Xiao‐Na Sun, Ao Liu, Kaidi Xu, Zhe Zheng, Kai Xu, Ming Dong, Bo Ding, Jian Li, Zhi‐Yuan Zhang, Chunju Li
Macrocycles are key tools for molecular recognition and self‐assembly. However, traditionally prevalent macrocyclic compounds exhibit specific cavities with diameters usually less than 1 nm, limiting their range of applications in supramolecular chemistry. The efficient synthesis of giant macrocycles remains a significant challenge because an increase in the monomer number results in cyclization‐entropy loss. In this study, we developed a low‐entropy‐penalty synthesis strategy for producing giant macrocycles in high yields. In this process, long and rigid monomers possessing two reaction modules were condensed with paraformaldehyde via Friedel–Crafts reaction. A series of giant macrocycles with cavities of sizes ranging from 2.0 to 4.7 nm were successfully synthesized with cyclization yields of up to 72%. Experimental results and theoretical calculations revealed that extending the monomer length rather than increasing the monomer numbers could notably reduce the cyclization‐entropy penalty and avoid configuration twists, thereby favoring the formation of giant macrocycles with large cavities. Significantly, the excellent self‐assembly capacity of these giant macrocycles promoted their assembly into organogels. The xerogels exhibited enhanced photoluminescence quantum efficiencies of up to 83.1%. Mechanism investigation revealed the excellent assembly capacity originated from the abundant π–π interactions sites of the giant macrocycles. The outstanding emission enhancement resulted from the restricted nonradiative decay processes of rotation/vibration and improved radiative decay process of fluorescence. This study provides an effective and general method for achieving giant macrocycles, thereby expanding the supramolecular toolbox for host–guest chemistry and assembly applications. Moreover, the intriguing assembly and photophysical properties demonstrate the feasibility of developing novel and unique properties by expanding the macrocycle size.
{"title":"Low‐entropy‐penalty synthesis of giant macrocycles for good self‐assembly and emission enhancement","authors":"Xiao‐Na Sun, Ao Liu, Kaidi Xu, Zhe Zheng, Kai Xu, Ming Dong, Bo Ding, Jian Li, Zhi‐Yuan Zhang, Chunju Li","doi":"10.1002/agt2.607","DOIUrl":"https://doi.org/10.1002/agt2.607","url":null,"abstract":"Macrocycles are key tools for molecular recognition and self‐assembly. However, traditionally prevalent macrocyclic compounds exhibit specific cavities with diameters usually less than 1 nm, limiting their range of applications in supramolecular chemistry. The efficient synthesis of giant macrocycles remains a significant challenge because an increase in the monomer number results in cyclization‐entropy loss. In this study, we developed a low‐entropy‐penalty synthesis strategy for producing giant macrocycles in high yields. In this process, long and rigid monomers possessing two reaction modules were condensed with paraformaldehyde via Friedel–Crafts reaction. A series of giant macrocycles with cavities of sizes ranging from 2.0 to 4.7 nm were successfully synthesized with cyclization yields of up to 72%. Experimental results and theoretical calculations revealed that extending the monomer length rather than increasing the monomer numbers could notably reduce the cyclization‐entropy penalty and avoid configuration twists, thereby favoring the formation of giant macrocycles with large cavities. Significantly, the excellent self‐assembly capacity of these giant macrocycles promoted their assembly into organogels. The xerogels exhibited enhanced photoluminescence quantum efficiencies of up to 83.1%. Mechanism investigation revealed the excellent assembly capacity originated from the abundant π–π interactions sites of the giant macrocycles. The outstanding emission enhancement resulted from the restricted nonradiative decay processes of rotation/vibration and improved radiative decay process of fluorescence. This study provides an effective and general method for achieving giant macrocycles, thereby expanding the supramolecular toolbox for host–guest chemistry and assembly applications. Moreover, the intriguing assembly and photophysical properties demonstrate the feasibility of developing novel and unique properties by expanding the macrocycle size.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142215612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lei Chen, Mengna Peng, Wei He, Xiaoli Hu, Jian Xiao, Linqi Shi, Yong Liu, Yuanfeng Li
