The three-dimensional permanent cross-linked network formed by cross-linkers after curing can endow coated fabrics with excellent mechanical properties and washing resistance. However, their insoluble and nonmelting nature makes it challenging to peel the coatings from the fabric surface, seriously hindering the recycling and reuse of waste textiles. To address this issue, this study successfully constructed a fluorine-free superhydrophobic coating on cotton fabric that features mechanical robustness, high durability, self-healing capability and on-demand peelability by incorporating covalent adaptable networks (CANs) consisting of imine and C–N bonds into the superhydrophobic coating system. The coatings are fabricated through the aldehyde-amine Schiff-base reaction between polylysine and aldehyde-modified cotton fabric, as well as the Michael addition reaction with styrene–butadiene rubber (SBR) emulsions. Benefiting from the mechanical reinforcement of the CANs, the coated fabrics exhibit excellent washability and sanding abrasion resistance; meanwhile, thermal-induced dynamic exchange of the CANs can heal coating damages, further enhancing the durability of the superhydrophobic coating. In addition, leveraging the acid-triggered dissociation characteristic of dynamic imine bonds, the coating achieves gentle peeling (∼92.4% peeling rate) after prewetting with ethanol, acid treatment, and scrubbing with continuous water. The peeling solution is environmentally friendly and causes moderate damage to the fibers (∼26%). This study provides a viable pathway for the design of next-generation coating systems and the recycling and regeneration of waste textiles, aligning with the goals of cleaner production and sustainable resource utilization.
{"title":"Structural Design and Interface Peeling of Superhydrophobic Coatings for the Recycling of Waste Coated Textiles","authors":"Linhao Cai, Yinghui Wang, Maxiaoqi Zhu, Hui Li, Xin Lin, Liulu Zhang, Jiaxin Chen, Yu Wang, Ming Yang, Zijun Yi, Wen Zhang, Yingjie Cai","doi":"10.1021/acssuschemeng.5c10755","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10755","url":null,"abstract":"The three-dimensional permanent cross-linked network formed by cross-linkers after curing can endow coated fabrics with excellent mechanical properties and washing resistance. However, their insoluble and nonmelting nature makes it challenging to peel the coatings from the fabric surface, seriously hindering the recycling and reuse of waste textiles. To address this issue, this study successfully constructed a fluorine-free superhydrophobic coating on cotton fabric that features mechanical robustness, high durability, self-healing capability and on-demand peelability by incorporating covalent adaptable networks (CANs) consisting of imine and C–N bonds into the superhydrophobic coating system. The coatings are fabricated through the aldehyde-amine Schiff-base reaction between polylysine and aldehyde-modified cotton fabric, as well as the Michael addition reaction with styrene–butadiene rubber (SBR) emulsions. Benefiting from the mechanical reinforcement of the CANs, the coated fabrics exhibit excellent washability and sanding abrasion resistance; meanwhile, thermal-induced dynamic exchange of the CANs can heal coating damages, further enhancing the durability of the superhydrophobic coating. In addition, leveraging the acid-triggered dissociation characteristic of dynamic imine bonds, the coating achieves gentle peeling (∼92.4% peeling rate) after prewetting with ethanol, acid treatment, and scrubbing with continuous water. The peeling solution is environmentally friendly and causes moderate damage to the fibers (∼26%). This study provides a viable pathway for the design of next-generation coating systems and the recycling and regeneration of waste textiles, aligning with the goals of cleaner production and sustainable resource utilization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098327","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}
Pterostilbene is a bioactive compound with diverse health-promoting properties and has garnered growing interest in biomedical and industrial applications. However, traditional production methods based on plant extraction or chemical synthesis are limited by a low yield, high cost, and sustainability concerns. Microbial fermentation therefore represents a promising alternative for scalable and ecofriendly pterostilbene production. In this study, a comprehensive multiomics analysis was conducted to elucidate the mechanisms underlying efficient de novo pterostilbene biosynthesis in engineered Escherichia coli. The high-producing strain exhibited enhanced energy generation, improved precursor and cofactor availability, and a reprogrammed oxidative stress response. Guided by these omics insights, targeted genetic modifications further increased the pterostilbene yield, with the optimized strain achieving a titer of 150.47 mg/L, which is the highest de novo production reported to date in a bacterial system. These findings highlight the potential of E. coli as a robust platform for the biosynthesis of value-added natural products and provide a rational framework for engineering microbial cell factories optimized for biosynthetic pathways that are both energetically demanding and redox-regulated.
