Tianlai Xia,Peng Sun,Laihui Xiao,Andrew P. Dove,Rachel K. O’Reilly
The creation of polymeric assemblies with reconfigurable surface functionality remains a major challenge for programmable soft materials. Covalent modification strategies can provide stable functional materials, but often require harsh reaction conditions or irreversible bond formation. Here, we integrate noncovalent interactions with crystallization-driven self-assembly (CDSA) to construct polymer platelets with region-selective functionalization and controllable responsiveness under mild conditions. Polycaprolactone-based platelets bearing cyclodextrin, barbituric acid, or related recognition motifs were prepared and subsequently orthogonal modified with complementary fluorescent guests through host–guest interactions or hydrogen bonding. Confocal fluorescence microscopy confirmed platelet-localized dye incorporation, while competitive displacement and relabeling demonstrated reversible molecular loading and release without disrupting platelet structural integrity. This work establishes supramolecular modification of CDSA-based assemblies as a modular route to soft materials with controllable and reconfigurable molecular functionality under mild conditions.
{"title":"Dynamically and Reversibly Functionalized Self-Assembled Platelets via Noncovalent Interactions","authors":"Tianlai Xia,Peng Sun,Laihui Xiao,Andrew P. Dove,Rachel K. O’Reilly","doi":"10.1021/jacs.6c17888","DOIUrl":"https://doi.org/10.1021/jacs.6c17888","url":null,"abstract":"The creation of polymeric assemblies with reconfigurable surface functionality remains a major challenge for programmable soft materials. Covalent modification strategies can provide stable functional materials, but often require harsh reaction conditions or irreversible bond formation. Here, we integrate noncovalent interactions with crystallization-driven self-assembly (CDSA) to construct polymer platelets with region-selective functionalization and controllable responsiveness under mild conditions. Polycaprolactone-based platelets bearing cyclodextrin, barbituric acid, or related recognition motifs were prepared and subsequently orthogonal modified with complementary fluorescent guests through host–guest interactions or hydrogen bonding. Confocal fluorescence microscopy confirmed platelet-localized dye incorporation, while competitive displacement and relabeling demonstrated reversible molecular loading and release without disrupting platelet structural integrity. This work establishes supramolecular modification of CDSA-based assemblies as a modular route to soft materials with controllable and reconfigurable molecular functionality under mild conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"43 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281904","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}
He Ma,Yushen Kang,Weiquan Xu,Jiang-Fei Xu,Xi Zhang
Bioresponsive groups are fundamental tools in engineering activatable constructs. Herein, we first demonstrated that the oxime group was a bioresponsive group by designing oxime-naphthalene diimide (NONDI). The oxime group could be reduced to an iminyl group by bacteria, and NONDI was completely converted into iminyl-naphthalene diimide (NHNDI). Mechanistically, that reduction triggered homolytic cleavage of the N–O bond in the oxime group and released a hydroxyl radical. NONDI could be reduced stepwise to NHNDI, NHNDI•–, and NHNDI2–, yielding four distinct colors which depended on the bacteria with reducibility from weak to strong. In other words, NONDI enables visual classification of bacteria by their reducing ability. In addition, the intense NIR-II absorption of NHNDI•– endows it with photothermal antibacterial properties. This work uncovers fundamental principles of oxime bioresponsiveness under reducing conditions for the first time, providing a new platform for designing new activatable materials.
