Xiaofeng Wu, Fan Xing, Yang Yang, Xiaoyang Liu, Gyoungmi Kim, Qiaochu Jiang, Ying Xu, Jing-Jing Hu, Gaolin Liang, Juyoung Yoon
Photoimmunotherapy has been a promising method for eradicating malignant tumors, but remains largely limited by tumor hypoxia and off-target adverse effects. To address these limitations, we develop hypoxia-tolerant small ligand-caged photosensitizer (PS) P1/P2 that are delivered to tumor based on an albumin-hijacking strategy by exploiting endogenous serum albumin as a tumor-localized carrier, achieving exceptional tumor accumulation and overcoming tumor hypoxia to realize the combined photoimmunotherapy. Albumin can trigger the acetyl group of P1/P2, initiating a 1,6-rearrangement elimination cascade to release a quinone methide intermediate captured by albumin to form a stable adduct via site-specific 1,6-Michael addition, as verified by in vitro experiments, including high performance liquid chromatography, mass spectra, spectroscopic spectra, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analyses but control probes P3/P4 fail. In vivo imaging revealed that P1/P2 displayed more enhanced tumor accumulation post injection than P3/P4 did in 4T1-bearing mouse models and P1 further enabled broad-spectrum efficacy across several tumor models. Moreover, by light-irradiation-generating superoxide anions and hydroxyl radicals, P1-mediated photodynamic therapy achieves tumor-inhibiting action with approximately 92% regression in a breast mouse model and triggers immunogenic cell death induction, synergizing with programmed death-ligand 1 therapy to further activate systemic antitumor immunity and suppress both primary and distant tumors with approximately 95% tumor growth inhibition. Crucially, this platform may extend its applicability to diverse payloads such as imaging agents, therapeutics, and immunomodulators by replacing the PS warhead and advance delivery methods for clinical imaging and therapy.
{"title":"Caged Ligand-Decorated Near-Infrared Photosensitizer with In Vivo Albumin-Hijacking Capacity for Tumor-Targeted Hypoxia-Tolerant Photoimmunotherapy of Cancer","authors":"Xiaofeng Wu, Fan Xing, Yang Yang, Xiaoyang Liu, Gyoungmi Kim, Qiaochu Jiang, Ying Xu, Jing-Jing Hu, Gaolin Liang, Juyoung Yoon","doi":"10.1021/jacs.5c16988","DOIUrl":"https://doi.org/10.1021/jacs.5c16988","url":null,"abstract":"Photoimmunotherapy has been a promising method for eradicating malignant tumors, but remains largely limited by tumor hypoxia and off-target adverse effects. To address these limitations, we develop hypoxia-tolerant small ligand-caged photosensitizer (PS) <b>P1</b>/<b>P2</b> that are delivered to tumor based on an albumin-hijacking strategy by exploiting endogenous serum albumin as a tumor-localized carrier, achieving exceptional tumor accumulation and overcoming tumor hypoxia to realize the combined photoimmunotherapy. Albumin can trigger the acetyl group of <b>P1</b>/<b>P2</b>, initiating a 1,6-rearrangement elimination cascade to release a quinone methide intermediate captured by albumin to form a stable adduct via site-specific 1,6-Michael addition, as verified by in vitro experiments, including high performance liquid chromatography, mass spectra, spectroscopic spectra, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analyses but control probes <b>P3</b>/<b>P4</b> fail. In vivo imaging revealed that <b>P1</b>/<b>P2</b> displayed more enhanced tumor accumulation post injection than <b>P3</b>/<b>P4</b> did in 4T1-bearing mouse models and <b>P1</b> further enabled broad-spectrum efficacy across several tumor models. Moreover, by light-irradiation-generating superoxide anions and hydroxyl radicals, <b>P1</b>-mediated photodynamic therapy achieves tumor-inhibiting action with approximately 92% regression in a breast mouse model and triggers immunogenic cell death induction, synergizing with programmed death-ligand 1 therapy to further activate systemic antitumor immunity and suppress both primary and distant tumors with approximately 95% tumor growth inhibition. Crucially, this platform may extend its applicability to diverse payloads such as imaging agents, therapeutics, and immunomodulators by replacing the PS warhead and advance delivery methods for clinical imaging and therapy.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122269","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}
