Alex Maokhamphiou , Matthieu Zinet , William Guerin , Arnaud Soisson , Morgane Petit , Guillaume Jobard , Fernande da Cruz-Boisson , Karim Delage , Romain Tavernier , Véronique Bounor-Legaré
This study proposes a new and elegant way to synthesize thermosetting phenolic resins through a green, solvent-free and versatile reactive extrusion route. In that frame, terephthalaldehyde (TPA), a non-toxic aromatic dialdehyde, has been selected to replace formaldehyde while resorcinol has been chosen as a replacement of phenol. The syntheses were performed without solvent at temperatures between 150 and 170 °C with a reaction time of around 3 minutes. The resins were synthesized at different TPA-to-resorcinol molar ratios (0.6 and 1.6). This study investigates the mechanism and chemical reactions occurring during the reactive extrusion by characterizing the resin composition through NMR and mass spectrometry (<1500 g mol−1). In addition, differential scanning calorimetry (DSC) analyses were carried out to study the kinetics of the reactions and to estimate the activation energies (32–54 kJ mol−1) through various calculation methods (Flynn–Wall–Ozawa, Friedman, and Vyazovkin methods). It was demonstrated that multiple and consecutive reactions (electrophilic aromatic substitution and condensation) occur during the reactive extrusion process. Additionally, the resins synthesized by reactive extrusion exhibited an exothermic post-reactivity signature in DSC, enabling the estimation of the conversion degrees of 0.63 and 0.59, respectively, for ratios of 0.6 and 1.6. Finally, the resins obtained through reactive extrusion demonstrate great thermal stability even prior to post-heating.
{"title":"Novel sustainable synthesis of a formaldehyde-free thermosetting phenolic resin through solvent-free reactive extrusion†","authors":"Alex Maokhamphiou , Matthieu Zinet , William Guerin , Arnaud Soisson , Morgane Petit , Guillaume Jobard , Fernande da Cruz-Boisson , Karim Delage , Romain Tavernier , Véronique Bounor-Legaré","doi":"10.1039/d4gc05352d","DOIUrl":"10.1039/d4gc05352d","url":null,"abstract":"<div><div>This study proposes a new and elegant way to synthesize thermosetting phenolic resins through a green, solvent-free and versatile reactive extrusion route. In that frame, terephthalaldehyde (TPA), a non-toxic aromatic dialdehyde, has been selected to replace formaldehyde while resorcinol has been chosen as a replacement of phenol. The syntheses were performed without solvent at temperatures between 150 and 170 °C with a reaction time of around 3 minutes. The resins were synthesized at different TPA-to-resorcinol molar ratios (0.6 and 1.6). This study investigates the mechanism and chemical reactions occurring during the reactive extrusion by characterizing the resin composition through NMR and mass spectrometry (<1500 g mol<sup>−1</sup>). In addition, differential scanning calorimetry (DSC) analyses were carried out to study the kinetics of the reactions and to estimate the activation energies (32–54 kJ mol<sup>−1</sup>) through various calculation methods (Flynn–Wall–Ozawa, Friedman, and Vyazovkin methods). It was demonstrated that multiple and consecutive reactions (electrophilic aromatic substitution and condensation) occur during the reactive extrusion process. Additionally, the resins synthesized by reactive extrusion exhibited an exothermic post-reactivity signature in DSC, enabling the estimation of the conversion degrees of 0.63 and 0.59, respectively, for ratios of 0.6 and 1.6. Finally, the resins obtained through reactive extrusion demonstrate great thermal stability even prior to post-heating.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3887-3904"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792993","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}
Li Quan Lee , Hui Ling Chan , Hao Zhou , Hu Zhao , Qingshuo Ao , Hao Huang , Chi Cheng Chong , Yan Zhou , Hong Li