The presence of bacterial biofilms and the occurrence of excessive inflammatory response greatly imped the healing process of chronic wounds in diabetic patients. However, effective strategies to simultaneously address these issues are still lacking. Here, a microenvironment‐adaptive nanodecoy (GC@Pd) is constructed via the coordination and in situ reduction of palladium ions on gallic acid‐modified chitosan (GC) to promote wound healing by synergistic biofilm eradication, inflammation alleviation, and immunoregulation. During the weakly acidic conditions of the biofilm infection stage, GC@Pd serves as a nanodecoy to induce bacterial aggregation. Subsequently, through its oxidase‐like activity generating reactive oxygen species and the hyperthermia from photothermal effects, it effectively eliminates the biofilm. As the local microenvironment of diabetic wounds transitions to an alkaline inflammatory state, the enzyme‐like activity of GC@Pd adapts to catalase‐like activity, effectively eliminating reactive oxygen species at the site of inflammation. Additionally, GC@Pd could selectively capture pro‐inflammatory cytokines through Michael addition reactions. In vivo experiments and transcriptomic analysis confirmed that GC@Pd could accelerate the wound transition from inflammatory to proliferative phase by eliminating biofilm infection and reducing the inflammatory response, thus promoting diabetic chronic wound healing. The nanodecoy provides a potential therapeutic strategy for treating biofilm‐infected diabetic chronic wounds.
{"title":"Microenvironment‐adaptive nanodecoy synergizes bacterial eradication, inflammation alleviation, and immunomodulation in promoting biofilm‐associated diabetic chronic wound healing cascade","authors":"Lei Chen, Mengna Peng, Wei He, Xiaoli Hu, Jian Xiao, Linqi Shi, Yong Liu, Yuanfeng Li","doi":"10.1002/agt2.640","DOIUrl":"https://doi.org/10.1002/agt2.640","url":null,"abstract":"The presence of bacterial biofilms and the occurrence of excessive inflammatory response greatly imped the healing process of chronic wounds in diabetic patients. However, effective strategies to simultaneously address these issues are still lacking. Here, a microenvironment‐adaptive nanodecoy (GC@Pd) is constructed via the coordination and in situ reduction of palladium ions on gallic acid‐modified chitosan (GC) to promote wound healing by synergistic biofilm eradication, inflammation alleviation, and immunoregulation. During the weakly acidic conditions of the biofilm infection stage, GC@Pd serves as a nanodecoy to induce bacterial aggregation. Subsequently, through its oxidase‐like activity generating reactive oxygen species and the hyperthermia from photothermal effects, it effectively eliminates the biofilm. As the local microenvironment of diabetic wounds transitions to an alkaline inflammatory state, the enzyme‐like activity of GC@Pd adapts to catalase‐like activity, effectively eliminating reactive oxygen species at the site of inflammation. Additionally, GC@Pd could selectively capture pro‐inflammatory cytokines through Michael addition reactions. In vivo experiments and transcriptomic analysis confirmed that GC@Pd could accelerate the wound transition from inflammatory to proliferative phase by eliminating biofilm infection and reducing the inflammatory response, thus promoting diabetic chronic wound healing. The nanodecoy provides a potential therapeutic strategy for treating biofilm‐infected diabetic chronic wounds.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141926200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yu Yang, Hao Lu, Dan Fang, Yuyuan Zhang, Yuteng Tang, Songsong Zhao, Jun Yan, Xiaojie Qin, Jianlei Shen, Fan Yang
Solid bubbles have expanded the SERS assay toolbox, but their detection performance in biofluids is still hampered by the irrational design of the plasmonic sensing interface. A plasmonic bubble aggregate‐driven DNA‐encoded SERS assay is reported here that enables simultaneous, ultrasensitive, and specific detection of multiple miRNAs in blood samples for accurate cancer diagnosis. In this assay, the buoyancy of plasmonic bubbles allows them to self‐aggregate at a droplet apex for SERS reconfiguration, form single‐layer bubble aggregates with plasmonic nanogaps, and prevent the coffee ring effect during evaporation assembly. Furthermore, DNA‐encoded plasmonic bubbles seamlessly couple with dual‐color catalytic hybridization assembly to amplify the specific miRNA‐responsive Raman signal, and function as both an analyte concentrator and a Raman signal aggregator without external forces. Using these merits, this magnet‐free, portable assay achieves femtomolar dual‐miRNA quantitation with single‐base resolution, simultaneous miRNA detection across four cell lines, and accurate cancer diagnosis (AUC = 1) via analyzing 40 blood samples with machine learning, thus providing a promising tool for clinical diagnosis.