Carbon buried beneath the surface of a metal catalyst has long been suspected to play a key role in graphene and nanotube synthesis, carbon gasification, carbon fuel cells, and Fischer–Tropsch reactions, but the lack of a technique to detect this carbon unambiguously has stymied its definitive identification in that chemistry. This study reports the first vibrational spectroscopic identification of carbon occupying sites beneath a surface, along with its distinction from surface-adsorbed carbon, by the incident energy dependence of its high-resolution electron energy loss intensity. Its assignment is corroborated by its purposeful synthesis via collision-induced absorption, a technique designed to cleanly synthesize bulk carbon by bombardment of surface-bound carbon with 6 eV Xe atoms that pound it beneath the surface. On a Au–Ni(111) surface alloy, subsurface carbon is found to occupy multiple interstitial sites within the dislocation loop below the alloy surface and in Ni octahedral sites, yielding frequencies of 368, 442 and 509, and 694 cm–1, respectively, consistent with previous density functional calculations. Discovery of the spectroscopic signature of bulk carbon provides a handle for its role and/or its reactivity to be explored and ultimately controlled and optimized over that of surface bound carbon in heterogeneous catalytic reactions and materials properties.
{"title":"Production of Subsurface Carbon by Collision Induced Absorption and Its Vibrational Spectroscopic Identification in Au–Ni(111)","authors":"Santosh K. Singh, Volkan Cinar, S. T. Ceyer","doi":"10.1021/jacs.5c19883","DOIUrl":"https://doi.org/10.1021/jacs.5c19883","url":null,"abstract":"Carbon buried beneath the surface of a metal catalyst has long been suspected to play a key role in graphene and nanotube synthesis, carbon gasification, carbon fuel cells, and Fischer–Tropsch reactions, but the lack of a technique to detect this carbon unambiguously has stymied its definitive identification in that chemistry. This study reports the first vibrational spectroscopic identification of carbon occupying sites beneath a surface, along with its distinction from surface-adsorbed carbon, by the incident energy dependence of its high-resolution electron energy loss intensity. Its assignment is corroborated by its purposeful synthesis via collision-induced absorption, a technique designed to cleanly synthesize bulk carbon by bombardment of surface-bound carbon with 6 eV Xe atoms that pound it beneath the surface. On a Au–Ni(111) surface alloy, subsurface carbon is found to occupy multiple interstitial sites within the dislocation loop below the alloy surface and in Ni octahedral sites, yielding frequencies of 368, 442 and 509, and 694 cm<sup>–1</sup>, respectively, consistent with previous density functional calculations. Discovery of the spectroscopic signature of bulk carbon provides a handle for its role and/or its reactivity to be explored and ultimately controlled and optimized over that of surface bound carbon in heterogeneous catalytic reactions and materials properties.","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":"146122304","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}
Dan Ferenc Segedin, Jinkwon Kim, Harrison LaBollita, Nicole K. Taylor, Kyeong-Yoon Baek, Suk Hyun Sung, Ari B. Turkiewicz, Grace A. Pan, Abigail Y. Jiang, Maria Bambrick-Santoyo, Tobias Schwaigert, Casey K. Kim, Anirudh Tenneti, Alexander J. Grutter, Shin Muramoto, Alpha T. N’Diaye, Ismail El Baggari, Donald A. Walko, Charles M. Brooks, Antia S. Botana, Darrell G. Schlom, Hua Zhou, Julia A. Mundy
Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, we report a new family of layered perovskites realized through topochemical oxidation of Lan+1NinO3n+1+δ (n = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial c-axis expansion─17.8% for La2NiO4+δ (n = 1)─that monotonically decreases with increasing n. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.
