Robin Coeck , Nathalie Claes , Thomas Cuypers , Sara Bals , Dirk E. De Vos
The reductive amination of fatty acids (FAs) and fatty acid methyl esters (FAMEs) has been identified as a green and effective method to produce N,N-dimethylalkylamines (ADMAs). With current technology, this reaction requires at least two reaction steps. Here, we report a heterogeneous catalytic system for the one-pot synthesis of ADMAs from FA(ME)s, utilizing solely H2 and methylamines (i.e. di- and trimethylamine). The reaction requires two recyclable catalysts: ortho-Nb2O5 for the amidation of FA(ME)s and PtVOx/SiO2 for the hydrogenation of the in situ generated fatty amide to ADMAs. The developed system has a wide range of applicability: it is able to convert all natural FAs to ADMAs (yields up to 90%) and also other tertiary amines were synthesized. Aside from the development of a sustainable and industrially applicable process (e.g. utilizing benign solvents or performing solventless reactions), a kinetic model was developed that describes the reaction rate's relationship with key process parameters such as the H2 pressure and water content. By tuning the reaction conditions, different ratios of primary, secondary and tertiary fatty amines can be obtained.
{"title":"The sustainable and catalytic synthesis of N,N-alkylated fatty amines from fatty acids and esters†","authors":"Robin Coeck , Nathalie Claes , Thomas Cuypers , Sara Bals , Dirk E. De Vos","doi":"10.1039/d4gc05740f","DOIUrl":"10.1039/d4gc05740f","url":null,"abstract":"<div><div>The reductive amination of fatty acids (FAs) and fatty acid methyl esters (FAMEs) has been identified as a green and effective method to produce <em>N</em>,<em>N</em>-dimethylalkylamines (ADMAs). With current technology, this reaction requires at least two reaction steps. Here, we report a heterogeneous catalytic system for the one-pot synthesis of ADMAs from FA(ME)s, utilizing solely H<sub>2</sub> and methylamines (<em>i.e.</em> di- and trimethylamine). The reaction requires two recyclable catalysts: <em>ortho</em>-Nb<sub>2</sub>O<sub>5</sub> for the amidation of FA(ME)s and PtVO<sub><em>x</em></sub>/SiO<sub>2</sub> for the hydrogenation of the <em>in situ</em> generated fatty amide to ADMAs. The developed system has a wide range of applicability: it is able to convert all natural FAs to ADMAs (yields up to 90%) and also other tertiary amines were synthesized. Aside from the development of a sustainable and industrially applicable process (<em>e.g.</em> utilizing benign solvents or performing solventless reactions), a kinetic model was developed that describes the reaction rate's relationship with key process parameters such as the H<sub>2</sub> pressure and water content. By tuning the reaction conditions, different ratios of primary, secondary and tertiary fatty amines can be obtained.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1410-1422"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099924","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}
Allylamine is a versatile scaffold in organic synthesis. Common methods for its asymmetric α-C–H functionalization require protection of the NH2 group to prevent N-nucleophilic interference. Direct asymmetric α-C–H functionalization of N-unprotected allylamine (with low α-C–H acidity) remains challenging and underdeveloped to date. In this paper, we report a chiral pyridoxal catalyzed direct asymmetric addition reaction of N-unprotected allylamines to trifluoromethyl ketones, yielding synthetically and pharmaceutically valuable α-trifluoromethyl-β-amino alcohols with up to 87% yield and 99% enantiomeric excess (ee). Despite unsatisfactory diastereoselectivity for products, the isomers can be conveniently separated and further utilized. pKa calculations indicate that the α-C–H acidity of activated allylamine increases by 1018-fold in the presence of chiral pyridoxal, verifying the powerful catalytic capability of chiral pyridoxal for asymmetric α-C–H functionalization of primary amines.
