Afterglow imaging, leveraging persistent luminescence following light cessation, has emerged as a promising modality for surgical interventions. However, the scarcity of efficient near‐infrared (NIR) responsive afterglow materials, along with their inherently low brightness and lack of cyclic modulation in afterglow emission, has impeded their widespread adoption. Addressing these challenges requires a strategic repurposing of afterglow materials that improve on such limitations. Here, an afterglow probe, composed of bovine serum albumin (BSA) coated with an afterglow material, a semiconducting polymer dye (SP1), called BSA@SP1 demonstrating a substantial amplification of the afterglow luminescence (≈3‐fold) compared to polymer‐lipid coated PFODBT (DSPE‐PEG@SP1) under same experimental conditions is developed. This enhancement is believed to be attributed to the electron‐rich matrix provided by BSA that immobilizes SP1 and enhances the generation of 1O2 radicals, which improves the afterglow luminescence brightness. Through molecular docking, physicochemical characterization, and optical assessments, BSA@SP1's superior afterglow properties, cyclic afterglow behavior, long‐term colloidal stability, and biocompatibility are highlighted. Furthermore, superior tissue permeation profiling of afterglow signals of BSA@SP1's compared to fluorescence signals using ex vivo tumor‐mimicking phantoms and various porcine tissue types (skin, muscle, and fat) is demonstrated. Expanding on this, to showcase BSA@SP1's potential in image‐guided surgeries, tumor‐mimicking phantoms within porcine lungs and conducted direct comparisons between fluorescence and afterglow‐guided interventions to illustrate the latter's superiority is implanted. Overall, the study introduces a promising strategy for enhancing current afterglow materials through protein complexation, resulting in both ultrahigh signal‐to‐background ratios and cyclic afterglow signals.
{"title":"Near‐Infrared Afterglow Luminescence Amplification via Albumin Complexation of Semiconducting Polymer Nanoparticles for Surgical Navigation in Ex Vivo Porcine Models","authors":"Nathaniel Bendele, Ken Kitamura, Isabella Vasquez, Asma Harun, McKenzie Carroll, Indrajit Srivastava","doi":"10.1002/adfm.202407753","DOIUrl":"https://doi.org/10.1002/adfm.202407753","url":null,"abstract":"Afterglow imaging, leveraging persistent luminescence following light cessation, has emerged as a promising modality for surgical interventions. However, the scarcity of efficient near‐infrared (NIR) responsive afterglow materials, along with their inherently low brightness and lack of cyclic modulation in afterglow emission, has impeded their widespread adoption. Addressing these challenges requires a strategic repurposing of afterglow materials that improve on such limitations. Here, an afterglow probe, composed of bovine serum albumin (BSA) coated with an afterglow material, a semiconducting polymer dye (SP1), called BSA@SP1 demonstrating a substantial amplification of the afterglow luminescence (≈3‐fold) compared to polymer‐lipid coated PFODBT (DSPE‐PEG@SP1) under same experimental conditions is developed. This enhancement is believed to be attributed to the electron‐rich matrix provided by BSA that immobilizes SP1 and enhances the generation of <jats:sup>1</jats:sup>O<jats:sub>2</jats:sub> radicals, which improves the afterglow luminescence brightness. Through molecular docking, physicochemical characterization, and optical assessments, BSA@SP1's superior afterglow properties, cyclic afterglow behavior, long‐term colloidal stability, and biocompatibility are highlighted. Furthermore, superior tissue permeation profiling of afterglow signals of BSA@SP1's compared to fluorescence signals using ex vivo tumor‐mimicking phantoms and various porcine tissue types (skin, muscle, and fat) is demonstrated. Expanding on this, to showcase BSA@SP1's potential in image‐guided surgeries, tumor‐mimicking phantoms within porcine lungs and conducted direct comparisons between fluorescence and afterglow‐guided interventions to illustrate the latter's superiority is implanted. Overall, the study introduces a promising strategy for enhancing current afterglow materials through protein complexation, resulting in both ultrahigh signal‐to‐background ratios and cyclic afterglow signals.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141561269","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}
Cement‐based materials can be modified for microwave reflection/absorption. Admixtures (particles or short fibers) include conductive, dielectric, and magnetic ones, used solely or in combination. Synergism occurs with conductive and magnetic admixtures, due to the enabled eddy current. The conductive admixture promotes absorption and reflection, whether steel rebars are present or not. Regardless of the admixtures, rebars, or aggregates, absorption loss dominates over reflection loss. Steel microfiber is more effective than carbon fiber. Fly ash enhances the absorption slightly, due to the included iron oxide. Because of the skin effect, a small admixture unit size is preferred. Thus, carbon nanofiber is more effective than carbon fiber, if it is adequately dispersed. Fine particles (such as silica fume) as an additional admixture help the dispersion. Nanoscale admixtures tend to fill the pores, so their functional effectiveness is limited. Carbon black (nanoparticles) is less effective than carbon fiber, but it is inexpensive and the combined use of carbon fiber and carbon black is effective. The high cost of the nanofibers and the difficulty of their dispersion limit their practicality. Another approach involves porous admixtures or aggregates for reducing the impedance mismatch so that reflection is lessened and more radiation enters the cement‐based material.