Biofuels, such as biogas, are crucial for a sustainable and green energy future. Biogas can be generated from abundant biomass wastes, e.g., corrugated cardboard waste (CBW), which has surged owing to e-commerce growth. Anaerobic digestion (AD) of CBW to generate biogas is challenged by the rate-limiting step of enzymatic hydrolysis and solid mass transport constraints. To address these issues, acid hydrolysis of carbohydrate components of CBW to a water-soluble sugar mixture is a more efficient alternative. Typical acid hydrolysis employs fossil fuel-derived sulphuric acid as the catalyst, which is unsustainable and may inhibit downstream bioprocesses. Herein, we report a novel mechanochemical-microwave pretreatment strategy that effectively overcomes the mass transport constraint of enzymatic hydrolysis. We replace the commonly used sulphuric acid with a renewable organic acid (e.g., oxalic acid) as a green catalyst. Our new process with a green catalyst exhibits several advantages. The new mechanochemical treatment leveraging the catalytic effect during milling efficiently shrinks the CBW size, disintegrates its structure, and disperses the acid catalyst into CBW particles. The addition of oxalic acid facilitates dual-effect transformation of cellulose by reducing its degree of polymerization and converting crystalline cellulose into reactive amorphous cellulose through esterification of the C6–OH group, which disrupts intra- and intermolecular hydrogen bonds. Building on this, microwave-assisted hydrolysis further breaks down cellulose, where oxalic acid undergoes deprotonation to form hydronium ions, facilitating the cleavage of β-1,4 glycosidic bonds and releasing glucose products. This integrated process enhances overall efficiency and enables a much greener pretreatment. As a result, CBW's recalcitrant complex structure is effectively broken down, achieving a remarkable sugar yield of 52.3 g per 100 g dried CBW. The AD of the treated CBW, without additional separation steps, produced biogas with a high methane content of 69.9%, which is comparable to that of the control pure glucose feed. Notably, this whole-mixture approach significantly simplifies the process and boosts initial methane production without compromising long-term methane production potential. Moreover, life cycle assessment reveals that the process has a global warming potential comparable to that of traditional waste management processes, and the oxalic acid catalyst has a lower environmental impact than sulphuric acid, thus showing promise for enhanced sustainability.
{"title":"Green catalyst-based cardboard waste conversion into biogas†","authors":"Li Quan Lee , Hui Ling Chan , Hao Zhou , Hu Zhao , Qingshuo Ao , Hao Huang , Chi Cheng Chong , Yan Zhou , Hong Li","doi":"10.1039/d5gc00740b","DOIUrl":"10.1039/d5gc00740b","url":null,"abstract":"<div><div>Biofuels, such as biogas, are crucial for a sustainable and green energy future. Biogas can be generated from abundant biomass wastes, <em>e.g.</em>, corrugated cardboard waste (CBW), which has surged owing to e-commerce growth. Anaerobic digestion (AD) of CBW to generate biogas is challenged by the rate-limiting step of enzymatic hydrolysis and solid mass transport constraints. To address these issues, acid hydrolysis of carbohydrate components of CBW to a water-soluble sugar mixture is a more efficient alternative. Typical acid hydrolysis employs fossil fuel-derived sulphuric acid as the catalyst, which is unsustainable and may inhibit downstream bioprocesses. Herein, we report a novel mechanochemical-microwave pretreatment strategy that effectively overcomes the mass transport constraint of enzymatic hydrolysis. We replace the commonly used sulphuric acid with a renewable organic acid (<em>e.g.</em>, oxalic acid) as a green catalyst. Our new process with a green catalyst exhibits several advantages. The new mechanochemical treatment leveraging the catalytic effect during milling efficiently shrinks the CBW size, disintegrates its structure, and disperses the acid catalyst into CBW particles. The addition of oxalic acid facilitates dual-effect transformation of cellulose by reducing its degree of polymerization and converting crystalline cellulose into reactive amorphous cellulose through esterification of the C6–OH group, which disrupts intra- and intermolecular hydrogen bonds. Building on this, microwave-assisted hydrolysis further breaks down cellulose, where oxalic acid undergoes deprotonation to form hydronium ions, facilitating the cleavage of β-1,4 glycosidic bonds and releasing glucose products. This integrated process enhances overall efficiency and enables a much greener pretreatment. As a result, CBW's recalcitrant complex structure is effectively broken down, achieving a remarkable sugar yield of 52.3 g per 100 g dried CBW. The AD of the treated CBW, without additional separation steps, produced biogas with a high methane content of 69.9%, which is comparable to that of the control pure glucose feed. Notably, this whole-mixture approach significantly simplifies the process and boosts initial methane production without compromising long-term methane production potential. Moreover, life cycle assessment reveals that the process has a global warming potential comparable to that of traditional waste management processes, and the oxalic acid catalyst has a lower environmental impact than sulphuric acid, thus showing promise for enhanced sustainability.