Although a variety of Russian doll-styled non-intertwined box-in-box complexes have been reported, the utilization of this unique complexation pattern for the improvement of a specific property or function remains a challenging target. Herein, we report the construction of a box-in-cage assembly in aqueous solution from an anionic arenecage (ArCage) and the tetracationic little blue box (LBB) originally developed by Stoddart. Driven by both ion-pairing and donor-acceptor interactions, box-in-cage complex ArCage•LBB affords extremely high binding constant (Ka) of 6.35 × 107 M−1. Stabilized by donor-acceptor interaction and hydrophobicity, LBB includes a variety of naphthalene derivative guests in water, with Ka values ranging from 9.80 × 104 M−1 to 2.81 × 107 M−1. In the presence of ArCage, the Ka values for the complexation of LBB with naphthalenediols, naphthols and naphthalene increases significantly, by up to 4.87 times, through exclusive encapsulation of the complexes by ArCage with the Russian doll mechanism. Enhancement of the hydrophobic cavity of LBB facilitated by ArCage has been proposed to account for the increased stability of the complexes formed between LBB and the naphthalene guests.
{"title":"Giant Arenecage Enhancing Binding Affinity of Little Blue Box for Naphthalene Guests through Host-in-Host Mechanism","authors":"Xiaoyun Dong, Congying Guo, Jiangshan Zhang, Qiao-Yan Qi, Hui Wang, Myongsoo Lee, Dan-Wei Zhang, Zhan-Ting Li","doi":"10.31635/ccschem.025.202506895","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506895","url":null,"abstract":"Although a variety of Russian doll-styled non-intertwined box-in-box complexes have been reported, the utilization of this unique complexation pattern for the improvement of a specific property or function remains a challenging target. Herein, we report the construction of a box-in-cage assembly in aqueous solution from an anionic arenecage (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>ArCage</bold></b>) and the tetracationic little blue box (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>LBB</bold></b>) originally developed by Stoddart. Driven by both ion-pairing and donor-acceptor interactions, box-in-cage complex <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>ArCage•LBB</bold></b> affords extremely high binding constant (<i>K</i><sub>a</sub>) of 6.35 × 10<sup>7</sup> M<sup>−1</sup>. Stabilized by donor-acceptor interaction and hydrophobicity, LBB includes a variety of naphthalene derivative guests in water, with Ka values ranging from 9.80 × 10<sup>4</sup> M<sup>−1</sup> to 2.81 × 10<sup>7</sup> M<sup>−1</sup>. In the presence of ArCage, the Ka values for the complexation of LBB with naphthalenediols, naphthols and naphthalene increases significantly, by up to 4.87 times, through exclusive encapsulation of the complexes by ArCage with the Russian doll mechanism. Enhancement of the hydrophobic cavity of LBB facilitated by ArCage has been proposed to account for the increased stability of the complexes formed between LBB and the naphthalene guests.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"16 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759456","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 : 2025-12-15DOI: 10.31635/ccschem.025.202506332
Zhaozhao Zhu, Wu Tang, Xun Huang, Junjie Wang, Xiaobin Niu, Jun Song Chen, Bin Liu, Rui Wu, Zidong Wei
Developing advanced electrocatalysts integrated with optimized electrolyte systems is crucial for efficient acidic electrochemical CO2 reduction, but it remains highly challenging. Here, we present a novel Ni@NCNT/HPNF-3.4 catalyst comprising Ni nanoparticles encapsulated in N-doped carbon nanotubes, which are anchored to hollow porous carbon nanofibers. This hierarchical architecture not only provides abundant active sites but also selectively enriches K+ while effectively inhibiting H+ migration. In a pH=1.5 phytic acid-electrolyte with 1 M KCl, the Ni@NCNT/HPNF-3.4 catalyst achieves over 99% CO faradaic efficiency across a wide potential range (−0.8 to −1.5 V versus reversible hydrogen electrode). It shows a high single-pass conversion efficiency of 74.2% at a flow rate of 2 sccm. Finite element simulations further confirm the structure-induced K+ concentration gradient, and in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis highlights the critical role of the *COOH intermediate stabilization. This catalyst design significantly mitigates carbonate deposition, thereby enhancing both selectivity and the potential for scalability in CO2 electroreduction.
