Molecular assemblies that form distinct out-of-equilibrium states in response to varying energy inputs represent a promising platform for designing advanced, autonomous adaptive materials capable of flexibly and diversely responding to environmental stimuli. Herein, we describe a supramolecular polymer system that integrates azobenzene photoisomerization with hydrogen-bond-directed supramolecular polymorphism, enabling the formation of distinct out-of-equilibrium states under varied light intensities. trans isomers of an azobenzene derivative featuring a barbituric acid merocyanine unit self-assemble into lamellar crystals via two-dimensional nanosheet stacking. Ultraviolet light irradiation of a nanosheet dispersion in nonpolar media at different intensities modulates the proportion of cis isomers, eliciting unique out-of-equilibrium states. Specifically, a strong light facilitates the coassembly of trans and cis isomers into one-dimensional nanofibers through hydrogen bond rearrangement, whereas weaker light drives Ostwald ripening, transforming two-dimensional nanosheets into three-dimensional multilayered structures. High-speed atomic force microscopy reveals the intricate dynamic processes driving these transitions.
{"title":"Light-intensity-dependent out-of-equilibrium processes toward dimensionally distinct nanopolymorphs","authors":"Kenta Tamaki, Hiroki Hanayama, Sougata Datta, Fabien Silly, Yuki Wada, Daisuke Hashizume, Kiyohiro Adachi, Takayuki Uchihashi, Masaki Kawano, Christian Ganser, Shiki Yagai","doi":"10.1016/j.chempr.2025.102818","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102818","url":null,"abstract":"Molecular assemblies that form distinct out-of-equilibrium states in response to varying energy inputs represent a promising platform for designing advanced, autonomous adaptive materials capable of flexibly and diversely responding to environmental stimuli. Herein, we describe a supramolecular polymer system that integrates azobenzene photoisomerization with hydrogen-bond-directed supramolecular polymorphism, enabling the formation of distinct out-of-equilibrium states under varied light intensities. <em>t</em><em>rans</em> isomers of an azobenzene derivative featuring a barbituric acid merocyanine unit self-assemble into lamellar crystals via two-dimensional nanosheet stacking. Ultraviolet light irradiation of a nanosheet dispersion in nonpolar media at different intensities modulates the proportion of <em>cis</em> isomers, eliciting unique out-of-equilibrium states. Specifically, a strong light facilitates the coassembly of <em>trans</em> and <em>cis</em> isomers into one-dimensional nanofibers through hydrogen bond rearrangement, whereas weaker light drives Ostwald ripening, transforming two-dimensional nanosheets into three-dimensional multilayered structures. High-speed atomic force microscopy reveals the intricate dynamic processes driving these transitions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"170 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145531587","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102592
Yasu Chen , Tongkun Wang , Ziqiang Wang , Chen Zhu
Axially chiral molecules play a pivotal role across diverse scientific disciplines, yet the enantioselective synthesis of pentatomic bi(hetero)aryls remains a significant challenge due to their inherently low rotational energy barriers. Here, we devise a method of central-to-axial chirality transfer, leveraging a cascade of radical homolytic substitution and the Pummerer rearrangement to achieve the enantioselective synthesis of axially chiral isothiazole frameworks for the first time. The intramolecular radical homolytic substitution proceeds under photoredox-neutral conditions, generating chiral cyclic sulfinamides that render precise enantiocontrol in the subsequent chirality transfer during the Pummerer rearrangement. Comprehensive density functional theory (DFT) calculations provide mechanistic insights, elucidating the origination of axial chirality. This approach provides a versatile platform for the asymmetric synthesis of isothiazole atropisomers with broad structural diversity and excellent enantioselectivities.