{"title":"Multiomics Elucidation and Engineering Optimization of Efficient Pterostilbene Biosynthesis in Escherichia coli","authors":"Zhibo Yan, Yong Liu, Ling Qin, Yuping Shen, Mingtao Huang, Jian-Zhong Liu","doi":"10.1021/acssuschemeng.5c11378","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11378","url":null,"abstract":"Pterostilbene is a bioactive compound with diverse health-promoting properties and has garnered growing interest in biomedical and industrial applications. However, traditional production methods based on plant extraction or chemical synthesis are limited by a low yield, high cost, and sustainability concerns. Microbial fermentation therefore represents a promising alternative for scalable and ecofriendly pterostilbene production. In this study, a comprehensive multiomics analysis was conducted to elucidate the mechanisms underlying efficient <i>de novo</i> pterostilbene biosynthesis in engineered <i>Escherichia coli</i>. The high-producing strain exhibited enhanced energy generation, improved precursor and cofactor availability, and a reprogrammed oxidative stress response. Guided by these omics insights, targeted genetic modifications further increased the pterostilbene yield, with the optimized strain achieving a titer of 150.47 mg/L, which is the highest <i>de novo</i> production reported to date in a bacterial system. These findings highlight the potential of <i>E. coli</i> as a robust platform for the biosynthesis of value-added natural products and provide a rational framework for engineering microbial cell factories optimized for biosynthetic pathways that are both energetically demanding and redox-regulated.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098330","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}
Mycelium-based composite (MBC) shows great potential for replacing petroleum-based plastic products in various engineering applications, but its inefficient biomanufacturing has long been a significant challenge for upscale production and industrialization. This paper presents a novel and efficient preparation of MBC from the ingenious mixture of lignin-rich Camellia oleifera Abel. shell (COS) and the lignin-first fungus Ganoderma sessile (G. sessile). The preparation process has been reduced from 2–6 weeks to 8 days by combining liquid and solid-state fermentations. The chemical and physical pathways of COS and mycelium during solid-state fermentation were specifically explored to elucidate the transformation mechanism of the composite. The adhesive-free, layered, porous structure with different particle sizes of COS provided the developed MBC with a superb compressive strength of up to 0.73 MPa and a low thermal conductivity of up to 0.041 (±0.001) W m–1 K–1. The protein-rich mycelium network within and on the surface grants the developed MBC (peak heat release rate of 121.7 kW m–2) with superior fire resistance over the widely used expanded polystyrene (peak heat release rate of 177.3 kW m–2). This work not only offers an effective solution of valorizing COS agroforestry waste but also establishes an efficient, feasible process of MBC manufacturing.
{"title":"Chemical and Physical Insights of Efficient Conversion of Lignin-Rich Camellia oleifera Shell to Thermal and Fire Resistant Mycelium-Based Composite","authors":"Zijie Zhong, Jiawei Huang, Chenchen Wang, Yonghui Zhou, Meiyan Yang, Jilei Fu, Jia Shao, Chuanshuang Hu","doi":"10.1021/acssuschemeng.5c11478","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11478","url":null,"abstract":"Mycelium-based composite (MBC) shows great potential for replacing petroleum-based plastic products in various engineering applications, but its inefficient biomanufacturing has long been a significant challenge for upscale production and industrialization. This paper presents a novel and efficient preparation of MBC from the ingenious mixture of lignin-rich <i>Camellia oleifera</i> Abel. shell (COS) and the lignin-first fungus <i>Ganoderma sessile</i> (<i>G. sessile</i>). The preparation process has been reduced from 2–6 weeks to 8 days by combining liquid and solid-state fermentations. The chemical and physical pathways of COS and mycelium during solid-state fermentation were specifically explored to elucidate the transformation mechanism of the composite. The adhesive-free, layered, porous structure with different particle sizes of COS provided the developed MBC with a superb compressive strength of up to 0.73 MPa and a low thermal conductivity of up to 0.041 (±0.001) W m<sup>–1</sup> K<sup>–1</sup>. The protein-rich mycelium network within and on the surface grants the developed MBC (peak heat release rate of 121.7 kW m<sup>–2</sup>) with superior fire resistance over the widely used expanded polystyrene (peak heat release rate of 177.3 kW m<sup>–2</sup>). This work not only offers an effective solution of valorizing COS agroforestry waste but also establishes an efficient, feasible process of MBC manufacturing.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"97 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098331","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}