{"title":"DNA‐encoded plasmonic bubbles aggregating dual‐microRNA SERS signals for cancer diagnosis","authors":"Yu Yang, Hao Lu, Dan Fang, Yuyuan Zhang, Yuteng Tang, Songsong Zhao, Jun Yan, Xiaojie Qin, Jianlei Shen, Fan Yang","doi":"10.1002/agt2.636","DOIUrl":"https://doi.org/10.1002/agt2.636","url":null,"abstract":"Solid bubbles have expanded the SERS assay toolbox, but their detection performance in biofluids is still hampered by the irrational design of the plasmonic sensing interface. A plasmonic bubble aggregate‐driven DNA‐encoded SERS assay is reported here that enables simultaneous, ultrasensitive, and specific detection of multiple miRNAs in blood samples for accurate cancer diagnosis. In this assay, the buoyancy of plasmonic bubbles allows them to self‐aggregate at a droplet apex for SERS reconfiguration, form single‐layer bubble aggregates with plasmonic nanogaps, and prevent the coffee ring effect during evaporation assembly. Furthermore, DNA‐encoded plasmonic bubbles seamlessly couple with dual‐color catalytic hybridization assembly to amplify the specific miRNA‐responsive Raman signal, and function as both an analyte concentrator and a Raman signal aggregator without external forces. Using these merits, this magnet‐free, portable assay achieves femtomolar dual‐miRNA quantitation with single‐base resolution, simultaneous miRNA detection across four cell lines, and accurate cancer diagnosis (AUC = 1) via analyzing 40 blood samples with machine learning, thus providing a promising tool for clinical diagnosis.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141928726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tian Lan, Yabo Dong, Jiajia Shi, Xing Wang, Zejian Xu, Yan Zhang, Lianzhou Jiang, Weibiao Zhou, Xiaonan Sui
To address the unique challenges of diabetic wound healing, wound dressings, particularly multifunctional hydrogels have garnered considerable interest. For the first time, a novel environmentally friendly soy protein‐based hydrogel is developed to accelerate the healing of diabetic chronic wounds. Specifically, this hydrogel framework is in direct formation through the dynamic Schiff base between oxidized guar gum and epigallocatechin‐3‐gallate (EGCG)‐modified soy protein isolate. Meantime, the addition of Ag+ enhances the cross‐linking of the hydrogel network by forming metal‐ligand bonds with the catechol groups in EGCG. Interestingly, the stretchability (up to 380%), swelling, and rheology properties of the hydrogel can be controlled by fine‐tuning the density of metal‐ligand bonds, endowing them with a high potential for precise matching. Additionally, various dynamic bonds endow hydrogel with excellent self‐healing ability, adhesiveness, and injectability. This hydrogel also exhibits good antibacterial properties, biocompatibility, and cell migration capabilities. Both in vivo and in vitro experiments demonstrated the outstanding anti‐inflammatory capacity of the hydrogel and its ability to modulate macrophage polarization. Consequently, the hydrogel has proven effective in promoting wound healing in a diabetic full‐thickness wound model through enhanced angiogenesis and collagen deposition. This eco‐friendly plant protein hydrogel offers a sustainable solution for wound care and environmental protection.