{"title":"Central-to-axial chirality transfer to construct atropisomeric isothiazoles","authors":"Yasu Chen , Tongkun Wang , Ziqiang Wang , Chen Zhu","doi":"10.1016/j.chempr.2025.102592","DOIUrl":"10.1016/j.chempr.2025.102592","url":null,"abstract":"<div><div>Axially chiral molecules play a pivotal role across diverse scientific disciplines, yet the enantioselective synthesis of pentatomic bi(hetero)aryls remains a significant challenge due to their inherently low rotational energy barriers. Here, we devise a method of central-to-axial chirality transfer, leveraging a cascade of radical homolytic substitution and the Pummerer rearrangement to achieve the enantioselective synthesis of axially chiral isothiazole frameworks for the first time. The intramolecular radical homolytic substitution proceeds under photoredox-neutral conditions, generating chiral cyclic sulfinamides that render precise enantiocontrol in the subsequent chirality transfer during the Pummerer rearrangement. Comprehensive density functional theory (DFT) calculations provide mechanistic insights, elucidating the origination of axial chirality. This approach provides a versatile platform for the asymmetric synthesis of isothiazole atropisomers with broad structural diversity and excellent enantioselectivities.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102592"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088049","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102621
Tingting Huang , Kun Yang , Wei Hu , Lina Feng , Zipeng Wu , Hui Chen , Jianguo Wang , Zebing Zeng
Luminescent diradicals are promising for various applications, but their rational design remains challenging. Herein, based on a stepwise symmetry-breaking strategy, we showcase a delicate manipulation of intramolecular charge-transfer (ICT) characters in organic open-shell systems to yield a class of stable luminescent diradicaloids featuring progressively increased contributions of dipolar zwitterionic forms to their ground- and excited-state electronic structures. This stands in stark contrast to most other diradicals bearing only diradical and quinoidal resonances and therefore yielded not only unique dual absorption transition sets with low-energy bands across the deep-near-infrared (NIR) regions of 800–1,100 nm but also gradually red-shifted NIR-II luminescence reaching 1,250 nm. This emission wavelength surpasses the ICT-free counterpart by 430 nm and ranks among the longest for organic open-shell emitters. Our results established a practical approach toward organic diradicals with tunable NIR-II emissions and provided valuable insights into the structural-property relations within these less-explored asymmetric open-shell systems.
{"title":"Manipulation of intramolecular charge transfer in NIR-II emissive organic diradicaloids via a symmetry-breaking design","authors":"Tingting Huang , Kun Yang , Wei Hu , Lina Feng , Zipeng Wu , Hui Chen , Jianguo Wang , Zebing Zeng","doi":"10.1016/j.chempr.2025.102621","DOIUrl":"10.1016/j.chempr.2025.102621","url":null,"abstract":"<div><div>Luminescent diradicals are promising for various applications, but their rational design remains challenging. Herein, based on a stepwise symmetry-breaking strategy, we showcase a delicate manipulation of intramolecular charge-transfer (ICT) characters in organic open-shell systems to yield a class of stable luminescent diradicaloids featuring progressively increased contributions of dipolar zwitterionic forms to their ground- and excited-state electronic structures. This stands in stark contrast to most other diradicals bearing only diradical and quinoidal resonances and therefore yielded not only unique dual absorption transition sets with low-energy bands across the deep-near-infrared (NIR) regions of 800–1,100 nm but also gradually red-shifted NIR-II luminescence reaching 1,250 nm. This emission wavelength surpasses the ICT-free counterpart by 430 nm and ranks among the longest for organic open-shell emitters. Our results established a practical approach toward organic diradicals with tunable NIR-II emissions and provided valuable insights into the structural-property relations within these less-explored asymmetric open-shell systems.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102621"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144237936","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102618
Ang Cao , Ke Zhang , Jerome Vernieres , Lau Halkier Wandall , Rikke Egeberg Tankard , Jakob Kibsgaard , Ib Chorkendorff , Jens K. Nørskov
A spin-mediated promotion mechanism was recently proposed to explain how relatively inert magnetic metals can be activated for ammonia synthesis by introducing metal promoters to quench the surface spin. We herein systematically screen promising promoters and found that many metal promotors are adsorbed at step sites of Co or Ni under ammonia synthesis conditions and act to enhance the activity. We further discuss what can happen for promoters where adsorption on the metal surface is unfavorable. Particularly, metallic Nb would be a good promotor for Co, and we experimentally and theoretically show that it will phase separate and transform into NbN during the reaction, but NbN can still act as a spin promotor at the interface between NbN and Co, leading to a high activity. This work supports the spin effect beyond metal promoters, which could offer more possibilities for utilizing spin effect for designing a wider variety of active catalysts.