Pub Date : 2026-01-30DOI: 10.1021/acssuschemeng.5c13556
Jiahao Wang, Boyang Li, Nuo Cheng, Peng Xu, Qiang Feng, Xiaolong Li, Shukun Shen, Daodao Hu, Jintao Wan
Thymol-based bio-epoxy resins have recently garnered increased interest, but thymol-derived amine curing agents for epoxies remain little known. Herein starting from thymol-derived bisphenol E with 100% bio-based content, a bio-based aromatic diamine (DABP) is synthesized efficiently in 93% yield by attaching amino-substituted diphenyl ether moieties. DABP is used a hardener to cross-link two different epoxies, i.e., a conventional bisphenol A epoxy resin (E54) and a bio-based thymol bisphenol E (DHEP) one, while 4,4′-diaminodiphenyl ether (ODA) is used as a benchmarking hardener, with partially bio-based (DABP/E54), fully bio-based (DABP/DHEP), and fossil-based ODA/E54 epoxy formulations obtained. DABP is well compatible with both epoxies with improved processability and good curing reactivity. The DABP/E54, DABP/DHEP, and ODA/E54 thermosets exhibit Tg of 149, 179, and 182 °C, respectively, and high gel contents (>97%). Compared with ODA, DABP delivers lower absorption (1.7% vs 3.5%) in boiling water, much higher fracture toughness and energy (0.82 vs 0.69 MPa·m1/2 and 0.91 vs 0.32 kJ/m2), lower dielectric loss factor (0.009 vs 0.011 at 10 MHz), and higher adhesion strength (12.2 vs 10.1 MPa) to its cured E54 formulations. Furthermore, DABP/DHEP having more thymol building blocks demonstrates more outstanding performance (water absorption = 1.1%, adhesion strength = 26.8 MPa, and fracture energy = 1.13 kJ/m2), far better than those of ODA/E54. Taken together, DABP could be efficiently synthesized from bio-based and bulk feedstocks, be well compatible with epoxies, and endow the resultant thermosets with multiple advantages. In particular, the combination of DABP and DHEP delivers superior properties, exhibiting its promise as a structural adhesive.
以百里香为基础的生物环氧树脂最近获得了越来越多的兴趣，但百里香衍生的胺固化剂用于环氧树脂仍然知之甚少。以百里香衍生的100%生物基双酚E为原料，结合氨基取代二苯基醚，以93%的收率高效合成了生物基芳香二胺（DABP）。DABP被用作交联两种不同环氧树脂的硬化剂，即传统的双酚a环氧树脂（E54）和生物基百里酚双酚E (DHEP)，而4,4 ' -二氨基二苯醚（ODA）被用作基准硬化剂，得到部分生物基（DABP/E54）、完全生物基（DABP/DHEP）和化石基ODA/E54环氧树脂配方。DABP与两种环氧树脂均有良好的相容性，具有较好的加工性能和良好的固化反应性。DABP/E54、DABP/DHEP和ODA/E54热固性材料的Tg分别为149℃、179℃和182℃，凝胶含量高（97%）。与ODA相比，DABP在沸水中的吸收率更低（1.7% vs 3.5%），断裂韧性和能量更高（0.82 vs 0.69 MPa·m1/2和0.91 vs 0.32 kJ/m2），介质损耗系数更低（10 MHz时0.009 vs 0.011），粘附强度更高（12.2 vs 10.1 MPa）。此外，含有更多百里酚组成块的DABP/DHEP的吸水率为1.1%，粘接强度为26.8 MPa，断裂能为1.13 kJ/m2，其性能远优于ODA/E54。综上所述，DABP可以高效地从生物基和大宗原料中合成，与环氧树脂具有良好的相容性，并赋予所得热固性材料多种优势。特别是，DABP和DHEP的组合提供了卓越的性能，展示了其作为结构粘合剂的前景。
{"title":"Thymol-Based Aromatic Diamine Hardener from Efficient Synthesis to High-Performance Fully Bio-Based Epoxy Thermosets and High-Strength Adhesives","authors":"Jiahao Wang, Boyang Li, Nuo Cheng, Peng Xu, Qiang Feng, Xiaolong Li, Shukun Shen, Daodao Hu, Jintao Wan","doi":"10.1021/acssuschemeng.5c13556","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13556","url":null,"abstract":"Thymol-based bio-epoxy resins have recently garnered increased interest, but thymol-derived amine curing agents for epoxies remain little known. Herein starting from thymol-derived bisphenol E with 100% bio-based content, a bio-based aromatic diamine (DABP) is synthesized efficiently in 93% yield by attaching amino-substituted diphenyl ether moieties. DABP is used a hardener to cross-link two different epoxies, i.e., a conventional bisphenol A epoxy resin (E54) and a bio-based thymol bisphenol E (DHEP) one, while 4,4′-diaminodiphenyl ether (ODA) is used as a benchmarking hardener, with partially bio-based (DABP/E54), fully bio-based (DABP/DHEP), and fossil-based ODA/E54 epoxy formulations obtained. DABP is well compatible with both epoxies with improved processability and good curing reactivity. The DABP/E54, DABP/DHEP, and ODA/E54 thermosets exhibit <i>T</i><sub>g</sub> of 149, 179, and 182 °C, respectively, and high gel contents (>97%). Compared with ODA, DABP delivers lower absorption (1.7% vs 3.5%) in boiling water, much higher fracture toughness and energy (0.82 vs 0.69 MPa·m<sup>1/2</sup> and 0.91 vs 0.32 kJ/m<sup>2</sup>), lower dielectric loss factor (0.009 vs 0.011 at 10 MHz), and higher adhesion strength (12.2 vs 10.1 MPa) to its cured E54 formulations. Furthermore, DABP/DHEP having more thymol building blocks demonstrates more outstanding performance (water absorption = 1.1%, adhesion strength = 26.8 MPa, and fracture energy = 1.13 kJ/m<sup>2</sup>), far better than those of ODA/E54. Taken together, DABP could be efficiently synthesized from bio-based and bulk feedstocks, be well compatible with epoxies, and endow the resultant thermosets with multiple advantages. In particular, the combination of DABP and DHEP delivers superior properties, exhibiting its promise as a structural adhesive.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098334","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}