{"title":"Advancing self‐healing soy protein hydrogel with dynamic Schiff base and metal‐ligand bonds for diabetic chronic wound recovery","authors":"Tian Lan, Yabo Dong, Jiajia Shi, Xing Wang, Zejian Xu, Yan Zhang, Lianzhou Jiang, Weibiao Zhou, Xiaonan Sui","doi":"10.1002/agt2.639","DOIUrl":"https://doi.org/10.1002/agt2.639","url":null,"abstract":"To address the unique challenges of diabetic wound healing, wound dressings, particularly multifunctional hydrogels have garnered considerable interest. For the first time, a novel environmentally friendly soy protein‐based hydrogel is developed to accelerate the healing of diabetic chronic wounds. Specifically, this hydrogel framework is in direct formation through the dynamic Schiff base between oxidized guar gum and epigallocatechin‐3‐gallate (EGCG)‐modified soy protein isolate. Meantime, the addition of Ag<jats:sup>+</jats:sup> enhances the cross‐linking of the hydrogel network by forming metal‐ligand bonds with the catechol groups in EGCG. Interestingly, the stretchability (up to 380%), swelling, and rheology properties of the hydrogel can be controlled by fine‐tuning the density of metal‐ligand bonds, endowing them with a high potential for precise matching. Additionally, various dynamic bonds endow hydrogel with excellent self‐healing ability, adhesiveness, and injectability. This hydrogel also exhibits good antibacterial properties, biocompatibility, and cell migration capabilities. Both in vivo and in vitro experiments demonstrated the outstanding anti‐inflammatory capacity of the hydrogel and its ability to modulate macrophage polarization. Consequently, the hydrogel has proven effective in promoting wound healing in a diabetic full‐thickness wound model through enhanced angiogenesis and collagen deposition. This eco‐friendly plant protein hydrogel offers a sustainable solution for wound care and environmental protection.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141933989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ultralong thermally activated delayed fluorescence (UTADF) materials play an important role in realizing time‐dependent color‐tunable afterglow. Some typical carbazole (Cz) derivatives have been reported to exhibit UTADF properties. However, a 10‐fold difference in TADF lifetime was found between commercial Cz derivatives and the corresponding lab‐synthesized ones, which indicated that UTADF may not be derived from the single Cz derivatives as reported. To reveal the real mechanism, we synthesized three Cz derivatives and one isomer to form three host‐guest pairs for optical studies. The photophysical properties revealed that UTADF originated from the intermolecular charge transfer between host and guest, while the ultralong organic phosphorescence was from the guest. Thanks to the rich color variations in luminescence displayed by 4‐(1H‐benzo[f]indol‐1‐yl)−4′‐(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile/4,4′‐di(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile (CBP‐2CN) at different delay times, it can be applied to realize multi‐dimensional encryption in both delay time and luminescent color.
{"title":"Ultralong thermally activated delayed fluorescence based on intermolecular charge transfer induced by isomer in carbazole derivative","authors":"Junru Chen, Xianhe Zhang, Zongliang Xie, Bin Liu","doi":"10.1002/agt2.638","DOIUrl":"https://doi.org/10.1002/agt2.638","url":null,"abstract":"Ultralong thermally activated delayed fluorescence (UTADF) materials play an important role in realizing time‐dependent color‐tunable afterglow. Some typical carbazole (Cz) derivatives have been reported to exhibit UTADF properties. However, a 10‐fold difference in TADF lifetime was found between commercial Cz derivatives and the corresponding lab‐synthesized ones, which indicated that UTADF may not be derived from the single Cz derivatives as reported. To reveal the real mechanism, we synthesized three Cz derivatives and one isomer to form three host‐guest pairs for optical studies. The photophysical properties revealed that UTADF originated from the intermolecular charge transfer between host and guest, while the ultralong organic phosphorescence was from the guest. Thanks to the rich color variations in luminescence displayed by 4‐(1H‐benzo[f]indol‐1‐yl)−4′‐(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile/4,4′‐di(9H‐carbazol‐9‐yl)‐[1,1′‐biphenyl]−3,3′‐dicarbonitrile (CBP‐2CN) at different delay times, it can be applied to realize multi‐dimensional encryption in both delay time and luminescent color.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photodynamic therapy is a highly recommended alternative treatment for solid tumors, such as cutaneous or luminal tumors, in clinical practice. However, conventional photosensitizers (PSs) often induce undesirable phototoxic effects because of their normal tissue distribution and a reduction in antitumor effects resulting from aggregation‐caused quenching effects. The present study developed a novel nano‐formulated aggregation‐induced emission (AIE)‐characteristic PS, nab‐TTVPHE, which is composed of human serum albumin as a carrier and TTVPHE as a therapeutic agent, as a more effective cancer treatment with lower phototoxic effects. Notably, the reactive oxygen species generated by TTVPHE were shielded by the nanoaggregate structure, and the photodynamic activity was after nanostructure dissociation. Nab‐TTVPHE was actively internalized in tumor cells via secreted protein, acidic and rich in cysteine and released to form nanoaggregates. TTVPHE accumulated in mitochondria, where it triggered mitochondrial damage under light irradiation via its photodynamic activity and induced pyroptosis via the caspase‐3/gasdermin E (GSDME) signaling pathway to kill tumor cells. Therefore, this nano‐formulated AIE‐characteristic PS provides an innovative strategy for cancer treatment with lower phototoxic effect and the ability to boost potential antitumor immunity via GSDME‐mediated pyroptosis.
