Tim Engelhardt, Leonid Shupletsov, Christin Gellrich, Cécilia Bauden, Przemyslaw Galek, Ahmed Bahrawy, Sonila Xhafa, Irena Senkovska, Julia Grothe, Stefan Kaskel
From concept to realization, the integration of porous redox-active metal–organic frameworks (MOFs) into asymmetric electrochemical capacitors for the assembly of electrochemical capacitor-diodes (CAPodes) is reported. CAPodes are innovative electrochemical capacitor analogues of diodes, designed for unidirectional charge storage and logic gate applications. The novel devices deliberately utilize two distinct electroactive metal–organic frameworks with characteristic redox potentials acting as positively or negatively polarizable electrode materials, respectively. The first proof-of-concept devices presented here make use of the Chichibabin-like diradicaloid formation upon oxidation of the N,N,N',N'-benzidinetetrabenzoate linker in DUT-65/66 and N,N,N',N'-(1,4-phenylenebis-(azanetriyl))-tetrabenzoate in DUT-232/233 at high oxidation potentials as a positively polarizable electrode material paired with the highly reversible two-step reduction in Zn(ndi) (ndi2− = 1,4-bis[(3,5-dimethyl)-pyrazolate-4-yl]naphthalene-diimide). The novel porous MOF-CAPode achieves a remarkable figure of merit with rectification ratios (RR) up to RRI = 23 and RRII = 94% at 10 mV s−1. The new MOF-based CAPodes operate efficiently in “AND” and “OR” logic gates, demonstrating logic operation under varying input voltages up to 3.0 V and frequencies of up to 40 mHz.
{"title":"Electroactive Metal–Organic Frameworks Enabling Unidirectional Electrochemical Capacitors and Logic Gates (MOF-CAPode)","authors":"Tim Engelhardt, Leonid Shupletsov, Christin Gellrich, Cécilia Bauden, Przemyslaw Galek, Ahmed Bahrawy, Sonila Xhafa, Irena Senkovska, Julia Grothe, Stefan Kaskel","doi":"10.1002/anie.2048229","DOIUrl":"https://doi.org/10.1002/anie.2048229","url":null,"abstract":"From concept to realization, the integration of porous redox-active metal–organic frameworks (MOFs) into asymmetric electrochemical capacitors for the assembly of electrochemical capacitor-diodes (CAPodes) is reported. CAPodes are innovative electrochemical capacitor analogues of diodes, designed for unidirectional charge storage and logic gate applications. The novel devices deliberately utilize two distinct electroactive metal–organic frameworks with characteristic redox potentials acting as positively or negatively polarizable electrode materials, respectively. The first proof-of-concept devices presented here make use of the Chichibabin-like diradicaloid formation upon oxidation of the <i>N,N,N',N'</i>-benzidinetetrabenzoate linker in DUT-65/66 and <i>N,N,N',N'</i>-(1,4-phenylenebis-(azanetriyl))-tetrabenzoate in DUT-232/233 at high oxidation potentials as a positively polarizable electrode material paired with the highly reversible two-step reduction in Zn(ndi) (ndi<sup>2</sup><sup>−</sup> = 1,4-bis[(3,5-dimethyl)-pyrazolate-4-yl]naphthalene-diimide). The novel porous MOF-CAPode achieves a remarkable figure of merit with rectification ratios (RR) up to <i>RR<sub>I</sub></i> = 23 and <i>RR<sub>II</sub></i> = 94% at 10 mV s<sup>−1</sup>. The new MOF-based CAPodes operate efficiently in “AND” and “OR” logic gates, demonstrating logic operation under varying input voltages up to 3.0 V and frequencies of up to 40 mHz.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726496","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}
Narrowband multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters are pivotal for wide-color-gamut displays, yet they often encounter an inherent trade-off between emission redshift and spectral broadening. In this study, we present a molecular design strategy that incorporates antiaromatic four-membered rings into a boron- and nitrogen-embedded MR framework to achieve aromaticity localization. This approach enhances the aromaticity localization within the MR skeleton, effectively suppressing vibrational coupling and narrowing the emission spectrum, while simultaneously extending the π-conjugation to induce a bathochromic shift-thereby counteracting the typical broadening that accompanies redshift. Relative to the DABNA-1 parent molecule, the designed emitter exhibits a substantially redshifted emission maximum from 460 to 523 nm, along with a narrowed full-width at half-maximum (FWHM) from 27 to 16 nm. The corresponding organic light-emitting diode (OLED) achieves a narrow FWHM of 21.5 nm with CIE coordinates of (0.26, 0.70), a maximum external quantum efficiency (EQEmax) of 36.1%, and a significantly low efficiency roll-off. Remarkably, the device demonstrates superior operational stability with an LT90 lifetime of 1469 h at an initial luminance of 1000 cd m-2. This work establishes a novel paradigm in molecular design for realizing long-wavelength MR-TADF emitters that concurrently achieve high color purity and excellent electroluminescence performance.
