers, preoxidized β-O-4 polymers, and native oxidized lignin, resulting in the production of corresponding ketones and phenols. Notably, this approach attained a turnover frequency (TOF) that is 17 times higher than that of the reported Ir-catalytic system in the photocatalytic depolymerization of the lignin model dimers. It has been observed via meticulous experimentation that HEH₂ can be activated by CPB-QDs via single electron transfer (SET), generating HEH₂⋅⁺ as a hydrogen donor while also serving as a hole quencher. Moreover, HEH₂⋅⁺ readily forms an active transition state with the substrates via hydrogen bonding. Subsequently, the proton-coupled electron transfer (PCET) from HEH₂⋅⁺ to the carbonyl group of the substrate generates a C_α⋅ intermediate.     

Catalysts developed from waste plastics: a versatile system for biomass conversion

The end-of-life treatment for post-consumer plastic waste constitutes one of modern society’s greatest problems, whereby highly unsustainable landfilling and incineration are the two main disposal routes. At present, the chemical upcycling of plastic waste is largely limited to its pyrolytic conversion into hydrocarbon fuels or nanomaterials. Herein, we demonstrate the upcycling of high-volume plastic waste by turning them into catalysts for biomass valorization. Many existing studies synthesize organocatalysts from a bottom-up approach using specialized monomers. Yet, transforming widely available waste polymers into functionalized materials for catalysis remains relatively unexplored. In this study, homogeneous and cross-linked heterogeneous catalysts derived from waste polystyrene food containers are shown to convert readily available saccharide precursors from biomass into 5-hydroxymethylfurfural (5-HMF), a key biorefinery platform chemical, under short reaction times and mild conditions. In addition, the heterogeneous catalyst can be reused multiple times with little loss of yield between repeated runs. Other than 5-HMF, doping the reaction with water or halide salts also allowed the formation of valuable products such as formic acid and diformylfuran. Our work expands on existing upcycling options for post-consumer plastic waste by giving them a new lease of life as value-added catalysts.     

Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2O2 Photosynthesis Coupled with Biomass Valorization

H₂O₂ photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value-added products. Here, a series of COFs (i.e. Cu₃-BT-COF, Cu₃-pT-COF and TFP-BT-COF) with regulated redox molecular junctions have been prepared to study H₂O₂ photosynthesis coupled with furfuryl alcohol (FFA) photo-oxidation to furoic acid (FA). The FA generation efficiency of Cu₃-BT-COF was found to be 575 mM g⁻¹ (conversion ≈100 % and selectivity >99 %) and the H₂O₂ production rate can reach up to 187 000 μM g⁻¹, which is much higher than Cu₃-pT-COF, TFP-BT-COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H₂O₂ production and FFA photo-oxidation to increase the efficiency. This is the first report about COFs for H₂O₂ photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous-crystalline catalysts in this field.     

Site-Selective Electrochemical C−H Carboxylation of Arenes with CO2

Herein, a direct, metal-free, and site-selective electrochemical C−H carboxylation of arenes by reductive activation using CO₂ as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo- and regioselectivity, setting the stage for the challenging site-selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron-deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst-free, metal-free and base-free, which makes it extremely attractive for potential applications.     

Green approaches in the valorization of plant wastes: Recent insights and future directions

Modern biorefinery technologies use a wide range of plant fibers/wastes and bioconversion techniques to produce a variety of biofuels and other goods. Plant waste, or lignocellulose, is one of the world's most easily accessible, sustainable, and biodegradable bioresources and has been identified as a valuable alternative raw material for the production of a variety of biofuels and chemicals. Furthermore, the generation of platform chemicals and biofuels from plant wastes benefits the environment and the economy. We will cover current advances in biotechnologies for valorizing plant lignocellulosic wastes to produce a wide range of high-value products such as biofuels, biocatalysts, biologically active chemicals, and so on in this brief communication. Furthermore, significant emphasis has been made on the green conversion of lignin into useful compounds, produced in large quantities as a by-product of paper and pulp or other industrial processes.     