{"title":"Safe transportation and targeted destruction: Albumin encapsulated aggregation‐induced emission photosensitizer nanoaggregate for tumor photodynamic therapy through mitochondria damage‐triggered pyroptosis","authors":"Juanmei Cao, Yong Qu, Shaojie Zhu, Jinshan Zhan, Yiting Xu, Yifan Jin, Yuqing Wang, Zhuoxia Li, Chuxing Chai, Xiangwei Wu, Meng Gao, Changzheng Huang, Min Li","doi":"10.1002/agt2.637","DOIUrl":"https://doi.org/10.1002/agt2.637","url":null,"abstract":"Photodynamic therapy is a highly recommended alternative treatment for solid tumors, such as cutaneous or luminal tumors, in clinical practice. However, conventional photosensitizers (PSs) often induce undesirable phototoxic effects because of their normal tissue distribution and a reduction in antitumor effects resulting from aggregation‐caused quenching effects. The present study developed a novel nano‐formulated aggregation‐induced emission (AIE)‐characteristic PS, nab‐TTVPHE, which is composed of human serum albumin as a carrier and TTVPHE as a therapeutic agent, as a more effective cancer treatment with lower phototoxic effects. Notably, the reactive oxygen species generated by TTVPHE were shielded by the nanoaggregate structure, and the photodynamic activity was after nanostructure dissociation. Nab‐TTVPHE was actively internalized in tumor cells via secreted protein, acidic and rich in cysteine and released to form nanoaggregates. TTVPHE accumulated in mitochondria, where it triggered mitochondrial damage under light irradiation via its photodynamic activity and induced pyroptosis via the caspase‐3/gasdermin E (GSDME) signaling pathway to kill tumor cells. Therefore, this nano‐formulated AIE‐characteristic PS provides an innovative strategy for cancer treatment with lower phototoxic effect and the ability to boost potential antitumor immunity via GSDME‐mediated pyroptosis.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Intermolecular charge transfer (inter-CT) is commonly considered to quench luminescence in molecular aggregates, especially for near-infrared (NIR) emission. Herein, by elaborate comparison of π-bridge effects in donor/acceptor (D/A) molecules, it is disclosed that a π-bridge is essential in D/A molecule to involve inter-CT in aggregates for inducing desired thermally activated delayed fluorescence (TADF) and largely suppressing non-radiative decays, and importantly, electron-donating π-bridge is critical to maximize radiative decay for inter-CT dominated emission by effective electronic coupling with bright intramolecular charge transfer (intra-CT) for high-efficiency NIR emission. As a proof-of-concept, TPATAP with thienyl as π-bridge realized prominent photoluminescence quantum yields of 18.9% at 788 nm in solid films, and achieved record-high maximum external quantum efficiencies of 4.53% at 785 nm in devices. These findings provide fresh insight into interplay between inter-CT and intra-CT in molecular aggregates and open a new avenue to attenuate the limitation of energy gap law for developing highly efficient NIR emitters and improving the luminescent efficiency of various inter-CT systems, such as organic photovoltaic, organic long persistent luminescence, etc.