窄带多共振热激活延迟荧光（MR-TADF）发射器是宽色域显示的关键，但它们经常遇到发射红移和光谱展宽之间的内在权衡。在这项研究中，我们提出了一种分子设计策略，将反芳香四元环纳入硼和氮嵌入的MR框架中，以实现芳香性定位。这种方法增强了MR骨架内的芳香性定位，有效地抑制了振动耦合并缩小了发射光谱，同时扩展了π共轭以诱导深色位移，从而抵消了伴随红移的典型展宽。与DABNA-1亲本分子相比，设计的发射体在460 ~ 523 nm范围内具有明显的红移，在27 ~ 16 nm范围内具有窄化的半峰全宽。相应的有机发光二极管（OLED）实现了21.5 nm的窄频宽，CIE坐标为（0.26,0.70），最大外量子效率（EQEmax）为36.1%，效率滚降明显较低。值得注意的是，该器件在初始亮度为1000 cd m-2时的LT90寿命为1469小时，表现出卓越的操作稳定性。这项工作为实现长波长MR-TADF发射器建立了一种新的分子设计范式，同时实现了高颜色纯度和优异的电致发光性能。
{"title":"Harnessing Antiaromatic Perturbation in Multiple‑Resonance TADF Emitter for Simultaneous Bathochromic Shift and Spectral Narrowing.","authors":"Meiyan Liu,Chenglong Li,Jianping Zhou,Hai Zhang,Minqiang Mai,Chuanqin Cheng,Dongdong Zhang,Lian Duan","doi":"10.1002/anie.3901040","DOIUrl":"https://doi.org/10.1002/anie.3901040","url":null,"abstract":"Narrowband multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters are pivotal for wide-color-gamut displays, yet they often encounter an inherent trade-off between emission redshift and spectral broadening. In this study, we present a molecular design strategy that incorporates antiaromatic four-membered rings into a boron- and nitrogen-embedded MR framework to achieve aromaticity localization. This approach enhances the aromaticity localization within the MR skeleton, effectively suppressing vibrational coupling and narrowing the emission spectrum, while simultaneously extending the π-conjugation to induce a bathochromic shift-thereby counteracting the typical broadening that accompanies redshift. Relative to the DABNA-1 parent molecule, the designed emitter exhibits a substantially redshifted emission maximum from 460 to 523 nm, along with a narrowed full-width at half-maximum (FWHM) from 27 to 16 nm. The corresponding organic light-emitting diode (OLED) achieves a narrow FWHM of 21.5 nm with CIE coordinates of (0.26, 0.70), a maximum external quantum efficiency (EQEmax) of 36.1%, and a significantly low efficiency roll-off. Remarkably, the device demonstrates superior operational stability with an LT90 lifetime of 1469 h at an initial luminance of 1000 cd m-2. This work establishes a novel paradigm in molecular design for realizing long-wavelength MR-TADF emitters that concurrently achieve high color purity and excellent electroluminescence performance.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"243 1","pages":"e3901040"},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726262","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}
Pub Date : 2026-04-21DOI: 10.1002/anie.2026-m1704060700
Anissa Haim, Sandra Liebscher, Rasmus Klintrot, Lorenzo Vallino, Marcelo Masman, Andreas H. Simon, Marianne Hahn, Sven Hennig, Saskia Neubacher, Frank Bordusa, Tom N. Grossmann
The in-situ cyclization of proteins (INCYPRO) is employed to enhance the robustness of a D-stereospecific hydrolase (grey) an enzyme with very low intrinsic stability. In Research Article e21611, Saskia Neubacher, Frank Bordusa, Tom N. Grossmann, and co-workers use tailored crosslinkers (red) to generate covalently constrained macrocyclic enzyme architectures. The cover shows a crosslinked enzyme dimer (grey) which exhibits enhanced catalytic activity and stability and serves as the basis for the design of a highly resilient biocatalyst.