{"title":"The Co/NbN interphase as an effective ammonia synthesis catalyst","authors":"Ang Cao , Ke Zhang , Jerome Vernieres , Lau Halkier Wandall , Rikke Egeberg Tankard , Jakob Kibsgaard , Ib Chorkendorff , Jens K. Nørskov","doi":"10.1016/j.chempr.2025.102618","DOIUrl":"10.1016/j.chempr.2025.102618","url":null,"abstract":"<div><div>A spin-mediated promotion mechanism was recently proposed to explain how relatively inert magnetic metals can be activated for ammonia synthesis by introducing metal promoters to quench the surface spin. We herein systematically screen promising promoters and found that many metal promotors are adsorbed at step sites of Co or Ni under ammonia synthesis conditions and act to enhance the activity. We further discuss what can happen for promoters where adsorption on the metal surface is unfavorable. Particularly, metallic Nb would be a good promotor for Co, and we experimentally and theoretically show that it will phase separate and transform into NbN during the reaction, but NbN can still act as a spin promotor at the interface between NbN and Co, leading to a high activity. This work supports the spin effect beyond metal promoters, which could offer more possibilities for utilizing spin effect for designing a wider variety of active catalysts.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102618"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Diels-Alder reaction is a cornerstone of organic synthesis, enabling construction of complex molecular architectures through the cycloaddition of dienes and dienophiles. Among dienes, ortho-quinodimethane is an exceptionally powerful intermediate for building benzo-fused polycyclic skeletons found in biologically important molecules. However, the requirement for laborious precursor preparation remains a significant challenge. This study presents a palladium-catalyzed generation of ortho-quinodimethane via a multi-component reaction of readily available chemicals, specifically 2-vinylbromoarenes, diazo species, and carbon nucleophiles bearing a dienophile moiety, yielding polycyclic compounds. A key advance is the unprecedented reactivity of a benzyl-palladium intermediate, enabling C–C bond formation on the vinyl group. The convergent and diversity-generating nature of this reaction is demonstrated by the synthesis of a range of polycyclic compounds, including a natural product.
{"title":"Facile generation of ortho-quinodimethanes toward polycyclic compounds","authors":"Kazuya Inagaki , Yuna Onozawa , Yuki Fukuhara , Daisuke Yokogawa , Kei Muto , Junichiro Yamaguchi","doi":"10.1016/j.chempr.2025.102615","DOIUrl":"10.1016/j.chempr.2025.102615","url":null,"abstract":"<div><div>The Diels-Alder reaction is a cornerstone of organic synthesis, enabling construction of complex molecular architectures through the cycloaddition of dienes and dienophiles. Among dienes, <em>ortho</em>-quinodimethane is an exceptionally powerful intermediate for building benzo-fused polycyclic skeletons found in biologically important molecules. However, the requirement for laborious precursor preparation remains a significant challenge. This study presents a palladium-catalyzed generation of <em>ortho</em>-quinodimethane via a multi-component reaction of readily available chemicals, specifically 2-vinylbromoarenes, diazo species, and carbon nucleophiles bearing a dienophile moiety, yielding polycyclic compounds. A key advance is the unprecedented reactivity of a benzyl-palladium intermediate, enabling C–C bond formation on the vinyl group. The convergent and diversity-generating nature of this reaction is demonstrated by the synthesis of a range of polycyclic compounds, including a natural product.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102615"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192762","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102625
Beomsoon Park , Kyoungil Cho , Kyungmin Choi , Soon Hyeok Hong
Despite the invaluable properties and broad applications of synthetic elastomers, the management of waste rubbers and end-of-life tires typically involves mechanical recycling or conversion into low-grade fuel. This study introduces an effective and selective chemical recycling method for synthetic elastomers, including polybutadiene, polycycloalkenamers, and their copolymers, utilizing a synergistic tandem catalysis approach that combines isomerization and ring-closing metathesis. By exploiting the ring-chain equilibrium of oligomers, we have demonstrated the selective depolymerization of rubbers into C5–C7 cycloalkenes. Importantly, this method effectively depolymerizes post-consumer vulcanized rubbers, such as disposable rubbers and tires, converting them into highly valuable chemical feedstocks. These results highlight the significant potential of tandem dual catalysis for the selective chemical recycling of synthetic rubbers.
