Christopher Grainger, St. John Whittaker, Dencie Desrosiers, Stephanie S. Lee, Alexander G. Shtukenberg, Bart Kahr
In this journal, Moses Gomberg’s 1900 revelation, “An Instance of Trivalent Carbon: Triphenylmethyl”, lauded on a centennial National Historic Chemical Landmark for challenging the “prevailing belief that carbon can only have four bonds”, shifts its place in our imaginations as the facts given here are accommodated. In 1898 Gomberg presumed that he had made a molecular complex of bromotriphenylmethane and two neutral I2 molecules. But he was mistaken. Instead, Gomberg produced a mixture of three persistent single crystals of the triphenylmethyl cation before he published his aforementioned, controversial paper. Trigonal carbon coordination was the crack in the valency rules that had organized chemistry prior to the invention of quantum mechanics. Gomberg did not recognize the wealth of trivalent carbon compounds he had in hand before the proposition of the radical and corresponding cation thereafter. This work alludes to a counterfactual history.
{"title":"Gomberg’s Earlier “Instance of Trivalent Carbon”","authors":"Christopher Grainger, St. John Whittaker, Dencie Desrosiers, Stephanie S. Lee, Alexander G. Shtukenberg, Bart Kahr","doi":"10.1021/jacs.5c21781","DOIUrl":"https://doi.org/10.1021/jacs.5c21781","url":null,"abstract":"In this journal, Moses Gomberg’s 1900 revelation, “An Instance of Trivalent Carbon: Triphenylmethyl”, lauded on a centennial National Historic Chemical Landmark for challenging the “prevailing belief that carbon can only have four bonds”, shifts its place in our imaginations as the facts given here are accommodated. In 1898 Gomberg presumed that he had made a molecular complex of bromotriphenylmethane and two neutral I<sub>2</sub> molecules. But he was mistaken. Instead, Gomberg produced a mixture of three persistent single crystals of the triphenylmethyl cation before he published his aforementioned, controversial paper. Trigonal carbon coordination was the crack in the valency rules that had organized chemistry prior to the invention of quantum mechanics. Gomberg did not recognize the wealth of trivalent carbon compounds he had in hand before the proposition of the radical and corresponding cation thereafter. This work alludes to a counterfactual history.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122262","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}
Elizabeth Zhang, John Holoubek, Hao Lyu, Yuqi Li, Jacob Florian, Sanzeeda Baig Shuchi, Jane K.J. Lee, Lukas Michalek, Tianyang Chen, Zhouyi Chen, Il Rok Choi, Xuelin Guo, Luca Mondonico, Yi Cui, Zhenan Bao
Lithium metal batteries offer high energy density but suffer from persistent interphase instability, where continuous corrosion, solid electrolyte interphase (SEI) growth and poor lithium deposition morphology remain key barriers to long cycle and calendar life. Here, we introduce a novel concept of dynamic monolayers on Li metal anodes, consisting of electric field-responsive molecules that assemble into packed, structured layers at the lithium interphase under an applied voltage. We employed electrochemical quartz crystal microbalance with dissipation monitoring for in situ verification of the field responsiveness and packing behavior of these molecules. Dynamic monolayers with stronger packing are found to promote more inorganic-rich SEI and chunkier lithium growth, as directly observed by cryogenic X-ray photoelectron spectroscopy and operando optical microscopy. Together, these interfacial improvements translate into enhanced Coulombic Efficiency, reduced overpotential, and improved long-term cycling stability across Li||Cu, Li||Li, ultrathin lithium (20 μm) and anode-free NMC811 configurations. Dynamic monolayers potentially provide a broadly applicable approach for tackling interfacial challenges across a range of alkali metal battery systems.
