Green Chemistry最新文献

{"title":"Engineering industrial fungus Aspergillus oryzae for the sustainable biosynthesis of ergot alkaloids†","authors":"Meili Xiao, Yan Wang, Lu Yu, Xing Yan, Zhihua Zhu, Ernuo Tian, Yinmei Wang, Gen Zou, Zhihua Zhou and Pingping Wang","doi":"10.1039/D4GC04643A","DOIUrl":"https://doi.org/10.1039/D4GC04643A","url":null,"abstract":"<p >Ergot alkaloids (EAs) are a class of indole derivatives used as prescription drugs for the treatment of neurological diseases. Due to the limited production of EAs by <em>Claviceps</em> and the enantioselective difficulties encountered in chemical synthesis, a sustainable supply of EAs remains challenging. Recently, numerous attempts have been made to produce EAs using heterologous hosts. However, these efforts have only resulted in the production of the precursor, lysergic acid (LA), with low efficiency. Here, we report the <em>de novo</em> high-efficient biosynthesis of LA and a series of LA-derived EAs in <em>Aspergillus oryzae</em> cell factories. Based on genome sequencing of the EA-producing strain, <em>C. purpurea</em> 22.07, an EA biosynthetic gene cluster was annotated and characterized. After introducing and optimizing the agroclavine (AG) biosynthetic pathway in <em>A. oryzae</em>, we constructed an efficient chassis strain for AG production. We then confirmed the function of the annotated CloA′ to catalyze the successive oxidation of AG into LA and isolysergic acid (ILA) in this AG-producing chassis and realize their <em>de novo</em> production with titers of 52.68 ± 1.49 and 6.32 ± 2.08 mg L<small>⁻¹</small>, respectively. The subsequent introduction of the downstream non-ribosomal peptide synthetase genes LpsB′ and LpsC′ enabled the complete biosynthesis of ergometrine and a series of its analogs, achieving a total titer of more than 160 mg L<small>⁻¹</small>. The unexpected biosynthesis of isolysergyl-glycine and lysergyl-glycine revealed a novel function of LpsC′, which utilizes glycine as a substrate. Our work successfully realized the complete biosynthesis of a series of EAs in an industrially feasible fungus, which will open new avenues for manufacturing EAs in a green and sustainable manner.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 438-449"},"PeriodicalIF":9.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870224","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":"Electrochemical dehydrogenative annulation for the synthesis of 4-oxo-oxazolines†","authors":"Yong Yuan, Xincong Liu, Feng Zhang, Chunyan Bai, Yuyan Tao, Xiazhen Bao, Dongsheng Ji and Congde Huo","doi":"10.1039/D4GC05119J","DOIUrl":"https://doi.org/10.1039/D4GC05119J","url":null,"abstract":"<p >A metal- and oxidizing reagent-free electrochemical dehydrogenative annulation of enamides with <em>O</em>-nucleophiles has been developed, leading to a series of 4-oxo-oxazolines under environmentally friendly conditions. The present method demonstrates broad substrate scope and wide functional group tolerance. In addition to water, alcohols and carboxylic acids were also competent reaction partners. The merit of this electrochemical protocol has also been demonstrated by the gram-scale reaction and the synthesis of 2-(3,4-dimethoxyphenyl)-5-methyl-4,5-dihydrooxazol-4-ol (an antitumor nature product precursor). The mechanistic results suggest that the formation and homolytic cleavage of the N–Br bond is key to the success of this electrochemical dehydrogenative annulation reaction.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 96-101"},"PeriodicalIF":9.3,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825985","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":"Enhancing the reactivity of a P450 decarboxylase with ionic liquids†","authors":"Jake H. Nicholson, Mayara Chagas de Avila, Ricardo Rodrigues de Melo, Leticia Maria Zanphorlin and Alex P. S. Brogan","doi":"10.1039/D4GC05292G","DOIUrl":"https://doi.org/10.1039/D4GC05292G","url":null,"abstract":"<p >The cytochrome P450 family of enzymes have been shown to be powerful biocatalysts for a wide range of selective transformations. However, the industrial uptake of P450 enzymes has been low due to issues with enzyme stability and the requirement for exogenous cofactors to drive the reaction. Herein we describe a facile and scalable method for the stabilisation and solubilisation of a P450 decarboxylase enzyme in ionic liquids. The utilisation of ionic liquids allowed for solubilisation of the relatively water-insoluble fatty acid substrate of the