{"title":"Topochemical Oxidation of Ruddlesden–Popper Nickelates Reveals Distinct Structural Family: Oxygen-Intercalated Layered Perovskites","authors":"Dan Ferenc Segedin, Jinkwon Kim, Harrison LaBollita, Nicole K. Taylor, Kyeong-Yoon Baek, Suk Hyun Sung, Ari B. Turkiewicz, Grace A. Pan, Abigail Y. Jiang, Maria Bambrick-Santoyo, Tobias Schwaigert, Casey K. Kim, Anirudh Tenneti, Alexander J. Grutter, Shin Muramoto, Alpha T. N’Diaye, Ismail El Baggari, Donald A. Walko, Charles M. Brooks, Antia S. Botana, Darrell G. Schlom, Hua Zhou, Julia A. Mundy","doi":"10.1021/jacs.5c12712","DOIUrl":"https://doi.org/10.1021/jacs.5c12712","url":null,"abstract":"Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, we report a new family of layered perovskites realized through topochemical oxidation of La<sub><i>n</i>+1</sub>Ni<sub><i>n</i></sub>O<sub>3<i>n</i>+1+δ</sub> (<i>n</i> = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial <i>c</i>-axis expansion─17.8% for La<sub>2</sub>NiO<sub>4+δ</sub> (<i>n</i> = 1)─that monotonically decreases with increasing <i>n</i>. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122266","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}
Chiral amides are privileged motifs widely found in pharmaceuticals and natural products, spurring the development of robust synthetic methods. While carbamoyl chlorides are convenient and versatile electrophilic precursors, their application in the stereoselective synthesis of sterically hindered amides, particularly those bearing tetrasubstituted stereocenters, remains a formidable challenge. To address this, we have developed a cobalt-catalyzed asymmetric carbamoyl addition to imines, which enables efficient access to structurally demanding α,α-disubstituted α-amino amides under mild conditions with excellent enantioselectivity. Furthermore, this modular strategy facilitates a one-pot cascade to synthesize enantioenriched 2,5-diketopiperazines (DKPs), important scaffolds in medicinal chemistry. Mechanistic studies reveal stereoselective carbamoyl radical addition to forge the chiral C–C bond.
{"title":"Co-Catalyzed Asymmetric Carbamoyl Radical Addition of Imines","authors":"Wenyu Zhao, Xingyi Shen, Zhaozhao Li, Xuxia Zhang, Aiqi Li, Xianqing Wu, Jingping Qu, Yifeng Chen","doi":"10.1021/jacs.5c22992","DOIUrl":"https://doi.org/10.1021/jacs.5c22992","url":null,"abstract":"Chiral amides are privileged motifs widely found in pharmaceuticals and natural products, spurring the development of robust synthetic methods. While carbamoyl chlorides are convenient and versatile electrophilic precursors, their application in the stereoselective synthesis of sterically hindered amides, particularly those bearing tetrasubstituted stereocenters, remains a formidable challenge. To address this, we have developed a cobalt-catalyzed asymmetric carbamoyl addition to imines, which enables efficient access to structurally demanding α,α-disubstituted α-amino amides under mild conditions with excellent enantioselectivity. Furthermore, this modular strategy facilitates a one-pot cascade to synthesize enantioenriched 2,5-diketopiperazines (DKPs), important scaffolds in medicinal chemistry. Mechanistic studies reveal stereoselective carbamoyl radical addition to forge the chiral C–C bond.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122332","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}
Evgeniia Ikonnikova, Jung Cho, Xiaodong Zou, Andre Sutrisno, Allen W Burton, Trong Pham, Tom Willhammar
The structural diversity of zeolites depends strongly on the use of organic structure-directing agents (OSDAs) that guide their formation. Low-dimensional zeolitic materials, such as layered or chain-like phases, can serve as key intermediates in topotactic condensation pathways, yet the mechanisms governing their formation and transformation remain poorly understood. Here, we report three low-dimensional zeolitic materials, EMM-75P, EM-L01, and EM-L02, synthesized using benzimidazolium cations as OSDAs. Their structures were determined by three-dimensional electron diffraction (3D ED), including the atomic structure of the OSDAs, revealing their confinement within the framework to shed light on their structure-directing role. The bulky benzimidazolium OSDAs prevent the formation of materials with three-dimensional framework structures and instead direct the formation of low-dimensional zeotypes. Upon calcination, the two-dimensional layered aluminosilicate zeotype EMM-75P undergoes topotactic condensation to form a three-dimensional zeolite, EMM-75, with a previously unreported zeolite framework topology. Aluminosilicate EM-L01 is a 2D analogue of STF/SFF zeolite frameworks and partially condensed to an STF-topology upon calcination, whereas EM-L02, a 1D silicate composed of double 6-ring chains, packed analogous to the CHA zeolite framework, collapses during the thermal treatment. The detailed structural characterization of these three materials provides insights into the mechanism of topotactic condensation and demonstrates how such pathways can lead to new zeolite materials.