Heterologous biosynthesis of paclitaxel (Taxol) has recently become a hot research topic due to its potential to alleviate resource scarcity and shorten production cycles. However, the poor expression and low efficiency of catalytic components and challenges in combinatorial regulation remain critical bottlenecks, hindering the efficient synthesis of paclitaxel and its intermediates. In this study, we constructed an early stage biosynthesis pathway of paclitaxel from glycerol in an Escherichia coli (E. coli) cell factory. A 10.3-fold increase in taxadiene titer (up to 131 mg/L) was achieved through the engineering of isopentenyl diphosphate isomerase and geranylgeranyl diphosphate synthase, accompanied by a substrate channeling strategy. Promoter and protein engineering were then employed to optimize the production of taxadien-5α-ol and taxadien-5α-yl-acetate, resulting in titers of 17.9 and 7.6 mg/L, respectively. Finally, cofactor engineering strategies involving intracellular heme supplementation and NADPH regeneration were applied to synthesize taxadiene-5α,10β-diol-5-acetate, yielding titers of 8.7 mg/L in shake-flask cultivation and 18.5 mg/L in a 5 L jar fermenter. To the best of our knowledge, this represents the highest level reported to date in E. coli. The engineered strains and enzymes constructed in this study will serve as a solid foundation for subsequent paclitaxel biosynthesis, and the engineering strategies employed here may be applied to the de novo biosynthesis of terpenoids in microbial cell factories.
{"title":"Reconstruction of the Early Stage Paclitaxel Biosynthesis Pathway in Escherichia coli by Integrating Enzyme and Metabolic Engineering Approaches","authors":"Wen-Liang Xie, Chen-Yi Sun, Chun-Xiu Li, Gao-Wei Zheng, Jian-He Xu","doi":"10.1021/acssuschemeng.5c11338","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11338","url":null,"abstract":"Heterologous biosynthesis of paclitaxel (Taxol) has recently become a hot research topic due to its potential to alleviate resource scarcity and shorten production cycles. However, the poor expression and low efficiency of catalytic components and challenges in combinatorial regulation remain critical bottlenecks, hindering the efficient synthesis of paclitaxel and its intermediates. In this study, we constructed an early stage biosynthesis pathway of paclitaxel from glycerol in an <i>Escherichia coli</i> (<i>E. coli</i>) cell factory. A 10.3-fold increase in taxadiene titer (up to 131 mg/L) was achieved through the engineering of isopentenyl diphosphate isomerase and geranylgeranyl diphosphate synthase, accompanied by a substrate channeling strategy. Promoter and protein engineering were then employed to optimize the production of taxadien-5α-ol and taxadien-5α-yl-acetate, resulting in titers of 17.9 and 7.6 mg/L, respectively. Finally, cofactor engineering strategies involving intracellular heme supplementation and NADPH regeneration were applied to synthesize taxadiene-5α,10β-diol-5-acetate, yielding titers of 8.7 mg/L in shake-flask cultivation and 18.5 mg/L in a 5 L jar fermenter. To the best of our knowledge, this represents the highest level reported to date in <i>E. coli</i>. The engineered strains and enzymes constructed in this study will serve as a solid foundation for subsequent paclitaxel biosynthesis, and the engineering strategies employed here may be applied to the <i>de novo</i> biosynthesis of terpenoids in microbial cell factories.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089918","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}
Pub Date : 2026-01-30DOI: 10.1021/acssuschemeng.5c10534
Zhejian Cao, Nihal Kottan, Santosh Pandit, Jian Zhang, Maria Faresjö, Francoise M. Amombo Noa, Lars Öhrström, Ivan Mijakovic
Mechano-bactericidal (MB) surfaces mitigate the formation of bacterial biofilm through physical interactions without the use of antibiotics. One challenge of MB surfaces is that unremoved dead bacteria and other debris on MB surfaces could impede contact between bacteria and surface nanostructures, thus reducing their bactericidal efficiency. Herein, we report metal–organic framework (MOF)–polycaprolactone (PCL) composites as self-cleaning MB surfaces. The MIL-88B-on-UiO-66 (MoU) hybrids with nano features provide MB actions and PCL with biodegradability enables surface cleaning and refreshment. The MoU-PCL composite demonstrated effective antibacterial performance toward Pseudomonas aeruginosa (77.0%) and Staphylococcus epidermidis (89.6%) for 72 h growth. The surface degradation of MoU-PCL composites over 4 weeks confirmed the feasibility of removing surface debris and dangling MOFs to offer long-term MB performance. Our approach enables the development of MB surfaces for applications requiring a relatively long service period.