蛋白质的原位环化（INCYPRO）被用于增强d立体特异性水解酶（灰色）的鲁棒性，这种酶具有非常低的内在稳定性。在研究论文e21611中，Saskia Neubacher, Frank Bordusa, Tom N. Grossmann和同事使用定制交联剂（红色）生成共价约束的大环酶结构。封面显示了一种交联酶二聚体（灰色），它表现出增强的催化活性和稳定性，并作为设计高弹性生物催化剂的基础。
{"title":"Inside Front Cover: Multicyclic D-Stereospecific Hydrolase Dimer With High Sustained Activity","authors":"Anissa Haim, Sandra Liebscher, Rasmus Klintrot, Lorenzo Vallino, Marcelo Masman, Andreas H. Simon, Marianne Hahn, Sven Hennig, Saskia Neubacher, Frank Bordusa, Tom N. Grossmann","doi":"10.1002/anie.2026-m1704060700","DOIUrl":"https://doi.org/10.1002/anie.2026-m1704060700","url":null,"abstract":"The in-situ cyclization of proteins (INCYPRO) is employed to enhance the robustness of a D-stereospecific hydrolase (grey) an enzyme with very low intrinsic stability. In Research Article e21611, Saskia Neubacher, Frank Bordusa, Tom N. Grossmann, and co-workers use tailored crosslinkers (red) to generate covalently constrained macrocyclic enzyme architectures. The cover shows a crosslinked enzyme dimer (grey) which exhibits enhanced catalytic activity and stability and serves as the basis for the design of a highly resilient biocatalyst.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726561","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}
Yifei Liang, Fulai Liu, Fan Liu, Rui Shi, Jing Li, Lei Kang, Yong Chen
Hydroxymethylsulfonate (HMS) is an important cleaning agent in the electronics industry and serves as a crucial intermediate in the synthesis of surfactants and pharmaceuticals. Conventional industrial production of HMS relies on toxic and volatile formaldehyde, presenting considerable safety and environmental risks. Herein, we report a solar-driven photocatalytic route for the synthesis of HMS from waste SO2 and polyethylene terephthalate (PET)-derived ethylene glycol (EG) under ambient conditions, using a Cu single-atom-decorated TiO2 catalyst (Cu1/TiO2). The optimized Cu1/TiO2 catalyst achieves an HMS yield rate of ∼ 2.31 mmol gcat−1 h−1 with a 77.5% carbon selectivity, along with a H2 evolution rate of ∼ 4.36 mmol gcat−1 h−1. Mechanistic studies reveal that the atomically dispersed Cu sites act as electron sinks, which enhance charge separation and induce electronic modulation of TiO2. This modulation facilitates the adsorption and activation of reactants while lowering the energy barrier for the formation of a key *CHOH─CH2OH intermediate via EG dehydrogenation. This resulting intermediate then undergoes nucleophilic attack by hole-generated •SO3−, triggering C─C cleavage to form HMS. This work establishes a sustainable and waste-valorizing route for organosulfur synthesis.