{"title":"Low-Dimensional Zeotypes Templated by Stacked Cyclic Benzimidazolium Revealed by Electron Crystallography.","authors":"Evgeniia Ikonnikova, Jung Cho, Xiaodong Zou, Andre Sutrisno, Allen W Burton, Trong Pham, Tom Willhammar","doi":"10.1021/jacs.5c22569","DOIUrl":"https://doi.org/10.1021/jacs.5c22569","url":null,"abstract":"<p><p>The structural diversity of zeolites depends strongly on the use of organic structure-directing agents (OSDAs) that guide their formation. Low-dimensional zeolitic materials, such as layered or chain-like phases, can serve as key intermediates in topotactic condensation pathways, yet the mechanisms governing their formation and transformation remain poorly understood. Here, we report three low-dimensional zeolitic materials, EMM-75P, EM-L01, and EM-L02, synthesized using benzimidazolium cations as OSDAs. Their structures were determined by three-dimensional electron diffraction (3D ED), including the atomic structure of the OSDAs, revealing their confinement within the framework to shed light on their structure-directing role. The bulky benzimidazolium OSDAs prevent the formation of materials with three-dimensional framework structures and instead direct the formation of low-dimensional zeotypes. Upon calcination, the two-dimensional layered aluminosilicate zeotype EMM-75P undergoes topotactic condensation to form a three-dimensional zeolite, EMM-75, with a previously unreported zeolite framework topology. Aluminosilicate EM-L01 is a 2D analogue of <b>STF</b>/<b>SFF</b> zeolite frameworks and partially condensed to an <b>STF</b>-topology upon calcination, whereas EM-L02, a 1D silicate composed of double 6-ring chains, packed analogous to the <b>CHA</b> zeolite framework, collapses during the thermal treatment. The detailed structural characterization of these three materials provides insights into the mechanism of topotactic condensation and demonstrates how such pathways can lead to new zeolite materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146123259","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}
We show the dynamic covalent exchange between merocyanines and imines and demonstrate how the equilibrium composition can be shifted with visible light. For this purpose, we exploited a negative photochromic T-type merocyanine that engages in a covalent exchange with an aniline nucleophile to provide an imine. Since the merocyanine can quantitatively be converted into its spiropyran isomer that is nonreactive in the exchange, the system can be shifted and trapped in the static spiropyran state. In the dark, however, the system thermally reverts back to the dynamic merocyanine that re-engages in the exchange. The process of shifting/trapping and re-equilibration can be repeated multiple times. The system provides opportunities for designing materials that allow for spatial and temporal control over their dynamic properties.