{"title":"Direct asymmetric α-C–H functionalization of N-unprotected allylamine catalyzed by chiral pyridoxal†","authors":"Hanyu Liang , Jiaxuan Cao , Hailong Zhang , Longjie Huang , Siqi Liu , Tianhao Wu , Xiao Xiao , Baoguo Zhao","doi":"10.1039/d4gc05739b","DOIUrl":"10.1039/d4gc05739b","url":null,"abstract":"<div><div>Allylamine is a versatile scaffold in organic synthesis. Common methods for its asymmetric α-C–H functionalization require protection of the NH<sub>2</sub> group to prevent N-nucleophilic interference. Direct asymmetric α-C–H functionalization of N-unprotected allylamine (with low α-C–H acidity) remains challenging and underdeveloped to date. In this paper, we report a chiral pyridoxal catalyzed direct asymmetric addition reaction of N-unprotected allylamines to trifluoromethyl ketones, yielding synthetically and pharmaceutically valuable α-trifluoromethyl-β-amino alcohols with up to 87% yield and 99% enantiomeric excess (ee). Despite unsatisfactory diastereoselectivity for products, the isomers can be conveniently separated and further utilized. p<em>K</em><sub>a</sub> calculations indicate that the α-C–H acidity of activated allylamine increases by 10<sup>18</sup>-fold in the presence of chiral pyridoxal, verifying the powerful catalytic capability of chiral pyridoxal for asymmetric α-C–H functionalization of primary amines.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1374-1380"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107412","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}
Huiwen Tian , Huanhuan Yang , Xueqi Liu , Yu Jia , Qun Xu
The CO2 electrochemical reduction reaction (CO2RR) is a promising alternative way to convert CO2 into high value-added fuels and chemicals with renewable electricity as an energy source to solve the current environmental problems. However, the low catalytic efficiency and poor stability of the CO2RR are challenges that need to be addressed. In this review, we summarize the advanced progress in the confinement effect on the CO2RR. In a confined environment, controlled diffusion behaviors of reactants, intermediates and products and charge transfer can effectively facilitate the CO2RR. Meanwhile, the local increase in pH due to the limited diffusion of the electrolyte and in situ-generated OH− can induce slow proton adsorption kinetics, resulting in inhibition of proton-involving reactions, especially the competitive reaction of hydrogen evolution. Besides, confinement structures can effectively stabilize active metal sites against corrosion, fragmentation, dissolution, agglomeration, and over-reduction due to the protection of limited space or/and confined intermediates. Therefore, attempts to illustrate the relationship between confinement architectures and their catalytic performance are necessary, and they are discussed in this review, and the current challenges and potential strategies for future CO2RR research are envisioned.
{"title":"Confinement effect on the electrochemical CO2 reduction reaction","authors":"Huiwen Tian , Huanhuan Yang , Xueqi Liu , Yu Jia , Qun Xu","doi":"10.1039/d4gc05274a","DOIUrl":"10.1039/d4gc05274a","url":null,"abstract":"<div><div>The CO<sub>2</sub> electrochemical reduction reaction (CO<sub>2</sub>RR) is a promising alternative way to convert CO<sub>2</sub> into high value-added fuels and chemicals with renewable electricity as an energy source to solve the current environmental problems. However, the low catalytic efficiency and poor stability of the CO<sub>2</sub>RR are challenges that need to be addressed. In this review, we summarize the advanced progress in the confinement effect on the CO<sub>2</sub>RR. In a confined environment, controlled diffusion behaviors of reactants, intermediates and products and charge transfer can effectively facilitate the CO<sub>2</sub>RR. Meanwhile, the local increase in pH due to the limited diffusion of the electrolyte and <em>in situ</em>-generated OH<sup>−</sup> can induce slow proton adsorption kinetics, resulting in inhibition of proton-involving reactions, especially the competitive reaction of hydrogen evolution. Besides, confinement structures can effectively stabilize active metal sites against corrosion, fragmentation, dissolution, agglomeration, and over-reduction due to the protection of limited space or/and confined intermediates. Therefore, attempts to illustrate the relationship between confinement architectures and their catalytic performance are necessary, and they are discussed in this review, and the current challenges and potential strategies for future CO<sub>2</sub>RR research are envisioned.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1238-1253"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100266","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}