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3964-3979"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792984","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}
Qiwei Gao , Zhuo Chen , Junrun Feng , Xiaoyan Zhou , Ziming Wan , Lun Zhang , Hao Gu , Lin Sheng , Pengfei Yao , Feng Ryan Wang , Zhangxiang Hao
Aqueous zinc-ion batteries (AZIBs) have become popular for energy storage devices due to their cost-effectiveness, high capacity and environmental friendliness. However, the uncontrolled growth of dendrites and corrosion at the zinc anode have seriously hindered AZIBs’ further development. The construction of protective interface layers is a promising strategy to mitigate and suppress the above problems. Herein, we propose the in situ construction of a protective layer of Sn at the zinc anode by coating a suspension of stannous oxalate, which regulates the zinc nucleation sites and induces the deposition of Zn (002) crystal planes, inhibiting the uncontrolled growth of zinc dendrites. The hydrophobic Sn metal protective layer isolated the contact between the active water and the zinc anode and suppressed the corrosion of the zinc anode. As a result, the modified Zn//Zn symmetric cell has a cycle life of 2300 h at 1 mA cm−2, with a significant reduction in the polarisation overpotential. The MnO2//Zn full cell assembled with the modified Zn anode also showed good performance with a specific capacity of 94.74 mA h g−1 after 1000 cycles. This work exemplifies the potential of metal salts in the development of stable metal electrodes.
{"title":"In situ generated tin protective layers from stannous oxalate for dendrite-free zinc anodes†","authors":"Qiwei Gao , Zhuo Chen , Junrun Feng , Xiaoyan Zhou , Ziming Wan , Lun Zhang , Hao Gu , Lin Sheng , Pengfei Yao , Feng Ryan Wang , Zhangxiang Hao","doi":"10.1039/d4gc06270a","DOIUrl":"10.1039/d4gc06270a","url":null,"abstract":"<div><div>Aqueous zinc-ion batteries (AZIBs) have become popular for energy storage devices due to their cost-effectiveness, high capacity and environmental friendliness. However, the uncontrolled growth of dendrites and corrosion at the zinc anode have seriously hindered AZIBs’ further development. The construction of protective interface layers is a promising strategy to mitigate and suppress the above problems. Herein, we propose the <em>in situ</em> construction of a protective layer of Sn at the zinc anode by coating a suspension of stannous oxalate, which regulates the zinc nucleation sites and induces the deposition of Zn (002) crystal planes, inhibiting the uncontrolled growth of zinc dendrites. The hydrophobic Sn metal protective layer isolated the contact between the active water and the zinc anode and suppressed the corrosion of the zinc anode. As a result, the modified Zn//Zn symmetric cell has a cycle life of 2300 h at 1 mA cm<sup>−2</sup>, with a significant reduction in the polarisation overpotential. The MnO<sub>2</sub>//Zn full cell assembled with the modified Zn anode also showed good performance with a specific capacity of 94.74 mA h g<sup>−1</sup> after 1000 cycles. This work exemplifies the potential of metal salts in the development of stable metal electrodes.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3990-3999"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792986","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}
Bo Zhang , Xiaoling Xiu , Lifeng Chen , Xin Sui , Ruyi Zheng , Yuhe Guo , Xue Cai , Zhiqiang Liu , Yuguo Zheng