{"title":"Self-Cleaning Mechano-Bactericidal Surfaces by Metal–Organic Framework Embedded Polycaprolactone Composites","authors":"Zhejian Cao, Nihal Kottan, Santosh Pandit, Jian Zhang, Maria Faresjö, Francoise M. Amombo Noa, Lars Öhrström, Ivan Mijakovic","doi":"10.1021/acssuschemeng.5c10534","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10534","url":null,"abstract":"Mechano-bactericidal (MB) surfaces mitigate the formation of bacterial biofilm through physical interactions without the use of antibiotics. One challenge of MB surfaces is that unremoved dead bacteria and other debris on MB surfaces could impede contact between bacteria and surface nanostructures, thus reducing their bactericidal efficiency. Herein, we report metal–organic framework (MOF)–polycaprolactone (PCL) composites as self-cleaning MB surfaces. The MIL-88B-on-UiO-66 (MoU) hybrids with nano features provide MB actions and PCL with biodegradability enables surface cleaning and refreshment. The MoU-PCL composite demonstrated effective antibacterial performance toward <i>Pseudomonas aeruginosa</i> (77.0%) and <i>Staphylococcus epidermidis</i> (89.6%) for 72 h growth. The surface degradation of MoU-PCL composites over 4 weeks confirmed the feasibility of removing surface debris and dangling MOFs to offer long-term MB performance. Our approach enables the development of MB surfaces for applications requiring a relatively long service period.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089915","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}
Pub Date : 2026-01-30DOI: 10.1021/acssuschemeng.5c11191
Chaohui He, Jinglin Guo, Zhen-Wu Shao, Zhenzhen Jia, Yujuan Zhang, Tao Li, Xiao-Qing Wang, Tuoping Hu
Low-concentration coalbed gases are vital energy resources, but more significant amounts of N2 severely limit the efficient utilization of their primary component CH4. Due to their similar physicochemical properties, separating CH4 from N2 remains highly challenging. Adsorption using porous materials has emerged as a promising approach for CH4/N2 separation. Herein, we developed an in situ ligand reaction strategy to engineer the pore shape and chemical environment of a copper-based metal–organic framework (NUC-201Cu), achieving efficient CH4/N2 mixture separation. Structural characterization elucidated the successful modulation of pore geometry and in situ conversion of CN groups into tetrazole groups during the one-spot MOF synthesis process. The single-component adsorption isotherm of NUC-201Cu exhibits a high CH4 adsorption capacity of 36.4 cm3/g at 298 K and 1 bar, surpassing most reported MOFs for CH4/N2 separation. Theoretical calculations unveiled that the suitable pore geometry and polarized tetrazole groups optimized pore environments to establish preferential interactions with CH4 via C–H···N hydrogen bonds. In situ time-dependent infrared spectroscopy further confirmed the strong host–guest interaction between the framework and CH4. Breakthrough experiments verified the exceptional CH4/N2 separation performance of NUC-201Cu under different dynamic separation processes. This research establishes an in situ ligand reaction strategy to optimize the pore adsorption environment for effective separation of CH4/N2.