Jian Gan , Yifei Zhan , Jing Fan , Jifu Wang , Qi Gao , Caoxing Huang , Wenji Yu , Kai Zhang
A Pickering emulsion, stabilized by amphiphilic solid particles, is a highly functional and stable system that has attracted significant research interest. Lignin, an amphiphilic biomacromolecule found widely in nature, can be transformed into nanoparticles using modern nanotechnology with great potential for use in Pickering emulsions. Despite numerous studies exploring the function of colloidal lignin particles (CLPs) in producing Pickering emulsions, there are few systematic reviews on the state-of-the-art works related to CLP-stabilized Pickering emulsions. In this review, we summarize recent advances in synthesis processes, formation mechanisms, structural characteristics and surface properties of CLPs on the stability and functionality of Pickering emulsion systems. We also highlight advanced applications of CLP-stabilized Pickering emulsions at present and propose future development directions for improving their synthesis technology using lignin as a stabilizer to enhance their properties. Our hope is that this review will serve as a roadmap for scientists engaged in research on CLP-Pickering emulsions across different scientific fields to achieve optimal material performance goals.
{"title":"Pickering multiphase materials using plant-based colloidal lignin nanoparticles","authors":"Jian Gan , Yifei Zhan , Jing Fan , Jifu Wang , Qi Gao , Caoxing Huang , Wenji Yu , Kai Zhang","doi":"10.1039/d4gc05713a","DOIUrl":"10.1039/d4gc05713a","url":null,"abstract":"<div><div>A Pickering emulsion, stabilized by amphiphilic solid particles, is a highly functional and stable system that has attracted significant research interest. Lignin, an amphiphilic biomacromolecule found widely in nature, can be transformed into nanoparticles using modern nanotechnology with great potential for use in Pickering emulsions. Despite numerous studies exploring the function of colloidal lignin particles (CLPs) in producing Pickering emulsions, there are few systematic reviews on the state-of-the-art works related to CLP-stabilized Pickering emulsions. In this review, we summarize recent advances in synthesis processes, formation mechanisms, structural characteristics and surface properties of CLPs on the stability and functionality of Pickering emulsion systems. We also highlight advanced applications of CLP-stabilized Pickering emulsions at present and propose future development directions for improving their synthesis technology using lignin as a stabilizer to enhance their properties. Our hope is that this review will serve as a roadmap for scientists engaged in research on CLP-Pickering emulsions across different scientific fields to achieve optimal material performance goals.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1300-1330"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05713a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107407","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}
Shaohan Xu , Jingui Zheng , Lingzhi Sun , Xun Pan , Ruochen Yang , Jianrong Zeng , Guohua Zhao
The electrocatalytic CO2 reaction with other gases to synthesize value-added products at high current densities is challenging due to the limited diffusion rate for low-solubility gases in aqueous electrolytes. To enhance the mass transfer process, herein, a membrane electrode assembly (MEA) electrolyzer is employed to achieve high-rate electrochemical C–C coupling of CO2 and gaseous formaldehyde. Based on the simultaneous gas-phase delivery of reactants to the catalytic surface, an acetate production rate of 654 mg L−1 h−1 is achieved at a current density over 150 mA cm−2 on a Cu-MOF coated Cu2O catalyst. In situ FT-IR, Raman spectroscopy, and in situ XAFS combined with DFT suggest that the energy barrier of C–C coupling between *CO and *CH2OH is significantly lowered due to the insertion of Cu-MOF, thus promoting the production of acetate. This work provides a novel strategy for electrochemical treatment of waste gas coupling to synthesize high-value products with potential industrial applications.