{"title":"Establishing Oxime as a Bioresponsive Group on Naphthalene Diimide: Visual Bacterial Classification and NIR-II Photothermal Antibacterial","authors":"He Ma,Yushen Kang,Weiquan Xu,Jiang-Fei Xu,Xi Zhang","doi":"10.1021/jacs.6c18889","DOIUrl":"https://doi.org/10.1021/jacs.6c18889","url":null,"abstract":"Bioresponsive groups are fundamental tools in engineering activatable constructs. Herein, we first demonstrated that the oxime group was a bioresponsive group by designing oxime-naphthalene diimide (NONDI). The oxime group could be reduced to an iminyl group by bacteria, and NONDI was completely converted into iminyl-naphthalene diimide (NHNDI). Mechanistically, that reduction triggered homolytic cleavage of the N–O bond in the oxime group and released a hydroxyl radical. NONDI could be reduced stepwise to NHNDI, NHNDI•–, and NHNDI2–, yielding four distinct colors which depended on the bacteria with reducibility from weak to strong. In other words, NONDI enables visual classification of bacteria by their reducing ability. In addition, the intense NIR-II absorption of NHNDI•– endows it with photothermal antibacterial properties. This work uncovers fundamental principles of oxime bioresponsiveness under reducing conditions for the first time, providing a new platform for designing new activatable materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149275132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Sanxingdui gold masks are Au–Ag–Pb ternary alloys in which preferential corrosion of intergranular active Pb-containing phases causes severe embrittlement and threatens long-term preservation. Here, corrosion inhibitors for these vulnerable microdomains were evaluated by integrating microstructural characterization, scanning electrochemical cell microscopy (SECCM), and density functional theory (DFT) calculations. Sodium cysteinate (NaCys), sodium hexametaphosphate (SHMP), sodium silicate (NaSi), and sodium salts of saturated fatty acids (NaCn, C6–C18) were screened on simulated Au–Ag–Pb alloys. NaCys and SHMP induced pronounced Pb depletion, while NaSi formed a hydrophilic, cracked deposit with limited protection. In contrast, NaCn showed a pronounced but non-monotonic carbon-chain-length dependence. NaC9, NaC10, and NaC12 exhibited the best overall performance, with NaC10 providing the highest and most stable localized inhibition. Shorter chains produced less ordered and less hydrophobic films, whereas longer chains were limited by poor effective solubility and interfacial accessibility. DFT calculations showed that inhibition cannot be predicted from adsorption strength alone. By combining adsorption energy, Pb defect formation energy, and interfacial retention energy, we established an interfacial reaction criterion distinguishing stable film formation from inhibitor-induced Pb extraction, thereby introducing the concept of effective inhibitor interfacial reactivity for mechanism-guided conservation. This approach provides a targeted strategy for protecting Sanxingdui gold masks and other complex multiphase metallic heritage objects.
{"title":"From Localized Electrochemical Behavior to Interfacial Reaction Mechanisms: Evaluation of Corrosion Inhibitors for Active Pb-Containing Phases in Sanxingdui Embrittled Gold Masks","authors":"Shengyu Liu,Ting Yu,Xiangyu Sun,Jiachen Qin,Haizi Lu,Tao Yang,Danyang Xu,Yanru Ma,Cheng Ma,Siyuan Sun,Gang Hu,Meiqin Zhang","doi":"10.1021/jacs.6c17490","DOIUrl":"https://doi.org/10.1021/jacs.6c17490","url":null,"abstract":"The Sanxingdui gold masks are Au–Ag–Pb ternary alloys in which preferential corrosion of intergranular active Pb-containing phases causes severe embrittlement and threatens long-term preservation. Here, corrosion inhibitors for these vulnerable microdomains were evaluated by integrating microstructural characterization, scanning electrochemical cell microscopy (SECCM), and density functional theory (DFT) calculations. Sodium cysteinate (NaCys), sodium hexametaphosphate (SHMP), sodium silicate (NaSi), and sodium salts of saturated fatty acids (NaCn, C6–C18) were screened on simulated Au–Ag–Pb alloys. NaCys and SHMP induced pronounced Pb depletion, while NaSi formed a hydrophilic, cracked deposit with limited protection. In contrast, NaCn showed a pronounced but non-monotonic carbon-chain-length dependence. NaC9, NaC10, and NaC12 exhibited the best overall performance, with NaC10 providing the highest and most stable localized inhibition. Shorter chains produced less ordered and less hydrophobic films, whereas longer chains were limited by poor effective solubility and interfacial accessibility. DFT calculations showed that inhibition cannot be predicted from adsorption strength alone. By combining adsorption energy, Pb defect formation energy, and interfacial retention energy, we established an interfacial reaction criterion distinguishing stable film formation from inhibitor-induced Pb extraction, thereby introducing the concept of effective inhibitor interfacial reactivity for mechanism-guided conservation. This approach provides a targeted strategy for protecting Sanxingdui gold masks and other complex multiphase metallic heritage objects.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281803","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}
