Extracellular chromatin is a composite DNA–protein assembly that is difficult to recognize selectively using conventional cationic nucleic acid scavengers. Inspired by the spatially organized recognition of biomacromolecular assemblies, we developed a library of valency-programmed poly(ethylene glycol)-aminoglycoside conjugates that preferentially recognize neutrophil extracellular trap (NET)–associated chromatin while retaining antibacterial activity. Screening aminoglycoside identity and scaffold valency identified 8-arm poly(ethylene glycol)-netilmicin (8-arm Netil) as the lead construct. Its flexible multivalent architecture enabled simultaneous contacts with DNA phosphates and histone-associated sites, generating cooperative electrostatic and hydrogen-bonding interactions. At equal netilmicin equivalents, 8-arm Netil retained stronger chromatin binding than free netilmicin and the 2- and 4-arm conjugates, whereas cationic poly(amidoamine) dendrimers failed to reproduce its combined affinity and selectivity. 8-arm Netil bound DNA–histone chromatin with a dissociation constant of 5.73 × 10–8 M, and showed substantially weaker interactions with isolated DNA, histones, and serum albumin. This multivalent recognition suppressed NET-induced Toll-like receptor 4 and 9 signaling while preserving antibacterial activity. In bacterial peritonitis and polymicrobial sepsis models, 8-arm Netil reduced bacterial dissemination, extracellular chromatin burden, inflammation, and mortality. This work establishes valency-programmed aminoglycoside presentation as a chemical strategy for recognizing and neutralizing composite extracellular chromatin.
{"title":"Star-Shaped Multivalent Molecular Scavengers for Neutrophil Extracellular Trap-Associated Chromatin Neutralization and Sepsis Treatment","authors":"Chuanxu Cheng,Quanxin Ning,Juan Du,Jianati Dawulieti,Chenyang Guo,Madi Sun,Kunbao Zhang,Haijun Li,Qunjie Bi,Jian Li,Zhen Wu,Ziping Wu,Li-Li Li,Hanyao Huang,Zhi-Liang Ji,Jin-Zhi Du,Chao Yang,Kam W. Leong,Dan Shao","doi":"10.1021/jacs.6c15992","DOIUrl":"https://doi.org/10.1021/jacs.6c15992","url":null,"abstract":"Extracellular chromatin is a composite DNA–protein assembly that is difficult to recognize selectively using conventional cationic nucleic acid scavengers. Inspired by the spatially organized recognition of biomacromolecular assemblies, we developed a library of valency-programmed poly(ethylene glycol)-aminoglycoside conjugates that preferentially recognize neutrophil extracellular trap (NET)–associated chromatin while retaining antibacterial activity. Screening aminoglycoside identity and scaffold valency identified 8-arm poly(ethylene glycol)-netilmicin (8-arm Netil) as the lead construct. Its flexible multivalent architecture enabled simultaneous contacts with DNA phosphates and histone-associated sites, generating cooperative electrostatic and hydrogen-bonding interactions. At equal netilmicin equivalents, 8-arm Netil retained stronger chromatin binding than free netilmicin and the 2- and 4-arm conjugates, whereas cationic poly(amidoamine) dendrimers failed to reproduce its combined affinity and selectivity. 8-arm Netil bound DNA–histone chromatin with a dissociation constant of 5.73 × 10–8 M, and showed substantially weaker interactions with isolated DNA, histones, and serum albumin. This multivalent recognition suppressed NET-induced Toll-like receptor 4 and 9 signaling while preserving antibacterial activity. In bacterial peritonitis and polymicrobial sepsis models, 8-arm Netil reduced bacterial dissemination, extracellular chromatin burden, inflammation, and mortality. This work establishes valency-programmed aminoglycoside presentation as a chemical strategy for recognizing and neutralizing composite extracellular chromatin.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"57 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210912","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}
Manuel J. Scharf,Sander Folkerts,Moritz E. Hansen,Lorenzo A. A. Fitze,Douglas Strasoldo-Graffemberg,Claudia S. Zhang,Erick M. Carreira
We report the first and enantioselective total synthesis of the bacterial sesterterpene natural product sestermobaraene F, featuring a highly substituted cyclopropane embedded in a 5/3/7/6/5-pentacyclic skeleton. The route involves preparation of a key bicyclo[3.1.0]hexane building block through a Lewis acid-mediated photochemical rearrangement of a quinol benzoate, which was investigated mechanistically. Convergent fragment coupling set the stage for installment of the central ring through a 6-endo-trig cycloisomerization. In this regard, the generation of a substituted formal 3° cyclopropyl radical from a methylenecyclopropane under Co-catalysis is novel. The subsequent challenging chemo- and stereoselective reduction of the tetrasubstituted enone was accomplished by employing Yamamoto’s sterically demanding ATPH Lewis acid. In the final steps, regioselective ring expansion allowed for completion of the natural product. Notably, the study presents a potential strategy to access other 5/3/7/6/5-pentacyclic sesterterpenes.