{"title":"Electrocatalytic C–C coupling of CO2 and formaldehyde to synthesize acetate via membrane electrode assembly†","authors":"Shaohan Xu , Jingui Zheng , Lingzhi Sun , Xun Pan , Ruochen Yang , Jianrong Zeng , Guohua Zhao","doi":"10.1039/d4gc05419a","DOIUrl":"10.1039/d4gc05419a","url":null,"abstract":"<div><div>The electrocatalytic CO<sub>2</sub> reaction with other gases to synthesize value-added products at high current densities is challenging due to the limited diffusion rate for low-solubility gases in aqueous electrolytes. To enhance the mass transfer process, herein, a membrane electrode assembly (MEA) electrolyzer is employed to achieve high-rate electrochemical C–C coupling of CO<sub>2</sub> and gaseous formaldehyde. Based on the simultaneous gas-phase delivery of reactants to the catalytic surface, an acetate production rate of 654 mg L<sup>−1</sup> h<sup>−1</sup> is achieved at a current density over 150 mA cm<sup>−2</sup> on a Cu-MOF coated Cu<sub>2</sub>O catalyst. <em>In situ</em> FT-IR, Raman spectroscopy, and <em>in situ</em> XAFS combined with DFT suggest that the energy barrier of C–C coupling between *CO and *CH<sub>2</sub>OH is significantly lowered due to the insertion of Cu-MOF, thus promoting the production of acetate. This work provides a novel strategy for electrochemical treatment of waste gas coupling to synthesize high-value products with potential industrial applications.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1488-1498"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099798","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}
The title paper reported a green and efficient one-pot method for synthesizing 5-aryl-pyrimido[4,5-b]quinoline-dione derivatives via a three-component reaction involving anilines, aldehydes and barbituric acids. However, these starting materials can theoretically yield two possible structural variants. Under the same reaction conditions as the title paper, the 1H NMR spectrum of the synthesized compound (4f) provided data that challenge the structural assignment of the proposed target compound.
{"title":"Comment on “l-Proline-promoted three-component reaction of anilines, aldehydes and barbituric acids/malononitrile: regioselective synthesis of 5-arylpyrimido[4,5-b]quinoline-diones and 2-amino-4-arylquinoline-3-carbonitriles in water” by A. Khalafi-Nezhad, S. Sarikhani, E. Shaikhi Shahidzadeh and F. Panahi, Green Chem., 2012, 14, 2876†","authors":"Ting Chen , Syrine Mahdadi , Stéphanie Desbène-Finck","doi":"10.1039/d4gc02524e","DOIUrl":"10.1039/d4gc02524e","url":null,"abstract":"<div><div>The title paper reported a green and efficient one-pot method for synthesizing 5-aryl-pyrimido[4,5-<em>b</em>]quinoline-dione derivatives <em>via</em> a three-component reaction involving anilines, aldehydes and barbituric acids. However, these starting materials can theoretically yield two possible structural variants. Under the same reaction conditions as the title paper, the <sup>1</sup>H NMR spectrum of the synthesized compound (4f) provided data that challenge the structural assignment of the proposed target compound.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1570-1575"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100245","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}
Dandan Xie , Lingfen Kong , Jiehua Hu , Heng Li , Yuanpeng Wang
Given the depletion of fossil fuels and the environmental issues they cause, the search for alternative, clean, and renewable energy sources has made significant progress. Among them, the photo-fermentative production of bioenergy stands out as an attractive and environmentally friendly approach. This review comprehensively examines the key biological and technological characteristics and mechanisms involved in the production of biohydrogen and biomethane through photo-fermentation. Specifically, it discusses the use of wastewater or biowaste as feedstocks for photobiological hydrogen production, key factors influencing biohydrogen yields, and various enhancement methods. Building on the insights gained from biohydrogen production, we further explore the processes, methods, and mechanisms for enhancing photo-fermentative biomethane production areas that have not been thoroughly reviewed elsewhere. By linking biohydrogen and biomethane production, this study underscores the complementary roles of these bioenergy sources within a unified photo-fermentative framework. Additionally, it offers a comparative analysis of biohydrogen and biomethane in terms of mechanisms, feedstock utilization, environmental impact, economic viability and efficiency. The aim is to highlight recent advancements in this field, identify challenges and future perspectives, and discuss the potential of photobiological biohydrogen and biomethane as sustainable bioenergy sources.