开发先进的电催化剂与优化的电解质系统是有效的酸性电化学CO2还原的关键，但仍然具有很高的挑战性。在这里，我们提出了一种新的Ni@NCNT/HPNF-3.4催化剂，该催化剂将Ni纳米颗粒包裹在n掺杂的碳纳米管中，并将其固定在空心多孔碳纳米纤维上。这种分层结构不仅提供了丰富的活性位点，而且选择性地富集K+，同时有效地抑制H+迁移。在pH=1.5的植酸-电解液和1 M KCl中，Ni@NCNT/HPNF-3.4催化剂在宽电位范围内（−0.8至−1.5 V vs可逆氢电极）实现了99%以上的CO法拉第效率。在2 sccm的流量下，单次转换效率高达74.2%。有限元模拟进一步证实了结构诱导的K+浓度梯度，原位衰减全反射表面增强红外吸收光谱分析强调了*COOH中间稳定的关键作用。这种催化剂设计显著减轻了碳酸盐沉积，从而提高了CO2电还原的选择性和可扩展性。
{"title":"Potassium Ion Enrichment via Hollow Porous N-Doped Carbon Nanofibers Encapsulating Nickel Nanoparticles Boosts Acidic CO2-to-CO Electroreduction","authors":"Zhaozhao Zhu, Wu Tang, Xun Huang, Junjie Wang, Xiaobin Niu, Jun Song Chen, Bin Liu, Rui Wu, Zidong Wei","doi":"10.31635/ccschem.025.202506332","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506332","url":null,"abstract":"Developing advanced electrocatalysts integrated with optimized electrolyte systems is crucial for efficient acidic electrochemical CO<sub>2</sub> reduction, but it remains highly challenging. Here, we present a novel Ni@NCNT/HPNF-3.4 catalyst comprising Ni nanoparticles encapsulated in N-doped carbon nanotubes, which are anchored to hollow porous carbon nanofibers. This hierarchical architecture not only provides abundant active sites but also selectively enriches K<sup>+</sup> while effectively inhibiting H<sup>+</sup> migration. In a pH=1.5 phytic acid-electrolyte with 1 M KCl, the Ni@NCNT/HPNF-3.4 catalyst achieves over 99% CO faradaic efficiency across a wide potential range (−0.8 to −1.5 V versus reversible hydrogen electrode). It shows a high single-pass conversion efficiency of 74.2% at a flow rate of 2 sccm. Finite element simulations further confirm the structure-induced K<sup>+</sup> concentration gradient, and in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis highlights the critical role of the *COOH intermediate stabilization. This catalyst design significantly mitigates carbonate deposition, thereby enhancing both selectivity and the potential for scalability in CO<sub>2</sub> electroreduction.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"178 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785735","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 : 2025-12-13DOI: 10.31635/ccschem.025.202506644
Zihan Wang, Shi-Kai Tian, Muliang Zhang
Despite the widespread utility of the Chan–Lam reaction for C–N bond formation, its application to alkyl boronic acids remains significantly underdeveloped. In this study, we present a unified strategy that employs photoinduced copper catalysis to extend reactivity to alkyl boronic acids while maintaining compatibility with aryl boronic acids, thereby establishing a generalized Chan–Lam coupling protocol. A key to this advancement is the identification of ammonium persulfate [(NH4)2S2O8] as a bifunctional oxidant that not only drives turnover of the photoinduced copper catalytic cycle but also enables selective C–B bond cleavage to generate radical intermediates. This dual reactivity facilitates efficient formation of both C(sp3)–N and C(sp2)–N bonds with a broad range of nitrogen nucleophiles, including indazoles, azaindoles, pyrazoles, azaindazoles, aminopyridines, amides, sulfonamides, and sulfoximines, which constitute privileged motifs in blockbuster pharmaceuticals. These transformations occur under mild conditions, enabled by a single catalytic platform.