{"title":"Enantioselective Total Synthesis of Sestermobaraene F","authors":"Manuel J. Scharf,Sander Folkerts,Moritz E. Hansen,Lorenzo A. A. Fitze,Douglas Strasoldo-Graffemberg,Claudia S. Zhang,Erick M. Carreira","doi":"10.1021/jacs.6c14482","DOIUrl":"https://doi.org/10.1021/jacs.6c14482","url":null,"abstract":"We report the first and enantioselective total synthesis of the bacterial sesterterpene natural product sestermobaraene F, featuring a highly substituted cyclopropane embedded in a 5/3/7/6/5-pentacyclic skeleton. The route involves preparation of a key bicyclo[3.1.0]hexane building block through a Lewis acid-mediated photochemical rearrangement of a quinol benzoate, which was investigated mechanistically. Convergent fragment coupling set the stage for installment of the central ring through a 6-endo-trig cycloisomerization. In this regard, the generation of a substituted formal 3° cyclopropyl radical from a methylenecyclopropane under Co-catalysis is novel. The subsequent challenging chemo- and stereoselective reduction of the tetrasubstituted enone was accomplished by employing Yamamoto’s sterically demanding ATPH Lewis acid. In the final steps, regioselective ring expansion allowed for completion of the natural product. Notably, the study presents a potential strategy to access other 5/3/7/6/5-pentacyclic sesterterpenes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218936","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}
Ana Clara Zampirolli Leal,Domagoj Fijan,Kaitlin M. Landy,Kyle J. Gibson,Byeongdu Lee,Sajib Barua,Xiaobing Zuo,Sharon C. Glotzer,Chad A. Mirkin
DNA-mediated colloidal crystal engineering enables the construction of highly ordered three-dimensional nanoparticle superlattices. Traditionally, anisotropic programmable atom equivalents (PAEs) have been employed to introduce directional bonding interactions needed to form lower-symmetry, more complex lattices, whereas isotropic, spherical PAEs typically yield high-symmetry structures. Here, we design programmable DNA junction-dendrons that impart directional interactions between isotropic gold nanoparticle-core PAEs, with a four-way junction (4WJ), rather than the nanoparticle shape, governing assembly directionality. This strategy decouples directional DNA bonding from nanoparticle-core geometry. Unlike prior junction-dendron systems, the defined geometry of rigid 4WJs enables direct interrogation of how junction-imposed directionality influences crystallization. In this system, DNA 4WJs serve as dendron cores and coassemble with isotropic gold nanoparticle-core PAEs. By systematically varying junction size and conformational rigidity, we establish structure–directionality relationships that govern crystal symmetry and lattice parameters. Molecular dynamics simulations and small-angle X-ray scattering (SAXS) reveal that rigid 4WJs adopt a stacked Holliday conformation, promoting anisotropic bonding and enabling the formation of simple hexagonal (SH, P6/mmm) and distorted hexagonal close-packed (distorted HCP, P63/mmc) lattices, dictated by the dendron-to-nanoparticle size ratio. Coarse-grained molecular dynamics simulations further show that junction-accessible binding topologies, determined by junction size, govern this transition. In contrast, flexible junctions drive a symmetry transition from P6/mmm to P63/mmc at constant size ratios. These results establish 4WJ rigidity and conformation as primary determinants of crystal symmetry and demonstrate that junction geometry can program and resolve directional bonding, expanding the structural and compositional diversity of colloidal crystals.