l-Cysteine, a vital sulfur-containing amino acid, is extensively utilized in the pharmaceutical, food, cosmetics, and feed industries; it also plays a crucial role in the sulfur cycle on the Earth. Here, we report the development of a plasmid-free engineered Escherichia coli strain for enhanced l-cysteine production. Initially, the l-cysteine/l-cystine shuttle system was restructured to adapt to the new engineered strain. For the critical metabolic node CysE, a genomic multi-copy strategy was employed to enhance its expression extensively, thereby increasing the metabolic flux of the carbon module. A substrate channel for l-cysteine was then constructed to enhance biosynthetic efficiency. The multi-module co-localization strategy was designed to couple the module enzyme with the efflux system, which coordinates the biosynthesis and transport of the product. Moreover, a CysB mutant was screened to promote sulfur assimilation globally. By enhancing the carbon and sulfur module, the strain GCB2 produced 35.54 g L−1 of l-cysteine in a 5 L bioreactor, with a glucose yield of 0.125 g g−1, a sulfur assimilation of 92.44%, and a productivity of 0.555 g L−1 h−1. To our knowledge, this is the highest-known production, laying the foundation for future industrial applications. The strategy we developed in this study can also be applied for the production of other chemicals.
{"title":"Coupling a rebuild shuttle system with biosynthetic pathway and transcription factor engineering for enhanced l-cysteine production†","authors":"Bo Zhang , Xiaoling Xiu , Lifeng Chen , Xin Sui , Ruyi Zheng , Yuhe Guo , Xue Cai , Zhiqiang Liu , Yuguo Zheng","doi":"10.1039/d5gc00433k","DOIUrl":"10.1039/d5gc00433k","url":null,"abstract":"<div><div> <span>l</span>-Cysteine, a vital sulfur-containing amino acid, is extensively utilized in the pharmaceutical, food, cosmetics, and feed industries; it also plays a crucial role in the sulfur cycle on the Earth. Here, we report the development of a plasmid-free engineered <em>Escherichia coli</em> strain for enhanced <span>l</span>-cysteine production. Initially, the <span>l</span>-cysteine/<span>l</span>-cystine shuttle system was restructured to adapt to the new engineered strain. For the critical metabolic node CysE, a genomic multi-copy strategy was employed to enhance its expression extensively, thereby increasing the metabolic flux of the carbon module. A substrate channel for <span>l</span>-cysteine was then constructed to enhance biosynthetic efficiency. The multi-module co-localization strategy was designed to couple the module enzyme with the efflux system, which coordinates the biosynthesis and transport of the product. Moreover, a CysB mutant was screened to promote sulfur assimilation globally. By enhancing the carbon and sulfur module, the strain GCB2 produced 35.54 g L<sup>−1</sup> of <span>l</span>-cysteine in a 5 L bioreactor, with a glucose yield of 0.125 g g<sup>−1</sup>, a sulfur assimilation of 92.44%, and a productivity of 0.555 g L<sup>−1</sup> h<sup>−1</sup>. To our knowledge, this is the highest-known production, laying the foundation for future industrial applications. The strategy we developed in this study can also be applied for the production of other chemicals.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3944-3956"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792997","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}
We developed a uniform, hybrid machine learning (ML) model, integrating both supervised learning (SL) and reinforcement learning (RL), based on several datasets across different CO2 and CH4 conversion reactions in an atmospheric pressure glow discharge plasma, to advance plasma-based CO2 and CH4 conversion. Given its complex and dynamic characteristics, the SL model employs artificial neural networks (ANN) to predict performance, demonstrating excellent alignment with the entire experimental data. The RL model subsequently provides the optimization protocol, which prioritizes coarse adjustments to high-impact parameters then fine-tuning low-impact ones, to obtain the best performance. Furthermore, we also investigated the simultaneous optimization of the syngas ratio (SR) and energy cost (EC), resulting in a maximum SR of 2.12, combined with a minimum EC (syngas) of 2.04 eV per molecule (i.e., 352 kJ mol−1), which is close to the best experimental data obtained for further methanol synthesis, when accounting for suitable weighting between SR and EC in the model. Our study emphasizes the importance of interpreting ML results based on prior knowledge and human analysis. We hope this work encourages a more critical view on the application of ML when studying plasma-based gas conversion.
