Duncan K. Brownsey, Alexandre Alain Schoepfer, Jerome Waser
Highly functionalized cyclopropanes are often sought after chemical motifs as building blocks in synthetic and medicinal chemistry. However, their stereoselective synthesis using catalytic methods remains a challenge. Herein we report the first carboetherification of cyclopropenes using a palladium-catalyzed tethering strategy. This reaction was compatible with various functional groups, and could be performed using aryl, alkynyl and vinyl coupling partners. The carboetherification proceeded in a stereoselective manner imparted by the trifluoromethylated tether and afforded pentasubstituted spirocyclopropanes as single diastereoisomers, extending significantly the scope of metal-catalyzed difunctionalization of strained alkenes. This process could be easily scaled up to a gram scale, and product modifications were enabled either by acid mediated ring-opening or by accessing free alcohols and amines.
{"title":"Stereoselective Palladium-Catalyzed Carboetherification of Cyclopropenes via a Tethering Strategy","authors":"Duncan K. Brownsey, Alexandre Alain Schoepfer, Jerome Waser","doi":"10.1039/d5sc09351a","DOIUrl":"https://doi.org/10.1039/d5sc09351a","url":null,"abstract":"Highly functionalized cyclopropanes are often sought after chemical motifs as building blocks in synthetic and medicinal chemistry. However, their stereoselective synthesis using catalytic methods remains a challenge. Herein we report the first carboetherification of cyclopropenes using a palladium-catalyzed tethering strategy. This reaction was compatible with various functional groups, and could be performed using aryl, alkynyl and vinyl coupling partners. The carboetherification proceeded in a stereoselective manner imparted by the trifluoromethylated tether and afforded pentasubstituted spirocyclopropanes as single diastereoisomers, extending significantly the scope of metal-catalyzed difunctionalization of strained alkenes. This process could be easily scaled up to a gram scale, and product modifications were enabled either by acid mediated ring-opening or by accessing free alcohols and amines.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920467","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}
Understanding the in situ surface structure of electrodes is crucial for unraveling the synergistic mechanisms of electrolytes in interfacial electrocatalysis. Herein, using in situ electrochemical scanning tunneling microscopy (EC-STM), we unveil the electrolyte concentration-driven roughening of Au(111) surfaces under cathodic polarization. As the concentration of alkali metal cations (AM+) ([AM+]) decreases, the AM+-induced surface structure evolution proceeds from surface corrosion at 1 M, to the formation of surface pits alongside surface nanoclusters composed of released Au atoms at 0.5-0.3 M, and ultimately to the generation of pit-free nanoclusters via surface atomic migration at 0.2 M. Moreover, surface modifications modulate the electrode surface structure, enabling more pronounced structure evolution at lower bulk [AM+]. Electrochemical measurements correlate increased surface roughness with enhanced CO2 reduction reaction (CO2RR) performance. The results provide new perspective on understanding the role of AM+ in regulating the electrochemical interface, and microscopic insights into AM+ concentration-driven in situ surface structures, which is important for understanding electrolyte-mediated surface structure-activity relationships.