{"title":"A Review of Microwave Absorption and Reflection by Cement‐Based Materials, With Emphasis on Electromagnetic Interference Shielding and Admixture Effects","authors":"D. D. L. Chung","doi":"10.1002/adfm.202408220","DOIUrl":"https://doi.org/10.1002/adfm.202408220","url":null,"abstract":"Cement‐based materials can be modified for microwave reflection/absorption. Admixtures (particles or short fibers) include conductive, dielectric, and magnetic ones, used solely or in combination. Synergism occurs with conductive and magnetic admixtures, due to the enabled eddy current. The conductive admixture promotes absorption and reflection, whether steel rebars are present or not. Regardless of the admixtures, rebars, or aggregates, absorption loss dominates over reflection loss. Steel microfiber is more effective than carbon fiber. Fly ash enhances the absorption slightly, due to the included iron oxide. Because of the skin effect, a small admixture unit size is preferred. Thus, carbon nanofiber is more effective than carbon fiber, if it is adequately dispersed. Fine particles (such as silica fume) as an additional admixture help the dispersion. Nanoscale admixtures tend to fill the pores, so their functional effectiveness is limited. Carbon black (nanoparticles) is less effective than carbon fiber, but it is inexpensive and the combined use of carbon fiber and carbon black is effective. The high cost of the nanofibers and the difficulty of their dispersion limit their practicality. Another approach involves porous admixtures or aggregates for reducing the impedance mismatch so that reflection is lessened and more radiation enters the cement‐based material.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553453","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}
Mahdieh Shokrollahi Barough, Amir Seyfoori, Esfandyar Askari, Mehdi Mahdavi, Ramin Sarrami Forooshani, Behnam Sadeghi, Mohammad Hossein Kazemi, Reza Falak, Ali Khademhosseini, Nazanin Mojtabavi, Mohsen Akbari
Injectable hydrogels for cancer immunotherapy are effective for both active and passive approaches. Tumor‐infiltrating lymphocyte (TIL) immunoshaping can change the tumor microenvironment to favor tumor cell elimination. The primary objective of immunoshaping is to reduce regulatory T‐cells (Tregs), which can enhance the effectiveness of ex vivo immune cell therapy in solid tumors. A shear‐thinning injectable hydrogel that consists of gelatin and Laponite (Gel‐Lap) is used in this study. By optimizing the formulation, their immunotherapeutic and anti‐tumor properties are examined. Gemcitabine (GEM), an anti‐metabolite cancer chemotherapy agent, is loaded into a Gel‐Lap hydrogel (immunogel). The study compares the effects of immunogel on 4T1 inoculated breast cancer animal models. Results show that immunogel increases survival rates and significantly inhibits metastasis. The Treg cell population reduction is observed up to 70% in TILs and splenocyte population in line with CD8+ T‐cells population increment in inguinal lymph nodes near the tumor region; the CD8+ T‐cells function may be mediated through overexpression of eomesodermin (EOMES) as cytotoxic T lymphocyte (CTL) activation transcription factor. The human 3D cell culture model confirmed results in animal data demonstrating T‐cell migration through the hydrogel and anticancer efficacy. Local delivery of GEM using our silicate‐based hydrogel holds promise for editing tumor microenvironment in favor of systemic immune responses.
