Green Chemistry最新文献

{"title":"Towards high atom economy in whole-cell redox biocatalysis: up-scaling light-driven cyanobacterial ene-reductions in a flat panel photobioreactor.","authors":"Hanna C Grimm, Peter Erlsbacher, Hitesh Medipally, Lenny Malihan-Yap, Lucija Sovic, Johannes Zöhrer, Sergey N Kosourov, Yagut Allahverdiyeva, Caroline E Paul, Robert Kourist","doi":"10.1039/d4gc05686h","DOIUrl":"https://doi.org/10.1039/d4gc05686h","url":null,"abstract":"<p><p>Light-driven biotransformations in recombinant cyanobacteria benefit from the atom-efficient regeneration of reaction equivalents like NADPH from water and light by oxygenic photosynthesis. The self-shading of photosynthetic cells throughout the reaction volume, along with the need for extended light paths, limits adequate light supply and significantly restricts the potential for upscaling. Here, we present a flat panel photobioreactor (1 cm optical path length) as a scalable system to provide efficient illumination at high cell densities. The genes of five ene-reductases from different classes were expressed in <i>Synechocystis</i> sp. PCC 6803. The strains were characterised in the light-driven reduction of a set of prochiral substrates. With specific activities up to 150 U g_CDW ^-1 under standard conditions in small-scale reactions, the recombinant strains harbouring the ene-reductases TsOYE C25G I67T and OYE3 showed the highest specific activities observed so far in photobiotransformations and were selected for the up-scale in the flat panel photobioreactor in 120 mL-scale. The strain producing OYE3 exhibited a specific activity as high as 56.1 U g_CDW ^-1. The corresponding volumetric productivity of 1 g L^-1 h^-1 compares favourably to other photosynthesis-driven processes. This setup facilitated the conversion of 50 mM over approximately 8 hours to an isolated yield of 87%. The atom economy of 88% compares favourably to the use of the sacrificial co-substrates glucose and formic acid with 49% and 78%, respectively. Determination of the complete <i>E</i>-Factor of 203 including water reveals that the volumetric yield and water required for cultivation are crucial for the sustainability. In summary, our results point out key factors for the sustainability of light-driven whole-cell biotransformations, and provide a solid basis for future optimisation and up-scale campaigns of photosynthesis-driven bioproduction.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" ","pages":""},"PeriodicalIF":9.3,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11749524/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Palladium-catalyzed amination oxidation of electron-rich olefins in green media†","authors":"Yongpeng Zheng, Yaodan Wu, Jianxiao Li, Wanqing Wu, Shaorong Yang, Chaorong Qi and Huanfeng Jiang","doi":"10.1039/D4GC05771F","DOIUrl":"https://doi.org/10.1039/D4GC05771F","url":null,"abstract":"<p >A palladium-catalyzed amination oxidation of electron-rich olefins with anilines under air at room temperature in ionic liquids was accomplished. Herein, H<small>₂</small>O<small>₂</small> serves as the oxidant and the oxygen source of the carbonyl group. Notably, this new approach provides a practical and straightforward route to access a broad range of privileged amino acid structures with good yields and excellent regioselectivities. Significantly, internal olefins were also compatible with this transformation.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1018-1022"},"PeriodicalIF":9.3,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid gram-scale microwave-assisted synthesis of organic anodes for sodium-ion batteries with environmental impact assessment.","authors":"Constantin Puscalau, Aamod V Desai, Erlantz Lizundia, Romy Ettlinger, Mohamed Adam, Russell E Morris, A Robert Armstrong, Begum Tokay, Andrea Laybourn","doi":"10.1039/d4gc05530f","DOIUrl":"https://doi.org/10.1039/d4gc05530f","url":null,"abstract":"<p><p>Development of sustainable synthesis methods of organic electrode materials (OEMs) for sodium (Na)-ion batteries must take hold rapidly in large scale-synthesis if subsequent commercialisation is to occur. We report a facile and rapid gram-scale synthesis method based on microwave irradiation for disodium naphthalene-2,6-dicarboxylate (Na-NDC) and mono/disodium benzene-1,4-dicarboxylate (Na-BDC) as model compounds. Phase purity and formation of materials was confirmed by various characterisation techniques. The electrochemical performance was tested in both half and full cell formats and compared to material obtained <i>via</i> smaller scale synthesis, revealing state-of-the art performance in terms of capacity retention and cyclability. The environmental impacts upon organic anode synthesis were quantified according to <i>cradle-to-gate</i> life cycle assessment (LCA). The results allow for the identification of environmental hotspots during production, indicating areas for future process optimisation. Interestingly, remarkably reduced impacts are obtained compared to conventional syntheses at milligram scale. Additionally, this work suggests potential significant improvements upon additional upscaling and solvent recycling.