{"title":"Electrolyte Concentration Modulates the Surface Structure Evolution of Au(111) Cathodes","authors":"Yue Feng, Yu-Qi Wang, Jiaju Fu, Zi-Cong Wang, Dong Wang, Li-jun Wan","doi":"10.1039/d5sc07564e","DOIUrl":"https://doi.org/10.1039/d5sc07564e","url":null,"abstract":"Understanding the in situ surface structure of electrodes is crucial for unraveling the synergistic mechanisms of electrolytes in interfacial electrocatalysis. Herein, using in situ electrochemical scanning tunneling microscopy (EC-STM), we unveil the electrolyte concentration-driven roughening of Au(111) surfaces under cathodic polarization. As the concentration of alkali metal cations (AM<small><sup>+</sup></small>) ([AM<small><sup>+</sup></small>]) decreases, the AM<small><sup>+</sup></small>-induced surface structure evolution proceeds from surface corrosion at 1 M, to the formation of surface pits alongside surface nanoclusters composed of released Au atoms at 0.5-0.3 M, and ultimately to the generation of pit-free nanoclusters via surface atomic migration at 0.2 M. Moreover, surface modifications modulate the electrode surface structure, enabling more pronounced structure evolution at lower bulk [AM<small><sup>+</sup></small>]. Electrochemical measurements correlate increased surface roughness with enhanced CO<small><sub>2</sub></small> reduction reaction (CO<small><sub>2</sub></small>RR) performance. The results provide new perspective on understanding the role of AM<small><sup>+</sup></small> in regulating the electrochemical interface, and microscopic insights into AM<small><sup>+</sup></small> concentration-driven in situ surface structures, which is important for understanding electrolyte-mediated surface structure-activity relationships.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908086","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}
Zhixin Xie, Junpeng Deng, Dan Liu, Jieyu Lin, Tao Jiang, Xiaohui Wang, Wei Liu, Lin Ma, Fengyan Song, Zuping Xiong, Junru Chen, Jianyu Zhang, Carl Redshaw, Zujin Zhao, Xing Feng, Ben Zhong Tang
Understanding chiral dynamic mechanisms (from chirality generation and transfer, and amplification) is crucial for circularly polarized luminescent (CPL) materials. Herein, intrinsically chiral bipyrenyl-based enantiomers, R-5 and S-5, were first synthesized as model compounds to gain a deeper insight into their chiroptical properties and chirality amplification mechanisms. These enantiomers not only exhibit typical aggregation-induced emission (AIE) with a high solid-state fluorescence efficiency up to 0.66, but also display significant chirality amplification upon aggregation, with amplified |gCD| from 4.73 × 10−5 (10−7 M) to 7.34 × 10−3 (10−3 M), and |glum| values up to 4.68 × 10−4 in the solid state. Morphological and CP-fs-TA studies reveal that the amplified chiroptical properties stem from helical self-assembly and prolonged excited-state chiral conformational reorganization in aggregates. This work establishes a design strategy for high-performance CPL materials by integrating intrinsic chirality, AIE properties, and dynamic chirality amplification mechanisms.
{"title":"Unlocking intrinsically chiral bipyrenyl-based aggregation-induced emission luminogens: circularly polarized luminescence and dynamic chirality amplification","authors":"Zhixin Xie, Junpeng Deng, Dan Liu, Jieyu Lin, Tao Jiang, Xiaohui Wang, Wei Liu, Lin Ma, Fengyan Song, Zuping Xiong, Junru Chen, Jianyu Zhang, Carl Redshaw, Zujin Zhao, Xing Feng, Ben Zhong Tang","doi":"10.1039/d5sc08358c","DOIUrl":"https://doi.org/10.1039/d5sc08358c","url":null,"abstract":"Understanding chiral dynamic mechanisms (from chirality generation and transfer, and amplification) is crucial for circularly polarized luminescent (CPL) materials. Herein, intrinsically chiral bipyrenyl-based enantiomers, <strong><em>R-</em>5</strong> and <strong><em>S-</em>5</strong>, were first synthesized as model compounds to gain a deeper insight into their chiroptical properties and chirality amplification mechanisms. These enantiomers not only exhibit typical aggregation-induced emission (AIE) with a high solid-state fluorescence efficiency up to 0.66, but also display significant chirality amplification upon aggregation, with amplified |<em>g</em><small><sub>CD</sub></small>| from 4.73 × 10<small><sup>−5</sup></small> (10<small><sup>−7</sup></small> M) to 7.34 × 10<small><sup>−3</sup></small> (10<small><sup>−3</sup></small> M), and |<em>g</em><small><sub>lum</sub></small>| values up to 4.68 × 10<small><sup>−4</sup></small> in the solid state. Morphological and CP-fs-TA studies reveal that the amplified chiroptical properties stem from helical self-assembly and prolonged excited-state chiral conformational reorganization in aggregates. This work establishes a design strategy for high-performance CPL materials by integrating intrinsic chirality, AIE properties, and dynamic chirality amplification mechanisms.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908285","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}
Similar to PtIV prodrugs, AuIII anticancer complexes are believed to undergo intracellular reduction, thereby gaining their activity from the resulting AuI species. Unlike for PtIV, the underlying mechanism of this process remains poorly understood for AuIII. To elucidate this mechanism, we investigated the reaction of [Au(ppy)Cl2], a model AuIII complex (ppy: phenylpyridine), with two biologically relevant reductants: lipoic acid (lpa) and N-acetyl-L-cysteine-methyl ester (NAC-OMe). Our findings reveal that lpa transfers a hydride to the Au, while cysteine derivatives only bind to the metal. The Au–H complex, even visible in protic solvents by NMR spectroscopy, produced by lpa is essential for enabling a sequence of oxidative addition and reductive elimination reactions that lead to AuI species eventually. These observations provide valuable insights into the mechanisms by which anticancer gold drug candidates are reduced within the cell.