{"title":"Gemcitabine‐Loaded Injectable Hydrogel for Localized Breast Cancer Immunotherapy","authors":"Mahdieh Shokrollahi Barough, Amir Seyfoori, Esfandyar Askari, Mehdi Mahdavi, Ramin Sarrami Forooshani, Behnam Sadeghi, Mohammad Hossein Kazemi, Reza Falak, Ali Khademhosseini, Nazanin Mojtabavi, Mohsen Akbari","doi":"10.1002/adfm.202403910","DOIUrl":"https://doi.org/10.1002/adfm.202403910","url":null,"abstract":"Injectable hydrogels for cancer immunotherapy are effective for both active and passive approaches. Tumor‐infiltrating lymphocyte (TIL) immunoshaping can change the tumor microenvironment to favor tumor cell elimination. The primary objective of immunoshaping is to reduce regulatory <jats:italic>T</jats:italic>‐cells (Tregs), which can enhance the effectiveness of ex vivo immune cell therapy in solid tumors. A shear‐thinning injectable hydrogel that consists of gelatin and Laponite (Gel‐Lap) is used in this study. By optimizing the formulation, their immunotherapeutic and anti‐tumor properties are examined. Gemcitabine (GEM), an anti‐metabolite cancer chemotherapy agent, is loaded into a Gel‐Lap hydrogel (immunogel). The study compares the effects of immunogel on 4T1 inoculated breast cancer animal models. Results show that immunogel increases survival rates and significantly inhibits metastasis. The Treg cell population reduction is observed up to 70% in TILs and splenocyte population in line with CD8+ <jats:italic>T</jats:italic>‐cells population increment in inguinal lymph nodes near the tumor region; the CD8+ <jats:italic>T</jats:italic>‐cells function may be mediated through overexpression of eomesodermin (EOMES) as cytotoxic T lymphocyte (CTL) activation transcription factor. The human 3D cell culture model confirmed results in animal data demonstrating <jats:italic>T</jats:italic>‐cell migration through the hydrogel and anticancer efficacy. Local delivery of GEM using our silicate‐based hydrogel holds promise for editing tumor microenvironment in favor of systemic immune responses.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553455","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}
Limin Deng, Yue Zhang, Yakun Tang, Yuandong Li, Wenjie Ma, Lang Liu, Sen Dong, Yuliang Cao
Fe‐based sulfate materials have attracted much attention in the cathode of sodium‐ion batteries (SIBs) due to their low cost and high operating voltage, as well as possessing application prospects comparable to hard carbon in the anode based on Fe0/Fe2+/Fe3+ redox properties. However, the poor conductivity and the tendency to agglomerate have limited their further application. Herein, the study constructs a dual‐conductive structure that the Na2.31Fe1.72(SO4)3 particles with amorphous carbon in situ‐coated embedded in ketjen black (KB) conducting carbon networks (NFS/KB) via a solid phase ball‐milling strategy, which effectively enhanced inherent conductivity and electron transfer efficiency among particles of the Fe‐based sulphate. The NFS/KB can provide a reversible capacity of 92 mAh g−1 at 0.1 C and stable cycling stability at high current (85% retention after 500 cycles at 20 C) as cathode of SIBs. Surprisingly, as anode of SIBs, the NFS/KB delivers a rate performance (149 mAh g−1 at 10 C) that is superior to that of hard carbon. Notably, further application of the material to symmetric SIBs also achieves favorable results. This work effectively enhances the performance of Fe‐based sulphate materials in SIBs with a low‐cost carbon modification method, providing a new approach for the low‐cost symmetric SIBs.