enzyme and the modified enzyme was found to be significantly more thermally stable in ionic liquids relative to the enzyme in aqueous media. The shift to non-aqueous solvent allowed for the enzyme to operate in the <em>V</em><small>_max</small> region, which when coupled with the improved thermal stability, ultimately resulted in a 1000-fold increase in the process intensity of fatty acid decarboxylation. A novel photochemical method for driving the reaction was also discovered which removed the requirement for exogenous H<small>₂</small>O<small>₂</small> to be added to the reaction. These results highlight the potential of this strategy as it facilitates a holistic process of biocatalysis engineering where by solvent consideration and increased thermal stability significantly broadens the capability of the enzyme, crucial for the wider realization of industrial biocatalysis.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 517-526"},"PeriodicalIF":9.3,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05292g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870207","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":"Advances of the past 12 years in decarboxylation of biomass carboxylic acids to biofuels and high-value chemicals via photo- or electrocatalysis","authors":"Chen-Qiang Deng and Jin Deng","doi":"10.1039/D4GC04788E","DOIUrl":"https://doi.org/10.1039/D4GC04788E","url":null,"abstract":"<p >The utilization of renewable platform molecules as feedstocks for manufacturing high-value-added fine chemicals and liquid fuels has become crucial for green and sustainable chemistry and represents a rewarding challenge for today's society. Photochemistry and electrochemistry are effective and powerful tools for the transformation of biomass molecules through free radical intermediates under mild reaction conditions. Numerous direct decarboxylative reactions, without the need for prefunctionalization of carboxylic acids, by photocatalysis or electrocatalysis have been developed during the last few years, with more efficient, step-economical, and low energy consumption processes. In this review, we summarize recent advances in photochemical and electrochemical decarboxylative reactions for the synthesis of alkane fuels and high-value chemicals by utilizing biomass-derived free carboxylic acids as a sustainable source. These transformations can be categorized into four main types as follows: (1) decarboxylative reduction, (2) decarboxylative elimination, (3) decarboxylative coupling, and (4) decarboxylative oxidation. The scope and limitations of these conversions and mechanisms are discussed in detail. Finally, the challenges and perspectives for light or electrically driven decarboxylative transformation of renewable carboxylic acid feedstocks are proposed.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 275-292"},"PeriodicalIF":9.3,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870252","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":"Retraction: Copper catalyzed direct C–H double methylation of aromatic aldehydes employing methanol as an alkylating agent","authors":"Sereena Sunny and Ramasamy Karvembu","doi":"10.1039/D4GC90130D","DOIUrl":"https://doi.org/10.1039/D4GC90130D","url":null,"abstract":"<p >Retraction of ‘Copper catalyzed direct C–H double methylation of aromatic aldehydes employing methanol as an alkylating agent’ by Sereena Sunny and Ramasamy Karvembu, <em>Green Chem.</em>, 2024, https://doi.org/10.1039/D4GC02415J.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 24","pages":" 12090-12090"},"PeriodicalIF":9.3,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc90130d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798193","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":"Metal-free catalytic nucleophilic substitution of primary alcohols with secondary phosphine oxides†","authors":"Xiantao Ma, Xiaoyu Yan, Jing Yu, Jiarui Guo, Jiakun Bian, Ran Yan, Qing Xu and Li-Biao Han","doi":"10.1039/D4GC04409F","DOIUrl":"https://doi.org/10.1039/D4GC04409F","url":null,"abstract":"<p >Due to their inert nature and low reactivities, the dehydrative version of the MA reaction has not been achieved under metal-free conditions. Here, we develop a direct and efficient metal-free nucleophilic substitution reaction of primary alcohols with secondary phosphine oxides using trimethyliodosilane (TMSI) as the catalyst, providing a simple and green method for synthesis of useful tertiary phosphine oxides. This method is very effective as it can be extended to various primary alcohols, including benzylic and allylic, and even the more inert primary aliphatic alcohols. Many products can be obtained with high purity by simple washing and/or recrystallization under column chromatography-free conditions. This method can also be scaled up easily and applied in one-pot step-wise transformations to synthesize useful chemicals. Mechanism studies suggested that the reaction can be considered as a dehydrative version of the Michaelis–Arbuzov reaction and that both alcohol dehydroxylation and dehydrogenation processes may be involved in the reaction.