{"title":"Generalization of the Chan–Lam Reaction via Photoinduced Copper Catalysis","authors":"Zihan Wang, Shi-Kai Tian, Muliang Zhang","doi":"10.31635/ccschem.025.202506644","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506644","url":null,"abstract":"Despite the widespread utility of the Chan–Lam reaction for C–N bond formation, its application to alkyl boronic acids remains significantly underdeveloped. In this study, we present a unified strategy that employs photoinduced copper catalysis to extend reactivity to alkyl boronic acids while maintaining compatibility with aryl boronic acids, thereby establishing a generalized Chan–Lam coupling protocol. A key to this advancement is the identification of ammonium persulfate [(NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub>] as a bifunctional oxidant that not only drives turnover of the photoinduced copper catalytic cycle but also enables selective C–B bond cleavage to generate radical intermediates. This dual reactivity facilitates efficient formation of both C(sp<sup>3</sup>)–N and C(sp<sup>2</sup>)–N bonds with a broad range of nitrogen nucleophiles, including indazoles, azaindoles, pyrazoles, azaindazoles, aminopyridines, amides, sulfonamides, and sulfoximines, which constitute privileged motifs in blockbuster pharmaceuticals. These transformations occur under mild conditions, enabled by a single catalytic platform.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"10 1","pages":"1-20"},"PeriodicalIF":11.2,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731741","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 : 2025-12-13DOI: 10.31635/ccschem.025.202506459
Xiaohui Li, Wenhui Ge, Lichuan Chen, Qingqing Wu, Yuqing Ye, Xiangqian Tang, Xiaojuan Huang, Jieyao Lv, Jie Bai, Zitong Liu, Colin J. Lambert, Wenjing Hong
Developing multifunctional single-molecule devices is a crucial step toward constructing highly integrated molecular circuits. However, it remains challenging due to the difficulty in manipulating the transmission spectra of single-molecule channels that determine the device functionality without altering the channel structures. In this work, we use a supramolecular control strategy to demonstrate the multifunctional single-molecule devices by switching between destructive quantum interference and constructive quantum interference without changing the channel structure. When the electrolyte is switched from a nonimidazolium solution to imidazolium ionic liquid, the devices’ operational behavior transitions from that of an active anti-ambipolar transistor with a high on/off ratio of 120 to that of a passive, gate-insensitive conductor with a negligible field-effect response. Furthermore, we propose two types of single-molecule logic gates with an electrical signal as the output, based on the multifunctional single-molecule devices. Theoretical calculations indicate that the antiresonance transmission of the azulene channel can be manipulated to an off-resonance feature through the electrostatic interaction between imidazolium cations and the azulene ring. Our work provides a nondestructive strategy for designing multifunctional single-molecule devices, which offers new insights into the functional customization and sophisticated logic operations of future molecular circuits.