Contact-electro-catalysis (CEC) enables mechanically driven interfacial redox reactions through contact-induced charge transfer. Most CEC systems rely on dielectric or insulating materials, whereas the role of semiconductor carrier dynamics remains largely unexplored. Here we establish a tribovoltaic effect-driven CEC mechanism at a MoS2–water solid–liquid interface, where mechanical contact dynamically modulates semiconductor carriers and interfacial electron transfer. Electrical measurements and in situ Raman spectroscopy reveal that contact electrification and tribovoltaic carrier modulation synergistically regulate the interfacial electronic state. This coupled charge-transfer process promotes oxygen reduction to H2O2, which is subsequently activated to generate highly reactive •OH. Notably, under identical experimental conditions, the MoS2-based tribovoltaic-CEC system exhibits approximately 88-fold higher •OH production from H2O2 than conventional FEP- and PVDF-based CEC systems. Radical trapping, theoretical calculations and in situ fluorescence imaging further establish the relationship between interfacial charge transfer, oxygen activation and reactive oxygen species generation. Under ultrasound-assisted conditions, the system achieves approximately 90% degradation of tetracycline and efficient bacterial disinfection in real lake water. Our findings reveal the tribovoltaic effect as a potential mechanistic contributor to semiconductor catalytic activity, offering a new perspective on and a potential strategy for dynamically tuning solid–liquid interfacial catalysis through mechanically regulated carrier transfer.
{"title":"Tribovoltaic Effect-Driven Contact-Electro-Catalysis at a MoS2–Water Interface","authors":"Xin-Yue Liu,Qian Hu,Cheng-Zi Hong,Tao Zhu,Yu-Lian Sun,Haimei Li,Peng Jiang","doi":"10.1021/jacs.6c17833","DOIUrl":"https://doi.org/10.1021/jacs.6c17833","url":null,"abstract":"Contact-electro-catalysis (CEC) enables mechanically driven interfacial redox reactions through contact-induced charge transfer. Most CEC systems rely on dielectric or insulating materials, whereas the role of semiconductor carrier dynamics remains largely unexplored. Here we establish a tribovoltaic effect-driven CEC mechanism at a MoS2–water solid–liquid interface, where mechanical contact dynamically modulates semiconductor carriers and interfacial electron transfer. Electrical measurements and in situ Raman spectroscopy reveal that contact electrification and tribovoltaic carrier modulation synergistically regulate the interfacial electronic state. This coupled charge-transfer process promotes oxygen reduction to H2O2, which is subsequently activated to generate highly reactive •OH. Notably, under identical experimental conditions, the MoS2-based tribovoltaic-CEC system exhibits approximately 88-fold higher •OH production from H2O2 than conventional FEP- and PVDF-based CEC systems. Radical trapping, theoretical calculations and in situ fluorescence imaging further establish the relationship between interfacial charge transfer, oxygen activation and reactive oxygen species generation. Under ultrasound-assisted conditions, the system achieves approximately 90% degradation of tetracycline and efficient bacterial disinfection in real lake water. Our findings reveal the tribovoltaic effect as a potential mechanistic contributor to semiconductor catalytic activity, offering a new perspective on and a potential strategy for dynamically tuning solid–liquid interfacial catalysis through mechanically regulated carrier transfer.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"17 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281905","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}
Electro-oxidation technology holds great promise for wastewater treatment, yet its practical application remains hindered by insufficient selectivity in oxidative species generation and limited electrode stability under harsh operating conditions. Here, we devise a layer-by-layer anion–cation engineering strategy to fabricate an Sb–F-stitched SnO2 bilayer anode (SF–SnO2 BA), in which a fluorine-regulated SnO2 catalytic layer is interfacially anchored onto a dense Sb–SnO2 interlayer coated on a Ti foam scaffold. This hierarchically stitched architecture simultaneously modulates interfacial charge transport and stabilizes the catalytic layer, leading to markedly enhanced electrocatalytic oxidation performance across a broad pH range (1–11). When integrated into a scalable flow-through electro-oxidation system, SF–SnO2 BA enabled highly efficient mineralization (>80%) of four representative industrial wastewaters at low energy consumption. Furthermore, the system also demonstrated remarkable operational durability, sustaining high mineralization efficiency (60–80%) over 14 consecutive days during continuous treatment of real aniline wastewater from a coal chemical plant. In situ spectroscopic investigations coupled with theoretical calculations collectively elucidated that water molecules are initially oxidized on the SF–SnO2 BA surface to form Sn–OH intermediates, which are subsequently transformed into Sn–O species at elevated potentials. Notably, the cooperative F···Sn–O* structural motif directs the generation of surface-confined •OH, which acts as the dominant oxidative species for pollutant degradation. This interfacially stitched bilayer anode offers a viable route toward green and sustainable electrochemical oxidation technologies for practical wastewater treatment.
