Enhancing therapeutic efficacy while reducing toxicity is a central objective of cancer treatment, and the precise, synchronous activation of combination therapies represents an effective strategy to address this issue. Herein, we design a heterobimetallic prodrug (LM-RCu) platform that enables in situ synthesis of cytotoxic copper (Cu) complex with concurrent activation of metal-based photosensitizer via intramolecular transmetalation to achieve tumor-targeted chemo-photodynamic-immunotherapy. The general LM-RCu contains a stimuli-responsive diethyldithiocarbamate (DTC) prochelator, a quenched Ru/Ir/Os-based photosensitizer (“OFF” state), and a DPA-Cu moiety, which skillfully acts as both Cu2+ reservoir for DTC and quencher for photosensitizers. Upon tumor-specific stimulation, structurally tunable LM-RCu releases DTC, which chelates Cu2+ from intramolecular DPA-Cu to in situ synthesize cytotoxic Cu(DTC)2 complex, while dissociation of DPA-Cu simultaneously activates photosensitizer (“ON” state). Representatively, the heterobimetallic Ru-Cu prodrug bRu-BCu is selectively triggered by tumor-elevated ROS to generate Cu(DTC)2 and synchronously activate Ru-based photosensitizer. Upon light irradiation, the activated photosensitizer produces type I/II ROS for cells killing while promoting more DTC release, thereby driving the self-boosting loop of Cu(DTC)2 generation and photosensitizer activation, inducing immunogenic PANoptosis to stimulate potent immune responses against primary/distant tumors with minimal toxicity. Overall, this universal and versatile prodrug platform provides an innovative strategy for precise and effective cancer therapy.
{"title":"Stimuli-Responsive Heterobimetallic Prodrug Platform Enables In Situ Copper Complex Synthesis and Photosensitizer Activation for Targeted Chemo-Photodynamic-Immunotherapy","authors":"Zeqian Huang, Jue Wang, Yao Liu, Dong Zheng, Huanxin Lin, Peirong Li, Yumei Dai, Yong Luo, Mingxia Zhang, Xiaoyu Xu, Chunshun Zhao","doi":"10.1002/adfm.202529655","DOIUrl":"https://doi.org/10.1002/adfm.202529655","url":null,"abstract":"Enhancing therapeutic efficacy while reducing toxicity is a central objective of cancer treatment, and the precise, synchronous activation of combination therapies represents an effective strategy to address this issue. Herein, we design a heterobimetallic prodrug (<b>LM-RCu</b>) platform that enables in situ synthesis of cytotoxic copper (Cu) complex with concurrent activation of metal-based photosensitizer via intramolecular transmetalation to achieve tumor-targeted chemo-photodynamic-immunotherapy. The general LM-RCu contains a stimuli-responsive diethyldithiocarbamate (<b>DTC</b>) prochelator, a quenched Ru/Ir/Os-based photosensitizer (“OFF” state), and a DPA-Cu moiety, which skillfully acts as both Cu<sup>2+</sup> reservoir for DTC and quencher for photosensitizers. Upon tumor-specific stimulation, structurally tunable LM-RCu releases DTC, which chelates Cu<sup>2+</sup> from intramolecular DPA-Cu to in situ synthesize cytotoxic Cu(DTC)<sub>2</sub> complex, while dissociation of DPA-Cu simultaneously activates photosensitizer (“ON” state). Representatively, the heterobimetallic Ru-Cu prodrug <b>bRu-BCu</b> is selectively triggered by tumor-elevated ROS to generate Cu(DTC)<sub>2</sub> and synchronously activate Ru-based photosensitizer. Upon light irradiation, the activated photosensitizer produces type I/II ROS for cells killing while promoting more DTC release, thereby driving the self-boosting loop of Cu(DTC)<sub>2</sub> generation and photosensitizer activation, inducing immunogenic PANoptosis to stimulate potent immune responses against primary/distant tumors with minimal toxicity. Overall, this universal and versatile prodrug platform provides an innovative strategy for precise and effective cancer therapy.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"34 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the field of structural DNA nanotechnology, it is a significant technical challenge for a moving molecular machine to achieve desirable processivity to remain attached to the track during its operation. Herein, a non-derailed three-wheel driving DNA harvester (TW-harvester) is demonstrated for quantitative evaluation of the malignant degree of tumor via imaging biomarker miRNA. The half-time of TW-harvester is 20.38 h, indicating substantially resistance to nuclease degradation. It circumvents the derailment event without sacrificing movement speed and persistently moves the surrounding spherical surface-mediated track, achieving a high assay sensitivity and specificity for intracellular molecular imaging. The limit of detection (LOD) is 5.4 pm, and the interference from coexisting homologous miRNAs is substantially avoided. The miRNA assay results are consistent with the gold standard qPCR assay, and cell imaging sensitivity is significantly better than the well-known FISH technique. The evaluation of cell proliferation is in good agreement with CCK-8 assay and Wound-healing assay, indicating the reliable information on tumor malignancy degree. Overall, the TW-harvester could be used to quantitatively estimate the proliferation, migration, and malignant degree of tumor cells, thereby holding great application prospects in predicting the tumorigenesis, metastasis, recurrence, and outcomes during cancer management and treatment.