{"title":"Identification of Au-hydrides as key intermediates in the reduction of Au(III) prodrugs to active Au(I) species under protic conditions","authors":"Jasmine Ochs, Nils Metzler-Nolte","doi":"10.1039/d5sc06212h","DOIUrl":"https://doi.org/10.1039/d5sc06212h","url":null,"abstract":"Similar to Pt<small><sup>IV</sup></small> prodrugs, Au<small><sup>III</sup></small> anticancer complexes are believed to undergo intracellular reduction, thereby gaining their activity from the resulting Au<small><sup>I</sup></small> species. Unlike for Pt<small><sup>IV</sup></small>, the underlying mechanism of this process remains poorly understood for Au<small><sup>III</sup></small>. To elucidate this mechanism, we investigated the reaction of [Au(ppy)Cl<small><sub>2</sub></small>], a model Au<small><sup>III</sup></small> complex (ppy: phenylpyridine), with two biologically relevant reductants: lipoic acid (lpa) and <em>N</em>-acetyl-<small>L</small>-cysteine-methyl ester (NAC-OMe). Our findings reveal that lpa transfers a hydride to the Au, while cysteine derivatives only bind to the metal. The Au–H complex, even visible in protic solvents by NMR spectroscopy, produced by lpa is essential for enabling a sequence of oxidative addition and reductive elimination reactions that lead to Au<small><sup>I</sup></small> species eventually. These observations provide valuable insights into the mechanisms by which anticancer gold drug candidates are reduced within the cell.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908283","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}
Jennifer Johns, Mukul Mahanti, Thomas Hansen, M. Carmen Galan
Lewis acids are frequently used as catalysts in glycosylation reactions, however these reagents often suffer from significant limitations such as sensitivity to moisture and poor stereocontrol. Chalcogenonium catalysts have recently emerged as a new class of catalysts with improved Lewis acidity and stability. Here we describe a proof of concept study of the use of 1,2-oxaselenonium salts as effective organocatalysts for the direct and stereoselective dehydrative glycosylation with 1-hydroxy carbohydrates to give deoxyglycosides. The reaction is high yielding, stereoselective and amenable to a wide range of nucleophiles, including primary, secondary and tertiary alcohols and thiols. Experimental and computational mechanistic investigations suggest that the reaction proceeds through a cooperative mechanism involving the hemiacetal donor, acceptor, and catalyst. In this process, the Lewis acidic selenonium catalyst activates the donor, while the incoming alcohol nucleophile engages in a stabilizing hydrogen-bond interaction with the chalcogenonium triflate counterion. DFT calculations suggest a loose SN2-like transition state with a high degree of oxocarbenium ion character, reminiscent of the mechanism observed for glycosyl-modifying enzymes. The methodology is exemplified on the stereoselective synthesis of a tetrasaccharide in 52% yield.