{"title":"Field-Responsive Dynamic Monolayer Regulated Interphase for Enhanced Lithium Metal Batteries","authors":"Elizabeth Zhang, John Holoubek, Hao Lyu, Yuqi Li, Jacob Florian, Sanzeeda Baig Shuchi, Jane K.J. Lee, Lukas Michalek, Tianyang Chen, Zhouyi Chen, Il Rok Choi, Xuelin Guo, Luca Mondonico, Yi Cui, Zhenan Bao","doi":"10.1021/jacs.5c19365","DOIUrl":"https://doi.org/10.1021/jacs.5c19365","url":null,"abstract":"Lithium metal batteries offer high energy density but suffer from persistent interphase instability, where continuous corrosion, solid electrolyte interphase (SEI) growth and poor lithium deposition morphology remain key barriers to long cycle and calendar life. Here, we introduce a novel concept of dynamic monolayers on Li metal anodes, consisting of electric field-responsive molecules that assemble into packed, structured layers at the lithium interphase under an applied voltage. We employed electrochemical quartz crystal microbalance with dissipation monitoring for in situ verification of the field responsiveness and packing behavior of these molecules. Dynamic monolayers with stronger packing are found to promote more inorganic-rich SEI and chunkier lithium growth, as directly observed by cryogenic X-ray photoelectron spectroscopy and <i>operando</i> optical microscopy. Together, these interfacial improvements translate into enhanced Coulombic Efficiency, reduced overpotential, and improved long-term cycling stability across Li||Cu, Li||Li, ultrathin lithium (20 μm) and anode-free NMC811 configurations. Dynamic monolayers potentially provide a broadly applicable approach for tackling interfacial challenges across a range of alkali metal battery systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122521","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}
Federico Belnome, Antonio Pulcinella, Stefano Bonciolini, Mattia Lepori, Oleksandr P. Datsenko, Zhen He, Matteo Gasparetto, Pavel K. Mykhailiuk, Bas de Bruin, Timothy Noël
The incorporation of fluorinated alkyl groups is a powerful strategy to fine-tune the physicochemical and biological properties of organic molecules. In particular, the trifluoroethyl (−CH2CF3) substituent offers a valuable C1-homologated analogue of trifluoromethylated motifs, yet methods for its direct introduction at sp3-hybridized carbon centers remain scarce. Here, we report a general and practical approach for the decarboxylative trifluoroethylation of aliphatic carboxylic acids under near visible-light irradiation. The transformation proceeds via photoinduced generation of a carbon-centered radical that adds to a bench-stable sulfonyl hydrazone reagent derived from trifluoroacetaldehyde, followed by light-driven fragmentation to furnish the desired trifluoroethylated products. The reaction operates under mild conditions, exhibits broad substrate scope, including primary, secondary, and tertiary acids, and tolerates diverse functional groups. Conceptually, the process can be viewed as a C1-homologative trifluoromethylation, offering a distinct retrosynthetic disconnection for the synthesis of trifluoroethyl-containing building blocks. Mechanistic studies combining experimental and computational analysis provide insight into the fragmentation behavior of the key alkylated sulfonyl hydrazide intermediate.
{"title":"A C1-Homologative Trifluoromethylation: Light-Driven Decarboxylative Trifluoroethylation of Carboxylic Acids","authors":"Federico Belnome, Antonio Pulcinella, Stefano Bonciolini, Mattia Lepori, Oleksandr P. Datsenko, Zhen He, Matteo Gasparetto, Pavel K. Mykhailiuk, Bas de Bruin, Timothy Noël","doi":"10.1021/jacs.5c21423","DOIUrl":"https://doi.org/10.1021/jacs.5c21423","url":null,"abstract":"The incorporation of fluorinated alkyl groups is a powerful strategy to fine-tune the physicochemical and biological properties of organic molecules. In particular, the trifluoroethyl (−CH<sub>2</sub>CF<sub>3</sub>) substituent offers a valuable C<sub>1</sub>-homologated analogue of trifluoromethylated motifs, yet methods for its direct introduction at sp<sup>3</sup>-hybridized carbon centers remain scarce. Here, we report a general and practical approach for the decarboxylative trifluoroethylation of aliphatic carboxylic acids under near visible-light irradiation. The transformation proceeds via photoinduced generation of a carbon-centered radical that adds to a bench-stable sulfonyl hydrazone reagent derived from trifluoroacetaldehyde, followed by light-driven fragmentation to furnish the desired trifluoroethylated products. The reaction operates under mild conditions, exhibits broad substrate scope, including primary, secondary, and tertiary acids, and tolerates diverse functional groups. Conceptually, the process can be viewed as a C<sub>1</sub>-homologative trifluoromethylation, offering a distinct retrosynthetic disconnection for the synthesis of trifluoroethyl-containing building blocks. Mechanistic studies combining experimental and computational analysis provide insight into the fragmentation behavior of the key alkylated sulfonyl hydrazide intermediate.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122261","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}