{"title":"Non-Derailed DNA Harvester for Persistently Harvesting Information on Malignant Degree of Tumor Cells via High-Confidence Quantification of Biomarkers","authors":"Wenhao Pan, Chang Xue, Qian Gao, Mengxue Luo, Dongyu Li, Linhuan Chen, Shidan Zhu, Zhifa Shen, Zai-Sheng Wu","doi":"10.1002/adfm.202527744","DOIUrl":"https://doi.org/10.1002/adfm.202527744","url":null,"abstract":"In the field of structural DNA nanotechnology, it is a significant technical challenge for a moving molecular machine to achieve desirable processivity to remain attached to the track during its operation. Herein, a non-derailed three-wheel driving DNA harvester (TW-harvester) is demonstrated for quantitative evaluation of the malignant degree of tumor via imaging biomarker miRNA. The half-time of TW-harvester is 20.38 h, indicating substantially resistance to nuclease degradation. It circumvents the derailment event without sacrificing movement speed and persistently moves the surrounding spherical surface-mediated track, achieving a high assay sensitivity and specificity for intracellular molecular imaging. The limit of detection (LOD) is 5.4 p<span>m</span>, and the interference from coexisting homologous miRNAs is substantially avoided. The miRNA assay results are consistent with the gold standard qPCR assay, and cell imaging sensitivity is significantly better than the well-known FISH technique. The evaluation of cell proliferation is in good agreement with CCK-8 assay and Wound-healing assay, indicating the reliable information on tumor malignancy degree. Overall, the TW-harvester could be used to quantitatively estimate the proliferation, migration, and malignant degree of tumor cells, thereby holding great application prospects in predicting the tumorigenesis, metastasis, recurrence, and outcomes during cancer management and treatment.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"90 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Neng-Hua Xu, Yan-Jiang Li, Hai-Yan Hu, Guang-Yu Zhang, Sun-Qi Su, Hong-Yong Dai, Yan-Fang Zhu, Li-Peng Zhang, Yan Yu, Yao Xiao
Among available cathode materials of sodium ion batteries (SIBs), the sodium layered transition metal oxides (NaxTMO2) stand out owing to their high specific capacity and suitable working voltage. However, they are commonly plagued by lattice collapse, irreversible phase transition, and poor air stability, which severely limit their cycle durability and rate capability. To address the persistent challenges of NaxTMO2, structural regulation strategies based on the pillar and pinning effects have emerged as effective approaches. The ions serving as pillars in the alkali metal layer can expand the interslab spacing and strengthen interlayer interactions, thus constructing efficient Na+ migration pathways and establishing a robust lattice framework. Similarly, the pinning ions in the TM and/or alkali metal layers acting as nails help to stabilize phase configuration, especially in deeply sodiated and desodiated states. Both pillar and pinning effects are extensively employed to optimize the structural stability, phase evolution behavior, and electrochemical properties of NaxTMO2. This review systematically summarizes recent advances in NaxTMO2 regulated by pillar and pinning effects, primarily focusing on their construction approaches and underlying enhancement mechanisms. Finally, we outline the ongoing challenges and future research directions for NaxTMO2 modified by the pillar or pinning effects.