{"title":"π-Bridge mediated coupling between inter- and intra-molecular charge transfer in aggregates for highly efficient near-infrared emission","authors":"Jingyi Xu, Jie Xue, Yu Dai, Jinyuan Zhang, Jiajun Ren, Chengyu Yao, Shaman Li, Qingyu Meng, Xueliang Wen, Haoyun Shao, Juan Qiao","doi":"10.1002/agt2.634","DOIUrl":"https://doi.org/10.1002/agt2.634","url":null,"abstract":"Intermolecular charge transfer (inter-CT) is commonly considered to quench luminescence in molecular aggregates, especially for near-infrared (NIR) emission. Herein, by elaborate comparison of π-bridge effects in donor/acceptor (D/A) molecules, it is disclosed that a π-bridge is essential in D/A molecule to involve inter-CT in aggregates for inducing desired thermally activated delayed fluorescence (TADF) and largely suppressing non-radiative decays, and importantly, electron-donating π-bridge is critical to maximize radiative decay for inter-CT dominated emission by effective electronic coupling with bright intramolecular charge transfer (intra-CT) for high-efficiency NIR emission. As a proof-of-concept, TPATAP with thienyl as π-bridge realized prominent photoluminescence quantum yields of 18.9% at 788 nm in solid films, and achieved record-high maximum external quantum efficiencies of 4.53% at 785 nm in devices. These findings provide fresh insight into interplay between inter-CT and intra-CT in molecular aggregates and open a new avenue to attenuate the limitation of energy gap law for developing highly efficient NIR emitters and improving the luminescent efficiency of various inter-CT systems, such as organic photovoltaic, organic long persistent luminescence, etc.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shijie Zhao, Hongyang Wang, Jiuxing He, Linlin Dong, Tianyou Xie, Yang Luo, Jie Li, Patrick Osei Lartey, Kunpeng Guo, Jialei Liu
Introducing fluorescent nanomaterials as artificial antennas of chloroplasts offers a promising approach to enhancing light harvesting in photosynthesis. However, this technology is limited by the dependence of the fluorescence efficiency of nanomaterials on dispersed states that cannot enable nanomaterials inside and outside leaves to play an antenna role. Here, we developed solution and solid dual‐state ultra‐efficient blue emissive carbon dots (DuB2‐CDs) by regulating the content of graphitic‐N, surface hydroxyl groups. and C–Si bonds based on a four‐component microwave synthesis. The as‐prepared DuB2‐CDs showed intense blue emission in aqueous solution and solid state, with absolute photoluminescence quantum yields of 84.04% and 95.69%, respectively. These features guaranteed that the internal (DuB2‐CDs infiltrating the mesophyll system) and external (DuB2‐CDs remaining on the surface of leaves) artificial antennas can simultaneously enhance the solar energy utilization efficiency of chloroplasts. Compared with the control groups without antenna use and internal antenna use only, the foliar application of DuB2‐CDs substantially enhanced the electron‐transport rate, net photosynthesis rate, psbA gene expression, NADPH production, and other plant physiological parameters of living plant during photosynthesis. This work provided a promising strategy for realizing dual‐state ultra‐efficient emissive CDs while maximizing living plant‐photosynthesis augmentation.
{"title":"Developing dual‐state ultra‐efficient emissive carbon dots as internal and external artificial antenna of chloroplasts to enhance plant‐photosynthesis","authors":"Shijie Zhao, Hongyang Wang, Jiuxing He, Linlin Dong, Tianyou Xie, Yang Luo, Jie Li, Patrick Osei Lartey, Kunpeng Guo, Jialei Liu","doi":"10.1002/agt2.625","DOIUrl":"https://doi.org/10.1002/agt2.625","url":null,"abstract":"Introducing fluorescent nanomaterials as artificial antennas of chloroplasts offers a promising approach to enhancing light harvesting in photosynthesis. However, this technology is limited by the dependence of the fluorescence efficiency of nanomaterials on dispersed states that cannot enable nanomaterials inside and outside leaves to play an antenna role. Here, we developed solution and solid dual‐state ultra‐efficient blue emissive carbon dots (DuB<jats:sub>2</jats:sub>‐CDs) by regulating the content of graphitic‐N, surface hydroxyl groups. and C–Si bonds based on a four‐component microwave synthesis. The as‐prepared DuB<jats:sub>2</jats:sub>‐CDs