Gianfranco Decandia, Gianluigi Albano, Katarina Gugujonović, Elisabeth Leeb, Angela Punzi, Pietro Cotugno, Riccardo Pò, Paolo Biagini, Carmine Gaeta, Mihai Irimia-Vladu, Markus Clark Scharber, Gianluca Maria Farinola
The first synthesis of π-conjugated polymers for organic solar cells (OSCs) via infrared (IR) irradiation-assisted Pd-catalyzed direct C–H bond arylation polymerization (DArP) is reported. Reactions have been carried out under air and nonanhydrous conditions, in the presence of a very small amount (only 3.0 equiv) of cyclopentyl methyl ether (CPME). Donor–acceptor (D-A) heteroaryl-based π-conjugated polymers having different structures have been obtained in short reaction time. A more detailed investigation has been carried out for the donor polymer PBDB-T: three batches, synthesized via IR irradiation-assisted DArP and, for two of them, subjected to end-capping reactions, were tested in organic solar cells (OSCs), achieving maximum power conversion efficiency (PCE) of 4.8% in non-optimized device, which is comparable to commercially available PBDB-T used as reference (5.9%). Our results confirm that the experimental advantages of DArP reactions combined with the use of IR irradiation and the quasi-solvent-free conditions represent a straightforward and sustainable route to heterocycle-based polymers for organic solar cells.
{"title":"A Fast and Convenient Synthesis of Heterocycle-Based Polymers via Infrared Irradiation-Assisted Direct C–H Bond Arylation Polymerization in Quasi-Solvent-Free Conditions","authors":"Gianfranco Decandia, Gianluigi Albano, Katarina Gugujonović, Elisabeth Leeb, Angela Punzi, Pietro Cotugno, Riccardo Pò, Paolo Biagini, Carmine Gaeta, Mihai Irimia-Vladu, Markus Clark Scharber, Gianluca Maria Farinola","doi":"10.1021/jacs.5c10309","DOIUrl":"https://doi.org/10.1021/jacs.5c10309","url":null,"abstract":"The first synthesis of π-conjugated polymers for organic solar cells (OSCs) via infrared (IR) irradiation-assisted Pd-catalyzed direct C–H bond arylation polymerization (DArP) is reported. Reactions have been carried out under air and nonanhydrous conditions, in the presence of a very small amount (only 3.0 equiv) of cyclopentyl methyl ether (CPME). Donor–acceptor (D-A) heteroaryl-based π-conjugated polymers having different structures have been obtained in short reaction time. A more detailed investigation has been carried out for the donor polymer <b>PBDB-T</b>: three batches, synthesized via IR irradiation-assisted DArP and, for two of them, subjected to end-capping reactions, were tested in organic solar cells (OSCs), achieving maximum power conversion efficiency (PCE) of 4.8% in non-optimized device, which is comparable to commercially available <b>PBDB-T</b> used as reference (5.9%). Our results confirm that the experimental advantages of DArP reactions combined with the use of IR irradiation and the quasi-solvent-free conditions represent a straightforward and sustainable route to heterocycle-based polymers for organic solar cells.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122265","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}
Artificial photosynthesis that converts CO2 into value-added chemicals under mild conditions remains a key goal in sustainable catalysis. Hybrid photocatalysts that integrate molecular CO2 reduction cocatalysts with semiconductor light absorbers provide a versatile platform to combine molecular-level selectivity with solid-state photostability. However, their quantum efficiencies have generally remained low, partly because side reactions of the molecular component have been overlooked. Here we show that suppressing a photochemical ligand-exchange reaction of a surface-anchored Ru complex, trans(Cl)-[Ru(bpy(CH2PO3H2)2)(CO)2Cl2], markedly enhances photocatalytic CO2 reduction over a well-established Ag-loaded polymeric carbon nitride hybrid. The suppression of this undesirable photochemical reaction is achievable under low-intensity visible light when the Ru complex is loaded at a high density. The optimized system achieves selective CO2-to-formate conversion with an apparent quantum yield of 27.7% at 400 nm and a formate selectivity greater than 99%. Spectroscopic analyses reveal that the suppression of photochemical ligand exchange maintains the original Ru coordination environment with large driving force for CO2 reduction, thereby stabilizing the catalytic cycle and facilitating efficient interfacial electron transfer. These results reveal an unrecognized limitation in molecule/semiconductor hybrid photocatalysts─photochemical ligand exchange of the molecular cocatalyst─and demonstrate that controlling such side reactions offers an important strategy to design high-efficiency CO2 reduction systems.