{"title":"Pillar and Pinning Effects in Sodium Oxide Cathodes: Atomic-Level Strategies for Structural Stability","authors":"Neng-Hua Xu, Yan-Jiang Li, Hai-Yan Hu, Guang-Yu Zhang, Sun-Qi Su, Hong-Yong Dai, Yan-Fang Zhu, Li-Peng Zhang, Yan Yu, Yao Xiao","doi":"10.1002/adfm.202531271","DOIUrl":"https://doi.org/10.1002/adfm.202531271","url":null,"abstract":"Among available cathode materials of sodium ion batteries (SIBs), the sodium layered transition metal oxides (Na<sub>x</sub>TMO<sub>2</sub>) stand out owing to their high specific capacity and suitable working voltage. However, they are commonly plagued by lattice collapse, irreversible phase transition, and poor air stability, which severely limit their cycle durability and rate capability. To address the persistent challenges of Na<sub>x</sub>TMO<sub>2</sub>, structural regulation strategies based on the pillar and pinning effects have emerged as effective approaches. The ions serving as pillars in the alkali metal layer can expand the interslab spacing and strengthen interlayer interactions, thus constructing efficient Na<sup>+</sup> migration pathways and establishing a robust lattice framework. Similarly, the pinning ions in the TM and/or alkali metal layers acting as nails help to stabilize phase configuration, especially in deeply sodiated and desodiated states. Both pillar and pinning effects are extensively employed to optimize the structural stability, phase evolution behavior, and electrochemical properties of Na<sub>x</sub>TMO<sub>2</sub>. This review systematically summarizes recent advances in Na<sub>x</sub>TMO<sub>2</sub> regulated by pillar and pinning effects, primarily focusing on their construction approaches and underlying enhancement mechanisms. Finally, we outline the ongoing challenges and future research directions for Na<sub>x</sub>TMO<sub>2</sub> modified by the pillar or pinning effects.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"22 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A major challenge in developing high-temperature polymer dielectrics is the difficulty in simultaneously achieving a high dielectric constant, a wide bandgap (Eg), and a high glass transition temperature (Tg). To address this challenge, this study designed and synthesized a series of polynorbornene imides with methyl groups at the para position and substituents of varying steric hindrance and electronegativity (F, Cl, Br, CF3) at the meta position from the perspective of molecular side-chain configuration. Molecular dynamics simulations and density functional theory calculations reveal that the steric hindrance of meta-substituents can regulate the side-chain configuration ratio in polymers. Specifically, as the substituent steric hindrance increases, the proportion of the isotactic configuration decreases while the syndiotactic configuration increases. The isotactic configuration enhances the polarization performance by strengthening the local dipole moment and the syndiotactic configuration improves insulation by increasing free volume and suppressing charge migration. The meta-chloro-substituted PNIM-Cl achieves a balance between isotactic and syndiotactic configurations through its moderate steric hindrance and electronegativity and results a high dielectric constant (4.04), a wide Eg (4.27 eV), and an elevated Tg (231.8°C). Consequently, the PNIM dielectric achieves remarkable discharged energy densities of 11.4 J cm−3 at 150°C and 6.4 J cm−3 at 200°C.