{"title":"Dual-Function Single-Molecule Devices via Supramolecular Control of Quantum Interference","authors":"Xiaohui Li, Wenhui Ge, Lichuan Chen, Qingqing Wu, Yuqing Ye, Xiangqian Tang, Xiaojuan Huang, Jieyao Lv, Jie Bai, Zitong Liu, Colin J. Lambert, Wenjing Hong","doi":"10.31635/ccschem.025.202506459","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506459","url":null,"abstract":"Developing multifunctional single-molecule devices is a crucial step toward constructing highly integrated molecular circuits. However, it remains challenging due to the difficulty in manipulating the transmission spectra of single-molecule channels that determine the device functionality without altering the channel structures. In this work, we use a supramolecular control strategy to demonstrate the multifunctional single-molecule devices by switching between destructive quantum interference and constructive quantum interference without changing the channel structure. When the electrolyte is switched from a nonimidazolium solution to imidazolium ionic liquid, the devices’ operational behavior transitions from that of an active anti-ambipolar transistor with a high on/off ratio of 120 to that of a passive, gate-insensitive conductor with a negligible field-effect response. Furthermore, we propose two types of single-molecule logic gates with an electrical signal as the output, based on the multifunctional single-molecule devices. Theoretical calculations indicate that the antiresonance transmission of the azulene channel can be manipulated to an off-resonance feature through the electrostatic interaction between imidazolium cations and the azulene ring. Our work provides a nondestructive strategy for designing multifunctional single-molecule devices, which offers new insights into the functional customization and sophisticated logic operations of future molecular circuits.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"147 1","pages":"1-27"},"PeriodicalIF":11.2,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731740","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 : 2025-12-12DOI: 10.31635/ccschem.025.202506881
Jiangyu Zhu, Dongyue An, Ying Song, Teng Wang, Yunqi Liu, Xuefeng Lu
Cycloarenes and heterocycloarenes, characterized by rigid fully fused π-conjugated structures and shape-persistent cavities, hold significant promise in synthetic chemistry, supramolecular sensors, and semiconductor materials. However, the synthesis of (hetero)cycloarenes with novel structures and specific functions remains a significant challenge in organic and material chemistry. Herein we report the first case of solution-synthesized dimeric heterocycloarenes (DHC1 and DHC2) with a fully fused conjugated bismacrocyclic framework via cyclocondensation reactions. The resultant dimeric heterocycloarenes feature two identical heterocycloarene subunits, bridged by a pyrazino[2,3-g]quinoxaline unit. Their bismacrocyclic structures were confirmed in real space at the submolecular level by scanning tunneling microscopy, and the distance between the centers of two macrocycles was measured to be ~2.4 nm. Interestingly, due to its particular bismacrocyclic structure and low electron density in the cavities, DHC2 displays efficient 1:1 binding with iodide ion, tending to form large-sized supramolecular aggregates in solution. Our study opens new avenues for the synthesis of porous carbon nanostructures and lays a foundation for (hetero)cycloarene derivatives in supramolecular polymer construction.
{"title":"Fully Fused Conjugated Dimeric Heterocycloarenes","authors":"Jiangyu Zhu, Dongyue An, Ying Song, Teng Wang, Yunqi Liu, Xuefeng Lu","doi":"10.31635/ccschem.025.202506881","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506881","url":null,"abstract":"Cycloarenes and heterocycloarenes, characterized by rigid fully fused π-conjugated structures and shape-persistent cavities, hold significant promise in synthetic chemistry, supramolecular sensors, and semiconductor materials. However, the synthesis of (hetero)cycloarenes with novel structures and specific functions remains a significant challenge in organic and material chemistry. Herein we report the first case of solution-synthesized dimeric heterocycloarenes (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>DHC1</bold></b> and <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>DHC2</bold></b>) with a fully fused conjugated bismacrocyclic framework via cyclocondensation reactions. The resultant dimeric heterocycloarenes feature two identical heterocycloarene subunits, bridged by a pyrazino[2,3-<i>g</i>]quinoxaline unit. Their bismacrocyclic structures were confirmed in real space at the submolecular level by scanning tunneling microscopy, and the distance between the centers of two macrocycles was measured to be ~2.4 nm. Interestingly, due to its particular bismacrocyclic structure and low electron density in the cavities, <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\u0000<bold>DHC2</bold></b> displays efficient 1:1 binding with iodide ion, tending to form large-sized supramolecular aggregates in solution. Our study opens new avenues for the synthesis of porous carbon nanostructures and lays a foundation for (hetero)cycloarene derivatives in supramolecular polymer construction.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"77 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759460","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}
MicroRNA-based therapeutics, particularly anti-miRNA oligonucleotides (AMOs), have emerged as promising agents for cancer treatment. However, the intrinsic bio-instability of linear AMOs has posed a significant challenge to their development. Herein, we present an innovative strategy employing enzymatically synthesized circular single-stranded DNA to achieve simultaneous suppression of multiple oncogenic miRNAs. Our one-pot-synthesized 132-nt circular AMO demonstrated enhanced exonuclease resistance, thereby significantly improving intracellular stability compared with its linear counterparts. Concurrently, the circular topology enabled simultaneous suppression of four oncogenic miRNAs (miR-21/221/155/10b) through the RNase H-dependent cleavage mechanism. Such synergistic inhibition can upregulate tumor suppressor mRNAs (PTEN, HIPK2, SOCS1, and HOXD10), effectively curtailing both proliferation and migration of MCF-7 cells. This chemical modification-free platform not only addresses the inherent stability issues of nucleic acid-based therapies but also establishes a versatile paradigm for multitargeted oligonucleotide therapeutics.