{"title":"Catalytic and selective chemical recycling of post-consumer rubbers into cycloalkenes","authors":"Beomsoon Park , Kyoungil Cho , Kyungmin Choi , Soon Hyeok Hong","doi":"10.1016/j.chempr.2025.102625","DOIUrl":"10.1016/j.chempr.2025.102625","url":null,"abstract":"<div><div>Despite the invaluable properties and broad applications of synthetic elastomers, the management of waste rubbers and end-of-life tires typically involves mechanical recycling or conversion into low-grade fuel. This study introduces an effective and selective chemical recycling method for synthetic elastomers, including polybutadiene, polycycloalkenamers, and their copolymers, utilizing a synergistic tandem catalysis approach that combines isomerization and ring-closing metathesis. By exploiting the ring-chain equilibrium of oligomers, we have demonstrated the selective depolymerization of rubbers into C<sub>5</sub>–C<sub>7</sub> cycloalkenes. Importantly, this method effectively depolymerizes post-consumer vulcanized rubbers, such as disposable rubbers and tires, converting them into highly valuable chemical feedstocks. These results highlight the significant potential of tandem dual catalysis for the selective chemical recycling of synthetic rubbers.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102625"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312134","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102617
Osama El-Zubir , James A. Quirk , James A. Dawson , Benjamin R. Horrocks , Andrew Houlton
Biology’s information carrier, DNA, through its reliable synthesis, controllable length, and sequence-coded self-assembly, provides a unique capability for molecular-material/-device design. However, the intrinsic lack of tunable optoelectronics associated, generally, with delocalized electronic structures means it commonly acts in a passive role to organize “functional” components. The introduction of metal ions into duplex DNA to overcome this limitation has been widely explored, but, to date, the demonstration of such electronically delocalized motifs has proved elusive. Here, we incorporate Au(I)-thionate coordination chains into discrete duplex-DNA molecules by substituting native guanosine with the sulfur-modified analog, 6-thioguanosine. The resulting “24-karat DNA” displays the associated photoluminescence of the metallo chain, along with chiro-optical properties indicating this is conformationally flexible, adopting a duplex-matching helical arrangement. Furthermore, due to the electronic delocalization in the coordination chain, these features can be modulated by a simple extension of the thioG-sequence and {μS-Au-}n chain length and so provide a new tunability to the electronic structure of DNA-based architectures.
{"title":"24-karat DNA: Integrating tunable electronically delocalized coordination chains into discrete DNA duplexes","authors":"Osama El-Zubir , James A. Quirk , James A. Dawson , Benjamin R. Horrocks , Andrew Houlton","doi":"10.1016/j.chempr.2025.102617","DOIUrl":"10.1016/j.chempr.2025.102617","url":null,"abstract":"<div><div>Biology’s information carrier, DNA, through its reliable synthesis, controllable length, and sequence-coded self-assembly, provides a unique capability for molecular-material/-device design. However, the intrinsic lack of tunable optoelectronics associated, generally, with delocalized electronic structures means it commonly acts in a passive role to organize “functional” components. The introduction of metal ions into duplex DNA to overcome this limitation has been widely explored, but, to date, the demonstration of such electronically delocalized motifs has proved elusive. Here, we incorporate Au(I)-thionate coordination chains into discrete duplex-DNA molecules by substituting native guanosine with the sulfur-modified analog, 6-thioguanosine. The resulting “24-karat DNA” displays the associated photoluminescence of the metallo chain, along with chiro-optical properties indicating this is conformationally flexible, adopting a duplex-matching helical arrangement. Furthermore, due to the electronic delocalization in the coordination chain, these features can be modulated by a simple extension of the thioG-sequence and {μS-Au-}<sub>n</sub> chain length and so provide a new tunability to the electronic structure of DNA-based architectures.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102617"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202217","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102664
Ryo Tanifuji , Erina Hosono , Hisae Kamakura , Yukiko Muramatsu , Satoshi Yoshida , Sota Sato , Yoshimi Ohashi , Shingo Dan , Hiroyuki Seimiya , Hiroki Oguri
Strategies for rational design and scaffold diversification of therapeutically valuable yet synthetically challenging natural products remain elusive, often overshadowed by structural simplification approaches. Herein, we report the molecular redesign of an antitumor drug, ecteinascidin 743, which achieves three pivotal objectives: (1) strategic shift of the bridgehead position from C4 to C5, (2) systematic customization of macrocycle size, and (3) incorporation of functional groups for further modification. Our approach generates diverse 14- to 17-membered macrocyclic frameworks bridged at C5, expanding the accessible chemical space beyond that of conventional C1- to C4-bridged scaffolds, while preserving the core structure essential for covalent DNA interactions. These novel macrocycles induce DNA double-strand breaks and exhibit sub-nanomolar anticancer efficacy comparable to ecteinascidins. This method shortens the conventional 21-step semi-synthetic protocol into a streamlined 6- to 10-step process, cutting the synthetic burden by over 50%.