{"title":"Solar-Driven Photocatalytic C─S Coupling for Organosulfur Synthesis Via Upcycling SO2 and Plastic Waste","authors":"Yifei Liang, Fulai Liu, Fan Liu, Rui Shi, Jing Li, Lei Kang, Yong Chen","doi":"10.1002/anie.1777088","DOIUrl":"https://doi.org/10.1002/anie.1777088","url":null,"abstract":"Hydroxymethylsulfonate (HMS) is an important cleaning agent in the electronics industry and serves as a crucial intermediate in the synthesis of surfactants and pharmaceuticals. Conventional industrial production of HMS relies on toxic and volatile formaldehyde, presenting considerable safety and environmental risks. Herein, we report a solar-driven photocatalytic route for the synthesis of HMS from waste SO<sub>2</sub> and polyethylene terephthalate (PET)-derived ethylene glycol (EG) under ambient conditions, using a Cu single-atom-decorated TiO<sub>2</sub> catalyst (Cu<sub>1</sub>/TiO<sub>2</sub>). The optimized Cu<sub>1</sub>/TiO<sub>2</sub> catalyst achieves an HMS yield rate of ∼ 2.31 mmol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> with a 77.5% carbon selectivity, along with a H<sub>2</sub> evolution rate of ∼ 4.36 mmol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>. Mechanistic studies reveal that the atomically dispersed Cu sites act as electron sinks, which enhance charge separation and induce electronic modulation of TiO<sub>2</sub>. This modulation facilitates the adsorption and activation of reactants while lowering the energy barrier for the formation of a key *CHOH─CH<sub>2</sub>OH intermediate via EG dehydrogenation. This resulting intermediate then undergoes nucleophilic attack by hole-generated •SO<sub>3</sub><sup>−</sup>, triggering C─C cleavage to form HMS. This work establishes a sustainable and waste-valorizing route for organosulfur synthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":"e1777088"},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147732209","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}
Ya Ting Gao,Ying Zhang,Bin Bin Chen,Li Ya Liang,Ming Jie Ye,Meng Qi Zhao,Xiao Yu Zhang,Fei Yang Xue,Jian Lv,Da Wei Li,Xiang Ma
Photoactivated room-temperature phosphorescence (pRTP) host-guest systems have received widespread attention due to their non-invasive photoresponsiveness, high reversibility, and color tunability. However, traditional polymer hosts often lack efficient photoactivation and sufficient stability due to passive oxygen penetration. Herein, we report a ureido-functionalized siloxane network derived from the hydrolysis of γ-ureidopropyltriethoxysilane (UPTES), which serves as a universal photoactivation platform for constructing pRTP systems via doping with various phosphorescent guest molecules. The UPTES-based systems can achieve superior photoactivation efficiency through the UV-induced oxygen consumption, boosting phosphorescence intensity by up to approximately 2100-fold and extending lifetime by approximately 65-fold. This ultrahigh contrast originates from the strongly active oxygen-trapping capability of the ureido groups within the siloxane network, which is crucial for establishing the initial 'off' state of guest phosphorescence via efficient oxygen-mediated quenching of triplet excitons. Notably, owing to the dense and robust siloxane network, these systems show excellent stability, maintaining efficient pRTP performance for at least 90 days even in aqueous solutions, organic reagents, or concentrated acid. This work not only presents an ultrastable host matrix for designing ultrahigh-contrast pRTP materials, but also enables the on-demand customization of pRTP systems for advanced multi-level information encryption.
{"title":"Engineering Ultrahigh-Contrast Photoactivated Room-Temperature Phosphorescence With a Robust and Universal Ureido-Functionalized Siloxane Network.","authors":"Ya Ting Gao,Ying Zhang,Bin Bin Chen,Li Ya Liang,Ming Jie Ye,Meng Qi Zhao,Xiao Yu Zhang,Fei Yang Xue,Jian Lv,Da Wei Li,Xiang Ma","doi":"10.1002/anie.7684555","DOIUrl":"https://doi.org/10.1002/anie.7684555","url":null,"abstract":"Photoactivated room-temperature phosphorescence (pRTP) host-guest systems have received widespread attention due to their non-invasive photoresponsiveness, high reversibility, and color tunability. However, traditional polymer hosts often lack efficient photoactivation and sufficient stability due to passive oxygen penetration. Herein, we report a ureido-functionalized siloxane network derived from the hydrolysis of γ-ureidopropyltriethoxysilane (UPTES), which serves as a universal photoactivation platform for constructing pRTP systems via doping with various phosphorescent guest molecules. The UPTES-based systems can achieve superior photoactivation efficiency through the UV-induced oxygen consumption, boosting phosphorescence intensity by up to approximately 2100-fold and extending lifetime by approximately 65-fold. This ultrahigh contrast originates from the strongly active oxygen-trapping capability of the ureido groups within the siloxane network, which is crucial for establishing the initial 'off' state of guest phosphorescence via efficient oxygen-mediated quenching of triplet excitons. Notably, owing to the dense and robust siloxane network, these systems show excellent stability, maintaining efficient pRTP performance for at least 90 days even in aqueous solutions, organic reagents, or concentrated acid. This work not only presents an ultrastable host matrix for designing ultrahigh-contrast pRTP materials, but also enables the on-demand customization of pRTP systems for advanced multi-level information encryption.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"260 1","pages":"e7684555"},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726257","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}
Clara Jans,Armaan Grewal,Xavier Abel-Snape,Mark Lautens
Enantioenriched benzofused 5- and 6- membered rings continue to be found as notable motifs in important molecules such as pharmaceuticals and natural products. A key synthetic strategy towards accessing these structures is via a metal-catalyzed intermolecular carbometalation step across a substituted olefin or alkyne. This review emphasizes recent advances towards accessing enantioenriched benzofused 5- and 6- membered rings via intermolecular carbometalation strategy, catalyzed by late and early transition metals. Through covering the key mechanistic investigations and computed conformational analyses, this review hopes to allow for a more unified understanding of how asymmetric control is attained across a diverse array of metals and ligands, and to highlight significant advances made in the past decade.