{"title":"Shifting Merocyanine-Imine Exchange with Visible Light","authors":"Alwin Drichel, Stefan Hecht","doi":"10.1021/jacs.5c17606","DOIUrl":"https://doi.org/10.1021/jacs.5c17606","url":null,"abstract":"We show the dynamic covalent exchange between merocyanines and imines and demonstrate how the equilibrium composition can be shifted with visible light. For this purpose, we exploited a negative photochromic T-type merocyanine that engages in a covalent exchange with an aniline nucleophile to provide an imine. Since the merocyanine can quantitatively be converted into its spiropyran isomer that is nonreactive in the exchange, the system can be shifted and trapped in the static spiropyran state. In the dark, however, the system thermally reverts back to the dynamic merocyanine that re-engages in the exchange. The process of shifting/trapping and re-equilibration can be repeated multiple times. The system provides opportunities for designing materials that allow for spatial and temporal control over their dynamic properties.","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":"146122297","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}
DNA-metal complexes represent a growing class of artificial metalloenzymes for enantioselective catalysis. Unlike protein pockets, the structural tunability of DNA scaffolds, such as the G-quadruplex, enables dynamic control over enantioselectivity. However, these catalysts often exhibit low catalytic efficiency and limited enantioselectivity switching, underscoring a high demand for rational design strategies to advance this field. Capitalizing on the programmable cytosine–cytosine base pairing in i-motif DNA (imDNA), we develop a tetrad-capping strategy to construct a copper(II) hybrid catalyst (imDNA(H+)/Cu2+) featuring hemiprotonated cytosine–cytosine base pairs (C–H+–C). This catalyst achieves quantitative conversions and up to 98% enantiomeric excess (ee) in Friedel–Crafts reactions. Remarkably, Ag+ ions reconfigure imDNA(H+) into a distinct imDNA(Ag+) conformation, realizing inversion of enantioselectivity (up to –93% ee) with the 4,4’-dimethyl-2,2’-bipyridine copper(II) complex (Cu2+(dmbpy)). The chiral inversion originates from distinct H+- and Ag+-regulated i-motif topologies. Comprehensive spectroscopic, electrophoretic, and thermodynamic analyses reveal that imDNA(Ag+) adopts an antiparallel strand orientation stabilized by four C–Ag+–C and two G–Ag+–G base pairs, in contrast to the capped imDNA(H+). The plausible binding sites of catalytic copper(II) species are proposed through binding assays and mutagenesis, where three Cu2+ ions are located within three loop regions of imDNA(H+), and two Cu2+(dmbpy) complexes might primarily interact with imDNA(Ag+) via end-stacking. This work establishes a general paradigm for designing tunable DNA hybrid catalysts via programmable base pairing, opening avenues for diverse enantioselective transformations.
{"title":"H+/Ag+ Switch of Enantioselectivity in i-Motif DNA-Based Friedel–Crafts Reactions","authors":"Xingchen Dong,Weijun Qin,Zixiao Wang,Wenqin Zhou,Shanmei Xu,Mengyao Wang,Jin Zhang,Linna Wang,Guoqing Jia,Yashao Chen,Changhao Wang","doi":"10.1021/jacs.5c20057","DOIUrl":"https://doi.org/10.1021/jacs.5c20057","url":null,"abstract":"DNA-metal complexes represent a growing class of artificial metalloenzymes for enantioselective catalysis. Unlike protein pockets, the structural tunability of DNA scaffolds, such as the G-quadruplex, enables dynamic control over enantioselectivity. However, these catalysts often exhibit low catalytic efficiency and limited enantioselectivity switching, underscoring a high demand for rational design strategies to advance this field. Capitalizing on the programmable cytosine–cytosine base pairing in i-motif DNA (imDNA), we develop a tetrad-capping strategy to construct a copper(II) hybrid catalyst (imDNA(H+)/Cu2+) featuring hemiprotonated