{"title":"Hypervalent Chalcogenonium Organocatalysis for the Direct Stereoselective Synthesis of Deoxyglycosides from Hemiacetals","authors":"Jennifer Johns, Mukul Mahanti, Thomas Hansen, M. Carmen Galan","doi":"10.1039/d5sc07018j","DOIUrl":"https://doi.org/10.1039/d5sc07018j","url":null,"abstract":"Lewis acids are frequently used as catalysts in glycosylation reactions, however these reagents often suffer from significant limitations such as sensitivity to moisture and poor stereocontrol. Chalcogenonium catalysts have recently emerged as a new class of catalysts with improved Lewis acidity and stability. Here we describe a proof of concept study of the use of 1,2-oxaselenonium salts as effective organocatalysts for the direct and stereoselective dehydrative glycosylation with 1-hydroxy carbohydrates to give deoxyglycosides. The reaction is high yielding, stereoselective and amenable to a wide range of nucleophiles, including primary, secondary and tertiary alcohols and thiols. Experimental and computational mechanistic investigations suggest that the reaction proceeds through a cooperative mechanism involving the hemiacetal donor, acceptor, and catalyst. In this process, the Lewis acidic selenonium catalyst activates the donor, while the incoming alcohol nucleophile engages in a stabilizing hydrogen-bond interaction with the chalcogenonium triflate counterion. DFT calculations suggest a loose S<small><sub>N</sub></small>2-like transition state with a high degree of oxocarbenium ion character, reminiscent of the mechanism observed for glycosyl-modifying enzymes. The methodology is exemplified on the stereoselective synthesis of a tetrasaccharide in 52% yield.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908085","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}
Patterning polymer brushes represents a significantly controllable approach to surface modifications, capable of producing tailored interfacial properties. Particularly, multi-component patterned polymer brushes consist of various polymer types, thereby offering enhanced versatility in surface functionalization and interface regulation. Here, we present a novel DNA hybridization-based micro-contact printing technique (μCP) for the fabrication of patternedpolymer brushes, which enhances the precision and controllability of the patterning process. Initially, μCP is employed to immobilize thiol end-functionalized single-stranded DNA (ssDNA) to a gold substrate. The immobilized ssDNA subsequently hybridizes with initiator-functionalized complementary ssDNA, facilitating surface-initiated atom transfer radical polymerization (SI-ATRP) within the delineated regions to fabricate patterned polymer brushes. This method enables precise control over the molecular weight, chemical composition, and functionality of polymer brushes, and also allows reversible grafting of polymer brushes by modulating the unwinding and rehybridization of double-stranded DNA (dsDNA). Furthermore, this surface grafting technique exhibits remarkable adaptability for constructing binary and ternary brush surfaces through the integration of diverse polymer types. Consequently, it provides a robust platform for the development of multifunctional surfaces tailored for specific applications, such as biosensing and diagnostics.