{"title":"Elucidating the Origin of Hidden Limitations in Ru-Complex/Ag/Polymeric Carbon Nitride Hybrid Photocatalysts for Visible-Light CO2 Reduction","authors":"Ryuichi Nakada, Rikuya Nagao, Jo Onodera, Xian Zhang, Masahito Oura, Megumi Okazaki, Toshiya Tanaka, Riku Koda, Minato Tanaka, Ken Onda, Kazuhiko Maeda","doi":"10.1021/jacs.5c21374","DOIUrl":"https://doi.org/10.1021/jacs.5c21374","url":null,"abstract":"Artificial photosynthesis that converts CO<sub>2</sub> into value-added chemicals under mild conditions remains a key goal in sustainable catalysis. Hybrid photocatalysts that integrate molecular CO<sub>2</sub> reduction cocatalysts with semiconductor light absorbers provide a versatile platform to combine molecular-level selectivity with solid-state photostability. However, their quantum efficiencies have generally remained low, partly because side reactions of the molecular component have been overlooked. Here we show that suppressing a photochemical ligand-exchange reaction of a surface-anchored Ru complex, <i>trans</i>(Cl)-[Ru(bpy(CH<sub>2</sub>PO<sub>3</sub>H<sub>2</sub>)<sub>2</sub>)(CO)<sub>2</sub>Cl<sub>2</sub>], markedly enhances photocatalytic CO<sub>2</sub> reduction over a well-established Ag-loaded polymeric carbon nitride hybrid. The suppression of this undesirable photochemical reaction is achievable under low-intensity visible light when the Ru complex is loaded at a high density. The optimized system achieves selective CO<sub>2</sub>-to-formate conversion with an apparent quantum yield of 27.7% at 400 nm and a formate selectivity greater than 99%. Spectroscopic analyses reveal that the suppression of photochemical ligand exchange maintains the original Ru coordination environment with large driving force for CO<sub>2</sub> reduction, thereby stabilizing the catalytic cycle and facilitating efficient interfacial electron transfer. These results reveal an unrecognized limitation in molecule/semiconductor hybrid photocatalysts─photochemical ligand exchange of the molecular cocatalyst─and demonstrate that controlling such side reactions offers an important strategy to design high-efficiency CO<sub>2</sub> reduction systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"83 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122307","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}
Heterointerfaces in composite electrodes play critical roles in catalytic performance, but methods for precise optimization of them are still lacking and remain challenging. Here, we propose an innovative ion-directional migration strategy to achieve precise optimization of heterointerfaces in a composite electrode of a solid oxide electrolysis cell (SOEC) for ultraefficient CO2 electrolysis. Specifically, a composite electrode composed of Sr2Fe1.5Mo0.5O6−δ perovskite and Ru0.05Ce0.95O2 fluorite with a Ru loading of only 0.89 wt % (denoted as SFM-005Ru@CeO2) is elaborately designed. Thermal treatment induces directed migration of Ru ions from the fluorite phase to the perovskite–fluorite heterointerfaces and subsurfaces of Sr2Fe1.5Mo0.5O6−δ, enabling precise optimization of the oxygen vacancy concentration and the electronic environment of Fe cations inside the perovskite phase at the subsurface, thereby markedly enhancing O2–/e– conductivity and CO2 reduction reaction (CO2RR) activity. Impressively, a SOEC supported by an La0.8Sr0.2Ga0.8Mg0.2O3−δ (LSGM, 140 μm) electrolyte and employing the SFM-005Ru@CeO2 composite with a precisely optimized heterointerface as the cathode delivers an ultrahigh current density of 3.80 A cm–2 @1.5 V at 800 °C for direct CO2 electrolysis, superior to all previously reported electrodes. It also shows excellent stability over 200 h under harsh operating conditions (750 °C, 1.6 A cm–2). This work opens up a new avenue to improve the performance of composite materials in various catalytic systems through precise heterointerface engineering.