{"title":"Programming Symmetry in Colloidal Crystal Engineering with DNA Using Four-Way Junction-Dendrons","authors":"Ana Clara Zampirolli Leal,Domagoj Fijan,Kaitlin M. Landy,Kyle J. Gibson,Byeongdu Lee,Sajib Barua,Xiaobing Zuo,Sharon C. Glotzer,Chad A. Mirkin","doi":"10.1021/jacs.6c15674","DOIUrl":"https://doi.org/10.1021/jacs.6c15674","url":null,"abstract":"DNA-mediated colloidal crystal engineering enables the construction of highly ordered three-dimensional nanoparticle superlattices. Traditionally, anisotropic programmable atom equivalents (PAEs) have been employed to introduce directional bonding interactions needed to form lower-symmetry, more complex lattices, whereas isotropic, spherical PAEs typically yield high-symmetry structures. Here, we design programmable DNA junction-dendrons that impart directional interactions between isotropic gold nanoparticle-core PAEs, with a four-way junction (4WJ), rather than the nanoparticle shape, governing assembly directionality. This strategy decouples directional DNA bonding from nanoparticle-core geometry. Unlike prior junction-dendron systems, the defined geometry of rigid 4WJs enables direct interrogation of how junction-imposed directionality influences crystallization. In this system, DNA 4WJs serve as dendron cores and coassemble with isotropic gold nanoparticle-core PAEs. By systematically varying junction size and conformational rigidity, we establish structure–directionality relationships that govern crystal symmetry and lattice parameters. Molecular dynamics simulations and small-angle X-ray scattering (SAXS) reveal that rigid 4WJs adopt a stacked Holliday conformation, promoting anisotropic bonding and enabling the formation of simple hexagonal (SH, P6/mmm) and distorted hexagonal close-packed (distorted HCP, P63/mmc) lattices, dictated by the dendron-to-nanoparticle size ratio. Coarse-grained molecular dynamics simulations further show that junction-accessible binding topologies, determined by junction size, govern this transition. In contrast, flexible junctions drive a symmetry transition from P6/mmm to P63/mmc at constant size ratios. These results establish 4WJ rigidity and conformation as primary determinants of crystal symmetry and demonstrate that junction geometry can program and resolve directional bonding, expanding the structural and compositional diversity of colloidal crystals.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218940","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}
Enantioenriched 1,3-disubstituted cycloalkanes are important structural motifs in pharmaceuticals and natural products, yet their stereoselective synthesis remains challenging owing to difficulties in remote control of regio- and stereoselectivities. Herein, we report an iridium-catalyzed enantio-convergent hydroheteroarylation of racemic unactivated cyclic alkenes through a dynamic kinetic asymmetric transformation (DYKAT). Racemic cyclohexenes, cycloheptenes, and cyclooctenes undergo hydroheteroarylation with excellent regio-, diastereo-, and enantioselectivity, providing 1,3-cis-disubstituted cycloalkanes in an enantio-convergent manner. The method enables the efficient construction of both tertiary–tertiary and quaternary–tertiary stereogenic relationships within saturated carbocyclic frameworks.