{"title":"Interfacially Stitched Bilayer Anodes Enforce Surface-Confined Hydroxyl Radical Chemistry in Complex Wastewater","authors":"Shi-Lin Xu,Wei Wang,Hao-Da Wang,Min-Jie Tong,Jie-Jie Chen,Han-Qing Yu,Yuen Wu,Xiao Zhou","doi":"10.1021/jacs.6c13125","DOIUrl":"https://doi.org/10.1021/jacs.6c13125","url":null,"abstract":"Electro-oxidation technology holds great promise for wastewater treatment, yet its practical application remains hindered by insufficient selectivity in oxidative species generation and limited electrode stability under harsh operating conditions. Here, we devise a layer-by-layer anion–cation engineering strategy to fabricate an Sb–F-stitched SnO2 bilayer anode (SF–SnO2 BA), in which a fluorine-regulated SnO2 catalytic layer is interfacially anchored onto a dense Sb–SnO2 interlayer coated on a Ti foam scaffold. This hierarchically stitched architecture simultaneously modulates interfacial charge transport and stabilizes the catalytic layer, leading to markedly enhanced electrocatalytic oxidation performance across a broad pH range (1–11). When integrated into a scalable flow-through electro-oxidation system, SF–SnO2 BA enabled highly efficient mineralization (>80%) of four representative industrial wastewaters at low energy consumption. Furthermore, the system also demonstrated remarkable operational durability, sustaining high mineralization efficiency (60–80%) over 14 consecutive days during continuous treatment of real aniline wastewater from a coal chemical plant. In situ spectroscopic investigations coupled with theoretical calculations collectively elucidated that water molecules are initially oxidized on the SF–SnO2 BA surface to form Sn–OH intermediates, which are subsequently transformed into Sn–O species at elevated potentials. Notably, the cooperative F···Sn–O* structural motif directs the generation of surface-confined •OH, which acts as the dominant oxidative species for pollutant degradation. This interfacially stitched bilayer anode offers a viable route toward green and sustainable electrochemical oxidation technologies for practical wastewater treatment.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281910","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}
Erica L. Debley,Guodong Rao,Mayukh Bhadra,Trisha Nguyen,Jason Shearer,R. David Britt,Elizabeth M. Nolan
Human calprotectin (CP, S100A8/S100A9 heterooligomer) is a multi-metal sequestering protein that contributes to the innate immune response by starving invading microbial pathogens of essential metal nutrients. Despite the ability of CP to withhold copper from microbial pathogens, its copper coordination chemistry is largely unexplored. Here we elucidate the Cu(II)-binding properties of CP-Ser [S100A8(C42S)/S100A9(C3S) variant] under conditions of high and low Ca(II) and present a working model for how CP sequesters Cu(II). Our biochemical and spectroscopic studies reveal that both the His3Asp and His6 sites bind Cu(II) with Ca(II)-dependent affinity, and Cu(II) binding to both sites is required for Cu(II)-dependent self-association of CP heterodimers to heterotetramers. Moreover, our spectroscopic data demonstrate that Cu(II) binds to the His6 site in a fluxional coordination environment, and that the mode of Cu(II) binding is allosterically modulated by Ca(II) coordination to the EF-hand domains and Cu(II) binding at the His3Asp site. Sequestration of Cu(II) using a fluxional His6 site contrasts with how CP captures other nutrient M(II) (M = Mn, Fe, Ni, Zn) at this site using a static and nearly idealized octahedral binding mode. This study reveals the remarkable ability of a fluxional site to participate in metal sequestration at the host–pathogen interface.