复合电极的异质界面在催化性能中起着至关重要的作用，但精确优化异质界面的方法仍然缺乏，而且仍然具有挑战性。在此，我们提出了一种创新的离子定向迁移策略，以实现固体氧化物电解电池（SOEC）复合电极中异质界面的精确优化，以实现超高效的CO2电解。具体来说，设计了一种由Sr2Fe1.5Mo0.5O6−δ钙钛矿和Ru0.05Ce0.95O2萤石组成的复合电极，Ru负载量仅为0.89 wt %（表示为SFM-005Ru@CeO2）。热处理诱导Ru离子从萤石相定向迁移到Sr2Fe1.5Mo0.5O6−δ的钙钛矿-萤石异质界面和亚表面，从而精确优化了钙钛矿亚表面内Fe离子的氧空位浓度和电子环境，从而显著提高了O2 - /e -电导率和CO2还原反应（CO2RR）活性。令人印象深刻的是，由la0.8 sr0.2 ga0.8 mg0.3 2o3−δ (LSGM, 140 μm)电解质支持的SOEC采用具有精确优化异质界面的SFM-005Ru@CeO2复合材料作为阴极，在800°C下可提供3.80 a cm-2 @1.5 V的超高电流密度，用于直接CO2电解，优于所有先前报道的电极。在恶劣的操作条件下（750°C, 1.6 A cm-2），它也表现出200小时以上的优异稳定性。这项工作为通过精确的异质界面工程来提高复合材料在各种催化体系中的性能开辟了一条新的途径。
{"title":"Directional Ion Migration Enables Precise Heterointerface Optimization for High-Temperature CO2 Electrolysis","authors":"Shuai Liu, Ruixi Qiao, Meiting Yang, Wei Feng, Baocheng Xiong, Desheng Feng, Guangming Yang, Wei-Hsiang Huang, Min-Hsin Yeh, Chih-Wen Pao, Zhiwei Hu, Xiaomin Xu, Wei Cao, Ran Ran, Wei Zhou, Yinlong Zhu","doi":"10.1021/jacs.5c21833","DOIUrl":"https://doi.org/10.1021/jacs.5c21833","url":null,"abstract":"Heterointerfaces in composite electrodes play critical roles in catalytic performance, but methods for precise optimization of them are still lacking and remain challenging. Here, we propose an innovative ion-directional migration strategy to achieve precise optimization of heterointerfaces in a composite electrode of a solid oxide electrolysis cell (SOEC) for ultraefficient CO<sub>2</sub> electrolysis. Specifically, a composite electrode composed of Sr<sub>2</sub>Fe<sub>1.5</sub>Mo<sub>0.5</sub>O<sub>6−δ</sub> perovskite and Ru<sub>0.05</sub>Ce<sub>0.95</sub>O<sub>2</sub> fluorite with a Ru loading of only 0.89 wt % (denoted as SFM-005Ru@CeO<sub>2</sub>) is elaborately designed. Thermal treatment induces directed migration of Ru ions from the fluorite phase to the perovskite–fluorite heterointerfaces and subsurfaces of Sr<sub>2</sub>Fe<sub>1.5</sub>Mo<sub>0.5</sub>O<sub>6−δ</sub>, enabling precise optimization of the oxygen vacancy concentration and the electronic environment of Fe cations inside the perovskite phase at the subsurface, thereby markedly enhancing O<sup>2–</sup>/e<sup>–</sup> conductivity and CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) activity. Impressively, a SOEC supported by an La<sub>0.8</sub>Sr<sub>0.2</sub>Ga<sub>0.8</sub>Mg<sub>0.2</sub>O<sub>3−δ</sub> (LSGM, 140 μm) electrolyte and employing the SFM-005Ru@CeO<sub>2</sub> composite with a precisely optimized heterointerface as the cathode delivers an ultrahigh current density of 3.80 A cm<sup>–2</sup> @1.5 V at 800 °C for direct CO<sub>2</sub> electrolysis, superior to all previously reported electrodes. It also shows excellent stability over 200 h under harsh operating conditions (750 °C, 1.6 A cm<sup>–2</sup>). This work opens up a new avenue to improve the performance of composite materials in various catalytic systems through precise heterointerface engineering.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"384 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122309","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}
Raoul F. Vaz, Leonid S. Brown, Vladimir Ladizhansky