基于 Fe0/Fe2+/Fe3+ 氧化还原特性，硫酸铁基材料在钠离子电池（SIB）阴极中的应用前景与硬碳相当，而且成本低、工作电压高，因此备受关注。然而，导电性差和容易团聚的缺点限制了它们的进一步应用。在本文中，研究人员通过固相球磨策略构建了一种双导电结构，即在Na2.31Fe1.72(SO4)3颗粒上原位包覆无定形碳，并将其嵌入到KB导电碳网络（NFS/KB）中，从而有效提高了硫酸铁基颗粒的固有导电性和颗粒间的电子转移效率。作为 SIB 的阴极，NFS/KB 在 0.1 摄氏度条件下可提供 92 mAh g-1 的可逆容量，并且在大电流条件下具有稳定的循环稳定性（20 摄氏度条件下循环 500 次后保持率为 85%）。令人惊讶的是，作为 SIB 的阳极，NFS/KB 的速率性能（10 C 时 149 mAh g-1）优于硬碳。值得注意的是，将这种材料进一步应用于对称 SIB 也能取得良好的效果。这项工作通过低成本的碳改性方法有效提高了硫酸铁基材料在 SIB 中的性能，为低成本对称 SIB 提供了一种新方法。
{"title":"Carbon Coated Fe‐Based Sulphate Nanoparticles within Continuous Conductive Network for Low‐Cost and High‐Performance Symmetrical Sodium‐Ion Batteries","authors":"Limin Deng, Yue Zhang, Yakun Tang, Yuandong Li, Wenjie Ma, Lang Liu, Sen Dong, Yuliang Cao","doi":"10.1002/adfm.202402145","DOIUrl":"https://doi.org/10.1002/adfm.202402145","url":null,"abstract":"Fe‐based sulfate materials have attracted much attention in the cathode of sodium‐ion batteries (SIBs) due to their low cost and high operating voltage, as well as possessing application prospects comparable to hard carbon in the anode based on Fe<jats:sup>0</jats:sup>/Fe<jats:sup>2+</jats:sup>/Fe<jats:sup>3+</jats:sup> redox properties. However, the poor conductivity and the tendency to agglomerate have limited their further application. Herein, the study constructs a dual‐conductive structure that the Na<jats:sub>2.31</jats:sub>Fe<jats:sub>1.72</jats:sub>(SO<jats:sub>4</jats:sub>)<jats:sub>3</jats:sub> particles with amorphous carbon in situ‐coated embedded in ketjen black (KB) conducting carbon networks (NFS/KB) via a solid phase ball‐milling strategy, which effectively enhanced inherent conductivity and electron transfer efficiency among particles of the Fe‐based sulphate. The NFS/KB can provide a reversible capacity of 92 mAh g<jats:sup>−1</jats:sup> at 0.1 C and stable cycling stability at high current (85% retention after 500 cycles at 20 C) as cathode of SIBs. Surprisingly, as anode of SIBs, the NFS/KB delivers a rate performance (149 mAh g<jats:sup>−1</jats:sup> at 10 C) that is superior to that of hard carbon. Notably, further application of the material to symmetric SIBs also achieves favorable results. This work effectively enhances the performance of Fe‐based sulphate materials in SIBs with a low‐cost carbon modification method, providing a new approach for the low‐cost symmetric SIBs.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553527","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}
Yujian Rao, Zhenliang Li, Tuo Zhang, Zhehan Wang, Weisheng Li, Xinran Wang, Litao Sun, Yuan Ren, Li Tao
Endowing transition metal dichalcogenides (TMDs) with mesoporous structure can greatly enhance their porosity, accessible specific surface area, and exposed active sites, leading to better performances in applications based on interfacial reactions. Current methods including hard‐template (nanocasting) method or thermal‐assisted conversion (TAC) still suffer from drawbacks such as cumbersome and environmentally unfriendly process, humidity sensitivity, or ill‐defined mesostructures. Herein, the study reports a facile synthesis of ordered mesoporous TMDs/carbon composites by direct organic–inorganic co‐assembly in dual solvent (DMF/H2O). The amphiphilic block copolymer polyethylene oxide‐b‐polystyrene (PEO‐b‐PS) is used as the organic template, and (NH4)2MoS4 or (NH4)2WS4 as the inorganic precursor. After solvent evaporation‐induced aggregation assembly and thermal treatments, it results in highly ordered mesoporous MoS2, WS2, and MoS2/WS2 with highly crystalline framework, high specific surface area (44‐91 m2 g−1) and large pore sizes (15–21 nm). Semiconductor gas sensors based on mesoporous TMDs exhibit extraordinary sensing performances toward NO2 at room temperature, including high sensitivity and ultrahigh selectivity, benefiting from its abundant adsorption sites for gas molecules, fast diffusion rate in well‐connected mesopores, and rich edge active sites. This work paves a facile way to develop novel ordered mesoporous TMDs‐based semiconductor materials for various applications.