cytosine–cytosine base pairs (C–H+–C). This catalyst achieves quantitative conversions and up to 98% enantiomeric excess (ee) in Friedel–Crafts reactions. Remarkably, Ag+ ions reconfigure imDNA(H+) into a distinct imDNA(Ag+) conformation, realizing inversion of enantioselectivity (up to –93% ee) with the 4,4’-dimethyl-2,2’-bipyridine copper(II) complex (Cu2+(dmbpy)). The chiral inversion originates from distinct H+- and Ag+-regulated i-motif topologies. Comprehensive spectroscopic, electrophoretic, and thermodynamic analyses reveal that imDNA(Ag+) adopts an antiparallel strand orientation stabilized by four C–Ag+–C and two G–Ag+–G base pairs, in contrast to the capped imDNA(H+). The plausible binding sites of catalytic copper(II) species are proposed through binding assays and mutagenesis, where three Cu2+ ions are located within three loop regions of imDNA(H+), and two Cu2+(dmbpy) complexes might primarily interact with imDNA(Ag+) via end-stacking. This work establishes a general paradigm for designing tunable DNA hybrid catalysts via programmable base pairing, opening avenues for diverse enantioselective transformations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"41 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111203","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}
Ruowen Liang,Chao Zhang,Ying Wang,Ling Wu,Yulai Zhao,Shijing Liang,Guiyang Yan,Jinlin Long
This work demonstrates an efficient halogen radical-mediated photocatalytic route for overcoming the kinetic bottleneck of CO2 cycloaddition with epoxides to produce cyclic carbonates. A novel organic–inorganic nanohybrid photocatalyst is smartly designed and prepared by grafting of perylene-3,4,9,10-tetracarboxylic diimide (PDI) molecules with UiO-66-NH2 metal–organic frameworks (UZN) to perform cycloaddition of CO2 to propylene oxide (PO) under visible light (λ ≥ 420 nm) irradiation. The PDI and UZN moieties are linked by an amide bridge to form a type II heterojunction interface, and the former serves as the hole collector, where halogen anions including Br–, Cl–, F–, and I– are directly oxidized to radicals, and the latter acts as the electron acceptor, where CO2 is adsorbed on the exposed Zr sites of [ZrO6] units and reduced to CO2–• radicals. The optimal PDI–UZN photocatalyst achieves an impressive propylene carbonate (PC) yield of 99.4% at a production rate of 34.1 mmol·g–1·h–1, with a benchmark apparent quantum efficiency of 35.9% at 400 nm. The combination of characterization results and density functional theory calculation clearly reveals that the formed Br• radicals are preferential to attacking the C–O bonds of PO adsorbed over the PDI moiety to generate C2H6–BrC–O• intermediates, which react with CO2–•, finally producing propylene carbonate (PC) by dehalogenation. The findings provide general guidance to design efficient photocatalysts for CO2 fixation and green organic photosynthesis.
{"title":"Efficient Halogen Radical-Mediated Photosynthesis of Cyclic Carbonates over Perylene Diimide-Grafted Zirconium Metal–Organic Frameworks with Visible Light Irradiation","authors":"Ruowen Liang,Chao Zhang,Ying Wang,Ling Wu,Yulai Zhao,Shijing Liang,Guiyang Yan,Jinlin Long","doi":"10.1021/jacs.5c17348","DOIUrl":"https://doi.org/10.1021/jacs.5c17348","url":null,"abstract":"This work demonstrates an efficient halogen radical-mediated photocatalytic route for overcoming the kinetic bottleneck of CO2 cycloaddition with epoxides to produce cyclic carbonates. A novel organic–inorganic nanohybrid photocatalyst is smartly designed and prepared by grafting of perylene-3,4,9,10-tetracarboxylic diimide (PDI) molecules with UiO-66-NH2 metal–organic frameworks (UZN) to perform cycloaddition of CO2 to propylene oxide (PO) under visible light (λ ≥ 420 nm) irradiation. The PDI and UZN moieties are linked by an amide bridge to form a type II heterojunction interface, and the former serves as the hole