Nonannular lipids tightly associate with membrane proteins, influencing their structure and function. Here, we present a solid-state NMR (ssNMR)-based strategy to localize such lipids on protein surfaces with a high specificity. We previously identified a tightly bound glycophospholipid which copurifies with Anabaena Sensory Rhodopsin trimers and displays resolved NMR signals. By introducing paramagnetic labels at defined sites and measuring paramagnetic relaxation enhancements (PREs), we triangulate the lipid’s position near a periplasmic intermonomer cleft. Docking calculations guided by PRE restraints further define a nonannular lipid binding site. Our approach provides a broadly applicable framework for mapping tightly bound lipids in membrane proteins under native-like conditions.
{"title":"Triangulating a Tightly Bound Lipid on a Membrane Protein by Paramagnetic Solid-State NMR","authors":"Raoul F. Vaz, Leonid S. Brown, Vladimir Ladizhansky","doi":"10.1021/jacs.5c22235","DOIUrl":"https://doi.org/10.1021/jacs.5c22235","url":null,"abstract":"Nonannular lipids tightly associate with membrane proteins, influencing their structure and function. Here, we present a solid-state NMR (ssNMR)-based strategy to localize such lipids on protein surfaces with a high specificity. We previously identified a tightly bound glycophospholipid which copurifies with <i>Anabaena</i> Sensory Rhodopsin trimers and displays resolved NMR signals. By introducing paramagnetic labels at defined sites and measuring paramagnetic relaxation enhancements (PREs), we triangulate the lipid’s position near a periplasmic intermonomer cleft. Docking calculations guided by PRE restraints further define a nonannular lipid binding site. Our approach provides a broadly applicable framework for mapping tightly bound lipids in membrane proteins under native-like conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122330","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}
Xiang Zhou, Zhonglin You, Baoting Wang, Yao Huang, Israel Fernández, Yang Xiong
Nitrogen-containing heterocycles are essential to chemical and life sciences due to their diverse biological activities and functional versatility. However, in contrast to 3D bioisosteres of the benzene ring, analogous bioisosteres of nitrogen-containing heterocycles remain quite limited despite several recent developments, where pyridone, a “central bioisostere” for amide, phenyl, pyridine, pyridine N-oxides, and phenols, should be especially highlighted. Herein, we report an effective route for the divergent synthesis of 3-azabicyclo[3.1.1]heptan-2-ones as promising pyridone bioisosteres from bicycle-butanes (BCBs) via Ir/Lewis acid-catalyzed programmed hydrogen atom transfer of C(sp3)–H bonds and subsequent cyclization under visible light. Mechanistic evidence and DFT calculations suggest that the acid catalyst was crucial for the success via isomerizing BCBs and modulating the reactivity of the diradical intermediates to unlock a challenging carbon-to-carbon DHAT and subsequent cyclization that allows the functionalization of various C(sp3)–H bonds, accessing underexplored 3-azabicyclo[3.1.1]heptan-2-ones. Lastly, further transformations and applications in synthetic chemistry and bioactive molecules reveal their promising potential in organic synthesis, materials science, and pharmaceuticals.