{"title":"Tailoring Pore Environment of Metal–Organic Framework via In Situ Ligand Reaction Strategy to Boost CH4/N2 Separation","authors":"Chaohui He, Jinglin Guo, Zhen-Wu Shao, Zhenzhen Jia, Yujuan Zhang, Tao Li, Xiao-Qing Wang, Tuoping Hu","doi":"10.1021/acssuschemeng.5c11191","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11191","url":null,"abstract":"Low-concentration coalbed gases are vital energy resources, but more significant amounts of N<sub>2</sub> severely limit the efficient utilization of their primary component CH<sub>4</sub>. Due to their similar physicochemical properties, separating CH<sub>4</sub> from N<sub>2</sub> remains highly challenging. Adsorption using porous materials has emerged as a promising approach for CH<sub>4</sub>/N<sub>2</sub> separation. Herein, we developed an in situ ligand reaction strategy to engineer the pore shape and chemical environment of a copper-based metal–organic framework (NUC-201Cu), achieving efficient CH<sub>4</sub>/N<sub>2</sub> mixture separation. Structural characterization elucidated the successful modulation of pore geometry and in situ conversion of CN groups into tetrazole groups during the one-spot MOF synthesis process. The single-component adsorption isotherm of NUC-201Cu exhibits a high CH<sub>4</sub> adsorption capacity of 36.4 cm<sup>3</sup>/g at 298 K and 1 bar, surpassing most reported MOFs for CH<sub>4</sub>/N<sub>2</sub> separation. Theoretical calculations unveiled that the suitable pore geometry and polarized tetrazole groups optimized pore environments to establish preferential interactions with CH<sub>4</sub> via C–H···N hydrogen bonds. In situ time-dependent infrared spectroscopy further confirmed the strong host–guest interaction between the framework and CH<sub>4</sub>. Breakthrough experiments verified the exceptional CH<sub>4</sub>/N<sub>2</sub> separation performance of NUC-201Cu under different dynamic separation processes. This research establishes an in situ ligand reaction strategy to optimize the pore adsorption environment for effective separation of CH<sub>4</sub>/N<sub>2</sub>.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"78 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089916","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}
Pub Date : 2026-01-30DOI: 10.1021/acssuschemeng.5c07357
Dan Wang, Shaohua Shi, Dezhao Zeng, Wenzheng Li, Yanfeng Fang, Cang Xiong, Baomin Wang
A detailed investigation of tricalcium aluminate (C3A) under CO2 exposure is essential for developing Al-rich materials via carbonation. In this study, the carbonation properties of C3A were investigated, including the carbonation kinetics, the contribution of mineral evolution to strength development, the effects of dissolution properties, and the influence of temperature and prehydration treatment. The results indicate that compared to other Portland cement clinkers, C3A exhibited the highest early carbonation rate (k1 = 59.96 min–1) due to its high dissolution rate but the lowest degree of carbonation (22.9%) due to its low Ca2+ leaching concentration (≤388.3 mg/L). Hydration took precedence over carbonation in C3A, forming hydrogarnet (C3AH6), which exhibited lower carbonation activity and was unfavorable for subsequent carbonation. The elastic modulus of C3A decreased from 4.89 ± 0.34 to 4.14 ± 0.42 GPa after 2 h of prehydration followed by 72 h of carbonation at 25 °C, as determined by three-dimensional digital image correlation. Increasing the temperature from 25 to 60 °C effectively promoted the carbonation of hydration products, primarily C3AH6 and Al-monocarbonate (C4AČH11), facilitating the formation of aragonite fibers and gibbsite. Aragonite fibers, with an average length of 1.914 μm, increased in content from 9.5 to 18.5 wt %, interlacing with each other to form an urchin-like structure that provided a fibrous effect, increasing the flexural strength from 5.85 ± 0.19 to 9.07 ± 0.34 MPa. Gibbsite increased in content from 7.0 to 13.4 wt % and tightly wrapped around the surfaces of unreacted C3A grains, working synergistically with CaCO3 crystals with an average elastic modulus of 59.2 GPa (determined by nanoindentation) to serve as cementing agents, increasing the compressive strength from 28.71 ± 2.45 to 45.14 ± 3.94 MPa and the elastic modulus from 4.89 ± 0.34 to 11.77 ± 0.99 GPa. In comparison, at 25 °C, C3A powder primarily produced nanospherical vaterite with a crystallite size of approximately 27 nm and only trace amounts of gibbsite (0.8–4.0 wt %).