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" ","pages":""},"PeriodicalIF":9.3,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11749190/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bis-pyrrolidone structures as versatile building blocks for the synthesis of bio-based polyesters and for the preparation of additives.","authors":"Nele Schulte, Giacomo Damonte, Valeria Marisa Rocca, Anamaria Todea, Orietta Monticelli, Alessandro Pellis","doi":"10.1039/d4gc04951a","DOIUrl":"https://doi.org/10.1039/d4gc04951a","url":null,"abstract":"<p><p>In this work, three bis-pyrrolidone-based structures (BP) were synthesized combining dimethyl itaconate (DMI), the dimethyl ester derivative of itaconic acid, with various aliphatic diamines having a C4 to C12 carbon chain length with the aim of developing novel bio-based building blocks. All three BPs were obtained with a purity >93% and could further be used without performing any tedious purification step, therefore allowing an easy scalability of the synthesis on a 10 g scale. Their potential application was demonstrated in two key areas of modern polymer science: (1) the enzymatic synthesis of polyesters and (2) their use as poly(lactic acid) (PLA) additives. Firstly, the possibility of obtaining oligoesters by reacting the BP monomers with various aliphatic diols in a solventless reaction system and under mild conditions (<i>T</i> < 90 °C) was demonstrated thanks to the use of enzymatic catalysis. Linear oligoesters having mean average molecular weights between 1000 g mol^-1 and 6100 g mol^-1 and dispersity values <2 were successfully obtained. When applying the BP structures as PLA additives, the incorporation of a 10% w w^-1 BP in the polyester matrix resulted in systems with an 8× increased elongation at break and a decrease in the glass transition temperature compared to the neat polymer matrix.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" ","pages":""},"PeriodicalIF":9.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11736262/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bisphosphonium-catalyzed ring-opening of cycloalkenes under visible-light irradiation†","authors":"Kaining Zhang, Jiazhao Wang, Wenlong Chen, Mingfeng Li, Shengfei Jin and Zhiwei Zuo","doi":"10.1039/D4GC05951D","DOIUrl":"https://doi.org/10.1039/D4GC05951D","url":null,"abstract":"<p >The selective cleavage of C<img>C double bonds to form carbonyl groups is a fundamental maneuver in retrosynthetic analysis, empowering swift alterations to molecular structures and efficient synthesis of sophisticated, multifunctional molecules. Traditional methods like ozonolysis are effective but come with safety, environmental, and economic challenges. To address these concerns, photochemical methods have recently emerged as ideal platforms for alkene oxidative cleavage through the utilization of photons as energy sources and open-shell radicals as reactive intermediates. Herein, we disclose an oxidant-free, operationally simple, and environmentally friendly protocol for the oxidative cleavage of cyclic alkenes <em>via in situ</em>-generated secondary alcohol intermediates. Facilitated by a bisphosphonium catalyst, the selective integration of alkoxy radical-mediated C–C bond scission with anti-Markovnikov alkene hydrofunctionalization led to the selective cleavage of cyclic alkenes and the formation of distal phenyl-substituted aldehydes with outstanding regioselectivity. This photocatalytic process accommodates both activated and unactivated cycloalkenes and operates under mild, redox-neutral conditions. Furthermore, the use of continuous-flow reactors has significantly improved photocatalytic efficiency, providing a robust and scalable solution for large-scale applications.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1023-1030"},"PeriodicalIF":9.