{"title":"Erasable and Regenerated Multicomponent Patterned Polymer Brushes","authors":"Yuhong Cui, Baoluo He, Qian Ye, Feng Zhou, Bin Li","doi":"10.1039/d5sc08183a","DOIUrl":"https://doi.org/10.1039/d5sc08183a","url":null,"abstract":"Patterning polymer brushes represents a significantly controllable approach to surface modifications, capable of producing tailored interfacial properties. Particularly, multi-component patterned polymer brushes consist of various polymer types, thereby offering enhanced versatility in surface functionalization and interface regulation. Here, we present a novel DNA hybridization-based micro-contact printing technique (μCP) for the fabrication of patternedpolymer brushes, which enhances the precision and controllability of the patterning process. Initially, μCP is employed to immobilize thiol end-functionalized single-stranded DNA (ssDNA) to a gold substrate. The immobilized ssDNA subsequently hybridizes with initiator-functionalized complementary ssDNA, facilitating surface-initiated atom transfer radical polymerization (SI-ATRP) within the delineated regions to fabricate patterned polymer brushes. This method enables precise control over the molecular weight, chemical composition, and functionality of polymer brushes, and also allows reversible grafting of polymer brushes by modulating the unwinding and rehybridization of double-stranded DNA (dsDNA). Furthermore, this surface grafting technique exhibits remarkable adaptability for constructing binary and ternary brush surfaces through the integration of diverse polymer types. Consequently, it provides a robust platform for the development of multifunctional surfaces tailored for specific applications, such as biosensing and diagnostics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908284","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 significant progress has been made in the oriented conversion of CO2 to long-chain linear α-olefins (LAOs), cooperatively regulating C–O bond activation and C–C coupling via tailored catalyst microstructures remains a persistent challenge. Herein, a highly efficient Na/FeMn/ZrO2 catalyst has been fabricated through a covalent anchoring strategy, which achieves a LAOs/C4+ selectivity of 68% and an O/P ratio of 5.1 in CO2 hydrogenation to LAOs. There is a pronounced interaction between Fe species and MnCO3 in Na/FeMn/ZrO2 catalysts, which promotes the formation and stabilization of iron carbides. Meanwhile, Fe5C2–ZrO2 interfaces possess strong adsorption capacity for CO intermediates, resulting in the accumulation of generated CO on the Fe5C2 active sites. The higher CO concentration on the Fe5C2–ZrO2 interface is beneficial to the C–C coupling reaction, thereby significantly improving the production of high-value olefins. These results will provide a theoretical basis and guidance for developing efficient catalysts for the oriented conversion of CO2 to LAOs.
{"title":"Highly efficient CO2 hydrogenation to long-chain linear α-olefins via CO intermediate enrichment over Na/FeMn/ZrO2 catalysts","authors":"Kangzhou Wang, Tong Liu, Pengqi Hai, Shunnosuke Fujii, Chufeng Liu, Hanyao Song, Caixia Zhu, Guangbo Liu, Jianli Zhang, Zhou-jun Wang, Noritatsu Tsubaki","doi":"10.1039/d5sc08926c","DOIUrl":"https://doi.org/10.1039/d5sc08926c","url":null,"abstract":"Although significant progress has been made in the oriented conversion of CO<small><sub>2</sub></small> to long-chain linear α-olefins (LAOs), cooperatively regulating C–O bond activation and C–C coupling <em>via</em> tailored catalyst microstructures remains a persistent challenge. Herein, a highly efficient Na/FeMn/ZrO<small><sub>2</sub></small> catalyst has been fabricated through a covalent anchoring strategy, which achieves a LAOs/C<small><sub>4+</sub></small> selectivity of 68% and an O/P ratio of 5.1 in CO<small><sub>2</sub></small> hydrogenation to LAOs. There is a pronounced interaction between Fe species and MnCO<small><sub>3</sub></small> in Na/FeMn/ZrO<small><sub>2</sub></small> catalysts, which promotes the formation and stabilization of iron carbides. Meanwhile, Fe<small><sub>5</sub></small>C<small><sub>2</sub></small>–ZrO<small><sub>2</sub></small> interfaces possess strong adsorption capacity for CO intermediates, resulting in the accumulation of generated CO on the Fe<small><sub>5</sub></small>C<small><sub>2</sub></small> active sites. The higher CO concentration on the Fe<small><sub>5</sub></small>C<small><sub>2</sub></small>–ZrO<small><sub>2</sub></small> interface is beneficial to the C–C coupling reaction, thereby significantly improving the production of high-value olefins. These results will provide a theoretical basis and guidance for developing efficient catalysts for the oriented conversion of CO<small><sub>2</sub></small> to LAOs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908290","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}
Selective control of reactive oxygen species (ROS) generation captures the imagination of scientists because of its broad potential applications in photochemical reactions and biomedicine. Herein, we develop a novel supramolecular method enabling selective control of 1O2 and O2˙− generation based on host–guest assembly in solution and the solid state. The cationic guest G-I (Cl− as counteranions) lacks the ability to sensitize ROS but is transformed into an efficient organic photosensitizer through face-to-face dimerization within the cucurbit[8]uril (Q[8] or CB[8]) cavity via host–guest interactions. Although the G-I@Q[8] complex retains an identical assembly structure in both solution and solid-state phases, the differing electron transfer pathways of Cl− counteranions between phases result in selective control of 1O2 and O2˙− generation. This control is readily achievable by employing the host–guest complex as homogeneous or heterogeneous photocatalysts. Importantly, X-ray structural analysis reveals that the dimerized G-I@Q[8] framework exhibits remarkable formaldehyde (HCHO) adsorption capability due to the outer-surface interactions of the Q[8] host, enabling the solid G-I@Q[8] complex to serve as a highly efficient adsorption–photocatalytic platform for HCHO remediation. This study advances our understanding of macrocycle-mediated host–guest assembly in controlling ROS generation and photocatalysts with multiple functions.