collector, where halogen anions including Br–, Cl–, F–, and I– are directly oxidized to radicals, and the latter acts as the electron acceptor, where CO2 is adsorbed on the exposed Zr sites of [ZrO6] units and reduced to CO2–• radicals. The optimal PDI–UZN photocatalyst achieves an impressive propylene carbonate (PC) yield of 99.4% at a production rate of 34.1 mmol·g–1·h–1, with a benchmark apparent quantum efficiency of 35.9% at 400 nm. The combination of characterization results and density functional theory calculation clearly reveals that the formed Br• radicals are preferential to attacking the C–O bonds of PO adsorbed over the PDI moiety to generate C2H6–BrC–O• intermediates, which react with CO2–•, finally producing propylene carbonate (PC) by dehalogenation. The findings provide general guidance to design efficient photocatalysts for CO2 fixation and green organic photosynthesis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111225","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}
Yuecheng Wang,Lin Yuan,Ziyi Hu,Yujie Ban,Weishen Yang
Membrane-based pervaporation offers an energy-efficient route for azeotrope separation, yet fabricating membranes that combine structural integrity with precise molecular sieving remains challenging. This work introduces a biomineralization-inspired strategy to synergistically engineer metal–organic framework MIL-100 membranes across micro-, nano-, and molecular scales by using a readily accessible and metastable CuBTC template membrane. The template-anchored point-by-point nucleation directs spatially precise assembly of MIL-100 nanocrystals into a dense, defect-free membrane. Concurrently, a dynamic competition between template “sacrifice” and preservation generates a hierarchical “ship-in-bottle” structure, where encapsulated CuBTC nanoclusters effectively narrow MIL-100 mesocages to molecular dimensions, enabling sharp water/organic discrimination. For a 90 wt % ethanol/water feed, it achieves a separation factor of 3200 with a flux of 2.58 kg m–2 h–1, outperforming state-of-the-art membranes. This bioinspired mineralization strategy provides a universal route for designing crystalline porous membranes with exceptional selectivity and stability for energy-efficient molecular separations.
基于膜的渗透蒸发为共沸物分离提供了一种节能途径，然而，制造结合结构完整性和精确分子筛选的膜仍然具有挑战性。这项工作介绍了一种受生物矿化启发的策略，通过使用易于接近和亚稳的CuBTC模板膜，在微、纳米和分子尺度上协同工程金属-有机框架MIL-100膜。模板锚定的逐点成核指导MIL-100纳米晶体在空间上精确组装成致密、无缺陷的膜。同时，模板“牺牲”和保存之间的动态竞争产生了分层的“瓶中船”结构，其中封装的CuBTC纳米团簇有效地将MIL-100的中程缩小到分子尺寸，从而实现了水/有机区分。对于90 wt %的乙醇/水进料，它达到3200的分离系数，通量为2.58 kg m-2 h-1，优于最先进的膜。这种受生物启发的矿化策略为设计具有卓越选择性和稳定性的晶体多孔膜提供了一种通用途径，用于节能分子分离。
{"title":"Synergistic Multiscale Design of Metal–Organic Framework Membrane via Biomineralization-Inspired Templating for High-Efficiency Azeotrope Separation","authors":"Yuecheng Wang,Lin Yuan,Ziyi Hu,Yujie Ban,Weishen Yang","doi":"10.1021/jacs.5c21467","DOIUrl":"https://doi.org/10.1021/jacs.5c21467","url":null,"abstract":"Membrane-based pervaporation offers an energy-efficient route for azeotrope separation, yet fabricating membranes that combine structural integrity with precise molecular sieving remains challenging. This work introduces a biomineralization-inspired strategy to synergistically engineer metal–organic framework MIL-100 membranes across micro-, nano-, and molecular scales by using a readily accessible and metastable CuBTC template membrane. The template-anchored point-by-point nucleation directs spatially precise assembly of MIL-100 nanocrystals into a dense, defect-free membrane. Concurrently, a dynamic competition between template “sacrifice” and preservation generates a hierarchical “ship-in-bottle” structure, where encapsulated CuBTC nanoclusters effectively narrow MIL-100 mesocages to molecular dimensions, enabling sharp water/organic discrimination. For a 90 wt % ethanol/water feed, it achieves a separation factor of 3200 with a flux of 2.58 kg m–2 h–1, outperforming state-of-the-art membranes. This bioinspired mineralization strategy provides a universal route for designing crystalline porous membranes with exceptional selectivity and stability for energy-efficient molecular separations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"91 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111200","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}