{"title":"Manipulating Polymer Side-Chain Configuration via Substituent Steric Hindrance for Enhanced High-Temperature Capacitive Energy Storage Performance","authors":"Xue Zhang, Xu Tong, Zhiqi Zhou, Changhai Zhang, Tiandong Zhang, Wenju Wu, Chao Wang, Shuya Fu, Chao Yin, Qingguo Chi","doi":"10.1002/adfm.202530435","DOIUrl":"https://doi.org/10.1002/adfm.202530435","url":null,"abstract":"A major challenge in developing high-temperature polymer dielectrics is the difficulty in simultaneously achieving a high dielectric constant, a wide bandgap (<i>E</i><sub>g</sub>), and a high glass transition temperature (<i>T</i><sub>g</sub>). To address this challenge, this study designed and synthesized a series of polynorbornene imides with methyl groups at the para position and substituents of varying steric hindrance and electronegativity (F, Cl, Br, CF<sub>3</sub>) at the meta position from the perspective of molecular side-chain configuration. Molecular dynamics simulations and density functional theory calculations reveal that the steric hindrance of <i>meta</i>-substituents can regulate the side-chain configuration ratio in polymers. Specifically, as the substituent steric hindrance increases, the proportion of the isotactic configuration decreases while the syndiotactic configuration increases. The isotactic configuration enhances the polarization performance by strengthening the local dipole moment and the syndiotactic configuration improves insulation by increasing free volume and suppressing charge migration. The <i>meta</i>-chloro-substituted PNIM-Cl achieves a balance between isotactic and syndiotactic configurations through its moderate steric hindrance and electronegativity and results a high dielectric constant (4.04), a wide <i>E</i><sub>g</sub> (4.27 eV), and an elevated <i>T</i><sub>g</sub> (231.8°C). Consequently, the PNIM dielectric achieves remarkable discharged energy densities of 11.4 J cm<sup>−</sup><sup>3</sup> at 150°C and 6.4 J cm<sup>−</sup><sup>3</sup> at 200°C.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"1 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An electrostatic model, based on the well-established charge equilibration method is presented, that allows for a fast prediction of partial atomic charges within non-reactive force fields for metal–organic frameworks with typical elemental compositions. The required molecular information is inferred in a topological fashion, with generic topological bond lengths, based on experimental covalent radii of the contained elements. The model is parameterized on the basis of atom types, that encode the local atomic coordination environment up the nearest bonded neighbors. Consequently, the model is geometry-independent, requiring only a graph representation of the molecular bonds, which is easily retrieved due to the explicit bond definitions in non-reactive force fields. Therefore, by sacrificing the dependence of the atomic charges on changes in the system's geometry, the proposed model avoids the computation of distance matrices, increasing the overall performance. By parameterizing the model on three different atomic encoding levels of increasing parametric resolution, the model's accuracy is systematically increased. To this end, a global optimization scheme is employed, in which the model parameters of atomic width, electronegativity and hardness, are trained to reproduce a set of reference charges. These, were obtained from the QMOF database, which hosts electronic structure properties computed for over 20 000 MOFs and related materials. Curated subsets of the QMOF database were generated depending on the employed atom encoding scheme with a balanced atom type incidence. These subsets were used for the training and testing of the new model, containing atomic reference charges of around 10 000 MOFs for selected metallic species and with comparable relative atom type distributions between the sets. The model is able to predict charges with an accuracy below 0.02 e for the most detailed atom typing scheme for a wide chemical space without the need to to correct for charge neutrality.
{"title":"Predicting Atomic Charges in MOFs by Topological Charge Equilibration","authors":"Babak Farhadi Jahromi, Sumukh Shankar Sharadaprasad, Rochus Schmid","doi":"10.1002/adfm.202523872","DOIUrl":"https://doi.org/10.1002/adfm.202523872","url":null,"abstract":"An electrostatic model, based on the well-established charge equilibration method is presented, that allows for a fast prediction of partial atomic charges within non-reactive force fields for metal–organic frameworks with typical elemental compositions. The required molecular information is inferred in a topological fashion, with generic topological bond lengths, based on experimental covalent radii of the contained elements. The model is parameterized on the basis of atom types, that encode the local atomic coordination environment up the nearest bonded neighbors. Consequently, the model is geometry-independent, requiring only a graph representation of the molecular bonds, which is easily retrieved due to the explicit bond definitions in non-reactive force fields. Therefore, by sacrificing the dependence of the atomic charges on changes in the system's geometry, the proposed model avoids the computation of distance matrices, increasing the overall performance. By parameterizing the model on three different atomic encoding levels of increasing parametric resolution, the model's accuracy is systematically increased. To this end, a global optimization scheme is employed, in which the model parameters of atomic width, electronegativity and hardness, are trained to reproduce a set of reference charges. These, were obtained from the QMOF database, which hosts electronic structure properties computed for over 20 000 MOFs and related materials. Curated subsets of the QMOF database were generated depending on the employed atom encoding scheme with a balanced atom type incidence. These subsets were used for the training and testing of the new model, containing atomic reference charges of around 10 000 MOFs for selected metallic species and with comparable relative atom type distributions between the sets. The model is able to predict charges with an accuracy below 0.02 <i>e</i> for the most detailed atom typing scheme for a wide chemical space without the need to to correct for charge neutrality.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"2 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A significant hurdle for the clinical translation of in vivo surface-enhanced Raman scattering (SERS) bioimaging is the scarcity of high-brightness near-infrared (NIR) contrast agents. To address this challenge, we develop such agents through the strategic optimization of gold nanorods (AuNRs) as plasmonic substrates and the selection of resonant Raman reporters. We quantitatively characterize the effective differential SERS cross-section of nanoparticles comprising AuNRs spectrally encoded with various Raman reporters. Our findings establish that the spectral overlap between the AuNR plasmon resonance, reporter absorption, and laser excitation wavelength is a critical parameter for achieving high brightness. Guided by this principle, we engineer NIR-I and NIR-II SERS agents using optimized AuNRs and selected resonant reporters, encapsulated within cell membranes derived from 4T1 breast cancer cells. These agents exhibit superior brightness and specific homotypic targeting toward 4T1 cells. In vivo studies in mice demonstrate their capability for precise tumor margin delineation and sensitive detection of microtumors (<100 µm) via NIR-I and NIR-II SERS imaging. Furthermore, the agents enable image-guided surgical resection of orthotopic 4T1 tumors, achieving complete tumor removal and significantly improving surgical outcomes. This work provides a foundational strategy for designing high-brightness NIR SERS contrast agents for advanced in vivo molecular imaging applications.