{"title":"1,3-cis-Disubstituted Cycloalkanes by Iridium-Catalyzed Enantio-convergent Migratory Hydroheteroarylation","authors":"En-Ze Lin,Jun-Kai Shi,Xin Sun,Bi-Jie Li","doi":"10.1021/jacs.6c16551","DOIUrl":"https://doi.org/10.1021/jacs.6c16551","url":null,"abstract":"Enantioenriched 1,3-disubstituted cycloalkanes are important structural motifs in pharmaceuticals and natural products, yet their stereoselective synthesis remains challenging owing to difficulties in remote control of regio- and stereoselectivities. Herein, we report an iridium-catalyzed enantio-convergent hydroheteroarylation of racemic unactivated cyclic alkenes through a dynamic kinetic asymmetric transformation (DYKAT). Racemic cyclohexenes, cycloheptenes, and cyclooctenes undergo hydroheteroarylation with excellent regio-, diastereo-, and enantioselectivity, providing 1,3-cis-disubstituted cycloalkanes in an enantio-convergent manner. The method enables the efficient construction of both tertiary–tertiary and quaternary–tertiary stereogenic relationships within saturated carbocyclic frameworks.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"163 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218947","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}
Tyler Wang,Fangyuan Liu,Yan Zhou,Joseph A. Adewuyi,Zhengjie Li,Mingwei Ge,Haiyan Tan,Gaël Ung,Cong Su,Mengxia Liu
Imparting chiroptical activity of lanthanide transitions provides an attractive route to circularly polarized luminescence. However, obtaining intense emission from their Laporte-forbidden f–f transitions while also generating significant rotatory strength remains a formidable challenge in materials design. This work establishes a platform for efficient near-infrared (NIR) circularly polarized luminescence (CPL), centered on the telecom-relevant C-band around 1550 nm, from lanthanide dopants (Yb3+/Er3+) embedded in chiral perovskite nanocrystal (CsPbX3) hosts. Atomic-scale structural analyses reveal a preferential enrichment of lanthanide concentration near the nanocrystal surfaces, where chiral ligands distort the lattice, lowering the local symmetry. Spectroscopic measurements confirm the highly efficient host-to-dopant energy transfer, facilitating strong CPL, with a luminescence dissymmetry factor (glum) of 0.36 and a CPL brightness (BCPL) of 4.2 × 105 M–1 cm–1 at 1550 nm, representing nearly four orders of magnitude above the previous benchmark. With improved photostability, these results establish lanthanide-doped chiral perovskite nanocrystals as a promising route to telecom-relevant CPL.
{"title":"Local Symmetry Breaking Facilitates Near-Infrared Circularly Polarized Lanthanide Emission in Perovskite Nanocrystals","authors":"Tyler Wang,Fangyuan Liu,Yan Zhou,Joseph A. Adewuyi,Zhengjie Li,Mingwei Ge,Haiyan Tan,Gaël Ung,Cong Su,Mengxia Liu","doi":"10.1021/jacs.6c15479","DOIUrl":"https://doi.org/10.1021/jacs.6c15479","url":null,"abstract":"Imparting chiroptical activity of lanthanide transitions provides an attractive route to circularly polarized luminescence. However, obtaining intense emission from their Laporte-forbidden f–f transitions while also generating significant rotatory strength remains a formidable challenge in materials design. This work establishes a platform for efficient near-infrared (NIR) circularly polarized luminescence (CPL), centered on the telecom-relevant C-band around 1550 nm, from lanthanide dopants (Yb3+/Er3+) embedded in chiral perovskite nanocrystal (CsPbX3) hosts. Atomic-scale structural analyses reveal a preferential enrichment of lanthanide concentration near the nanocrystal surfaces, where chiral ligands distort the lattice, lowering the local symmetry. Spectroscopic measurements confirm the highly efficient host-to-dopant energy transfer, facilitating strong CPL, with a luminescence dissymmetry factor (glum) of 0.36 and a CPL brightness (BCPL) of 4.2 × 105 M–1 cm–1 at 1550 nm, representing nearly four orders of magnitude above the previous benchmark. With improved photostability, these results establish lanthanide-doped chiral perovskite nanocrystals as a promising route to telecom-relevant CPL.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"56 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218934","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}