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 102-108"},"PeriodicalIF":9.3,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826077","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":"Decatungstate-photocatalyzed tandem acylation/cyclization/self-hydrogenation of isocyanides with aldehydes to hydroxyalkylated N-heteroarenes via multiple hydrogen atom transfer†","authors":"Hong-Tao Ji, Qiong-Hui Peng, Jia-Sheng Wang, Yu-Han Lu, Hui Dai, Qing-Xia Luo and Wei-Min He","doi":"10.1039/D4GC04391J","DOIUrl":"https://doi.org/10.1039/D4GC04391J","url":null,"abstract":"<p >Both preventing the production of waste and achieving high atom economy are fundamental principles of green chemistry. Herein, the first example of a 100% atom economical construction of hydroxyalkylated N-heteroarenes, done through recyclable decatungstate-photocatalyzed tandem cyclization/self-hydrogenation of isocyanides with equimolar amounts of aldehydes without exogenous hydrogen reagent and under byproduct-free conditions, was developed. Mechanistic studies revealed that three sequential hydrogen atom transfer processes might be involved in this reaction and all the leaving hydrogens as hydrogen sources were incorporated into the target hydroxyalkylated products.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 24","pages":" 12084-12089"},"PeriodicalIF":9.3,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798192","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":"A green and efficient strategy to utilize spent SCR catalyst carriers: in situ remediation of Cu@TiO2 for photocatalytic hydrogen evolution†","authors":"Zhuo Wang, Ling Ma, Bingzhang Chen, Yubo Zhang, Kai Hong Wong, Wei Zhao, Chunxia Wang, Guoyong Huang and Shengming Xu","doi":"10.1039/D4GC04806G","DOIUrl":"https://doi.org/10.1039/D4GC04806G","url":null,"abstract":"<p >The selective utilization of titanium dioxide (TiO<small>₂</small>) carriers in spent selective catalytic reduction (SCR) catalysts offers a promising strategy to alleviate environmental pollution and recover high-value resources. Herein, we report a green and sustainable method for the <em>in situ</em> remediation of TiO<small>₂</small> carriers from spent SCR catalysts with a short process using a simple impregnation method to prepare recovered CR-TiO<small>₂</small> with the deposition of Cu. When employed in photocatalytic hydrogen production, CR-TiO<small>₂</small> achieved a hydrogen production rate of 388 μmol g<small>⁻¹</small> h<small>⁻¹</small>, which was 1.75 times higher than that of C-TiO<small>₂</small> (commercial TiO<small>₂</small>). Experimental results and DFT calculations demonstrated that the doping of Cu species broadened the light absorption range of TiO<small>₂</small> and promoted water dissociation, thus enhancing its photocatalytic performance. Finally, the process was evaluated by life cycle assessment (LCA), which showed a nearly 67.8%, 71.8%, 66.5%, and 83.2% reduction in fossil fuel depletion, ozone depletion, carbon dioxide and sulfur dioxide emissions, respectively, compared to the conventional electronic-grade TiO<small>₂</small> synthesis method. This work provides a sustainable way to produce clean, green energy by utilizing titanium resources recovered from spent SCR catalysts. Furthermore, it provides new insights into turning waste into treasure and opens up a new way to alleviate environmental problems.