showed intense blue emission in aqueous solution and solid state, with absolute photoluminescence quantum yields of 84.04% and 95.69%, respectively. These features guaranteed that the internal (DuB<jats:sub>2</jats:sub>‐CDs infiltrating the mesophyll system) and external (DuB<jats:sub>2</jats:sub>‐CDs remaining on the surface of leaves) artificial antennas can simultaneously enhance the solar energy utilization efficiency of chloroplasts. Compared with the control groups without antenna use and internal antenna use only, the foliar application of DuB<jats:sub>2</jats:sub>‐CDs substantially enhanced the electron‐transport rate, net photosynthesis rate, psbA gene expression, NADPH production, and other plant physiological parameters of living plant during photosynthesis. This work provided a promising strategy for realizing dual‐state ultra‐efficient emissive CDs while maximizing living plant‐photosynthesis augmentation.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuqi Wu, Fang Nan, Kewen Zhang, Wan Hao, Di Shi, Yang Li, Wei Deng, Nur Jarhen, Kaixuan Li, Yunyun Xiao, Jun Li, Xiao Lin
Osteoarthritis (OA) is associated with metabolic imbalance of articular cartilage and an increase of intracellular reactive oxygen species (ROS). Synergistic therapy based on the codelivery of ROS scavengers and antisense oligonucleotides (ASO) into chondrocytes has the potential to effectively treat OA. Here, we developed a novel biocompatible metal‐organic framework (MOF)‐encapsulated nanozyme/ASO delivery platform (miR/IrO2@ZIF‐8) for OA treatment. IrO2 nanoparticles with the catalytic activities of superoxide dismutase/catalase were synthesized using a hydrothermal method, resulting in excellent ROS scavenging performance. IrO2 was further loaded into zeolitic imidazolate framework‐8 (ZIF‐8) to maintain its catalytic efficacy and regulate its size, surface charge, and biocompatibility to enhance the therapeutic effect of the platform. As an effective ASO delivery carrier, the synthesized IrO2@ZIF‐8 exhibited high antagomiR‐181a loading and lysosomal escape capacity, enabling it to rebalance cartilage metabolism. In vitro experiments showed that miR/IrO2@ZIF‐8 could restore ROS levels, mitochondrial membrane potential, and lipid peroxidation in chondrocytes. At the same time, the expression levels of proinflammatory markers (IL‐1β, IL‐6, and COX‐2) as well as the extracellular matrix degrading enzymes (ADAMTS‐5 and MMP13) were downregulated, indicating effective antioxidant, anti‐inflammatory, and anticartilage degradation effects. Notably, miR/IrO2@ZIF‐8 was able to deliver IrO2 nanoparticles and antagomiR‐181a to the cartilage tissue at a depth of up to 1.5 mm, thus solving the problems of poor permeability and difficult retention of drugs in cartilage tissue. This further improves the synergistic therapeutic effect on OA by inhibiting cartilage degradation. The combination of MOF‐encapsulated IrO2 nanozymes with antagomiR‐181a has an excellent therapeutic effect on OA, offering a promising translational medicine paradigm.
{"title":"A novel metal‐organic framework encapsulated iridium oxide nanozyme enhanced antisense oligonucleotide combo for osteoarthritis synergistic therapy","authors":"Shuqi Wu, Fang Nan, Kewen Zhang, Wan Hao, Di Shi, Yang Li, Wei Deng, Nur Jarhen, Kaixuan Li, Yunyun Xiao, Jun Li, Xiao Lin","doi":"10.1002/agt2.635","DOIUrl":"https://doi.org/10.1002/agt2.635","url":null,"abstract":"Osteoarthritis (OA) is associated with metabolic imbalance of articular cartilage and an increase of intracellular reactive oxygen species (ROS). Synergistic therapy based on the codelivery of ROS scavengers and antisense oligonucleotides (ASO) into chondrocytes has the potential to effectively treat OA. Here, we developed a novel biocompatible metal‐organic framework (MOF)‐encapsulated nanozyme/ASO delivery platform (miR/IrO2@ZIF‐8) for OA treatment. IrO2 nanoparticles with the catalytic activities of superoxide dismutase/catalase were synthesized using a hydrothermal method, resulting in excellent ROS scavenging performance. IrO2 was further loaded into zeolitic imidazolate framework‐8 (ZIF‐8) to maintain its catalytic efficacy and regulate its size, surface charge, and biocompatibility to enhance the therapeutic effect of the platform. As an effective ASO delivery carrier, the synthesized