Resolving the mechanistic link between local coordination environments and dynamic surface restructuring is essential for advancing carbon dioxide activation and hydrogenation on copper-based catalysts. Here, we demonstrate that the configuration of steps and terraces governs the restructuring pathways on high-index Cu(hkl) surfaces with varying (111) × (100) step densities by integrating in situ spectroscopy/microscopy and theoretical simulation. On the Cu(211) surface [3(111) × (100)], low-coordinated step sites facilitate CO2 activation and the subsequent reaction-driven fragmentation of Cu into nanoclusters. These metastable ensembles serve as active sites that stabilize key intermediates─formate and methoxy─thereby driving sequential hydrogenation. In contrast, on the Cu(557) surface featuring a lower step density [6(111) × (100)], oxygen atoms derived from CO2 dissociation at step sites migrate onto the terraces, assembling into ordered oxide chains that passivate the active sites. Our findings reveal that modulating the step density could effectively dictate the surface reconstruction and the reaction activity of carbon dioxide hydrogenation over Cu-based catalysts.
{"title":"Unveiling the Role of Step Density in CO2 Activation and Hydrogenation on Copper Surfaces","authors":"Shui Lin,Yang Gu,Haolin Huang,Yicun Zhao,Yijing Zang,Tao Zhang,Yong Han,Hui Zhang,Bo Yang,Fan Yang,Yimin Li,Jun Cai,Zhi Liu","doi":"10.1021/jacs.6c13867","DOIUrl":"https://doi.org/10.1021/jacs.6c13867","url":null,"abstract":"Resolving the mechanistic link between local coordination environments and dynamic surface restructuring is essential for advancing carbon dioxide activation and hydrogenation on copper-based catalysts. Here, we demonstrate that the configuration of steps and terraces governs the restructuring pathways on high-index Cu(hkl) surfaces with varying (111) × (100) step densities by integrating in situ spectroscopy/microscopy and theoretical simulation. On the Cu(211) surface [3(111) × (100)], low-coordinated step sites facilitate CO2 activation and the subsequent reaction-driven fragmentation of Cu into nanoclusters. These metastable ensembles serve as active sites that stabilize key intermediates─formate and methoxy─thereby driving sequential hydrogenation. In contrast, on the Cu(557) surface featuring a lower step density [6(111) × (100)], oxygen atoms derived from CO2 dissociation at step sites migrate onto the terraces, assembling into ordered oxide chains that passivate the active sites. Our findings reveal that modulating the step density could effectively dictate the surface reconstruction and the reaction activity of carbon dioxide hydrogenation over Cu-based catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"4 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210909","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}
Andrew J. Neel,Gregorio J. Estrada,Feng Xu,Cecilia Bottechia,Longrui Chen,Yining Ji,John Y. L. Chung,Michael J. Di Maso,Cyndi Q. He,Artis Klapars,Jongrock Kong,François Lévesque,Tao Liang,Zhijian Liu,Xiaoshen Ma,Kevin M. Maloney,Jamie M. McCabe Dunn,Karthik Narsimhan,Jennifer Victoriano Obligacion,Douglas A. L. Otte,Nastaran Salehi Marzijarani,Stephan M. Rummelt,Heather Wang,Lu Wang,Mark Weisel,Matthew S. Winston
Herein we disclose a concise synthesis of inhaled soluble guanylate cyclase (isGC) stimulator Frespaciguat (MK-5475) that relies exclusively on complexity-increasing transformations from commodity chemicals. Key transformations include a solvent-free photochemical reaction that converts two gaseous reactants into a liquid product in high yield; a direct ester-to-amidine conversion using HMDS, water, and triflic acid; and a rare example of enantioselective methylation via copper-catalyzed asymmetric conjugate addition (ACA) to install a quaternary center using trimethylboroxine as a nucleophile. Given the general challenge of asymmetric methyl installation, we further demonstrate the utility of this methodology beyond the present setting and suggest its strategic value in synthetic planning where nonracemic, quaternary methyl-containing stereocenters are required.