{"title":"Visible-Light-Mediated Lewis Acid-Catalyzed Diradical Hydrogen Atom Transfer Reaction of Bicyclo[1.1.0]butanes","authors":"Xiang Zhou, Zhonglin You, Baoting Wang, Yao Huang, Israel Fernández, Yang Xiong","doi":"10.1021/jacs.5c18500","DOIUrl":"https://doi.org/10.1021/jacs.5c18500","url":null,"abstract":"Nitrogen-containing heterocycles are essential to chemical and life sciences due to their diverse biological activities and functional versatility. However, in contrast to 3D bioisosteres of the benzene ring, analogous bioisosteres of nitrogen-containing heterocycles remain quite limited despite several recent developments, where pyridone, a “central bioisostere” for amide, phenyl, pyridine, pyridine <i>N</i>-oxides, and phenols, should be especially highlighted. Herein, we report an effective route for the divergent synthesis of 3-azabicyclo[3.1.1]heptan-2-ones as promising pyridone bioisosteres from bicycle-butanes (BCBs) via Ir/Lewis acid-catalyzed programmed hydrogen atom transfer of C(sp<sup>3</sup>)–H bonds and subsequent cyclization under visible light. Mechanistic evidence and DFT calculations suggest that the acid catalyst was crucial for the success via isomerizing BCBs and modulating the reactivity of the diradical intermediates to unlock a challenging carbon-to-carbon DHAT and subsequent cyclization that allows the functionalization of various C(sp<sup>3</sup>)–H bonds, accessing underexplored 3-azabicyclo[3.1.1]heptan-2-ones. Lastly, further transformations and applications in synthetic chemistry and bioactive molecules reveal their promising potential in organic synthesis, materials science, and pharmaceuticals.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"110 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122299","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}
Qian Wang, Ruitao Wen, Monotosh Mondal, Zhen Shi, Scott Nalepa, Kelli Henshaw, Michael D. Schulz, Christina M. Rost, Carla Slebodnick, Lina Quan
Lead-based halide perovskites have demonstrated remarkable success in applications such as photovoltaics, photodetectors, and LEDs, owing to their defect tolerance and exceptional optical and electrical properties. However, the major issue of lead toxicity has drawn considerable attention, requiring an appropriate solution for the efficient, sustainable recycling or upcycling of lead halide perovskite precursors. In this study, we present a supramolecular approach to transform 3D perovskites into nonlinear optical hybrid materials by employing crown ethers as symmetry-breaking molecular templates. Robust hydrogen-bonding interactions between the crown ethers and the cationic components of the perovskites enable selective extraction and guided self-assembly of perovskite precursors (lead halides and organic amines) into supramolecular metal–halide hybrid crystals. These hybrids exhibit strong room-temperature nonlinear optical (NLO) responses, as confirmed by polarization-resolved second-harmonic generation (SHG) measurements showing a large modulation depth of ∼68%. In addition, the supramolecular crystals display enhanced photoluminescence and improved environmental stability compared with their parent perovskite phases. Notably, upon thermal annealing, they can be reverted to the pristine 3D perovskite phase with restored crystal structure and emission, completing a reversible and byproduct-free recycling loop. This work establishes a sustainable and reversible pathway that couples perovskite upcycling with emergent nonlinear optical functionality, enabling phase-preserving storage and on-demand regeneration.