{"title":"Investigation of Cu(II) Binding by Human Calprotectin Reveals an Unusual Fluxional Coordination Environment","authors":"Erica L. Debley,Guodong Rao,Mayukh Bhadra,Trisha Nguyen,Jason Shearer,R. David Britt,Elizabeth M. Nolan","doi":"10.1021/jacs.6c12304","DOIUrl":"https://doi.org/10.1021/jacs.6c12304","url":null,"abstract":"Human calprotectin (CP, S100A8/S100A9 heterooligomer) is a multi-metal sequestering protein that contributes to the innate immune response by starving invading microbial pathogens of essential metal nutrients. Despite the ability of CP to withhold copper from microbial pathogens, its copper coordination chemistry is largely unexplored. Here we elucidate the Cu(II)-binding properties of CP-Ser [S100A8(C42S)/S100A9(C3S) variant] under conditions of high and low Ca(II) and present a working model for how CP sequesters Cu(II). Our biochemical and spectroscopic studies reveal that both the His3Asp and His6 sites bind Cu(II) with Ca(II)-dependent affinity, and Cu(II) binding to both sites is required for Cu(II)-dependent self-association of CP heterodimers to heterotetramers. Moreover, our spectroscopic data demonstrate that Cu(II) binds to the His6 site in a fluxional coordination environment, and that the mode of Cu(II) binding is allosterically modulated by Ca(II) coordination to the EF-hand domains and Cu(II) binding at the His3Asp site. Sequestration of Cu(II) using a fluxional His6 site contrasts with how CP captures other nutrient M(II) (M = Mn, Fe, Ni, Zn) at this site using a static and nearly idealized octahedral binding mode. This study reveals the remarkable ability of a fluxional site to participate in metal sequestration at the host–pathogen interface.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"21 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The remote communication between active sites and the surrounding environment within a heterogeneous catalyst for the orderly bonding of reactive species is highly desired yet very challenging. Here we find that the phosphotungstate with a mesoporous framework (abbreviated as mPTA) has an extraordinary ability to accommodate ammonia but has no activity for catalytic reductive amination, while the Pd3(S-Adm)3(PPh3)3+ (Pd3 for short; S-Adm = 1-adamantanethiol) cluster enables the above reaction but insufficient ammonia occurring on the cluster leads to low activity and inferior selectivity. We thereby construct a transfer channel between the active cluster (Pd3) and the functional unit (mPTA), which is identified as an interfacial ladder of Pd–O–W, delivering ammonia molecules from the functional unit to the active center. The mPTA resembles a pump source to supply ammonia to meet the requirement for the reductive amination over the cluster, in which ammonia hops the ladder to expediently react with H2 and carbonyl compounds awaiting on Pd sites, finally giving rise to remarkable performances with a high yield of amines. We recognize that the interactive cooperation of inner catalysis with peripheral input across two different compounds holds promise in decoupling and controlling complex chemical ecosystems for high-quality productivity.