{"title":"Engineering Near-Infrared SERS Contrast Agents for High-Brightness In Vivo Spectroscopic Imaging","authors":"Yaxuan Lu, Beibei Shan, Ming Li","doi":"10.1002/adfm.202522527","DOIUrl":"https://doi.org/10.1002/adfm.202522527","url":null,"abstract":"A significant hurdle for the clinical translation of in vivo surface-enhanced Raman scattering (SERS) bioimaging is the scarcity of high-brightness near-infrared (NIR) contrast agents. To address this challenge, we develop such agents through the strategic optimization of gold nanorods (AuNRs) as plasmonic substrates and the selection of resonant Raman reporters. We quantitatively characterize the effective differential SERS cross-section of nanoparticles comprising AuNRs spectrally encoded with various Raman reporters. Our findings establish that the spectral overlap between the AuNR plasmon resonance, reporter absorption, and laser excitation wavelength is a critical parameter for achieving high brightness. Guided by this principle, we engineer NIR-I and NIR-II SERS agents using optimized AuNRs and selected resonant reporters, encapsulated within cell membranes derived from 4T1 breast cancer cells. These agents exhibit superior brightness and specific homotypic targeting toward 4T1 cells. In vivo studies in mice demonstrate their capability for precise tumor margin delineation and sensitive detection of microtumors (<100 µm) via NIR-I and NIR-II SERS imaging. Furthermore, the agents enable image-guided surgical resection of orthotopic 4T1 tumors, achieving complete tumor removal and significantly improving surgical outcomes. This work provides a foundational strategy for designing high-brightness NIR SERS contrast agents for advanced in vivo molecular imaging applications.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"182 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joydip De, Abhishek Kumar Gupta, Džiugas Litvinas, Francisco Tenopala-Carmona, Matthias Lehmann, Malte C. Gather, Eli Zysman-Colman
Controlling the supramolecular alignment of columnar mesogens offers a strategy to optimize charge transport and orientation of the transition dipole moment of emissive solution-processed films, ultimately enabling the fabrication of more efficient solution-processable OLEDs. Here, we report the development of multi-resonant thermally activated delayed fluorescent (MR-TADF) discotic liquid crystals (DLCs) containing a diindolocarbazole emissive core that is decorated with four mesogenic groups that are either branched (DICz-DMOC) or linear (DICz-DOD) in nature. DICz-DMOC adopts a columnar mesophase at room temperature, where the neat film shows homeotropic alignment to the substrate surface. Emission is broad and partially quenched as neat films due to the formation of aggregates, while in toluene and as 10 wt.% doped films in mCP, emission originates mainly from monomolecular species. The DLCs align horizontally, which also orients the transition dipole moment of the emitters preferentially horizontally, reflected in an anisotropy factor, a, of 0.22 for the solution-processed neat films. Solution-processed OLEDs (SP-OLEDs) containing DICz-DMOC as the emitter showed a maximum external quantum efficiency (EQEmax) of 10.0% in doped devices and 5.3% in non-doped devices, representing some of the highest device efficiencies using emitters bearing mesogenic groups.