{"title":"Strategies Toward Accessing Enantioenriched (Hetero)Benzo-Fused 5- and 6- Membered Rings via Intermolecular Carbometalation.","authors":"Clara Jans,Armaan Grewal,Xavier Abel-Snape,Mark Lautens","doi":"10.1002/anie.6839352","DOIUrl":"https://doi.org/10.1002/anie.6839352","url":null,"abstract":"Enantioenriched benzofused 5- and 6- membered rings continue to be found as notable motifs in important molecules such as pharmaceuticals and natural products. A key synthetic strategy towards accessing these structures is via a metal-catalyzed intermolecular carbometalation step across a substituted olefin or alkyne. This review emphasizes recent advances towards accessing enantioenriched benzofused 5- and 6- membered rings via intermolecular carbometalation strategy, catalyzed by late and early transition metals. Through covering the key mechanistic investigations and computed conformational analyses, this review hopes to allow for a more unified understanding of how asymmetric control is attained across a diverse array of metals and ligands, and to highlight significant advances made in the past decade.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":"e6839352"},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726368","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}
Ammonia (NH3) is essential for agriculture and industry, yet the Haber-Bosch process is energy-intensive and carbon-emissive. Electrochemical nitrate reduction reaction (NO3RR) offers a sustainable alternative by coupling NH3 synthesis with water remediation. However, challenges such as weak NO3 - adsorption, competing hydrogen evolution, and suboptimal catalyst microenvironments hinder performance. Here, we report a family of electrocatalysts, Pd⊂QA-Cagex + (x = 24, 12, 6), constructed by encapsulating Pd clusters within quaternized organic cages. These discrete hosts enable uniform metal cluster confinement and precise control over the interfacial microenvironment. Increasing cage charge density enriches interfacial NO3 - concentration, upshifts Pd d-band center, and enhances *NO3 activation. Simultaneously, potential-driven electron transfer from the counterion (Cl-) to -NH2 +- generates stable radicals in the cage skeleton, which mediate water activation to form hydrogen radicals (H•) that spill over to Pd sites, accelerating intermediate hydrogenation. The optimized Pd⊂QA-Cage24+ delivers a Faradaic efficiency of 95.44% and an NH3 yield of 25.70 mg h- 1 mgcat - 1 in neutral electrolytes, outperforming its lower-charge analogs. Moreover, it enables > 99.4% nitrate removal from eutrophic seawater, reducing NO3 - concentrations below potable water standards. This work introduces ionic cages as programmable interfacial modifiers, offering a supramolecular strategy to regulate electrochemical microenvironments and boost electrocatalytic NO3RR performance.
{"title":"Interfacial Charge-Regulated Microenvironments Enabled by Ionic Organic Cages for Boosting Electrocatalytic Nitrate Reduction to Ammonia.","authors":"Shuyuan Li,Jun-Hao Zhou,Shi-Long Han,Doufeng Wang,Ying-Ying Yu,Jun-Yu Li,Si-Hua Liu,Xiaojie Chen,Xinchun Yang,Jian-Ke Sun","doi":"10.1002/anie.4155022","DOIUrl":"https://doi.org/10.1002/anie.4155022","url":null,"abstract":"Ammonia (NH3) is essential for agriculture and industry, yet the Haber-Bosch process is energy-intensive and carbon-emissive. Electrochemical nitrate reduction reaction (NO3RR) offers a sustainable alternative by coupling NH3 synthesis with water remediation. However, challenges such as weak NO3 - adsorption, competing hydrogen evolution, and suboptimal catalyst microenvironments hinder performance. Here, we report a family of electrocatalysts, Pd⊂QA-Cagex + (x = 24, 12, 6), constructed by encapsulating Pd clusters within quaternized organic cages. These discrete hosts enable uniform metal cluster confinement and precise control over the interfacial microenvironment. Increasing cage charge density enriches interfacial NO3 - concentration, upshifts Pd d-band center, and enhances *NO3 activation. Simultaneously, potential-driven