{"title":"Supramolecular Templating of 3D Metal Halide Perovskites into Noncentrosymmetric Hybrids with High Nonlinear Optical Responses","authors":"Qian Wang, Ruitao Wen, Monotosh Mondal, Zhen Shi, Scott Nalepa, Kelli Henshaw, Michael D. Schulz, Christina M. Rost, Carla Slebodnick, Lina Quan","doi":"10.1021/jacs.5c19291","DOIUrl":"https://doi.org/10.1021/jacs.5c19291","url":null,"abstract":"Lead-based halide perovskites have demonstrated remarkable success in applications such as photovoltaics, photodetectors, and LEDs, owing to their defect tolerance and exceptional optical and electrical properties. However, the major issue of lead toxicity has drawn considerable attention, requiring an appropriate solution for the efficient, sustainable recycling or upcycling of lead halide perovskite precursors. In this study, we present a supramolecular approach to transform 3D perovskites into nonlinear optical hybrid materials by employing crown ethers as symmetry-breaking molecular templates. Robust hydrogen-bonding interactions between the crown ethers and the cationic components of the perovskites enable selective extraction and guided self-assembly of perovskite precursors (lead halides and organic amines) into supramolecular metal–halide hybrid crystals. These hybrids exhibit strong room-temperature nonlinear optical (NLO) responses, as confirmed by polarization-resolved second-harmonic generation (SHG) measurements showing a large modulation depth of ∼68%. In addition, the supramolecular crystals display enhanced photoluminescence and improved environmental stability compared with their parent perovskite phases. Notably, upon thermal annealing, they can be reverted to the pristine 3D perovskite phase with restored crystal structure and emission, completing a reversible and byproduct-free recycling loop. This work establishes a sustainable and reversible pathway that couples perovskite upcycling with emergent nonlinear optical functionality, enabling phase-preserving storage and on-demand regeneration.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"2675 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122302","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}
Kodimana Ramakrishnan Pradeep, Paribesh Acharyya, Pronoy Nandi, Thomas S. Ie, Beiye C. Li, David J. Gosztola, Gregory S. Engel, Richard D. Schaller, Mercouri G. Kanatzidis
Two-dimensional (2D) hybrid bismuth halide perovskites have emerged as promising lead-free materials for optoelectronic applications due to their solution processability and tunable structures. Here, we investigate 2D layered hybrid perovskite MA3Bi2I6Cl3 using temperature-dependent photoluminescence (PL) and femtosecond transient absorption spectroscopy. Our results reveal strong coupling between excitons and phonons, evidenced by giant Huang–Rhys factors, coherent phonon oscillations, and ultrafast carrier self-trapping into small-polaron and self-trapped exciton (STE) states. These processes appear as time-dependent ground-state bleach and photoinduced absorption features, highlighting the influence of the lattice in carrier dynamics. Wavelength- and time-resolved measurements reveal that PL emission is dominated by STEs, while free exciton emission is weak and short-lived. By comparing 2D MA3Bi2I6Cl3 with 0D MA3Bi2I9, which contains molecularly isolated [BiI6]3− octahedra and 2D MA3Bi2Br9 perovskites, we demonstrate how halide composition and structural dimensionality influence the balance between free exciton populations and carrier localization. These insights uncover the intrinsic kinetic landscape of photoexcited states in MA3Bi2I6Cl3. Overall, our study contributes to a mechanistic understanding of exciton–phonon interactions in lead-free 2D perovskites.
{"title":"Ultrafast Carrier Self-Trapping Driven by Strong Exciton–Phonon Coupling in 2D MA3Bi2I6Cl3 Perovskite","authors":"Kodimana Ramakrishnan Pradeep, Paribesh Acharyya, Pronoy Nandi, Thomas S. Ie, Beiye C. Li, David J. Gosztola, Gregory S. Engel, Richard D. Schaller, Mercouri G. Kanatzidis","doi":"10.1021/jacs.5c18767","DOIUrl":"https://doi.org/10.1021/jacs.5c18767","url":null,"abstract":"Two-dimensional (2D) hybrid bismuth halide perovskites have emerged as promising lead-free materials for optoelectronic applications due to their solution processability and tunable structures. Here, we investigate 2D layered hybrid perovskite MA<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub> using temperature-dependent photoluminescence (PL) and femtosecond transient absorption spectroscopy. Our results reveal strong coupling between excitons and phonons, evidenced by giant Huang–Rhys factors, coherent phonon oscillations, and ultrafast carrier self-trapping into small-polaron and self-trapped exciton (STE) states. These processes appear as time-dependent ground-state bleach and photoinduced absorption features, highlighting the influence of the lattice in carrier dynamics. Wavelength- and time-resolved measurements reveal that PL emission is dominated by STEs, while free exciton emission is weak and short-lived. By comparing 2D MA<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub> with 0D MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub>, which contains molecularly isolated [BiI<sub>6</sub>]<sup>3−</sup> octahedra and 2D MA<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> perovskites, we demonstrate how halide composition and structural dimensionality influence the balance between free exciton populations and carrier localization. These insights uncover the intrinsic kinetic landscape of photoexcited states in MA<sub>3</sub>Bi<sub>2</sub>I<sub>6</sub>Cl<sub>3</sub>. Overall, our study contributes to a mechanistic understanding of exciton–phonon interactions in lead-free 2D perovskites.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122300","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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