{"title":"Gas–Solid Carbonation Behavior of Tricalcium Aluminate: Kinetics, Mineral Evolution, and Strength Contribution","authors":"Dan Wang, Shaohua Shi, Dezhao Zeng, Wenzheng Li, Yanfeng Fang, Cang Xiong, Baomin Wang","doi":"10.1021/acssuschemeng.5c07357","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c07357","url":null,"abstract":"A detailed investigation of tricalcium aluminate (C<sub>3</sub>A) under CO<sub>2</sub> exposure is essential for developing Al-rich materials via carbonation. In this study, the carbonation properties of C<sub>3</sub>A were investigated, including the carbonation kinetics, the contribution of mineral evolution to strength development, the effects of dissolution properties, and the influence of temperature and prehydration treatment. The results indicate that compared to other Portland cement clinkers, C<sub>3</sub>A exhibited the highest early carbonation rate (<i>k</i><sub>1</sub> = 59.96 min<sup>–1</sup>) due to its high dissolution rate but the lowest degree of carbonation (22.9%) due to its low Ca<sup>2+</sup> leaching concentration (≤388.3 mg/L). Hydration took precedence over carbonation in C<sub>3</sub>A, forming hydrogarnet (C<sub>3</sub>AH<sub>6</sub>), which exhibited lower carbonation activity and was unfavorable for subsequent carbonation. The elastic modulus of C<sub>3</sub>A decreased from 4.89 ± 0.34 to 4.14 ± 0.42 GPa after 2 h of prehydration followed by 72 h of carbonation at 25 °C, as determined by three-dimensional digital image correlation. Increasing the temperature from 25 to 60 °C effectively promoted the carbonation of hydration products, primarily C<sub>3</sub>AH<sub>6</sub> and Al-monocarbonate (C<sub>4</sub>AČH<sub>11</sub>), facilitating the formation of aragonite fibers and gibbsite. Aragonite fibers, with an average length of 1.914 μm, increased in content from 9.5 to 18.5 wt %, interlacing with each other to form an urchin-like structure that provided a fibrous effect, increasing the flexural strength from 5.85 ± 0.19 to 9.07 ± 0.34 MPa. Gibbsite increased in content from 7.0 to 13.4 wt % and tightly wrapped around the surfaces of unreacted C<sub>3</sub>A grains, working synergistically with CaCO<sub>3</sub> crystals with an average elastic modulus of 59.2 GPa (determined by nanoindentation) to serve as cementing agents, increasing the compressive strength from 28.71 ± 2.45 to 45.14 ± 3.94 MPa and the elastic modulus from 4.89 ± 0.34 to 11.77 ± 0.99 GPa. In comparison, at 25 °C, C<sub>3</sub>A powder primarily produced nanospherical vaterite with a crystallite size of approximately 27 nm and only trace amounts of gibbsite (0.8–4.0 wt %).","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"79 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098329","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}
Pub Date : 2026-01-30DOI: 10.1021/acssuschemeng.5c11953
Zerong Jiang, Junbo Tang, Sifang Wang, Linan Zhao, Weixiang Liao, Sakil Mahmud, Shilin Li, Chun Hu, Zhu Wang
Establishing a direct interspecies electron transfer methanogenic pathway via ethanol-type fermentation offers an efficient strategy for energy recovery from sulfate-rich organic wastewater. This study rapidly established ethanol-type fermentation by integrating yeast addition and an elevated organic loading rate (OLR), thereby providing a self-sufficient ethanol substrate to enhance sludge conductivity. The results demonstrate that, with an OLR of 7.5 kg COD/m3/d, yeast addition enabled rapid establishment of ethanol-type fermentation. In addition, hydraulic retention time (HRT) significantly influenced ethanol production, which peaked at 1882.8 mg COD/L in the yeast group under an HRT of 12 h and OLR of 16 kg COD/m3/d. Crucially, yeast supplementation increased the abundance of cysteine synthase (cysC) and sulfite reductase (cysJ and cysI), boosting sulfate reduction efficiency from 34% to 88% under acidic conditions (pH about 4.3–4.8). Overall, the addition of yeast can rapidly establish ethanol fermentation and enhance sulfate reduction, especially at lower pH values. These findings provide a feasible strategy for the industrial treatment of sulfate-rich organic wastewater, aiming to enable efficient energy recovery alongside synergistic pollutant removal.
通过乙醇型发酵建立直接的种间电子转移产甲烷途径，为富硫酸盐有机废水的能量回收提供了有效的策略。本研究通过整合酵母添加和提高有机负荷率（OLR），迅速建立了乙醇型发酵，从而提供了自给自足的乙醇底物，以提高污泥的导电性。结果表明，在OLR为7.5 kg COD/m3/d的条件下，酵母可快速建立乙醇型发酵。此外，水力停留时间（HRT）显著影响乙醇产量，当HRT为12 h， OLR为16 kg COD/m3/d时，酵母组乙醇产量达到1882.8 mg COD/L。最重要的是，酵母的添加增加了半胱氨酸合成酶（cysC）和亚硫酸盐还原酶（cysJ和cysI）的丰度，在酸性条件下（pH约4.3-4.8），硫酸盐还原效率从34%提高到88%。总的来说，添加酵母可以迅速建立乙醇发酵，并增强硫酸盐还原，特别是在较低的pH值下。这些发现为富硫酸盐有机废水的工业处理提供了可行的策略，旨在实现高效的能源回收和协同污染物去除。