{"title":"Asymmetric Copper-Catalyzed Conjugate Addition with Trimethylboroxine Enables Direct Synthesis of Frespaciguat","authors":"Andrew J. Neel,Gregorio J. Estrada,Feng Xu,Cecilia Bottechia,Longrui Chen,Yining Ji,John Y. L. Chung,Michael J. Di Maso,Cyndi Q. He,Artis Klapars,Jongrock Kong,François Lévesque,Tao Liang,Zhijian Liu,Xiaoshen Ma,Kevin M. Maloney,Jamie M. McCabe Dunn,Karthik Narsimhan,Jennifer Victoriano Obligacion,Douglas A. L. Otte,Nastaran Salehi Marzijarani,Stephan M. Rummelt,Heather Wang,Lu Wang,Mark Weisel,Matthew S. Winston","doi":"10.1021/jacs.6c17539","DOIUrl":"https://doi.org/10.1021/jacs.6c17539","url":null,"abstract":"Herein we disclose a concise synthesis of inhaled soluble guanylate cyclase (isGC) stimulator Frespaciguat (MK-5475) that relies exclusively on complexity-increasing transformations from commodity chemicals. Key transformations include a solvent-free photochemical reaction that converts two gaseous reactants into a liquid product in high yield; a direct ester-to-amidine conversion using HMDS, water, and triflic acid; and a rare example of enantioselective methylation via copper-catalyzed asymmetric conjugate addition (ACA) to install a quaternary center using trimethylboroxine as a nucleophile. Given the general challenge of asymmetric methyl installation, we further demonstrate the utility of this methodology beyond the present setting and suggest its strategic value in synthetic planning where nonracemic, quaternary methyl-containing stereocenters are required.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218933","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}
Shuoao Wang,Zhanzhao Fu,Chunyao Fang,Haiyan Li,Bing Wang,Yi Huang,Ang Cao
Spin engineering has emerged as a promising strategy for tuning catalytic activity by manipulating the spin states of active sites. This strategy generally assumes that the local spin moment serves as a universal descriptor for adsorption strength, yet its validity remains largely unexplored. Here, we develop a reverse doping strategy that enables broad modulation of local spin moments in magnetic single-atom alloy catalysts, allowing the spin–adsorption relationship to be systematically revisited. We find that tuning the local spin moment does not uniformly translate into changes in adsorption energy, with particularly weak responses in the low-spin regime. Isolating the contribution of spin to adsorption energy reveals a nonlinear dependence on spin moment; the spin effect becomes pronounced only above a critical spin moment, close to one-half of the ground-state value of the corresponding isolated magnetic atom. Below the critical spin moment, adsorption-induced d-state reconstruction compensates for the spin effect, whereas this compensation breaks down above it. Importantly, this nonlinear behavior is observed across diverse adsorbates, suggesting its generality. These findings establish a critical spin-moment criterion for spin-regulated adsorption and redefine the applicability of spin engineering in heterogeneous catalysis.