{"title":"Constructing the Transfer Ladder between Active Sites and Functional Units within the Cluster-Based Catalyst for Reductive Amination","authors":"Hao Wang,Chenyang Shen,Hongqiao Lin,Yiqi Tian,Xu Liu,Shuangshuang Huang,Gongde Wu,Weiping Ding,Yan Zhu","doi":"10.1021/jacs.6c13494","DOIUrl":"https://doi.org/10.1021/jacs.6c13494","url":null,"abstract":"The remote communication between active sites and the surrounding environment within a heterogeneous catalyst for the orderly bonding of reactive species is highly desired yet very challenging. Here we find that the phosphotungstate with a mesoporous framework (abbreviated as mPTA) has an extraordinary ability to accommodate ammonia but has no activity for catalytic reductive amination, while the Pd3(S-Adm)3(PPh3)3+ (Pd3 for short; S-Adm = 1-adamantanethiol) cluster enables the above reaction but insufficient ammonia occurring on the cluster leads to low activity and inferior selectivity. We thereby construct a transfer channel between the active cluster (Pd3) and the functional unit (mPTA), which is identified as an interfacial ladder of Pd–O–W, delivering ammonia molecules from the functional unit to the active center. The mPTA resembles a pump source to supply ammonia to meet the requirement for the reductive amination over the cluster, in which ammonia hops the ladder to expediently react with H2 and carbonyl compounds awaiting on Pd sites, finally giving rise to remarkable performances with a high yield of amines. We recognize that the interactive cooperation of inner catalysis with peripheral input across two different compounds holds promise in decoupling and controlling complex chemical ecosystems for high-quality productivity.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"37 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149275133","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}
Ling-Hong Meng,Li-Yao Wang,Zhen Ying,Xiao-Ming Li,Xin Li,Li-Hong Yan,Bin-Gui Wang
Intermolecular Diels–Alder (DA) cycloadditions are pivotal for constructing complex polycyclic architectures. However, biological catalysts performing this transformation on diketopiperazine (DKP) cores remain largely unidentified. Here, we report a decentralized biosynthetic pathway in the deep-sea cold-seep sourced fungus Aspergillus chevalieri CS-122 that assembles chevalinulin A, a spiro[bicyclo[2.2.2]octane]-DKP alkaloid. This pathway involves two nonclustered enzymes, CalO and FadA. CalO is a cytochrome P450 that furnishes an essential exocyclic olefin, while FadA represents the first FAD oxidoreductase-like Diels–Alderase that catalyzes an intermolecular, endoselective [4 + 2] cycloaddition between neoechinulin B and 3,4-trans-cyclohexadiene. These enzymes function downstream of a conserved gene cluster, effectively decoupling core scaffold assembly from late-stage functionalization. This strategy likely underpins the extensive structural diversity of fungal DKP alkaloids. Notably, CalO and FadA were identified via an integrated transcriptomic and structure-guided computational pipeline, rather than sequence homology, demonstrating the efficacy of this approach in mining functional catalysts from genomic “dark matter”. Mutational analysis indicates that residues M193, Y226, Y315, and D446 are critical in FadA activity. This study reveals a decentralized biosynthetic paradigm linking clustered core assembly with dispersed diversification, establishing a general framework for engineering complex alkaloid scaffolds.
{"title":"Decentralized Biosynthesis of the Spiro-DKP Alkaloid Chevalinulin A Enabled by Nonclustered P450 and Intermolecular [4 + 2] Cyclase","authors":"Ling-Hong Meng,Li-Yao Wang,Zhen Ying,Xiao-Ming Li,Xin Li,Li-Hong Yan,Bin-Gui Wang","doi":"10.1021/jacs.6c17478","DOIUrl":"https://doi.org/10.1021/jacs.6c17478","url":null,"abstract":"Intermolecular Diels–Alder (DA) cycloadditions are pivotal for constructing complex polycyclic architectures. However, biological catalysts performing this transformation on diketopiperazine (DKP) cores remain largely unidentified. Here, we report a decentralized biosynthetic pathway in the deep-sea cold-seep sourced fungus Aspergillus chevalieri CS-122 that assembles chevalinulin A, a spiro[bicyclo[2.2.2]octane]-DKP alkaloid. This pathway involves two nonclustered enzymes, CalO and FadA. CalO is a cytochrome P450 that furnishes an essential exocyclic olefin, while FadA represents the first FAD oxidoreductase-like Diels–Alderase that catalyzes an intermolecular, endoselective [4 + 2] cycloaddition