{"title":"Machine learning-based prediction and optimization of plasma-based conversion of CO2 and CH4 in an atmospheric pressure glow discharge plasma†","authors":"Jiayin Li , Jing Xu , Evgeny Rebrov , Bart Wanten , Annemie Bogaerts","doi":"10.1039/d5gc00301f","DOIUrl":"10.1039/d5gc00301f","url":null,"abstract":"<div><div>We developed a uniform, hybrid machine learning (ML) model, integrating both supervised learning (SL) and reinforcement learning (RL), based on several datasets across different CO<sub>2</sub> and CH<sub>4</sub> conversion reactions in an atmospheric pressure glow discharge plasma, to advance plasma-based CO<sub>2</sub> and CH<sub>4</sub> conversion. Given its complex and dynamic characteristics, the SL model employs artificial neural networks (ANN) to predict performance, demonstrating excellent alignment with the entire experimental data. The RL model subsequently provides the optimization protocol, which prioritizes coarse adjustments to high-impact parameters then fine-tuning low-impact ones, to obtain the best performance. Furthermore, we also investigated the simultaneous optimization of the syngas ratio (SR) and energy cost (EC), resulting in a maximum SR of 2.12, combined with a minimum EC (syngas) of 2.04 eV per molecule (<em>i.e.</em>, 352 kJ mol<sup>−1</sup>), which is close to the best experimental data obtained for further methanol synthesis, when accounting for suitable weighting between SR and EC in the model. Our study emphasizes the importance of interpreting ML results based on prior knowledge and human analysis. We hope this work encourages a more critical view on the application of ML when studying plasma-based gas conversion.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3916-3931"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792995","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}
Zulin Xiao , Wenzhe Shang , Lei He , Tao Huang , Yuxin Xiao , Xiaoxia He , Xiang Li , Xueping Zong , Yidong Wan , Fusheng Li
The propargylation of imines is an effective means for constructing of homopropargyl amines, which are widely used in the synthesis of bioactive compounds and complex functional molecules. The traditional method involves nucleophilic addition to imines; however, the use of transition metals, harsh conditions, and limited tolerance of functional groups do not align with the principles of green synthesis. Herein, we developed an alternative metal-free catalyzed protocol that involves the propargylation of imines. Mechanistic studies demonstrate that the reaction likely involves the photocatalytic generation of α-amino radicals and propargyl radicals, followed by radical–radical cross-coupling. DFT calculations show that the C–C coupling of the α-aminyl radical and propargyl radical (ΔH = −36.74 kcal mol−1) is the most favorable. This method offers mild conditions, good functional group compatibility, readily available raw materials, a wide substrate scope, and excellent chemo- and regioselectivity. Furthermore, the homopropargyl amines could undergo various functional transformations under general conditions.