{"title":"Harnessing the Orientation of Columnar Discotic Liquid Crystals for Narrowband Blue Emission with Enhanced Out-Coupling Efficiency Toward Improvement of SP-OLEDs Performance","authors":"Joydip De, Abhishek Kumar Gupta, Džiugas Litvinas, Francisco Tenopala-Carmona, Matthias Lehmann, Malte C. Gather, Eli Zysman-Colman","doi":"10.1002/adfm.202528081","DOIUrl":"https://doi.org/10.1002/adfm.202528081","url":null,"abstract":"Controlling the supramolecular alignment of columnar mesogens offers a strategy to optimize charge transport and orientation of the transition dipole moment of emissive solution-processed films, ultimately enabling the fabrication of more efficient solution-processable OLEDs. Here, we report the development of multi-resonant thermally activated delayed fluorescent (MR-TADF) discotic liquid crystals (DLCs) containing a diindolocarbazole emissive core that is decorated with four mesogenic groups that are either branched (<b>DICz-DMOC</b>) or linear (<b>DICz-DOD</b>) in nature. <b>DICz-DMOC</b> adopts a columnar mesophase at room temperature, where the neat film shows homeotropic alignment to the substrate surface. Emission is broad and partially quenched as neat films due to the formation of aggregates, while in toluene and as 10 wt.% doped films in mCP, emission originates mainly from monomolecular species. The DLCs align horizontally, which also orients the transition dipole moment of the emitters preferentially horizontally, reflected in an anisotropy factor, <i>a</i>, of 0.22 for the solution-processed neat films. Solution-processed OLEDs (SP-OLEDs) containing <b>DICz-DMOC</b> as the emitter showed a maximum external quantum efficiency (EQE<sub>max</sub>) of 10.0% in doped devices and 5.3% in non-doped devices, representing some of the highest device efficiencies using emitters bearing mesogenic groups.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"311 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Integrating both high strength and high toughness into 2D nanocomposites remains a significant challenge owing to the limited interfacial interactions between nanosheets. Here, an interlayer inorganic ionic polymerization (IIIP) strategy is proposed to effectively achieve a combination of high strength and ultrahigh toughness. Specifically, calcium phosphate oligomers (CPO) are anchored onto montmorillonite (MMT) to obtain CPO/MMT composite nanosheets. Polyvinyl alcohol (PVA) and sodium alginate (SA) are incorporated into CPO/MMT interlayers to regulate ionic polymerization of CPO, thereby creating an organic–inorganic dual bridge between MMT nanosheets. The resulting PVA/SA/CPO/MMT (PSCM) film demonstrates a highly integrated structure across the nano- to macroscale, facilitated by the dual bridge. Consequently, the PSCM film exhibits a record-breaking ultrahigh toughness (111.7 ± 9.9 MJ m−3), surpassing all previously reported 2D nanocomposites, along with remarkable tensile strength (292.8 ± 12.7 MPa). The PSCM bulk assembled using films as building units demonstrates an excellent bending energy of 34.43 ± 1.97 MJ m−3 without fracture, along with remarkable toughness under extreme conditions (e.g., −196°C and 200°C). These high-performance PSCM demonstrate significant application potential in the field of structural engineering materials. The proposed IIIP strategy paves a new avenue for developing ultrahigh-toughness 2D nanocomposites.