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 240-247"},"PeriodicalIF":9.3,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825987","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":"Electro-oxidative upgrading of lignite alkali-soluble derivatives for clean production of fulvic acids using NiCo-LDH@NiC2O4/NF anode†","authors":"Haiyan Ge, Jining Zhou, Zhicai Wang, Xiaobiao Yan, Chunxiu Pan, Zhiping Lei, Zhanku Li, Jingchong Yan, Weidong Zhang, Shibiao Ren, Shigang Kang and Hengfu Shui","doi":"10.1039/D4GC04899G","DOIUrl":"https://doi.org/10.1039/D4GC04899G","url":null,"abstract":"<p >Utilizing renewable electricity and cost-effective carbon resources to facilitate water electrolysis for hydrogen production represents a promising and efficient technology for energy storage and conversion. Anode valorization <em>via</em> selective oxidation can produce valuable chemicals, offering a cleaner alternative to chemical oxidation. In this study, to upgrade lignite alkali-soluble derivatives (ASD), a novel NiCo-LDH@NiC<small>₂</small>O<small>₄</small>/NF electrode was developed using a continuous electrochemical deposition method. When employed as the anode, this electrode achieved an 85% conversion of mandelic acid (MA) to benzoic acid with over 95% selectivity at a constant potential of 1.5 V (<em>vs.</em> RHE) in a 1.0 M KOH solution over 1 h. Concurrently, 75% of ASD was successfully upgraded to fulvic acid (FA) with a selectivity exceeding 90%. Compared to NiCo-LDH/NF and NiC<small>₂</small>O<small>₄</small>/NF electrodes, the NiCo-LDH@NiC<small>₂</small>O<small>₄</small>/NF demonstrated superior electro-catalytic activity and stability. NiCo-LDH is the main active phase, while the pre-deposited NiC<small>₂</small>O<small>₄</small> significantly enhances both its catalytic activity and stability. The degradation of MA involves the cleavage of the ArC(OH)–C bond due to OH activation, whereas the depolymerization of ASD into FA is primarily attributed to the ring-opening oxidation of aromatic nuclei. The present work provides a green and efficient electro-oxidation strategy, coupled with a novel non-precious metal electrocatalyst, to produce coal-based aromatic carboxylic acids, marking a significant step towards more sustainable and environmentally friendly coal-based chemical manufacturing.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 473-484"},"PeriodicalIF":9.3,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870228","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":"Challenges and opportunities in catalytic hydrogenolysis of oxygenated plastics waste: polyesters, polycarbonates, and epoxy resins†","authors":"Harisekhar Mitta, Lingfeng Li, Mohammadhossein Havaei, Dambarudhar Parida, Elias Feghali, Kathy Elst, Annelore Aerts, Karolien Vanbroekhoven and Kevin M. Van Geem","doi":"10.1039/D4GC03784G","DOIUrl":"https://doi.org/10.1039/D4GC03784G","url":null,"abstract":"<p >This review comprehensively explores various homogeneous and heterogeneous catalytic systems for the hydrogenolysis of oxygenated plastic waste (OXPs), presenting an adaptable solution to plastic pollution and generating valuable feedstock. Research demonstrates enhanced hydrogenolysis efficiency with reduced energy consumption, yielding alcohols, alkanes, alkenes, and aromatics. The effectiveness of depolymerization and the product distribution are influenced by factors such as solvents, ligands, metals, catalyst support, and reaction conditions. Scaling up these processes remains challenging, highlighting the need for non-toxic, highly active catalysts. Promising homogeneous catalysts, such as Ru(triphos-Xyl), and heterogeneous catalysts, such as Ru/Nb<small>₂</small>O<small>₅</small>, show potential in OXP depolymerization but face cost-related scalability issues. Homogeneous catalysts encounter commercialization obstacles due to harsh reaction conditions and difficulties in product separation, whereas heterogeneous catalysts like Ru/Nb<small>₂</small>O<small>₅</small> provide effectiveness and stability with easier product separation. Nonetheless, challenges in scaling up, cost reduction, and catalyst reusability persist. Achieving economic viability is crucial for the commercialization of OXP hydrogenolysis and the reduction of plastic waste. The review emphasizes the shortage of depolymerization facilities for polyesters like poly(ethylene terephthalate) (PET), poly(bisphenol A carbonate) (BPA-PC), and epoxy resins (EP). It addresses recycling process challenges, focusing on sorting and supply chain issues, and identifies specific difficulties in recycling BPA-PC, PET, and EP materials, proposing chemical recycling as a viable solution to improve economic competitiveness and environmental sustainability.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 10-40"},"PeriodicalIF":9.3,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc03784g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826079","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}