{"title":"Circular Single-Stranded DNA for Simultaneous Suppression of Multiple miRNAs","authors":"Yufan Pan, Xin Li, Liangzhi Luo, Rui Xu, Chenyou Zhu, Sijie He, Jun Wu, Ruofan Chen, Yifan Jiang, Yuanchen Dong, Ziyang Hao, Dongsheng Liu","doi":"10.31635/ccschem.025.202506751","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506751","url":null,"abstract":"MicroRNA-based therapeutics, particularly anti-miRNA oligonucleotides (AMOs), have emerged as promising agents for cancer treatment. However, the intrinsic bio-instability of linear AMOs has posed a significant challenge to their development. Herein, we present an innovative strategy employing enzymatically synthesized circular single-stranded DNA to achieve simultaneous suppression of multiple oncogenic miRNAs. Our one-pot-synthesized 132-nt circular AMO demonstrated enhanced exonuclease resistance, thereby significantly improving intracellular stability compared with its linear counterparts. Concurrently, the circular topology enabled simultaneous suppression of four oncogenic miRNAs (miR-21/221/155/10b) through the RNase H-dependent cleavage mechanism. Such synergistic inhibition can upregulate tumor suppressor mRNAs (PTEN, HIPK2, SOCS1, and HOXD10), effectively curtailing both proliferation and migration of MCF-7 cells. This chemical modification-free platform not only addresses the inherent stability issues of nucleic acid-based therapies but also establishes a versatile paradigm for multitargeted oligonucleotide therapeutics.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"15 1","pages":"1-23"},"PeriodicalIF":11.2,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731744","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 : 2025-12-12DOI: 10.31635/ccschem.025.202506573
Zilin Zhao, Wangxi Fang, Dianyu Dong, Xinke Zhang, Ying Liu, Yuzhang Zhu, Kai Yang, Jian Jin
Designing polymer membranes for precise ion separation under highly acidic conditions remains a formidable challenge, particularly in lithium-ion battery (LIB) recycling, where lithium must be recovered from highly concentrated acid leachates containing complex mixtures of transition metals. Conventional polyamide (PA) membranes exhibit excellent ion selectivity but suffer from rapid degradation in strong acids due to amide hydrolysis. Here, we report a class of polytertiary amine (PTA) membranes that retained their ion-selective, crosslinked structure of PAs while replacing acid-vulnerable amide linkages with robust tertiary amines. These membranes not only endured harsh acidic conditions (e.g., 32 wt % H2SO4 for 60 days) but also provided two distinct ion separation capabilities: PTA-1 excluded multivalent metal ions while retaining Li+ for lithium purification, and PTA-2 separated Li+ from free protons, realizing direct, pressure-driven acid recovery—a function not previously achieved by membrane processes. When applied to real LIB cathode leachates, this PTA membrane system enabled a two-stage separation process, yielding battery-grade lithium streams (99.3% purity) and achieving over 90% lithium recovery alongside ∼75% sulfuric acid recycling. This work establishes a robust, amide-free membrane platform for selective ion separation in harsh environments and opens a new route toward sustainable, closed-loop LIB recycling.