由于纳米片之间的界面相互作用有限，将高强度和高韧性集成到二维纳米复合材料中仍然是一个重大挑战。本文提出了一种层间无机离子聚合（IIIP）策略，以有效地实现高强度和超高韧性的结合。具体来说，将磷酸钙低聚物（CPO）固定在蒙脱土（MMT）上，得到CPO/MMT复合纳米片。聚乙烯醇（PVA）和海藻酸钠（SA）加入到CPO/MMT纳米层中，调节CPO的离子聚合，从而在MMT纳米片之间形成有机-无机双桥。由此得到的PVA/SA/CPO/MMT （PSCM）薄膜在双桥的促进下，在纳米到宏观尺度上具有高度集成的结构。因此，PSCM薄膜表现出破纪录的超高韧性（111.7±9.9 MJ m−3），超过了之前报道的所有2D纳米复合材料，同时具有显著的抗拉强度（292.8±12.7 MPa）。使用薄膜作为构建单元组装的PSCM块体显示出优异的弯曲能34.43±1.97 MJ m - 3而不断裂，并且在极端条件下（例如- 196°C和200°C）具有显着的韧性。这些高性能PSCM在结构工程材料领域显示出巨大的应用潜力。提出的IIIP策略为开发超高韧性二维纳米复合材料开辟了新的途径。
{"title":"Interlayer Inorganic Ionic Polymerization of 2D Nanosheets for Ultratough Structural Materials","authors":"Peng Liao, Feixiang Zhang, Zeyu Gong, Lina Zhou, Junbo Gong, Yadong Yu","doi":"10.1002/adfm.74403","DOIUrl":"https://doi.org/10.1002/adfm.74403","url":null,"abstract":"Integrating both high strength and high toughness into 2D nanocomposites remains a significant challenge owing to the limited interfacial interactions between nanosheets. Here, an interlayer inorganic ionic polymerization (IIIP) strategy is proposed to effectively achieve a combination of high strength and ultrahigh toughness. Specifically, calcium phosphate oligomers (CPO) are anchored onto montmorillonite (MMT) to obtain CPO/MMT composite nanosheets. Polyvinyl alcohol (PVA) and sodium alginate (SA) are incorporated into CPO/MMT interlayers to regulate ionic polymerization of CPO, thereby creating an organic–inorganic dual bridge between MMT nanosheets. The resulting PVA/SA/CPO/MMT (PSCM) film demonstrates a highly integrated structure across the nano- to macroscale, facilitated by the dual bridge. Consequently, the PSCM film exhibits a record-breaking ultrahigh toughness (111.7 ± 9.9 MJ m<sup>−</sup><sup>3</sup>), surpassing all previously reported 2D nanocomposites, along with remarkable tensile strength (292.8 ± 12.7 MPa). The PSCM bulk assembled using films as building units demonstrates an excellent bending energy of 34.43 ± 1.97 MJ m<sup>−</sup><sup>3</sup> without fracture, along with remarkable toughness under extreme conditions (e.g., −196°C and 200°C). These high-performance PSCM demonstrate significant application potential in the field of structural engineering materials. The proposed IIIP strategy paves a new avenue for developing ultrahigh-toughness 2D nanocomposites.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"43 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zi-Hang He, Bin Li, Wei-Lin Wang, Xing Zhang, Chang Liu
Constructing sulfur vacancies (Sv) on monolayer MXene to modulate the valence states of metal sites, elucidating the underlying mechanisms responsible for the multiphase Fenton-like catalytic process, is of critical importance. Motivated by this inspiration, we pathbreakingly applied elemental regulation and defect engineering on monolayer MXene, with CoS collaboration, aiming to construct Sv to modulate the valence of Co sites in CoS and thereby enhance the catalytic performance toward PMS activation. Monolayer MXene incorporation effectively suppressed CoS aggregation, while sulfidation followed by calcination at 300°C created Sv on the MXene surface, denoted as Sv-CM. This regulation significantly boosted PMS activation and promoted the formation of highly reactive high-valent metal-oxo species (HVMS). Achieving complete bisphenol A (BPA) degradation within 5 min, the Sv-CM/PMS system outperforms most previously reported heterogeneous catalyst/PMS systems. This highly efficient catalytic oxidation process converts BPA into low-toxicity products via HVMS. Furthermore, the Sv-CM/PMS system demonstrated excellent durability, maintaining 100% BPA removal over 72 h of continuous operation. This study provides valuable insights into the rational design of Sv-CM and paves the way for its practical implementation for the Fenton-like catalytic process and water purification.