{"title":"A Critical Spin Moment Governs the Spin-Adsorption Relationship in Magnetic Single-Atom Alloys","authors":"Shuoao Wang,Zhanzhao Fu,Chunyao Fang,Haiyan Li,Bing Wang,Yi Huang,Ang Cao","doi":"10.1021/jacs.6c16682","DOIUrl":"https://doi.org/10.1021/jacs.6c16682","url":null,"abstract":"Spin engineering has emerged as a promising strategy for tuning catalytic activity by manipulating the spin states of active sites. This strategy generally assumes that the local spin moment serves as a universal descriptor for adsorption strength, yet its validity remains largely unexplored. Here, we develop a reverse doping strategy that enables broad modulation of local spin moments in magnetic single-atom alloy catalysts, allowing the spin–adsorption relationship to be systematically revisited. We find that tuning the local spin moment does not uniformly translate into changes in adsorption energy, with particularly weak responses in the low-spin regime. Isolating the contribution of spin to adsorption energy reveals a nonlinear dependence on spin moment; the spin effect becomes pronounced only above a critical spin moment, close to one-half of the ground-state value of the corresponding isolated magnetic atom. Below the critical spin moment, adsorption-induced d-state reconstruction compensates for the spin effect, whereas this compensation breaks down above it. Importantly, this nonlinear behavior is observed across diverse adsorbates, suggesting its generality. These findings establish a critical spin-moment criterion for spin-regulated adsorption and redefine the applicability of spin engineering in heterogeneous catalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"16 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218938","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}
Tao Shen,Mengyu Xie,Qianhong Gong,Zhaoyang Han,Jiaao Wang,Lei Chen,Jie Zhang,Jirong Mou,Yu-Hui Zhu,Juan Lian,Wei Bi,Yihan Yang,Zhenyu Xiao,Chao Yuan,Ke Chen,Konglin Wu,Sen Xin,Andreu Cabot,Dawei Yang
Sulfur cathodes are considered promising candidates for next-generation energy storage due to their high theoretical energy density, low cost, and elemental abundance. However, their practical deployment is limited by the polysulfide shuttle effect and sluggish sulfur redox reaction (SRR) kinetics. In this study, we design coordination-regulated cobalt single-atom catalysts (CoClNC) featuring an asymmetric Cl–Co–N3 coordination environment to investigate the relationship between SRR catalytic activity and spin state configuration. The incorporation of Cl atoms induces electron delocalization in Co(II), promoting a transition from a low-spin to higher-spin state. This spin-state modulation enhances dz2 orbital hybridization with the π* antibonding orbitals of polysulfides, thereby accelerating their redox conversion. Furthermore, the asymmetric coordination lowers the d-band electron occupancy, improving sulfur species adsorption and facilitating SRR kinetics. Lithium–sulfur batteries employing CoClNC/S cathodes demonstrate remarkable cycling stability, with an average capacity fade of only 0.023% per cycle. This work highlights a general strategy for spin and orbital engineering via coordination field modulation to boost SRR catalysis.
{"title":"Symmetry-Broken Coordination of Single-Atom Catalysts Unlocks Spin- and Orbital-Regulated Sulfur Redox in Lithium–Sulfur Batteries","authors":"Tao Shen,Mengyu Xie,Qianhong Gong,Zhaoyang Han,Jiaao Wang,Lei Chen,Jie Zhang,Jirong Mou,Yu-Hui Zhu,Juan Lian,Wei Bi,Yihan Yang,Zhenyu Xiao,Chao Yuan,Ke Chen,Konglin Wu,Sen Xin,Andreu Cabot,Dawei Yang","doi":"10.1021/jacs.6c17922","DOIUrl":"https://doi.org/10.1021/jacs.6c17922","url":null,"abstract":"Sulfur cathodes are considered promising candidates for next-generation energy storage due to their high theoretical energy density, low cost, and elemental abundance. However, their practical deployment is limited by the polysulfide shuttle effect and sluggish sulfur redox reaction (SRR) kinetics. In this study, we design coordination-regulated cobalt single-atom catalysts (CoClNC) featuring an asymmetric Cl–Co–N3 coordination environment to investigate the relationship between SRR catalytic activity and spin state configuration. The incorporation of Cl atoms induces electron delocalization in Co(II), promoting a transition from a low-spin to higher-spin state. This spin-state modulation enhances dz2 orbital hybridization with the π* antibonding orbitals of polysulfides, thereby accelerating their redox conversion. Furthermore, the asymmetric coordination lowers the d-band electron occupancy, improving sulfur species adsorption and facilitating SRR kinetics. Lithium–sulfur batteries employing CoClNC/S cathodes demonstrate remarkable cycling stability, with an average capacity fade of only 0.023% per cycle. This work highlights a general strategy for spin and orbital engineering via coordination field modulation to boost SRR catalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"19 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218954","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}