{"title":"Ion-Selective, Amide-Free Membranes with Exceptional Acid Tolerance for Lithium and Acid Recovery from Waste Batteries","authors":"Zilin Zhao, Wangxi Fang, Dianyu Dong, Xinke Zhang, Ying Liu, Yuzhang Zhu, Kai Yang, Jian Jin","doi":"10.31635/ccschem.025.202506573","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506573","url":null,"abstract":"Designing polymer membranes for precise ion separation under highly acidic conditions remains a formidable challenge, particularly in lithium-ion battery (LIB) recycling, where lithium must be recovered from highly concentrated acid leachates containing complex mixtures of transition metals. Conventional polyamide (PA) membranes exhibit excellent ion selectivity but suffer from rapid degradation in strong acids due to amide hydrolysis. Here, we report a class of polytertiary amine (PTA) membranes that retained their ion-selective, crosslinked structure of PAs while replacing acid-vulnerable amide linkages with robust tertiary amines. These membranes not only endured harsh acidic conditions (e.g., 32 wt % H<sub>2</sub>SO<sub>4</sub> for 60 days) but also provided two distinct ion separation capabilities: PTA-1 excluded multivalent metal ions while retaining Li+ for lithium purification, and PTA-2 separated Li+ from free protons, realizing direct, pressure-driven acid recovery—a function not previously achieved by membrane processes. When applied to real LIB cathode leachates, this PTA membrane system enabled a two-stage separation process, yielding battery-grade lithium streams (99.3% purity) and achieving over 90% lithium recovery alongside ∼75% sulfuric acid recycling. This work establishes a robust, amide-free membrane platform for selective ion separation in harsh environments and opens a new route toward sustainable, closed-loop LIB recycling.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"9 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746677","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 : 2025-12-11DOI: 10.31635/ccschem.025.202505768
Xiaoyu Yue, Tao Song, Jiaqi Cao, Xiaolong Zhang, Shuo Feng, Weiwei Shang, Jun Jiang, Linjiang Chen
Rapid and accurate quantification of chemical mixtures is vital in autonomous chemical experimentation, providing real-time feedback that guides decision-making and reduces resource consumption. Here, we present IR-Bot, an intelligent system that integrates robotic automation, infrared (IR) spectroscopy, quantum chemical simulations, and machine learning (ML) to enable autonomous, real-time mixture analysis. The autonomy is driven by a newly developed large-language-model-based IR Agent, working alongside a multiagent robotic system to orchestrate theoretical IR calculations, experimental data acquisition, and ML-driven interpretation. Central to IR-Bot is the Alignment-Prediction approach: experimental spectra are aligned with simulated references, and a pretrained prediction model then provides composition estimates. This fusion of pretraining, alignment, and prediction yields accurate, interpretable results for both binary and ternary mixtures, as demonstrated via a Suzuki coupling reaction. Moreover, IR-Bot’s explainable ML framework uncovers the specific vibrational modes guiding its predictions, offering deeper insights into fundamental chemical behavior. By enabling rapid, reliable, and autonomous composition analysis, IR-Bot paves the way for a new generation of data-driven laboratory workflows capable of dynamic decision-making and real-time modification of experimental conditions.
{"title":"IR-Bot: An Autonomous Robotic System for Real-Time Chemical Mixture Analysis via Infrared Spectroscopy and Machine Learning","authors":"Xiaoyu Yue, Tao Song, Jiaqi Cao, Xiaolong Zhang, Shuo Feng, Weiwei Shang, Jun Jiang, Linjiang Chen","doi":"10.31635/ccschem.025.202505768","DOIUrl":"https://doi.org/10.31635/ccschem.025.202505768","url":null,"abstract":"Rapid and accurate quantification of chemical mixtures is vital in autonomous chemical experimentation, providing real-time feedback that guides decision-making and reduces resource consumption. Here, we present IR-Bot, an intelligent system that integrates robotic automation, infrared (IR) spectroscopy, quantum chemical simulations, and machine learning (ML) to enable autonomous, real-time mixture analysis. The autonomy is driven by a newly developed large-language-model-based IR Agent, working alongside a multiagent robotic system to orchestrate theoretical IR calculations, experimental data acquisition, and ML-driven interpretation. Central to IR-Bot is the Alignment-Prediction approach: experimental spectra are aligned with simulated references, and a pretrained prediction model then provides composition estimates. This fusion of pretraining, alignment, and prediction yields accurate, interpretable results for both binary and ternary mixtures, as demonstrated via a Suzuki coupling reaction. Moreover, IR-Bot’s explainable ML framework uncovers the specific vibrational modes guiding its predictions, offering deeper insights into fundamental chemical behavior. By enabling rapid, reliable, and autonomous composition analysis, IR-Bot paves the way for a new generation of data-driven laboratory workflows capable of dynamic decision-making and real-time modification of experimental conditions.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"146 1","pages":"1-14"},"PeriodicalIF":11.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731745","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 : 2025-12-11DOI: 10.31635/ccschem.025.202506495