electron transfer from the counterion (Cl-) to -NH2 +- generates stable radicals in the cage skeleton, which mediate water activation to form hydrogen radicals (H•) that spill over to Pd sites, accelerating intermediate hydrogenation. The optimized Pd⊂QA-Cage24+ delivers a Faradaic efficiency of 95.44% and an NH3 yield of 25.70 mg h- 1 mgcat - 1 in neutral electrolytes, outperforming its lower-charge analogs. Moreover, it enables > 99.4% nitrate removal from eutrophic seawater, reducing NO3 - concentrations below potable water standards. This work introduces ionic cages as programmable interfacial modifiers, offering a supramolecular strategy to regulate electrochemical microenvironments and boost electrocatalytic NO3RR performance.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e4155022"},"PeriodicalIF":16.6,"publicationDate":"2026-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726280","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}
Catalytic nitrate (NO3 -) reduction (CNR) to dinitrogen (N2) offers an efficient strategy for remediating nitrogen pollution but is constrained by preferred ammonia (NH3) formation. This selectivity challenge arises because hydrogen atom (H*)-mediated pathway inherently favors N─H coupling over the desired N─N coupling. Here, we report a formic acid (HCOOH)-driven proton-coupled electron transfer (PCET) pathway on a precisely engineered Sn3/Pd catalyst. The catalyst design features a synergistic bimetallic interface where Pd sites facilitate HCOOH activation while triangular Sn3 ensembles selectively adsorb NO3 -. This direct PCET from HCOOH to NO3 - achieved a remarkable 96.5% NO3 - removal and 97.4% N2 selectivity at environmentally relevant concentrations (100 mg-N/L). Operando mass spectrometry and density functional theory (DFT) calculations reveal that Sn3 ensembles thermodynamically favored N─N coupling while also acting as a steric barrier that kinetically impedes H* migration to adsorbed N* intermediates, effectively suppressing NH3 formation. Furthermore, by integrating the CNR process with electro-synthesized HCOOH, we demonstrated a synergistic technology that slashed the carbon footprint of wastewater treatment by 43.3%, decreasing from 33.50 kg CO2-eq t-1 to 19.01 kg CO2-eq t-1. Our work establishes atomic ensemble engineering as a powerful strategy to steer catalytic pathway through PCET, offering a viable solution for sustainable NO3 - removal.
硝酸（NO3 -）催化还原（CNR）为修复氮污染提供了一种有效的策略，但受首选氨（NH3）生成的限制。这种选择性挑战的出现是因为氢原子（H*）介导的途径固有地倾向于N─H偶联而不是期望的N─N偶联。在这里，我们报道了甲酸（HCOOH）驱动的质子耦合电子转移（PCET）途径在精确设计的Sn3/Pd催化剂上。催化剂设计具有协同双金属界面，其中Pd位点促进HCOOH活化，而三角形Sn3系簇选择性吸附NO3 -。在环境相关浓度（100 mg-N/L）下，从HCOOH到NO3 -的直接PCET的NO3 -去除率为96.5%，N2选择性为97.4%。Operando质谱和密度泛函理论（DFT）计算表明，Sn3系综在热力学上有利于N─N耦合，同时也作为一个空间位阻，在动力学上阻碍H*迁移到吸附的N*中间体，有效地抑制了NH3的形成。此外，通过将CNR工艺与电合成HCOOH相结合，我们展示了一种协同技术，该技术将废水处理的碳足迹减少了43.3%，从33.50 kg co2当量t-1减少到19.01 kg co2当量t-1。我们的工作建立了原子系综工程作为通过PCET引导催化途径的有力策略，为可持续去除NO3提供了可行的解决方案。
{"title":"Bypassing Hydrogenation Pathway for Sustainable Nitrate Water Remediation via Direct N─N Coupling.","authors":"Weixing Zhang,Yancai Yao,Yuqing Hu,Jintong Lan,Furong Guo,Xiaoyi Zhang,Shengjiang Zhang,Lizhi Zhang","doi":"10.1002/anie.7025421","DOIUrl":"https://doi.org/10.1002/anie.7025421","url":null,"abstract":"Catalytic nitrate (NO3 -) reduction (CNR) to dinitrogen (N2) offers an efficient strategy for remediating nitrogen pollution but is constrained by preferred ammonia (NH3) formation. This selectivity challenge arises because hydrogen atom (H*)-mediated pathway inherently favors N─H coupling over the desired N─N coupling. Here, we report a formic acid (HCOOH)-driven proton-coupled electron transfer (PCET) pathway on a precisely engineered Sn3/Pd catalyst. The catalyst design features a synergistic bimetallic interface where Pd sites facilitate HCOOH activation while triangular Sn3 ensembles selectively adsorb NO3 -. This direct PCET from HCOOH to NO3 - achieved a remarkable 96.5% NO3 - removal and 97.4% N2 selectivity at environmentally relevant concentrations (100 mg-N/L). Operando mass spectrometry and