{"title":"A comparative review of biohydrogen and biomethane production from biowaste through photo-fermentation","authors":"Dandan Xie , Lingfen Kong , Jiehua Hu , Heng Li , Yuanpeng Wang","doi":"10.1039/d4gc06079b","DOIUrl":"10.1039/d4gc06079b","url":null,"abstract":"<div><div>Given the depletion of fossil fuels and the environmental issues they cause, the search for alternative, clean, and renewable energy sources has made significant progress. Among them, the photo-fermentative production of bioenergy stands out as an attractive and environmentally friendly approach. This review comprehensively examines the key biological and technological characteristics and mechanisms involved in the production of biohydrogen and biomethane through photo-fermentation. Specifically, it discusses the use of wastewater or biowaste as feedstocks for photobiological hydrogen production, key factors influencing biohydrogen yields, and various enhancement methods. Building on the insights gained from biohydrogen production, we further explore the processes, methods, and mechanisms for enhancing photo-fermentative biomethane production areas that have not been thoroughly reviewed elsewhere. By linking biohydrogen and biomethane production, this study underscores the complementary roles of these bioenergy sources within a unified photo-fermentative framework. Additionally, it offers a comparative analysis of biohydrogen and biomethane in terms of mechanisms, feedstock utilization, environmental impact, economic viability and efficiency. The aim is to highlight recent advancements in this field, identify challenges and future perspectives, and discuss the potential of photobiological biohydrogen and biomethane as sustainable bioenergy sources.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 5","pages":"Pages 1331-1347"},"PeriodicalIF":9.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100267","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}
Guanzheng Wu, Yu Cheng, Caoxing Huang, Cheng Yong and Yu Fu
The effective processing and utilization of lignocellulosic biomass (LCB) are essential for sustainable development. In this work, we present a novel ternary deep eutectic solvent (DES) system comprising glycerol, potassium carbonate (K2CO3), and polyethylene glycol 200 (PEG-200), designed to enhance the deconstruction of LCB through its low viscosity and improved solubility. The system's low viscosity (2.87–26.48 Pa s) ensures excellent fluidity and accessibility, significantly improving mass and heat transfer during reactions. Furthermore, the increased solubility (39.21–54.66% w/w) further boosts lignin dissolution, leading to more efficient separation. Under optimal conditions, the removal rates of hemicellulose and lignin reached 81.93% and 96.37%, respectively, with a cellulose yield of up to 73.65%. Moreover, the cellulose-rich residues resulting from this process exhibit desirable properties such as high crystallinity, excellent thermal stability, and robust processing capabilities, marking them as valuable materials for efficient downstream processing and applications. The development of this ternary DES system represents a greener and more sustainable approach to LCB treatment, offering a transformative solution poised to advance the future of bio-based industries. This innovative system not only improves the efficiency of biomass processing, but also aligns with environmental sustainability goals, supporting the broader adoption of eco-friendly technologies in industrial applications.