{"title":"Photoredox-catalyzed chemo- and regioselective synthesis of homopropargyl amines via radical–radical cross-coupling†","authors":"Zulin Xiao , Wenzhe Shang , Lei He , Tao Huang , Yuxin Xiao , Xiaoxia He , Xiang Li , Xueping Zong , Yidong Wan , Fusheng Li","doi":"10.1039/d4gc06252c","DOIUrl":"10.1039/d4gc06252c","url":null,"abstract":"<div><div>The propargylation of imines is an effective means for constructing of homopropargyl amines, which are widely used in the synthesis of bioactive compounds and complex functional molecules. The traditional method involves nucleophilic addition to imines; however, the use of transition metals, harsh conditions, and limited tolerance of functional groups do not align with the principles of green synthesis. Herein, we developed an alternative metal-free catalyzed protocol that involves the propargylation of imines. Mechanistic studies demonstrate that the reaction likely involves the photocatalytic generation of α-amino radicals and propargyl radicals, followed by radical–radical cross-coupling. DFT calculations show that the C–C coupling of the α-aminyl radical and propargyl radical (Δ<em>H</em> = −36.74 kcal mol<sup>−1</sup>) is the most favorable. This method offers mild conditions, good functional group compatibility, readily available raw materials, a wide substrate scope, and excellent chemo- and regioselectivity. Furthermore, the homopropargyl amines could undergo various functional transformations under general conditions.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 15","pages":"Pages 3957-3963"},"PeriodicalIF":9.3,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792998","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}
Hye Jin Lee, Yoonjae Lee, Eun-hyeok Yang, Jiyun Yoo, Seungjun Choi, Soonho Hwangbo, Young-Woong Suh, Jayeon Baek, Jeehoon Han and Yong Jin Kim
Correction for ‘Environmentally friendly process design for furan-based long-chain diester production aiming for bio-based lubricants’ by Hye Jin Lee et al., Green Chem., 2025, 27, 607–622, https://doi.org/10.1039/D4GC04191G.
对 Hye Jin Lee 等人的 "以生物基润滑油为目标的呋喃基长链二酯生产的环境友好型工艺设计 "的更正，《绿色化学》，2025 年，27 期，607-622，https://doi.org/10.1039/D4GC04191G。
{"title":"Correction: Environmentally friendly process design for furan-based long-chain diester production aiming for bio-based lubricants","authors":"Hye Jin Lee, Yoonjae Lee, Eun-hyeok Yang, Jiyun Yoo, Seungjun Choi, Soonho Hwangbo, Young-Woong Suh, Jayeon Baek, Jeehoon Han and Yong Jin Kim","doi":"10.1039/D5GC90039E","DOIUrl":"https://doi.org/10.1039/D5GC90039E","url":null,"abstract":"<p >Correction for ‘Environmentally friendly process design for furan-based long-chain diester production aiming for bio-based lubricants’ by Hye Jin Lee <em>et al.</em>, <em>Green Chem.</em>, 2025, <strong>27</strong>, 607–622, https://doi.org/10.1039/D4GC04191G.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 12","pages":" 3363-3363"},"PeriodicalIF":9.3,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d5gc90039e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632311","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}
Gilvan A. Correia , Chris H. J. Franco , Marina V. Kirillova , Fabrice Gallou , Alexander M. Kirillov
The development of sustainable protocols for the conversion of renewables such as terpenes into value-added products is currently in high demand, which motivates the search for inexpensive and environmentally tolerable catalytic systems and reaction conditions. In the present study, three new prospective catalysts featuring mono-, di-, and tricopper(ii) cores were easily assembled in aqueous ethanol medium from copper(ii) ions, amino alcohol and carboxylic acid ligands. Their catalytic performance was evaluated in water under micellar conditions with 1% of PS-750-M surfactant, while studying the mild oxidation of α-pinene as an abundant, low-cost, and renewable feedstock. A water-soluble monocopper(ii) complex proved to be the most promising catalyst for the oxidation of α-pinene with tert-butyl hydroperoxide under micellar conditions, leading to high substrate conversion (87%) and good yields of the main products (tert-butylperoxy-2-pinene, verbenone, and pinene oxide). A partially water-soluble 1D coordination polymer based on dicopper(ii) units also showed a notable catalytic behavior. The effects of different reaction parameters and mechanistic features were investigated. This work opens up the use of micellar catalysis systems and aqueous-medium conditions for the oxidative functionalization of α-pinene and other terpene feedstocks into value-added products.