between neoechinulin B and 3,4-trans-cyclohexadiene. These enzymes function downstream of a conserved gene cluster, effectively decoupling core scaffold assembly from late-stage functionalization. This strategy likely underpins the extensive structural diversity of fungal DKP alkaloids. Notably, CalO and FadA were identified via an integrated transcriptomic and structure-guided computational pipeline, rather than sequence homology, demonstrating the efficacy of this approach in mining functional catalysts from genomic “dark matter”. Mutational analysis indicates that residues M193, Y226, Y315, and D446 are critical in FadA activity. This study reveals a decentralized biosynthetic paradigm linking clustered core assembly with dispersed diversification, establishing a general framework for engineering complex alkaloid scaffolds.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281848","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}
Two-dimensional (2D) magnetic semiconductor heterostructures serve as an ideal material platform for the exploration of emergent physical phenomena and high-density integrated electronics, owing to the strong magneto-electric-optical coupling at their interfaces. Remarkably, the interfacial engineering also endows the heterosystem with pronounced multifield tunability, facilitating the development of next-generation low-power multifunctional devices. Nevertheless, their practical development remains hindered by low magnetic ordering temperatures and the lack of scalable synthetic methods. Here, we develop a dual precursor-assisted chemical vapor deposition strategy to achieve large-scale synthesis of room-temperature-operable FeSex/WSe2 magnetic semiconductor heterostructures with atomically sharp interfaces. The photoresponse of the as-fabricated heterostructure can be effectively programmed by an external magnetic field, achieving a prominent room-temperature modulation ratio exceeding 50%. Such impressive magneto-photoresponse originates from spin-dependent interfacial charge transfer. Furthermore, the synergistic tunability of photoelectric performance under varying illumination and magnetic fields facilitates the construction of an adaptive enhancement framework for magnetic sensing, which enables optimized low-contrast image recognition and paves the way for advanced in-sensor computing systems. This work not only provides a feasible synthetic route for large-scale preparation of 2D heterostructures, but also sheds new light on the design of multifunctional devices with multifield coupling characteristics.
{"title":"Giant Magneto-Photoresponse in 2D Room-Temperature Magnetic Semiconductor Heterostructures","authors":"Zijing Zhao,Jiaxuan Li,Enshu Xu,Xiaocang Han,Ziyuan Liu,Bailing Li,Yu Zhang,He Ma,Shiqi Yang,Zhuoya Feng,Jianhao Gao,Jihui Li,Liqiang Zhang,Dahai Wei,Su-Ting Han,Yiyang Xie,Xinping Zhang,Pengying Chang,Yanglong Hou,Xiaolei Wang","doi":"10.1021/jacs.6c17633","DOIUrl":"https://doi.org/10.1021/jacs.6c17633","url":null,"abstract":"Two-dimensional (2D) magnetic semiconductor heterostructures serve as an ideal material platform for the exploration of emergent physical phenomena and high-density integrated electronics, owing to the strong magneto-electric-optical coupling at their interfaces. Remarkably, the interfacial engineering also endows the heterosystem with pronounced multifield tunability, facilitating the development of next-generation low-power multifunctional devices. Nevertheless, their practical development remains hindered by low magnetic ordering temperatures and the lack of scalable synthetic methods. Here, we develop a dual precursor-assisted chemical vapor deposition strategy to achieve large-scale synthesis of room-temperature-operable FeSex/WSe2 magnetic semiconductor heterostructures with atomically sharp interfaces. The photoresponse of the as-fabricated heterostructure can be effectively programmed by an external magnetic field, achieving a prominent room-temperature modulation ratio exceeding 50%. Such impressive magneto-photoresponse originates from spin-dependent interfacial charge transfer. Furthermore, the synergistic tunability of photoelectric performance under varying illumination and magnetic fields facilitates the construction of an adaptive enhancement framework for magnetic sensing, which enables optimized low-contrast image recognition and paves the way for advanced in-sensor computing systems. This work not only provides a feasible synthetic route for large-scale preparation of 2D heterostructures, but also sheds new light on the design of multifunctional devices with multifield coupling characteristics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"15 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281804","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}