{"title":"A cucurbit[8]uril-triggered ionic photosensitizer in solution and solid states: selective control of 1O2 and O2˙− generation","authors":"Haigen Nie, Jiao Tan, Yi Luo, Xin-long Ni","doi":"10.1039/d5sc06904a","DOIUrl":"https://doi.org/10.1039/d5sc06904a","url":null,"abstract":"Selective control of reactive oxygen species (ROS) generation captures the imagination of scientists because of its broad potential applications in photochemical reactions and biomedicine. Herein, we develop a novel supramolecular method enabling selective control of <small><sup>1</sup></small>O<small><sub>2</sub></small> and O<small><sub>2</sub></small>˙<small><sup>−</sup></small> generation based on host–guest assembly in solution and the solid state. The cationic guest <strong>G-I</strong> (Cl<small><sup>−</sup></small> as counteranions) lacks the ability to sensitize ROS but is transformed into an efficient organic photosensitizer through face-to-face dimerization within the cucurbit[8]uril (Q[8] or CB[8]) cavity <em>via</em> host–guest interactions. Although the <strong>G-I@Q[8]</strong> complex retains an identical assembly structure in both solution and solid-state phases, the differing electron transfer pathways of Cl<small><sup>−</sup></small> counteranions between phases result in selective control of <small><sup>1</sup></small>O<small><sub>2</sub></small> and O<small><sub>2</sub></small>˙<small><sup>−</sup></small> generation. This control is readily achievable by employing the host–guest complex as homogeneous or heterogeneous photocatalysts. Importantly, X-ray structural analysis reveals that the dimerized <strong>G-I@Q[8]</strong> framework exhibits remarkable formaldehyde (HCHO) adsorption capability due to the outer-surface interactions of the Q[8] host, enabling the solid <strong>G-I@Q[8]</strong> complex to serve as a highly efficient adsorption–photocatalytic platform for HCHO remediation. This study advances our understanding of macrocycle-mediated host–guest assembly in controlling ROS generation and photocatalysts with multiple functions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908289","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}
You Wu, Yangpeng Zhang, Hao Zhao, Yang Peng, Hailing Ma, Fangyuan Kang, Zhonghua Li, Yang Liu, Qichun Zhang
The electrocatalytic reduction of nitrate (NO3RR) to ammonia presents a viable solution for addressing nitrate pollution and offers an environmentally-friendly, energy-efficient alternative for industrial ammonia synthesis. However, the absence of efficient electrocatalysts impedes its industrial application. In this study, we constructed a porphyrin organic cage (PB-2) through the covalent-bonded self-assembly. Subsequently, metalized porphyrin organic cages PB-M (M = Co, Ni, Cu) were synthesized via post-modification of PB-2. These PB-M were utilized to elucidate the reaction pathway and intrinsic structure-performance relationship of the NO3RR. Experimental results indicate that PB-Co exhibits the highest activity and ammonia selectivity (FENH3 = 95.8 ± 1.06%, NH3 yield rate = 995.5 ± 28.4 µmol h−1 mgcat−1). Theoretical calculations reveal that the d-p orbital hybridization between the Co 3d orbital in PB-Co and the NO3– 2p orbital is the strongest one. PB-Co with a high d-band center of –0.97 eV and high adsorption energy for NO3– and H2O, promoting charge transfer and the production of active hydrogen, thereby reducing the activation energy barrier of NO3–. This research illuminates the intrinsic structure-activity relationship of metalized PB-M for the NO3RR, potentially providing valuable insights for the design of efficient electrocatalysts.