{"title":"Adding value to terpenes: copper-catalyzed oxidation of α-pinene in water under micellar conditions†","authors":"Gilvan A. Correia , Chris H. J. Franco , Marina V. Kirillova , Fabrice Gallou , Alexander M. Kirillov","doi":"10.1039/d4gc06525e","DOIUrl":"10.1039/d4gc06525e","url":null,"abstract":"<div><div>The development of sustainable protocols for the conversion of renewables such as terpenes into value-added products is currently in high demand, which motivates the search for inexpensive and environmentally tolerable catalytic systems and reaction conditions. In the present study, three new prospective catalysts featuring mono-, di-, and tricopper(<span>ii</span>) cores were easily assembled in aqueous ethanol medium from copper(<span>ii</span>) ions, amino alcohol and carboxylic acid ligands. Their catalytic performance was evaluated in water under micellar conditions with 1% of PS-750-M surfactant, while studying the mild oxidation of α-pinene as an abundant, low-cost, and renewable feedstock. A water-soluble monocopper(<span>ii</span>) complex proved to be the most promising catalyst for the oxidation of α-pinene with <em>tert</em>-butyl hydroperoxide under micellar conditions, leading to high substrate conversion (87%) and good yields of the main products (<em>tert</em>-butylperoxy-2-pinene, verbenone, and pinene oxide). A partially water-soluble 1D coordination polymer based on dicopper(<span>ii</span>) units also showed a notable catalytic behavior. The effects of different reaction parameters and mechanistic features were investigated. This work opens up the use of micellar catalysis systems and aqueous-medium conditions for the oxidative functionalization of α-pinene and other terpene feedstocks into value-added products.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3178-3185"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06525e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632294","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}
Helena Gómez-Álvarez , Carlos del Cerro-Sánchez , Pablo Iturbe , Virginia Rivero-Buceta , Juan Nogales , Timothy D. H. Bugg , Eduardo Díaz
The design of new biocatalysts for funneling lignin depolymerization-derived dimers into added-value compounds is nowadays a major challenge in biological lignin valorization. Biphenyl 5,5′-dehydrodivanillate (DDVA) is a model-lignin dimer that contains the C5–C5′ linkage commonly found in lignin depolymerization mixtures. In this work, the metabolic potential of the industrially relevant Pseudomonas putida KT2440 bacterial strain was broadened by expressing synthetic DNA modules encoding selected metabolic and transport steps from the well-characterized DDVA degradation pathway of the Sphingobium lignivorans SYK-6 strain. By employing this heterologous expression strategy, we successfully developed an unprecedented resting cell-based bioprocess to convert DDVA into 5-carboxyvanillic acid (5CVA), a promising building block for the production of innovative bio-based polymers. This proof-of-concept study underscores the essential role of the associated DDVA transport systems. Furthermore, the findings reveal that P. putida KT2440 serves as an effective bacterial chassis for biotechnological processes that require the uptake of substrates through specific TonB-dependent transporters.