density functional theory (DFT) calculations reveal that Sn3 ensembles thermodynamically favored N─N coupling while also acting as a steric barrier that kinetically impedes H* migration to adsorbed N* intermediates, effectively suppressing NH3 formation. Furthermore, by integrating the CNR process with electro-synthesized HCOOH, we demonstrated a synergistic technology that slashed the carbon footprint of wastewater treatment by 43.3%, decreasing from 33.50 kg CO2-eq t-1 to 19.01 kg CO2-eq t-1. Our work establishes atomic ensemble engineering as a powerful strategy to steer catalytic pathway through PCET, offering a viable solution for sustainable NO3 - removal.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":"e7025421"},"PeriodicalIF":16.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147719567","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}
Afterglow luminescence holds great promise for biomedical imaging by eliminating tissue autofluorescence. Unimolecular afterglow systems avoid the need for nanoencapsulation, providing enhanced simplicity and structure flexibility as well as in vivo stability over common nanoparticle-based designs. However, rational design remains challenging, and only a few unimolecular systems have been reported. These systems often exhibit low signal intensity, which restricts their biomedical applications. To resolve it, we design a hemicyanine-based unimolecular organic afterglow platform (CyIA) with high afterglow brightness and structural tunability for in vivo activatable imaging. CyIA displays anti-Kasha/Kasha dual-emission with bright afterglow signal in aqueous solution, up to 108 p/s/cm2/sr, which is nearly three orders of magnitude higher than previously reported unimolecular organic afterglow probes. Leveraging the structural flexibility, a butyrylcholinesterase (BChE)-activatable afterglow probe (CyIAB-T) is fabricated. This probe enables a specific and sensitive detection of BChE in Alzheimer's disease (AD) model mice with higher contrast relative to fluorescence imaging. Importantly, this probe permits dynamic tracking of the age-dependent upregulation of BChE during AD progression. Therefore, this study establishes a versatile unimolecular organic afterglow scaffold with high intensity and structural flexibility for developing activatable afterglow probes for high-contrast biomedical imaging.
{"title":"Unimolecular Organic Afterglow Luminophore With Anti-Kasha/Kasha Emission for in Vivo Activatable Imaging.","authors":"Meng Zhao,Qingchuan Li,Yongqi Li,Liangyou Zhao,Weihao An,Gege Li,Qing Li,Qingqing Miao","doi":"10.1002/anie.3863987","DOIUrl":"https://doi.org/10.1002/anie.3863987","url":null,"abstract":"Afterglow luminescence holds great promise for biomedical imaging by eliminating tissue autofluorescence. Unimolecular afterglow systems avoid the need for nanoencapsulation, providing enhanced simplicity and structure flexibility as well as in vivo stability over common nanoparticle-based designs. However, rational design remains challenging, and only a few unimolecular systems have been reported. These systems often exhibit low signal intensity, which restricts their biomedical applications. To resolve it, we design a hemicyanine-based unimolecular organic afterglow platform (CyIA) with high afterglow brightness and structural tunability for in vivo activatable imaging. CyIA displays anti-Kasha/Kasha dual-emission with bright afterglow signal in aqueous solution, up to 108 p/s/cm2/sr, which is nearly three orders of magnitude higher than previously reported unimolecular organic afterglow probes. Leveraging the structural flexibility, a butyrylcholinesterase (BChE)-activatable afterglow probe (CyIAB-T) is fabricated. This probe enables a specific and sensitive detection of BChE in Alzheimer's disease (AD) model mice with higher contrast relative to fluorescence imaging. Importantly, this probe permits dynamic tracking of the age-dependent upregulation of BChE during AD progression. Therefore, this study establishes a versatile unimolecular organic afterglow scaffold with high intensity and structural flexibility for developing activatable afterglow probes for high-contrast biomedical imaging.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":"e3863987"},"PeriodicalIF":16.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147719570","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}