{"title":"Targeted Sulfur Vacancies on Monolayer MXene Boost Fenton-Like Catalysis for Sustainable Water Purification","authors":"Zi-Hang He, Bin Li, Wei-Lin Wang, Xing Zhang, Chang Liu","doi":"10.1002/adfm.202530083","DOIUrl":"https://doi.org/10.1002/adfm.202530083","url":null,"abstract":"Constructing sulfur vacancies (S<sub>v</sub>) on monolayer MXene to modulate the valence states of metal sites, elucidating the underlying mechanisms responsible for the multiphase Fenton-like catalytic process, is of critical importance. Motivated by this inspiration, we pathbreakingly applied elemental regulation and defect engineering on monolayer MXene, with CoS collaboration, aiming to construct S<sub>v</sub> to modulate the valence of Co sites in CoS and thereby enhance the catalytic performance toward PMS activation. Monolayer MXene incorporation effectively suppressed CoS aggregation, while sulfidation followed by calcination at 300°C created S<sub>v</sub> on the MXene surface, denoted as S<sub>v</sub>-CM. This regulation significantly boosted PMS activation and promoted the formation of highly reactive high-valent metal-oxo species (HVMS). Achieving complete bisphenol A (BPA) degradation within 5 min, the S<sub>v</sub>-CM/PMS system outperforms most previously reported heterogeneous catalyst/PMS systems. This highly efficient catalytic oxidation process converts BPA into low-toxicity products via HVMS. Furthermore, the S<sub>v</sub>-CM/PMS system demonstrated excellent durability, maintaining 100% BPA removal over 72 h of continuous operation. This study provides valuable insights into the rational design of S<sub>v</sub>-CM and paves the way for its practical implementation for the Fenton-like catalytic process and water purification.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"75 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Benjamin Kiendl, Arsène Chemin, Adam H. Day, Rocio B. Rodriguez, Sneha Choudhury, Franziska Buchner, Kaan Atak, Christoph Merschjann, Emina Hadzifejzovic, Tim D. W. Claridge, Karin Larsson, Amélie Venerosy, Mailis M. Lounasvuori, Natalia Zabarska, Boyan Iliev, Thomas J. S. Schubert, Hugues A. Girard, Jean-Charles Arnault, John S. Foord, Tristan Petit, Anke Krueger
Diamond, a wide-bandgap material with unique electronic properties, has shown great promise as a photoreduction catalyst due to its ability to produce highly reductive solvated electrons. However, this requires deep UV illumination, which hampers its sustainable application for real-world photocatalytic processes. Here, it is reported that the tailored introduction of suitable intra-bandgap states in diamond can be achieved by functionalizing nanoscale detonation diamond with a ruthenium-based photosensitizer. The nature of the electronic interaction between the diamond, its surface and the surface-bound moieties is elucidated through X-ray absorption, transient optical absorption, and ultraviolet photoemission spectroscopies both in vacuum and water. The electron emission upon irradiation with visible light is enabled by the surface-induced bangdap engineering. Solar-light-driven reduction of CO2 to formate is performed as a proof-of-concept reaction. The potential for photoexcited electron transfer (PET) mediated photosensitization in reductive diamond catalysis opens the way for the application of surface-engineered diamond as a sustainable photo(electro)catalyst.
{"title":"Intrabandgap States Engineering in Functionalized Nanodiamond to Generate Solvated Electrons for Photocatalysis Under Solar Illumination","authors":"Benjamin Kiendl, Arsène Chemin, Adam H. Day, Rocio B. Rodriguez, Sneha Choudhury, Franziska Buchner, Kaan Atak, Christoph Merschjann, Emina Hadzifejzovic, Tim D. W. Claridge, Karin Larsson, Amélie Venerosy, Mailis M. Lounasvuori, Natalia Zabarska, Boyan Iliev, Thomas J. S. Schubert, Hugues A. Girard, Jean-Charles Arnault, John S. Foord, Tristan Petit, Anke Krueger","doi":"10.1002/adfm.202523545","DOIUrl":"https://doi.org/10.1002/adfm.202523545","url":null,"abstract":"Diamond, a wide-bandgap material with unique electronic properties, has shown great promise as a photoreduction catalyst due to its ability to produce highly reductive solvated electrons. However, this requires deep UV illumination, which hampers its sustainable application for real-world photocatalytic processes. Here, it is reported that the tailored introduction of suitable intra-bandgap states in diamond can be achieved by functionalizing nanoscale detonation diamond with a ruthenium-based photosensitizer. The nature of the electronic interaction between the diamond, its surface and the surface-bound moieties is elucidated through X-ray absorption, transient optical absorption, and ultraviolet photoemission spectroscopies both in vacuum and water. The electron emission upon irradiation with visible light is enabled by the surface-induced bangdap engineering. Solar-light-driven reduction of CO<sub>2</sub> to formate is performed as a proof-of-concept reaction. The potential for photoexcited electron transfer (PET) mediated photosensitization in reductive diamond catalysis opens the way for the application of surface-engineered diamond as a sustainable photo(electro)catalyst.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"311 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：