{"title":"Strong d-p Orbital Hybridization in Cobalt Porphyrin Cages Promotes Electrochemical Nitrate Reduction to Ammonia","authors":"You Wu, Yangpeng Zhang, Hao Zhao, Yang Peng, Hailing Ma, Fangyuan Kang, Zhonghua Li, Yang Liu, Qichun Zhang","doi":"10.1039/d5sc07183f","DOIUrl":"https://doi.org/10.1039/d5sc07183f","url":null,"abstract":"The electrocatalytic reduction of nitrate (NO3RR) to ammonia presents a viable solution for addressing nitrate pollution and offers an environmentally-friendly, energy-efficient alternative for industrial ammonia synthesis. However, the absence of efficient electrocatalysts impedes its industrial application. In this study, we constructed a porphyrin organic cage (PB-2) through the covalent-bonded self-assembly. Subsequently, metalized porphyrin organic cages PB-M (M = Co, Ni, Cu) were synthesized via post-modification of PB-2. These PB-M were utilized to elucidate the reaction pathway and intrinsic structure-performance relationship of the NO3RR. Experimental results indicate that PB-Co exhibits the highest activity and ammonia selectivity (FENH3 = 95.8 ± 1.06%, NH3 yield rate = 995.5 ± 28.4 µmol h−1 mgcat−1). Theoretical calculations reveal that the d-p orbital hybridization between the Co 3d orbital in PB-Co and the NO3– 2p orbital is the strongest one. PB-Co with a high d-band center of –0.97 eV and high adsorption energy for NO3– and H2O, promoting charge transfer and the production of active hydrogen, thereby reducing the activation energy barrier of NO3–. This research illuminates the intrinsic structure-activity relationship of metalized PB-M for the NO3RR, potentially providing valuable insights for the design of efficient electrocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908291","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}
Hongbei Wei, Liren Xu, Ke Wei, Wenhai Bian, Yifan Wen, Wanyi Yu, Hui Zhang, Tony D. James, Xiaolong Sun
Aberrant aggregation of membrane proteins is a pathological hallmark of various diseases, including neurodegenerative disorders and cancer. The visualization of membrane protein aggregation has emerged as an important approach for investigating protein structure and function, as well as for studying disease mechanisms and therapeutic interventions. While significant progress has been made in modifying membrane proteins and studying related biological processes, membrane protein aggregation remains underexplored, largely due to the lack of simple and effective methods for directly labeling native proteins and tracking this process in real time. With this research, we present a fluorescent probe equipped with a membrane-anchoring unit and a covalent reactive moiety for visualizing membrane protein dynamics, which operates via a two-stage mechanism: first, rapid electrostatic interaction-mediated localization to the cell membrane, followed by chemoselective macrocyclization with thiol and amine groups on membrane proteins to form a fluorescent conjugate, whose emission is substantially enhanced due to restriction of twisted intramolecular charge transfer (TICT) within the confined microenvironment induced by protein aggregation. Leveraging this mechanism, the probe successfully reports membrane protein aggregation triggered by diverse stressors, such as redox imbalance and chemotherapeutic agents, while also capturing distinct membrane reorganization dynamics. With features of biocompatibility, wash-free performance, and long-term membrane retention, this probe provides an alternative tool for evaluating the complex structural dynamics of membrane proteins and offers potential for developing targeted therapeutic strategies.
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