{"title":"Bioconversion of a lignin-derived biphenyl dimer into the strategic building block 5-carboxyvanillic acid in Pseudomonas putida KT2440†","authors":"Helena Gómez-Álvarez , Carlos del Cerro-Sánchez , Pablo Iturbe , Virginia Rivero-Buceta , Juan Nogales , Timothy D. H. Bugg , Eduardo Díaz","doi":"10.1039/d4gc06537a","DOIUrl":"10.1039/d4gc06537a","url":null,"abstract":"<div><div>The design of new biocatalysts for funneling lignin depolymerization-derived dimers into added-value compounds is nowadays a major challenge in biological lignin valorization. Biphenyl 5,5′-dehydrodivanillate (DDVA) is a model-lignin dimer that contains the C<sub>5</sub>–C<sub>5′</sub> linkage commonly found in lignin depolymerization mixtures. In this work, the metabolic potential of the industrially relevant <em>Pseudomonas putida</em> KT2440 bacterial strain was broadened by expressing synthetic DNA modules encoding selected metabolic and transport steps from the well-characterized DDVA degradation pathway of the <em>Sphingobium lignivorans</em> SYK-6 strain. By employing this heterologous expression strategy, we successfully developed an unprecedented resting cell-based bioprocess to convert DDVA into 5-carboxyvanillic acid (5CVA), a promising building block for the production of innovative bio-based polymers. This proof-of-concept study underscores the essential role of the associated DDVA transport systems. Furthermore, the findings reveal that <em>P. putida</em> KT2440 serves as an effective bacterial chassis for biotechnological processes that require the uptake of substrates through specific TonB-dependent transporters.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3197-3206"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06537a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632296","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}
Jingying Chen , Deelan Yen Chan , TaoTao Yang , Daniele Parisi , Bart Reuvers , Theo Veldhuis , Francesco Picchioni , Jing Wu , Patrizio Raffa , Cor Koning
In this study, cross-linker free, fully bio-based, biodegradable superabsorbent polymers (SAPs) were synthesized from the multi-functional monomers citric acid (CA), monosodium citrate (MSC) and glycerol (GLY) by polycondensation and subsequent thermal self-cross-linking. All monomers (CA, MSC, GLY) used in this study were not only bio-based but also non-toxic. All of them contain more than two hydrophilic groups in one molecule, which shows great potential to be used in the production of SAPs. The structure, water absorbance capacity and biodegradability of the resulting SAPs were investigated in detail. Upon removal of the soluble fraction, the SAPs have a gel content of approximately 60% and exhibit a maximum absorption capacity of deionized water of 24 ± 2 g g−1. Moreover, the prepared SAPs show good biodegradability at 25 °C (40% biodegradability after 28 days) in an activated sludge-containing medium and are accordingly promising eco-friendly materials for potential use in our environment, not generating persistent microplastics like commercial non-biodegradable SAPs based on neutralized polyacrylic acid and polyacrylamides. Therefore, the bio-based SAPs described in this paper have promising application potential for the sustainable chemical industries including hygiene products and agricultural products, e.g. controlled-release fertilizer coatings and soil improvers.
{"title":"Bio-degradable, fully bio-based, thermally cross-linked superabsorbent polymers from citric acid and glycerol†","authors":"Jingying Chen , Deelan Yen Chan , TaoTao Yang , Daniele Parisi , Bart Reuvers , Theo Veldhuis , Francesco Picchioni , Jing Wu , Patrizio Raffa , Cor Koning","doi":"10.1039/d4gc06323f","DOIUrl":"10.1039/d4gc06323f","url":null,"abstract":"<div><div>In this study, cross-linker free, fully bio-based, biodegradable superabsorbent polymers (SAPs) were synthesized from the multi-functional monomers citric acid (CA), monosodium citrate (MSC) and glycerol (GLY) by polycondensation and subsequent thermal self-cross-linking. All monomers (CA, MSC, GLY) used in this study were not only bio-based but also non-toxic. All of them contain more than two hydrophilic groups in one molecule, which shows great potential to be used in the production of SAPs. The structure, water absorbance capacity and biodegradability of the resulting SAPs were investigated in detail. Upon removal of the soluble fraction, the SAPs have a gel content of approximately 60% and exhibit a maximum absorption capacity of deionized water of 24 ± 2 g g<sup>−1</sup>. Moreover, the prepared SAPs show good biodegradability at 25 °C (40% biodegradability after 28 days) in an activated sludge-containing medium and are accordingly promising eco-friendly materials for potential use in our environment, not generating persistent microplastics like commercial non-biodegradable SAPs based on neutralized polyacrylic acid and polyacrylamides. Therefore, the bio-based SAPs described in this paper have promising application potential for the sustainable chemical industries including hygiene products and agricultural products, <em>e.g.</em> controlled-release fertilizer coatings and soil improvers.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3234-3247"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06323f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632299","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}
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