{"title":"Deep eutectic solvent engineering: a novel ternary system for efficient lignocellulose extraction†","authors":"Guanzheng Wu, Yu Cheng, Caoxing Huang, Cheng Yong and Yu Fu","doi":"10.1039/D4GC05138F","DOIUrl":"https://doi.org/10.1039/D4GC05138F","url":null,"abstract":"<p >The effective processing and utilization of lignocellulosic biomass (LCB) are essential for sustainable development. In this work, we present a novel ternary deep eutectic solvent (DES) system comprising glycerol, potassium carbonate (K<small><sub>2</sub></small>CO<small><sub>3</sub></small>), and polyethylene glycol 200 (PEG-200), designed to enhance the deconstruction of LCB through its low viscosity and improved solubility. The system's low viscosity (2.87–26.48 Pa s) ensures excellent fluidity and accessibility, significantly improving mass and heat transfer during reactions. Furthermore, the increased solubility (39.21–54.66% w/w) further boosts lignin dissolution, leading to more efficient separation. Under optimal conditions, the removal rates of hemicellulose and lignin reached 81.93% and 96.37%, respectively, with a cellulose yield of up to 73.65%. Moreover, the cellulose-rich residues resulting from this process exhibit desirable properties such as high crystallinity, excellent thermal stability, and robust processing capabilities, marking them as valuable materials for efficient downstream processing and applications. The development of this ternary DES system represents a greener and more sustainable approach to LCB treatment, offering a transformative solution poised to advance the future of bio-based industries. This innovative system not only improves the efficiency of biomass processing, but also aligns with environmental sustainability goals, supporting the broader adoption of eco-friendly technologies in industrial applications.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 5","pages":" 1556-1569"},"PeriodicalIF":9.3,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107357","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}
Ryo Kato, Eugene Kuatsjah, Masaya Fujita, Alissa C. Bleem, Shojiro Hishiyama, Rui Katahira, Toshiya Senda, Gregg T. Beckham, Naofumi Kamimura and Eiji Masai
Sphingobium lignivorans SYK-6 catabolizes guaiacylglycerol-β-guaiacyl ether (GGE, a β-O-4-type dimer) and 1,2-diguaiacylpropane-1,3-diol (DGPD, a β-1-type dimer) derived from lignin. Recently, SLG_35860 containing TetR- and MarR-type transcriptional regulator motifs was suggested to be involved in the regulation of GGE and DGPD catabolism. Here we investigated the role of SLG_35860 in the transcriptional regulation of GGE and DGPD catabolism genes. SLG_35860 designated ligS repressed 11 genes involved in GGE and DGPD catabolism. LigS binds directly to specific sequences in the promoter region of each gene. The MarR domain was shown to be involved in these bindings; however, GGE, DGPD, and their metabolites did not function as effectors of LigS. We discovered unidentified compound(s) in the black liquor of oxygen-soda anthraquinone pulping of Japanese cedar that SYK-6 cannot metabolize and that acted as effector(s). Therefore, LigS constantly represses the transcription of the GGE and DGPD catabolism genes to low levels. Based on these findings, we examined the productivity of a polymer building block, 2-pyrone-4,6-dicarboxylic acid (PDC), from GGE, DGPD, and a GGE metabolite using an engineered ligS mutant. The rates of PDC production from each compound by this strain were 1.5–6.0 times higher than those of a PDC-producing strain carrying ligS.