Adoptive natural killer (NK) cell therapy for solid tumors faces critical challenges, including tumor antigen heterogeneity, impaired tumor infiltration, and suboptimal activation imposed by the immunosuppressive microenvironment. Here we developed an engineered nanoplatform featuring transmembrane DNA nanochannel-engineered artificial receptors (NCAR) to direct NK cells against solid tumors through two synergistic mechanisms: 1) Tumor Microenvironment (TME) Reprogramming: leveraging cholesterol-mediated insertion, NCAR incorporates into tumor membranes to disrupt phospholipid bilayers, inducing immunogenic cell death with the release of damage-associated molecular patterns (DAMPs; e.g., HMGB1, CRT), which remodels immunosuppression TME and recruits/activates NK cells. 2) Precision Targeting: NCAR forms programmable synthetic immune synapses with DNA nanoartificial ligands (NAL) engineered on NK cells via base-pairing. This antigen-independent assembly network establishes a universal membrane interface, enabling sustained tumor-targeted NK cell activation. The dual-component system enables sustained intratumoral accumulation of NK cells (>96 h), with a 15.1-fold increase in activated NKP46+GZB+ NK cells compared to controls. By bridging DNA nanotechnology with cell immunotherapy, our nanoplatform provides a universal strategy for navigating tumor-immune interactions, addressing key limitations of adoptive NK cell immunotherapy in solid tumors.
{"title":"Transmembrane DNA Nanochannel-Engineered Artificial Receptors for Navigating NK Cell Immunotherapy in Solid Tumors","authors":"Danyu Wang,Hua Yi,Jiali Zhang,Mengyu Huang,Yue Qiu,Yang Wang,Peiru Chen,Chan Liu,Tingyi Xu,Qiuxia Yang,Kuikun Yang,Zhenzhen Guo,Kaixiang Zhang","doi":"10.1021/jacs.5c16425","DOIUrl":"https://doi.org/10.1021/jacs.5c16425","url":null,"abstract":"Adoptive natural killer (NK) cell therapy for solid tumors faces critical challenges, including tumor antigen heterogeneity, impaired tumor infiltration, and suboptimal activation imposed by the immunosuppressive microenvironment. Here we developed an engineered nanoplatform featuring transmembrane DNA nanochannel-engineered artificial receptors (NCAR) to direct NK cells against solid tumors through two synergistic mechanisms: 1) Tumor Microenvironment (TME) Reprogramming: leveraging cholesterol-mediated insertion, NCAR incorporates into tumor membranes to disrupt phospholipid bilayers, inducing immunogenic cell death with the release of damage-associated molecular patterns (DAMPs; e.g., HMGB1, CRT), which remodels immunosuppression TME and recruits/activates NK cells. 2) Precision Targeting: NCAR forms programmable synthetic immune synapses with DNA nanoartificial ligands (NAL) engineered on NK cells via base-pairing. This antigen-independent assembly network establishes a universal membrane interface, enabling sustained tumor-targeted NK cell activation. The dual-component system enables sustained intratumoral accumulation of NK cells (>96 h), with a 15.1-fold increase in activated NKP46+GZB+ NK cells compared to controls. By bridging DNA nanotechnology with cell immunotherapy, our nanoplatform provides a universal strategy for navigating tumor-immune interactions, addressing key limitations of adoptive NK cell immunotherapy in solid tumors.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"18 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111222","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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