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrosynthesis of benzyl-<i>tert</i>-butylamine <i>via</i> nickel-catalyzed oxidation of benzyl alcohol.","authors":"P J L Broersen, V Paschalidou, A C Garcia","doi":"10.1039/d4gc05171h","DOIUrl":"10.1039/d4gc05171h","url":null,"abstract":"<p><p>The development of sustainable synthetic methods for converting alcohols to amines is of great interest due to their widespread use in pharmaceuticals and fine chemicals. In this work, we present an electrochemical approach by using green electrons for the selective oxidation of benzyl alcohol to benzaldehyde using a NiOOH catalyst, followed by its reductive amination to form benzyl-<i>tert</i>-butylamine. The number of Ni monolayer equivalents on the catalyst was found to significantly influence selectivity, with 2 monolayers achieving up to 90% faradaic efficiency (FE) for benzaldehyde in NaOH, while 10 monolayers performed best in a <i>tert</i>-butylamine solution (pH 11), yielding 100% FE for benzaldehyde. Reductive amination of benzaldehyde was optimized on Ag and Pb electrodes, with Ag achieving 39% FE towards the amine product, though hydrogen evolution remained a competing reaction. <i>In situ</i> FTIR spectroscopy confirmed the formation of benzaldehyde and its corresponding imine intermediate during oxidation, while reduction spectra supported the formation of the amine product. These results demonstrate the potential of paired electrolysis for alcohol-to-amine conversion, achieving an overall 35% FE for the synthesis of benzyl-<i>tert</i>-butylamine. This work paves the way for more efficient and sustainable electrochemical routes to amine synthesis.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" ","pages":""},"PeriodicalIF":9.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11713879/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photo-enzyme-coupled catalysis for selective oxidation of 2,5-diformylfuran into 2,5-furandicarboxylic acid†","authors":"Chenxi Zhang, Hongqing Zhao, Peng Zhan, Houchao Shan, Yanou Qi, Wenqiang Ren, Xiangshi Liu, Peiyong Qin, Di Cai and Tianwei Tan","doi":"10.1039/D4GC05475J","DOIUrl":"https://doi.org/10.1039/D4GC05475J","url":null,"abstract":"<p >The transformation of 2,5-diformylfuran (DFF) into renewable biomass-derived 2,5-furandicarboxylic acid (FDCA) is an attractive reaction. In this study, a novel photo-enzymatic catalysis system was established for selective oxidation of DFF into FDCA under mild conditions and through a one-pot process, in which 2-ethylanthraquinone served as the homogeneous photocatalyst for <em>in situ</em> H<small>₂</small>O<small>₂</small> production under visible light irradiation, while H<small>₂</small>O<small>₂</small> served as the oxidant for the organic peracid-assisted oxidation of DFF into FDCA by commercial lipase (Lipozyme 435). Results indicated that the constitution of the buffering system evidently influenced both photocatalyst and lipase activities in the coupling system, which further affected the kinetics of the tandem reactions and FDCA yield. Under optimized conditions (2 mg mL<small>⁻¹</small> of 2-ethylanthraquinone, 3 mg mL<small>⁻¹</small> of lipase, 7 W and <em>λ</em> &gt; 420 nm of the light source, and <em>tert</em>-butanol/ethanol ratio of 9 : 1 (v : v)), 84.14% ± 4.68% of FDCA yield with complete DFF conversion was realized. Mechanism investigation using molecular docking simulation indicated that H<small>₂</small>O<small>₂</small> produced from the light reaction was consumed by lipase to generate peracetic acid from ethyl acetate that drove the selective oxidation of aldehyde groups in the DFF molecule. The novel visible-light-driven photo-enzyme coupling system successfully addressed the challenges associated with manually adding, storing, and transporting H<small>₂</small>O<small>₂</small> in conventional DFF oxidation, thus showing promise in valorization of a broader range of aldehyde group-containing biomass-derived molecules into renewable chemicals.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1206-1213"},"PeriodicalIF":9.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemically enabled synthesis of multi-substituted pyrazoles via a radical cyclization cascade†","authors":"Wan-Jie Wei, Yan-Qing Zeng, Xian-Feng Liang, Fei-Hu Cui, Mao-Rui Wang, Ying-Ming Pan, Wen-Gui Duan and Hai-Tao Tang","doi":"10.1039/D4GC05685J","DOIUrl":"https://doi.org/10.1039/D4GC05685J","url":null,"abstract":"<p >Despite the widespread applications of aryl diazonium salts, capturing both aryl radicals and aryl diazo radicals simultaneously remains a significant challenge due to the extreme instability of the diazonium radicals. Herein, we report a mild and efficient electrochemical reduction approach employing aryl diazonium salts as dual synthons to synthesize valuable multi-substituted pyrazoles for the first time. Furthermore, this method demonstrates significant practical potential through the modification of pharmaceutical intermediates, and a two-step one-pot approach that utilizes anilines as starting materials.