{"title":"Metabolic modification of Sphingobium lignivorans SYK-6 for lignin valorization through the discovery of an unusual transcriptional repressor of lignin-derived dimer catabolism†","authors":"Ryo Kato, Eugene Kuatsjah, Masaya Fujita, Alissa C. Bleem, Shojiro Hishiyama, Rui Katahira, Toshiya Senda, Gregg T. Beckham, Naofumi Kamimura and Eiji Masai","doi":"10.1039/D4GC05328A","DOIUrl":"https://doi.org/10.1039/D4GC05328A","url":null,"abstract":"<p > <em>Sphingobium lignivorans</em> SYK-6 catabolizes guaiacylglycerol-β-guaiacyl ether (GGE, a β-O-4-type dimer) and 1,2-diguaiacylpropane-1,3-diol (DGPD, a β-1-type dimer) derived from lignin. Recently, SLG_35860 containing TetR- and MarR-type transcriptional regulator motifs was suggested to be involved in the regulation of GGE and DGPD catabolism. Here we investigated the role of SLG_35860 in the transcriptional regulation of GGE and DGPD catabolism genes. SLG_35860 designated <em>ligS</em> repressed 11 genes involved in GGE and DGPD catabolism. LigS binds directly to specific sequences in the promoter region of each gene. The MarR domain was shown to be involved in these bindings; however, GGE, DGPD, and their metabolites did not function as effectors of LigS. We discovered unidentified compound(s) in the black liquor of oxygen-soda anthraquinone pulping of Japanese cedar that SYK-6 cannot metabolize and that acted as effector(s). Therefore, LigS constantly represses the transcription of the GGE and DGPD catabolism genes to low levels. Based on these findings, we examined the productivity of a polymer building block, 2-pyrone-4,6-dicarboxylic acid (PDC), from GGE, DGPD, and a GGE metabolite using an engineered <em>ligS</em> mutant. The rates of PDC production from each compound by this strain were 1.5–6.0 times higher than those of a PDC-producing strain carrying <em>ligS</em>.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 5","pages":" 1540-1555"},"PeriodicalIF":9.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107403","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}
Robin Coeck, Nathalie Claes, Thomas Cuypers, Sara Bals and Dirk E. De Vos
The reductive amination of fatty acids (FAs) and fatty acid methyl esters (FAMEs) has been identified as a green and effective method to produce N,N-dimethylalkylamines (ADMAs). With current technology, this reaction requires at least two reaction steps. Here, we report a heterogeneous catalytic system for the one-pot synthesis of ADMAs from FA(ME)s, utilizing solely H2 and methylamines (i.e. di- and trimethylamine). The reaction requires two recyclable catalysts: ortho-Nb2O5 for the amidation of FA(ME)s and PtVOx/SiO2 for the hydrogenation of the in situ generated fatty amide to ADMAs. The developed system has a wide range of applicability: it is able to convert all natural FAs to ADMAs (yields up to 90%) and also other tertiary amines were synthesized. Aside from the development of a sustainable and industrially applicable process (e.g. utilizing benign solvents or performing solventless reactions), a kinetic model was developed that describes the reaction rate's relationship with key process parameters such as the H2 pressure and water content. By tuning the reaction conditions, different ratios of primary, secondary and tertiary fatty amines can be obtained.
{"title":"The sustainable and catalytic synthesis of N,N-alkylated fatty amines from fatty acids and esters†","authors":"Robin Coeck, Nathalie Claes, Thomas Cuypers, Sara Bals and Dirk E. De Vos","doi":"10.1039/D4GC05740F","DOIUrl":"https://doi.org/10.1039/D4GC05740F","url":null,"abstract":"<p >The reductive amination of fatty acids (FAs) and fatty acid methyl esters (FAMEs) has been identified as a green and effective method to produce <em>N</em>,<em>N</em>-dimethylalkylamines (ADMAs). With current technology, this reaction requires at least two reaction steps. Here, we report a heterogeneous catalytic system for the one-pot synthesis of ADMAs from FA(ME)s, utilizing solely H<small><sub>2</sub></small> and methylamines (<em>i.e.</em> di- and trimethylamine). The reaction requires two recyclable catalysts: <em>ortho</em>-Nb<small><sub>2</sub></small>O<small><sub>5</sub></small> for the amidation of FA(ME)s and PtVO<small><sub><em>x</em></sub></small>/SiO<small><sub>2</sub></small> for the hydrogenation of the <em>in situ</em> generated fatty amide to ADMAs. The developed system has a wide range of applicability: it is able to convert all natural FAs to ADMAs (yields up to 90%) and also other tertiary amines were synthesized. Aside from the development of a sustainable and industrially applicable process (<em>e.g.</em> utilizing benign solvents or performing solventless reactions), a kinetic model was developed that describes the reaction rate's relationship with key process parameters such as the H<small><sub>2</sub></small> pressure and water content. By tuning the reaction conditions, different ratios of primary, secondary and tertiary fatty amines can be obtained.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 5","pages":" 1410-1422"},"PeriodicalIF":9.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107415","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}
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