Chirality-induced biochemical response has emerged as a prominent research focus. This research demonstrates the chiral self-sorting assembly of atomically precise Au16 supramolecular rings via aurophilic interactions. Enantiomers (MR,RM'R,R)-Au16Cl8 and (PS,SP'S,S)-Au16Cl8 are fabricated through homochiral self-sorting assembly and are unaffected by anion types. But the chiral self-sorting assembly of (MR,RM'A,A)-Au16(PF6)8 and (PS,SP'A,A)-Au16(PF6)8 in a heterochiral system is influenced by anion types. Crucially, (MR,RM'R,R)-Au16Cl8 displayed superior in vitro antitumor efficacy with IC50 = 0.812 ± 0.002 µM against 4T1 cells compared to (PS,SP'S,S)-Au16Cl8 enantiomer. This enantioselectivity stems from asymmetric glutathione (GSH)-catalyzed decomposition of chiral supramolecular Au16 rings in the tumor microenvironment (apparent kinetic constants: kM = 14.97 × 10-5 min-1 × M-1 vs. kP = 8.56 × 10-5 min-1 × M-1 at 8 mM GSH), releasing the thioredoxin reductase (TrxR) inhibitor dppm2Au2Cl2. The chiral Au16 rings induce dual cell death via TrxR-inhibition-mediated apoptosis and GPX4-suppression-driven ferroptosis, validated by ROS (reactive oxygen species) accumulation, lipid peroxidation and caspase-3 activation. (MR,RM'R,R)-Au16Cl8 (20 mg/kg) achieved 55.4% tumor growth inhibition in 4T1-bearing mice with no detectable organ toxicity, outperforming auranofin in biosafety. This work establishes chiral self-sorting Au16 assemblies as promising platforms for enantioselective cancer therapy with high efficacy and low toxicity.
{"title":"Chiral Self-Sorting Assembly of Au16 Rings for Cancer Therapy via Enantioselectivity-Induced Ferroptosis and Apoptosis.","authors":"Jiaqiao Li,Fengyan Song,Ji Liu,Yifei Chen,Jianing Zhang,Mingyi Cao,Xiang-Ming Zeng,Minjian Wu,Yuting Miao,Liao-Yuan Yao,Shu-Yan Yu,Zhenwei Yuan,Ben Zhong Tang","doi":"10.1002/anie.202524447","DOIUrl":"https://doi.org/10.1002/anie.202524447","url":null,"abstract":"Chirality-induced biochemical response has emerged as a prominent research focus. This research demonstrates the chiral self-sorting assembly of atomically precise Au16 supramolecular rings via aurophilic interactions. Enantiomers (MR,RM'R,R)-Au16Cl8 and (PS,SP'S,S)-Au16Cl8 are fabricated through homochiral self-sorting assembly and are unaffected by anion types. But the chiral self-sorting assembly of (MR,RM'A,A)-Au16(PF6)8 and (PS,SP'A,A)-Au16(PF6)8 in a heterochiral system is influenced by anion types. Crucially, (MR,RM'R,R)-Au16Cl8 displayed superior in vitro antitumor efficacy with IC50 = 0.812 ± 0.002 µM against 4T1 cells compared to (PS,SP'S,S)-Au16Cl8 enantiomer. This enantioselectivity stems from asymmetric glutathione (GSH)-catalyzed decomposition of chiral supramolecular Au16 rings in the tumor microenvironment (apparent kinetic constants: kM = 14.97 × 10-5 min-1 × M-1 vs. kP = 8.56 × 10-5 min-1 × M-1 at 8 mM GSH), releasing the thioredoxin reductase (TrxR) inhibitor dppm2Au2Cl2. The chiral Au16 rings induce dual cell death via TrxR-inhibition-mediated apoptosis and GPX4-suppression-driven ferroptosis, validated by ROS (reactive oxygen species) accumulation, lipid peroxidation and caspase-3 activation. (MR,RM'R,R)-Au16Cl8 (20 mg/kg) achieved 55.4% tumor growth inhibition in 4T1-bearing mice with no detectable organ toxicity, outperforming auranofin in biosafety. This work establishes chiral self-sorting Au16 assemblies as promising platforms for enantioselective cancer therapy with high efficacy and low toxicity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e24447"},"PeriodicalIF":16.6,"publicationDate":"2026-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147726201","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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