{"title":"Strategic scaffold redesign of ecteinascidins: An approach for generating anticancer macrocycles","authors":"Ryo Tanifuji , Erina Hosono , Hisae Kamakura , Yukiko Muramatsu , Satoshi Yoshida , Sota Sato , Yoshimi Ohashi , Shingo Dan , Hiroyuki Seimiya , Hiroki Oguri","doi":"10.1016/j.chempr.2025.102664","DOIUrl":"10.1016/j.chempr.2025.102664","url":null,"abstract":"<div><div>Strategies for rational design and scaffold diversification of therapeutically valuable yet synthetically challenging natural products remain elusive, often overshadowed by structural simplification approaches. Herein, we report the molecular redesign of an antitumor drug, ecteinascidin 743, which achieves three pivotal objectives: (1) strategic shift of the bridgehead position from C4 to C5, (2) systematic customization of macrocycle size, and (3) incorporation of functional groups for further modification. Our approach generates diverse 14- to 17-membered macrocyclic frameworks bridged at C5, expanding the accessible chemical space beyond that of conventional C1- to C4-bridged scaffolds, while preserving the core structure essential for covalent DNA interactions. These novel macrocycles induce DNA double-strand breaks and exhibit sub-nanomolar anticancer efficacy comparable to ecteinascidins. This method shortens the conventional 21-step semi-synthetic protocol into a streamlined 6- to 10-step process, cutting the synthetic burden by over 50%.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102664"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652626","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102758
Asmaa Jrad , Bikash Garai , Samer Aouad , Gobinda Das , Connor M. Duncan , Mark A. Olson , Ali Trabolsi
Per- and polyfluoroalkyl substances (PFAS), known as “forever chemicals,” are persistent pollutants with serious environmental and health impacts. Conventional water treatment methods often fall short of removing PFAS, prompting interest in advanced adsorbents such as covalent organic frameworks (COFs). This review explores recent advances in the development of COFs tailored for PFAS removal. The discussion focuses on key adsorption mechanisms, including hydrophobic, fluorophilic, electrostatic, and hydrogen-bonding interactions. In addition, optimizing pore size and particle size to improve the adsorption of PFAS is highlighted. The potential of COFs for practical applications is evaluated through their integration into composites, membranes, and adsorption columns, which enable continuous flow treatment. Despite promising results, challenges remain, including scalability, synthesis complexity, and realistic testing at environmentally relevant PFAS concentrations. The outline of future research directions aims to drive the advancement of COF-based solutions that have the potential to revolutionize PFAS remediation in real-world applications.
{"title":"Redefining forever: Advancements, challenges, and opportunities in covalent organic frameworks for the remediation of forever chemicals","authors":"Asmaa Jrad , Bikash Garai , Samer Aouad , Gobinda Das , Connor M. Duncan , Mark A. Olson , Ali Trabolsi","doi":"10.1016/j.chempr.2025.102758","DOIUrl":"10.1016/j.chempr.2025.102758","url":null,"abstract":"<div><div>Per- and polyfluoroalkyl substances (PFAS), known as “forever chemicals,” are persistent pollutants with serious environmental and health impacts. Conventional water treatment methods often fall short of removing PFAS, prompting interest in advanced adsorbents such as covalent organic frameworks (COFs). This review explores recent advances in the development of COFs tailored for PFAS removal. The discussion focuses on key adsorption mechanisms, including hydrophobic, fluorophilic, electrostatic, and hydrogen-bonding interactions. In addition, optimizing pore size and particle size to improve the adsorption of PFAS is highlighted. The potential of COFs for practical applications is evaluated through their integration into composites, membranes, and adsorption columns, which enable continuous flow treatment. Despite promising results, challenges remain, including scalability, synthesis complexity, and realistic testing at environmentally relevant PFAS concentrations. The outline of future research directions aims to drive the advancement of COF-based solutions that have the potential to revolutionize PFAS remediation in real-world applications.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102758"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241672","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 : 2025-11-13DOI: 10.1016/j.chempr.2025.102782
Xue Chen , Yang Liu , Qing-Hui Guo
Stabilizing and characterizing cyclocarbons are a significant challenge in carbon materials science. In the August 14 issue of Science, Anderson and Gao employ a dynamic protection strategy to achieve the stable existence and comprehensive spectroscopic characterization of cyclo[48]carbon in ambient solution. This latest breakthrough will pave the way for uncovering new carbon allotropes.
{"title":"Catenated cyclocarbon: Stabilizing cyclo[48]carbon in solution with mechanical bonds","authors":"Xue Chen , Yang Liu , Qing-Hui Guo","doi":"10.1016/j.chempr.2025.102782","DOIUrl":"10.1016/j.chempr.2025.102782","url":null,"abstract":"<div><div>Stabilizing and characterizing cyclocarbons are a significant challenge in carbon materials science. In the August 14 issue of <em>Science</em>, Anderson and Gao employ a dynamic protection strategy to achieve the stable existence and comprehensive spectroscopic characterization of cyclo[48]carbon in ambient solution. This latest breakthrough will pave the way for uncovering new carbon allotropes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 11","pages":"Article 102782"},"PeriodicalIF":19.6,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247336","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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