Tumor-resident bacteria establish a profound immunosuppressive microenvironment that compromises cancer immunotherapy. While ablating these microbes holds therapeutic promise, broad-spectrum antibiotics can cause systemic dysbiosis, and the Gram-negative outer membrane can restrict the entry of conventional sonosensitizers, limiting the antibacterial efficacy of sonodynamic therapy (SDT). Here, we report an ultrasound-driven, bacteria-targeted immunotherapy utilizing polyarginine-functionalized peptide-sonosensitizer conjugates to achieve the in situ pulverization of the tumor Fusobacterium nucleatum (F. nucleatum), thereby eliciting potent innate antitumor immunity. The cationic conjugates electrostatically intercalate into Gram-negative bacterial membranes, inflicting a structural predisruption. Subsequent ultrasound irradiation synergizes localized sonochemical oxidation with mechanical shear forces to thoroughly shatter the bacteria. This targeted microbial fragmentation liberates massive quantities of pathogen-associated molecular patterns (PAMPs) that, unlike tumor-derived signals from conventional SDT, decisively reprogram macrophages toward an antitumor M1 phenotype to awaken innate immunity. Synchronized with tumor-specific antigens released via conjugate-induced immunogenic cell death, the liberated PAMPs synergistically amplify antigen presentation and optimally drive dendritic cell maturation. In a bacteria-colonized murine colorectal cancer model, this localized therapy markedly suppressed primary tumor growth and elicited both a pronounced abscopal effect against distant tumors and antitumor immune memory. By repurposing complicit bacteria into potent endogenous adjuvants, this ultrasound-driven strategy reverses bacteria-mediated immunosuppression, offering a transformative paradigm for treating microbiome-colonized solid tumors.
{"title":"Ultrasound-Driven Lysis of Tumor-Resident Bacteria Awakens Innate Immunity for Systemic Cancer Therapy","authors":"Wenya Zhou,Haoqi Zhu,Yu Liu,Haoze Li,Min Wu,Siqi Li,Rui Qu,Shaopeng Liu,Hanqing Qian,Bin Xue,Yi Cao,Xiqun Jiang,Xu Zhen","doi":"10.1021/jacs.6c14587","DOIUrl":"https://doi.org/10.1021/jacs.6c14587","url":null,"abstract":"Tumor-resident bacteria establish a profound immunosuppressive microenvironment that compromises cancer immunotherapy. While ablating these microbes holds therapeutic promise, broad-spectrum antibiotics can cause systemic dysbiosis, and the Gram-negative outer membrane can restrict the entry of conventional sonosensitizers, limiting the antibacterial efficacy of sonodynamic therapy (SDT). Here, we report an ultrasound-driven, bacteria-targeted immunotherapy utilizing polyarginine-functionalized peptide-sonosensitizer conjugates to achieve the in situ pulverization of the tumor Fusobacterium nucleatum (F. nucleatum), thereby eliciting potent innate antitumor immunity. The cationic conjugates electrostatically intercalate into Gram-negative bacterial membranes, inflicting a structural predisruption. Subsequent ultrasound irradiation synergizes localized sonochemical oxidation with mechanical shear forces to thoroughly shatter the bacteria. This targeted microbial fragmentation liberates massive quantities of pathogen-associated molecular patterns (PAMPs) that, unlike tumor-derived signals from conventional SDT, decisively reprogram macrophages toward an antitumor M1 phenotype to awaken innate immunity. Synchronized with tumor-specific antigens released via conjugate-induced immunogenic cell death, the liberated PAMPs synergistically amplify antigen presentation and optimally drive dendritic cell maturation. In a bacteria-colonized murine colorectal cancer model, this localized therapy markedly suppressed primary tumor growth and elicited both a pronounced abscopal effect against distant tumors and antitumor immune memory. By repurposing complicit bacteria into potent endogenous adjuvants, this ultrasound-driven strategy reverses bacteria-mediated immunosuppression, offering a transformative paradigm for treating microbiome-colonized solid tumors.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281817","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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