Pub Date : 2025-12-16DOI: 10.31635/ccschem.025.202507156
Jiaman Du, Yongjin Wang, Jiayang He, Hanchu Huang
Developing efficient and controllable methods to embed customized functional sequences into polymer backbones is essential for creating next-generation materials. Radical ring-opening polymerization of macrocyclic allylic sulfones is a promising technique for constructing polymers with extended main-chain architectures. However, directly controlling this polymerization has remained challenging due to the lack of reversible deactivation strategies for sulfonyl radicals. In this work, we address this challenge by using allyl sulfones as chain-transfer agents to reversibly deactivate sulfonyl radicals, thereby enabling effective control over this polymerization to produce sequence-controlled polymers with tunable molecular weights and narrow dispersities. The living nature of the polymerization is evidenced by a linear relationship between polymer molecular weight and monomer conversion, as well as the successful synthesis of diblock copolymers. Additionally, we establish a modular platform for the synthesis of macrocyclic allylic sulfones, thus enabling straightforward incorporation of diverse functional sequences into polymer backbones in a controlled manner. This research presents a new type of controlled macrocyclic radical ring-opening polymerization, expanding the possibilities for creating complex macromolecules with tailored main-chain functionalities.
{"title":"A Versatile Strategy for Embedding Functional Sequences into Polymer Backbones via Controlled Macrocyclic Radical Ring-Opening Polymerization","authors":"Jiaman Du, Yongjin Wang, Jiayang He, Hanchu Huang","doi":"10.31635/ccschem.025.202507156","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507156","url":null,"abstract":"Developing efficient and controllable methods to embed customized functional sequences into polymer backbones is essential for creating next-generation materials. Radical ring-opening polymerization of macrocyclic allylic sulfones is a promising technique for constructing polymers with extended main-chain architectures. However, directly controlling this polymerization has remained challenging due to the lack of reversible deactivation strategies for sulfonyl radicals. In this work, we address this challenge by using allyl sulfones as chain-transfer agents to reversibly deactivate sulfonyl radicals, thereby enabling effective control over this polymerization to produce sequence-controlled polymers with tunable molecular weights and narrow dispersities. The living nature of the polymerization is evidenced by a linear relationship between polymer molecular weight and monomer conversion, as well as the successful synthesis of diblock copolymers. Additionally, we establish a modular platform for the synthesis of macrocyclic allylic sulfones, thus enabling straightforward incorporation of diverse functional sequences into polymer backbones in a controlled manner. This research presents a new type of controlled macrocyclic radical ring-opening polymerization, expanding the possibilities for creating complex macromolecules with tailored main-chain functionalities.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"69 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759457","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.025.202506343
Shu-Li Guo, Xing Zhang, Bin Li, Chao-Yu Cui, Mo-Han Li, Bin-Bin Pan, Jia-Long Zhao, Xun-Cheng Su
Characterization of protein activity with high resolution in living cells is a major challenge for existing biophysical methods. The challenge in the live-cell labeling chemistry is to install a functional probe sitespecifically in the protein: 1) under mild conditions and in a manner that is not harmful to the cells; 2) with high selectivity and specificity; and 3) without affecting the three-dimensional structure of the target protein. We developed a site-specific protein tagging approach in living cells using a chemical reaction called the reversible Michael addition reaction-triggered neighbor group participation (RAT-NGP) chemistry. The RAT-NGP labeling approach shows high potency in selectively modifying two engineered solvent-exposed cysteines, while leaving the native cysteines in target proteins unchanged and without causing any significant changes in the target protein structures. NMR is a unique tool for providing atomic resolution information in proteins or protein complexes in cells and 19F NMR shows potentials in the live-cell assay because of its high sensitivity and background-free signals. 19F NMR demonstrated that this labeling approach is cell friendly, enabling high labeling efficiency of target proteins in live cells and effectively avoiding the intracellular glutathione (GSH) consumption. This method was used to determine protein-protein interactions in live cells with high resolution.
{"title":"Efficient precision labeling of proteins in live cells via highly selective thiol-chemistry illustrated by in-cell 19F-NMR","authors":"Shu-Li Guo, Xing Zhang, Bin Li, Chao-Yu Cui, Mo-Han Li, Bin-Bin Pan, Jia-Long Zhao, Xun-Cheng Su","doi":"10.31635/ccschem.025.202506343","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506343","url":null,"abstract":"Characterization of protein activity with high resolution in living cells is a major challenge for existing biophysical methods. The challenge in the live-cell labeling chemistry is to install a functional probe sitespecifically in the protein: 1) under mild conditions and in a manner that is not harmful to the cells; 2) with high selectivity and specificity; and 3) without affecting the three-dimensional structure of the target protein. We developed a site-specific protein tagging approach in living cells using a chemical reaction called the reversible Michael addition reaction-triggered neighbor group participation (RAT-NGP) chemistry. The RAT-NGP labeling approach shows high potency in selectively modifying two engineered solvent-exposed cysteines, while leaving the native cysteines in target proteins unchanged and without causing any significant changes in the target protein structures. NMR is a unique tool for providing atomic resolution information in proteins or protein complexes in cells and <sup>19</sup>F NMR shows potentials in the live-cell assay because of its high sensitivity and background-free signals. <sup>19</sup>F NMR demonstrated that this labeling approach is cell friendly, enabling high labeling efficiency of target proteins in live cells and effectively avoiding the intracellular glutathione (GSH) consumption. This method was used to determine protein-protein interactions in live cells with high resolution.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"43 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145785953","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}
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}
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