IrO2@ZIF‐8 exhibited high antagomiR‐181a loading and lysosomal escape capacity, enabling it to rebalance cartilage metabolism. In vitro experiments showed that miR/IrO2@ZIF‐8 could restore ROS levels, mitochondrial membrane potential, and lipid peroxidation in chondrocytes. At the same time, the expression levels of proinflammatory markers (IL‐1β, IL‐6, and COX‐2) as well as the extracellular matrix degrading enzymes (ADAMTS‐5 and MMP13) were downregulated, indicating effective antioxidant, anti‐inflammatory, and anticartilage degradation effects. Notably, miR/IrO2@ZIF‐8 was able to deliver IrO2 nanoparticles and antagomiR‐181a to the cartilage tissue at a depth of up to 1.5 mm, thus solving the problems of poor permeability and difficult retention of drugs in cartilage tissue. This further improves the synergistic therapeutic effect on OA by inhibiting cartilage degradation. The combination of MOF‐encapsulated IrO2 nanozymes with antagomiR‐181a has an excellent therapeutic effect on OA, offering a promising translational medicine paradigm.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141641766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kaijuan Li, Yuzheng Luo, Yunhui Wen, Wenrui Shan, Shaowei Shi
Nanoparticle surfactants (NPSs) that form via the reversible non‐covalent interactions between nanoparticles (NPs) and polymer ligands at the oil‐water interface have received great attention in constructing structured liquids with unique stimuli‐responsiveness. Introducing dynamic covalent interactions to generate NPSs is expected to achieve a balance between high mechanical strength and dynamic responsiveness of the interfacial assemblies. Here, we present the formation, assembly, and jamming of a new type of NPS by the co‐assembly between polydopamine NPs (PDA NPs) and poly(styrene‐co‐methacrylamidophenylboronic acid) at the oil‐water interface. Dynamic covalent boronate ester bonds form in situ at the interface and show multiple responsiveness when applying stimuli such as pH, H2O2, and temperature, allowing the controlled assembly/jamming of NPSs and reconfiguration of liquid constructs. Due to the photothermal property of PDA NPs, the temperature responsiveness of boronate ester bonds can also be triggered by irradiating the biphasic system with near‐infrared (NIR) light. Moreover, when bringing two droplets encapsulated with NPSs into contact and irradiating the contact area by NIR, thermal welding of droplets can be realized, offering a straightforward to construct droplet networks and modular liquid devices.
{"title":"Reconfigurable liquids enabled by dynamic covalent chemistry","authors":"Kaijuan Li, Yuzheng Luo, Yunhui Wen, Wenrui Shan, Shaowei Shi","doi":"10.1002/agt2.621","DOIUrl":"https://doi.org/10.1002/agt2.621","url":null,"abstract":"Nanoparticle surfactants (NPSs) that form via the reversible non‐covalent interactions between nanoparticles (NPs) and polymer ligands at the oil‐water interface have received great attention in constructing structured liquids with unique stimuli‐responsiveness. Introducing dynamic covalent interactions to generate NPSs is expected to achieve a balance between high mechanical strength and dynamic responsiveness of the interfacial assemblies. Here, we present the formation, assembly, and jamming of a new type of NPS by the co‐assembly between polydopamine NPs (PDA NPs) and poly(styrene‐<jats:italic>co</jats:italic>‐methacrylamidophenylboronic acid) at the oil‐water interface. Dynamic covalent boronate ester bonds form in situ at the interface and show multiple responsiveness when applying stimuli such as pH, H<jats:sub>2</jats:sub>O<jats:sub>2</jats:sub>, and temperature, allowing the controlled assembly/jamming of NPSs and reconfiguration of liquid constructs. Due to the photothermal property of PDA NPs, the temperature responsiveness of boronate ester bonds can also be triggered by irradiating the biphasic system with near‐infrared (NIR) light. Moreover, when bringing two droplets encapsulated with NPSs into contact and irradiating the contact area by NIR, thermal welding of droplets can be realized, offering a straightforward to construct droplet networks and modular liquid devices.","PeriodicalId":501414,"journal":{"name":"Aggregate","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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