Philipp Schneider,Maximilian Fest,Muhammed Edirneli,Alexandra Friedrich,Jonas Klopf,Manuel Buckel,Johannes Chorbacher,Holger Helten
Cyclolinear oligo- and polyboranes are an emerging class of π-conjugated materials with potential use in organic (opto)-electronic devices and sensors. The range of boron-linked π-building blocks that can be effectively incorporated, however, is quite limited, since even a slight increase in their steric bulk leads to significant deviations from the planar molecular backbone required for effective charge delocalization. This can be mitigated by inserting an alkynyl spacer between the boron atom and one of these groups. However, such alkynylboranes have been scarcely studied to date, which is due to a lack of efficient synthetic methods. Here, we report on a catalytic silicon/boron exchange condensation process as a versatile synthetic route to alkynyl-spaced monoboranes 5, bisboranes 9, and polyboranes 13. This modular approach enables the variation of both the boron- and alkynyl-bound aryl substituent, while introduction of 2,6-bis(trifluoromethyl)phenyl (FXyl) as the third substituent on boron renders the resulting compounds air- and moisture-stable. The obtained conjugated boranes display a high degree of coplanarity of the central BC3 plane(s) with both the boron- and alkynyl-bound aryl or arylene substituents, respectively. This architecture allows effective conjugation over the entire molecular backbone, which is supported by single-crystal X-ray diffraction analysis, photophysical and electrochemical studies, and time-dependent density functional theory (TD-DFT) calculations. The obtained compounds generally exhibit favorable photophysical properties; some of them show very high quantum yields both in solution and as thin films in a polymer matrix, as well as solid-state emission.
{"title":"Catalytic Si/B Exchange Condensation Enables Modular Synthesis of Alkynyl-Spaced Conjugated Oligo- and Polyboranes","authors":"Philipp Schneider,Maximilian Fest,Muhammed Edirneli,Alexandra Friedrich,Jonas Klopf,Manuel Buckel,Johannes Chorbacher,Holger Helten","doi":"10.1021/jacs.6c15776","DOIUrl":"https://doi.org/10.1021/jacs.6c15776","url":null,"abstract":"Cyclolinear oligo- and polyboranes are an emerging class of π-conjugated materials with potential use in organic (opto)-electronic devices and sensors. The range of boron-linked π-building blocks that can be effectively incorporated, however, is quite limited, since even a slight increase in their steric bulk leads to significant deviations from the planar molecular backbone required for effective charge delocalization. This can be mitigated by inserting an alkynyl spacer between the boron atom and one of these groups. However, such alkynylboranes have been scarcely studied to date, which is due to a lack of efficient synthetic methods. Here, we report on a catalytic silicon/boron exchange condensation process as a versatile synthetic route to alkynyl-spaced monoboranes 5, bisboranes 9, and polyboranes 13. This modular approach enables the variation of both the boron- and alkynyl-bound aryl substituent, while introduction of 2,6-bis(trifluoromethyl)phenyl (FXyl) as the third substituent on boron renders the resulting compounds air- and moisture-stable. The obtained conjugated boranes display a high degree of coplanarity of the central BC3 plane(s) with both the boron- and alkynyl-bound aryl or arylene substituents, respectively. This architecture allows effective conjugation over the entire molecular backbone, which is supported by single-crystal X-ray diffraction analysis, photophysical and electrochemical studies, and time-dependent density functional theory (TD-DFT) calculations. The obtained compounds generally exhibit favorable photophysical properties; some of them show very high quantum yields both in solution and as thin films in a polymer matrix, as well as solid-state emission.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210910","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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