{"title":"Enhanced Ethanol-Type Fermentation from Sulfate-Laden Organic Wastewater through Yeast Supplementation and Increased Organic Loading Rate","authors":"Zerong Jiang, Junbo Tang, Sifang Wang, Linan Zhao, Weixiang Liao, Sakil Mahmud, Shilin Li, Chun Hu, Zhu Wang","doi":"10.1021/acssuschemeng.5c11953","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11953","url":null,"abstract":"Establishing a direct interspecies electron transfer methanogenic pathway via ethanol-type fermentation offers an efficient strategy for energy recovery from sulfate-rich organic wastewater. This study rapidly established ethanol-type fermentation by integrating yeast addition and an elevated organic loading rate (OLR), thereby providing a self-sufficient ethanol substrate to enhance sludge conductivity. The results demonstrate that, with an OLR of 7.5 kg COD/m<sup>3</sup>/d, yeast addition enabled rapid establishment of ethanol-type fermentation. In addition, hydraulic retention time (HRT) significantly influenced ethanol production, which peaked at 1882.8 mg COD/L in the yeast group under an HRT of 12 h and OLR of 16 kg COD/m<sup>3</sup>/d. Crucially, yeast supplementation increased the abundance of cysteine synthase (<i>cysC</i>) and sulfite reductase (<i>cysJ</i> and <i>cysI</i>), boosting sulfate reduction efficiency from 34% to 88% under acidic conditions (pH about 4.3–4.8). Overall, the addition of yeast can rapidly establish ethanol fermentation and enhance sulfate reduction, especially at lower pH values. These findings provide a feasible strategy for the industrial treatment of sulfate-rich organic wastewater, aiming to enable efficient energy recovery alongside synergistic pollutant removal.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"61 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098335","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}
Pub Date : 2026-01-29DOI: 10.1021/acssuschemeng.5c11316
Jun Zhang, , , Ao Yang, , , Zong Yang Kong, , , Lusi Ernawati, , , Weifeng Shen, , and , Qin Wang*,
This study proposes a pretraining enhanced multicomponent directed message passing neural network (PEMC D-MPNN) for predicting the solubility of H2S in ionic liquids (ILs). Traditional feature engineering methods often treat ILs as single entities, overlooking the different structural roles of the cations and anions. To address this, we introduce a multicomponent framework that separately encodes cation and anion structures using a D-MPNN, explicitly modeling their interactions. Given the limited experimental H2S solubility data, a pretraining strategy is employed utilizing the CheMeleon foundation model trained on one million molecules from PubChem to learn universal molecular representations, which are then fine-tuned for H2S solubility prediction. The proposed model integrates operational conditions (i.e., temperature and pressure) and leverages interpretability tools, such as SHapley Additive exPlanations (SHAP) and principal component analysis (PCA), to validate feature importance. The evaluation results demonstrate that the proposed PEMC D-MPNN model outperforms existing models (i.e., GPR, RF, XGBoost, SVM, DBN, RNN, DJINN, GP, GMDH), with an R2 of 0.9922, MAE of 0.0080, and RMSE of 0.0136 on 722 data points and an R2 of 0.9964, AAPRE of 5.0506%, and RMSE of 0.0099 on 1516 data points. External validation on unseen ILs, i.e.,1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, and 1-butylpyridinium tetrafluoroborate (with 139 data points) confirms strong generalization ability, highlighting the robustness of the proposed model and practical utility for IL screening and design.
{"title":"Pretraining Enhanced Multicomponent Graph Neural Network for H2S Solubility Prediction in Ionic Liquids","authors":"Jun Zhang, , , Ao Yang, , , Zong Yang Kong, , , Lusi Ernawati, , , Weifeng Shen, , and , Qin Wang*, ","doi":"10.1021/acssuschemeng.5c11316","DOIUrl":"10.1021/acssuschemeng.5c11316","url":null,"abstract":"<p >This study proposes a pretraining enhanced multicomponent directed message passing neural network (PEMC D-MPNN) for predicting the solubility of H<sub>2</sub>S in ionic liquids (ILs). Traditional feature engineering methods often treat ILs as single entities, overlooking the different structural roles of the cations and anions. To address this, we introduce a multicomponent framework that separately encodes cation and anion structures using a D-MPNN, explicitly modeling their interactions. Given the limited experimental H<sub>2</sub>S solubility data, a pretraining strategy is employed utilizing the CheMeleon foundation model trained on one million molecules from PubChem to learn universal molecular representations, which are then fine-tuned for H<sub>2</sub>S solubility prediction. The proposed model integrates operational conditions (i.e., temperature and pressure) and leverages interpretability tools, such as SHapley Additive exPlanations (SHAP) and principal component analysis (PCA), to validate feature importance. The evaluation results demonstrate that the proposed PEMC D-MPNN model outperforms existing models (i.e., GPR, RF, XGBoost, SVM, DBN, RNN, DJINN, GP, GMDH), with an R<sup>2</sup> of 0.9922, MAE of 0.0080, and RMSE of 0.0136 on 722 data points and an R<sup>2</sup> of 0.9964, AAPRE of 5.0506%, and RMSE of 0.0099 on 1516 data points. External validation on unseen ILs, i.e.,1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, and 1-butylpyridinium tetrafluoroborate (with 139 data points) confirms strong generalization ability, highlighting the robustness of the proposed model and practical utility for IL screening and design.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 5","pages":"2494–2506"},"PeriodicalIF":7.3,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070151","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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