Tongxin Song, Xu Liu, Yan Zhu
An intriguing topic in heterogeneous catalysis is the metal-support interaction (MSI), in which the typical role of the support is to disperse and stabilize metal particles and charge exchange between the metal and support. However, MSI remains elusive. To map out how the interaction dictates catalytic performance, metal catalysts with atomic precision and their combination with well-defined supports can provide new insights into the catalysis of supported metal catalysts. Atomically precise metal clusters have emerged as a novel catalytic material with a crystallographic structure that offers access to a fundamental understanding of MSI. This review systematically classifies supported cluster catalysts based on interaction strength into four categories: weak interaction (e.g., van der Waals forces), physical confinement, electrostatic interaction, and strong covalent anchoring. We highlight their unique catalytic behaviors in hydrogenation, oxidation, CO2 conversion, photocatalytic, and electrocatalytic reactions. The support-mediated catalytic enhancement mechanisms are elucidated through representative works, including dual-site synergistic activation, oxygen vacancy-mediated activation, hydrogen spillover facilitating proton transfer, and tandem catalysis. Finally, we also identify current challenges in supported cluster catalysts, while outlining promising pathways for industrial application in sustainable energy and environmental catalysis. The systematic analysis of structure-performance correlation will provide valuable guidance for designing high-performance supported metal catalysts.
{"title":"Toward Fundamental Insights into Heterogeneous Catalysis by Supported Atomically Precise Metal Clusters","authors":"Tongxin Song, Xu Liu, Yan Zhu","doi":"10.31635/ccschem.025.202506495","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506495","url":null,"abstract":"An intriguing topic in heterogeneous catalysis is the metal-support interaction (MSI), in which the typical role of the support is to disperse and stabilize metal particles and charge exchange between the metal and support. However, MSI remains elusive. To map out how the interaction dictates catalytic performance, metal catalysts with atomic precision and their combination with well-defined supports can provide new insights into the catalysis of supported metal catalysts. Atomically precise metal clusters have emerged as a novel catalytic material with a crystallographic structure that offers access to a fundamental understanding of MSI. This review systematically classifies supported cluster catalysts based on interaction strength into four categories: weak interaction (e.g., van der Waals forces), physical confinement, electrostatic interaction, and strong covalent anchoring. We highlight their unique catalytic behaviors in hydrogenation, oxidation, CO<sub>2</sub> conversion, photocatalytic, and electrocatalytic reactions. The support-mediated catalytic enhancement mechanisms are elucidated through representative works, including dual-site synergistic activation, oxygen vacancy-mediated activation, hydrogen spillover facilitating proton transfer, and tandem catalysis. Finally, we also identify current challenges in supported cluster catalysts, while outlining promising pathways for industrial application in sustainable energy and environmental catalysis. The systematic analysis of structure-performance correlation will provide valuable guidance for designing high-performance supported metal catalysts.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"13 1","pages":"1-29"},"PeriodicalIF":11.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731797","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}
During the synthesis of π-conjugated macrocycles, the competitive by-products (linear oligomers) strongly restrict the chances of tailoring their molecular structures/sizes and physicochemical properties and impede their potential application. To address this issue, here we adopted V-shaped dithienylethene (DTE) as a directing agent to successfully synthesize unprecedented π-extended covalent macrocycles with photoswitchable structures and near-infrared emission. These macrocycles possess diadem configurations, deep cavities up to 14.2 Å, and controllable ring-diameters ranging from 9.2 to 32.9 Å that exceed the dimensions of most reported π-conjugated macrocycles. They also exhibit unique photophysical properties absent in the macrocycles reported in the literature, simultaneously demonstrating near-infrared emission with high quantum yield (67%), facile phototailorable luminescence with high fatigue resistance, and ring-size-dependent photoresponse. Compared to the acyclic contrasts, these macrocycles show significantly redshifted absorption (by ∼30 nm) and emission (by 6–30 nm), relieved luminescence quenching, and greatly improved fatigue resistance (100 vs 20 cycles). The photocyclization process/sequence and mechanisms were studied via steady-state and transient spectra. As a proof-of-concept example, rewritable papers modified with these macrocycles have been prepared, where the largest macrocycle-based paper presents the highest “writing-erasing” stability (>100 cycles) and color contrast, supporting their potential applications in green printing, anticounterfeiting, and optical information storage.