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1006-1012"},"PeriodicalIF":9.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting engineering strategies for plastic hydrocracking applications: a machine learning-based multi-objective optimization framework†","authors":"Zhe Ma, Zhibo Zhang, Changyuan Wang, Jianlin Cao, Yibin Liu, Hao Yan, Xin Zhou, Xiang Feng and De Chen","doi":"10.1039/D4GC05259E","DOIUrl":"https://doi.org/10.1039/D4GC05259E","url":null,"abstract":"<p >The escalating global demand for plastics, combined with inadequate recycling strategies, has resulted in severe environmental challenges. While previous research has explored various waste plastic recycling methods, the development of efficient and sustainable technologies remains a complex, time-intensive endeavor, involving extensive experimental data, catalyst design, and process optimization. In this study, we introduce, for the first time, a novel waste plastic pyrolysis oil hydrocracking process (WPOH) and its optimized variant (WPOH-Pro), which uniquely integrates process simulation with advanced deep learning models for multi-objective optimization. This innovative approach accelerates process parameter optimization, setting it apart from existing studies. By leveraging deep learning and comprehensive process modeling, our framework not only optimizes economic performance but also addresses key environmental concerns. The results of our study indicate that the WPOH-Pro process enhances net profit by 50.44% relative to the WPOH process. This improvement is primarily attributed to increased yields of gasoline and naphtha, with an associated production cost of $4.58 million per annum. Furthermore, lifecycle analysis reveals a 22.9% reduction in non-renewable energy consumption, alongside a substantial decrease in greenhouse gas emissions, quantified at 390.24 tCO<small>₂</small>eq. per million GDP. In comparison with the WPOH process, the WPOH-Pro process achieves a reduction in CO<small>₂</small> emissions of 99.38 tCO<small>₂</small>eq. per million GDP. These findings highlight the ecological benefits of the WPOH-Pro process. This pioneering work in combining process simulation and deep learning-driven optimization offers a significant leap forward in the waste plastic recycling field. It provides a robust foundation for the engineering application of waste plastic hydrocracking technologies and serves as a valuable reference for promoting the circular economy. By offering practical insights into sustainable waste recycling, this study paves the way for future innovations and the industrial adoption of more efficient and environmentally friendly recycling technologies.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1169-1182"},"PeriodicalIF":9.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Removal of lithium from aqueous solutions by precipitation with sodium and choline alkanoate soaps†","authors":"Stijn Raiguel, Dženita Avdibegović and Koen Binnemans","doi":"10.1039/D4GC05586A","DOIUrl":"10.1039/D4GC05586A","url":null,"abstract":"<p >In order to comply with the expected tightening of discharge limits for lithium to surface waters, the lithium-ion battery industry will need access to methods to reduce the concentration of lithium in wastewater down to ppm levels. In this Communication, we discuss the possibility of using sodium and choline soaps as precipitating agents for lithium, comparing the two soap classes and probing the influence of the carbon chain length. It was found that lithium concentrations down to 10 ppm can be reached with sodium stearate, and down to 1 ppm with choline stearate, using a slight excess of the precipitating agent. However, in solutions containing sodium salts, sodium interferes with lithium removal, such that the equilibrium lithium concentration is proportional to the concentration of sodium in the feed. After precipitation, lithium could be recovered from the precipitate by dissolution in an ethanolic hydrogen chloride solution.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1013-1017"},"PeriodicalIF":9.3,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11702322/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}