Ultrasound enhanced aqueous extraction from rapeseed green biomass for polyphenol and protein valorization

The objective of this study was to investigate the effects of ultrasound-enhanced aqueous extraction on the valorization of polyphenols and proteins from rapeseed green biomass. Two types of biomass were studied: mature rapeseed stems collected around the time of seed harvest, and immature rapeseed stems used as a cover crop. Response Surface Methodology (RSM) was employed for obtaining optimal extraction conditions: ultrasound power of 400 W, treatment time of 50 min, sample length of 0.5 cm and agitation speed of 250 rpm. Compared to mature rapeseed stems, immature rapeseed stems require shorter treatment time (30 vs. 50 min), and exhibit higher extraction yield of polyphenols (100 vs. 86%) and proteins (18 vs. 11%) due to their less fibrous structures. These promising findings are opening doors to a potential market for rapeseed stems as a renewable biomass.     

电催化木质素升级转化成高附加值化学品和燃料的研究进展

为节能减排和能源结构调整以快速实现"碳中和",发展可再生、清洁与绿色的能源以替代传统化石能源已成为当今世界高质量发展的重要共识.生物质能作为一种典型的可再生能源,具有储量丰富、分布广泛、可有效转化成各种化工原料和燃料等特点逐步受到广泛关注并成为科研热点.木质素是生物质的重要组成部分,其含氧量低、热值高,可转化成高热值燃料;同时,木质素富含芳香结构单元,可以转化成各类高附加值化工原料及医药中间体.木质素解聚及其对应单体升级转化是木质素高效转化利用的关键技术.当前,传统热催化是其主要应用技术手段.然而,该类方法常在高温高压下进行,需消耗大量能源及众多繁琐操作步骤,不易规模化生产.相对而言,电催化技术能实现常温常压的木质素解聚及对应单体的升级转化,采用由可再生能源(例如风能、太阳能等)获得的清洁电力,则能实现完全绿色可持续生产,对未来经济社会的发展及"碳中和"的目标具有重大意义.本文综述了近年来电催化技术在木质素升级转化成高附加值燃料和化学品方面的应用,尤其是在木质素解聚及其对应单体于水溶液相关电解质中升级转化方面的应用.(1)针对总体研究背景进行了概述,总结了木质素研究的重要意义并概括了当前木质素研究的主要思路,并简单介绍了木质素结构单元及连接键等基本性质;(2)针对电催化技术在木质素应用方面进行了总结,包括反应类型和反应路径等;(3)总结了木质素常用的几种典型表征技术手段,如GC-MS、NMR、IR等;(4)总结了电催化木质素解聚及其单体升级转化研究现状,对电催化木质素解聚应用中木质素前体类型、电解质种类和电还原/氧化催化剂进行了详细介绍及客观评价,并对几种代表性单体的电催化加氢反应及氧化反应做了详细评述.在此基础上展望了电催化技术在木质素升级转化中的应用前景,指出了当前电催化技术在木质素升级转化应用中存在的实际问题,提出了电催化技术在木质素升级转化中的发展方向.     

Rhodium Single-Atom Catalyst Design through Oxide Support Modulation for Selective Gas-Phase Ethylene Hydroformylation

A frontier challenge in single-atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen-defective SnO₂ uniquely unite excellent TOF with essentially full selectivity in the gas-phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO₂, is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.     

Metamorphosis of a Commodity Plastic like PVC to Efficient Catalytic Single-Chain Nanoparticles

We perform the conversion of a commodity plastic of common use in pipes, window frames, medical devices, flexible hoses, etc. like polyvinyl chloride (PVC) to single-chain nanoparticles (SCNPs). SCNPs are versatile, protein-mimetic soft nano-objects of growing interest for catalysis, sensing, and nanomedicine, among other uses. We demonstrate that the metamorphosis process -as induced through metal-free click chemistry- leads to well-defined, uniform SCNPs that are stable during storage in the solid state for months. All the conversion process (from PVC isolation to PVC-SCNPs synthesis) can be run in a green, dipolar aprotic solvent and involving, when required, a simple mixture of ethanol and water (1/1 vol.) as non-solvent. The resulting PVC-SCNPs are investigated as recyclable, metalloenzyme-mimetic catalysts for several representative Cu(II)-catalyzed organic reactions. The method could be valid for the metamorphosis and valorization of other commodity plastics in which it is feasible to install azide functional groups in their linear polymer chains.