在π共轭大环的合成过程中，具有竞争性的副产物（线性低聚物）强烈地限制了其分子结构/尺寸和物理化学性质的调整，阻碍了其潜在的应用。为了解决这一问题，我们以v型二乙烯（DTE）为导向剂，成功合成了史无前例的具有光开关结构和近红外发射能力的π扩展共价大环。这些大环具有冠状结构，深空腔高达14.2 Å，可控制的环直径范围为9.2 ~ 32.9 Å，超过了大多数π共轭大环的尺寸。它们还表现出文献中所报道的大环所没有的独特的光物理性质，同时表现出具有高量子产率（67%）的近红外发射，具有高抗疲劳性的易光定制发光以及环尺寸相关的光响应。与无环对比相比，这些大环显示出明显的红移吸收（约30 nm）和发射（6-30 nm），减轻了发光猝灭，并大大提高了抗疲劳性（100 vs 20循环）。通过稳态光谱和瞬态光谱研究了其光循环过程、顺序和机理。作为概念验证的例子，已经制备了用这些大周期修饰的可重写纸张，其中最大的基于大周期的纸张具有最高的“书写-擦除”稳定性（>；100周期）和色彩对比度，支持其在绿色印刷，防伪和光学信息存储方面的潜在应用。
{"title":"Highly-Stable Near-Infrared-Emissive π-Extended Covalent Macrocycles with Ring-Size-Dependent Photoswitching","authors":"Xiaomin Zhang, Chun-Lin Sun, Lijian Ning, Gang Chang, Chao Feng, Jinkun Feng, Yanli Wang, Yuhui Song, Lu Liu, Jiarong Li, Yue Li, Mingming Zhang, Shuai Xue, Feng Liu, Qichun Zhang, Yiyong Mai, Yinjuan Huang","doi":"10.31635/ccschem.025.202506464","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506464","url":null,"abstract":"During the synthesis of π-conjugated macrocycles, the competitive by-products (linear oligomers) strongly restrict the chances of tailoring their molecular structures/sizes and physicochemical properties and impede their potential application. To address this issue, here we adopted V-shaped dithienylethene (DTE) as a directing agent to successfully synthesize unprecedented π-extended covalent macrocycles with photoswitchable structures and near-infrared emission. These macrocycles possess diadem configurations, deep cavities up to 14.2 Å, and controllable ring-diameters ranging from 9.2 to 32.9 Å that exceed the dimensions of most reported π-conjugated macrocycles. They also exhibit unique photophysical properties absent in the macrocycles reported in the literature, simultaneously demonstrating near-infrared emission with high quantum yield (67%), facile phototailorable luminescence with high fatigue resistance, and ring-size-dependent photoresponse. Compared to the acyclic contrasts, these macrocycles show significantly redshifted absorption (by ∼30 nm) and emission (by 6–30 nm), relieved luminescence quenching, and greatly improved fatigue resistance (100 vs 20 cycles). The photocyclization process/sequence and mechanisms were studied via steady-state and transient spectra. As a proof-of-concept example, rewritable papers modified with these macrocycles have been prepared, where the largest macrocycle-based paper presents the highest “writing-erasing” stability (>100 cycles) and color contrast, supporting their potential applications in green printing, anticounterfeiting, and optical information storage.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"10 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731747","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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