{"title":"Synthesis of Ordered Mesoporous Transition Metal Dichalcogenides by Direct Organic–Inorganic Co‐Assembly","authors":"Yujian Rao, Zhenliang Li, Tuo Zhang, Zhehan Wang, Weisheng Li, Xinran Wang, Litao Sun, Yuan Ren, Li Tao","doi":"10.1002/adfm.202408426","DOIUrl":"https://doi.org/10.1002/adfm.202408426","url":null,"abstract":"Endowing transition metal dichalcogenides (TMDs) with mesoporous structure can greatly enhance their porosity, accessible specific surface area, and exposed active sites, leading to better performances in applications based on interfacial reactions. Current methods including hard‐template (nanocasting) method or thermal‐assisted conversion (TAC) still suffer from drawbacks such as cumbersome and environmentally unfriendly process, humidity sensitivity, or ill‐defined mesostructures. Herein, the study reports a facile synthesis of ordered mesoporous TMDs/carbon composites by direct organic–inorganic co‐assembly in dual solvent (DMF/H<jats:sub>2</jats:sub>O). The amphiphilic block copolymer polyethylene oxide‐<jats:italic>b</jats:italic>‐polystyrene (PEO‐<jats:italic>b</jats:italic>‐PS) is used as the organic template, and (NH<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>MoS<jats:sub>4</jats:sub> or (NH<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>WS<jats:sub>4</jats:sub> as the inorganic precursor. After solvent evaporation‐induced aggregation assembly and thermal treatments, it results in highly ordered mesoporous MoS<jats:sub>2</jats:sub>, WS<jats:sub>2</jats:sub>, and MoS<jats:sub>2</jats:sub>/WS<jats:sub>2</jats:sub> with highly crystalline framework, high specific surface area (44‐91 m<jats:sup>2</jats:sup> g<jats:sup>−1</jats:sup>) and large pore sizes (15–21 nm). Semiconductor gas sensors based on mesoporous TMDs exhibit extraordinary sensing performances toward NO<jats:sub>2</jats:sub> at room temperature, including high sensitivity and ultrahigh selectivity, benefiting from its abundant adsorption sites for gas molecules, fast diffusion rate in well‐connected mesopores, and rich edge active sites. This work paves a facile way to develop novel ordered mesoporous TMDs‐based semiconductor materials for various applications.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553452","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}
Sodium layered oxide cathodes can uniquely benefit from the existing lithium‐ion battery industry as sodium‐ion batteries gain traction as a potential low‐cost, drop‐in replacement. However, achieving relevant energy density with a suitable cycle life remains a challenge for sodium layered oxides. At high operating potentials, several competing degradation mechanisms prevent P2‐type Na2/3Ni1/3Mn2/3O2 (≈550 Wh kg−1) from achieving meaningful cycle life—with bulk structural instability and surface reactivity being the primary retractors. Herein, the issue of particle cracking is addressed through detailed synthesis methods of “single‐crystal” materials. By comparison to a polycrystalline baseline, the single‐crystal materials quantify the capacity loss due to isolation of active material caused by intergranular particle cracking. The single crystal materials are then employed in cells with an advanced, “localized saturated electrolyte” (LSE) to demonstrate the magnitude of capacity loss due to electrolyte decomposition at the cathode surface. Mitigation of the surface reactivity through the LSE electrolyte effectively demonstrates the elevated importance of surface reactivity at high voltages despite the onset of egregious particle cracking. This work aims to guide future research into understanding molten‐salt assisted syntheses and advance the debate on surface versus bulk degradation.
{"title":"Deconstructing the High Voltage Degradation Mechanisms in Na2/3Ni1/3Mn2/3O2 with Single Crystals and Advanced Electrolyte","authors":"Joe Darga, Arumugam Manthiram","doi":"10.1002/adfm.202408642","DOIUrl":"https://doi.org/10.1002/adfm.202408642","url":null,"abstract":"Sodium layered oxide cathodes can uniquely benefit from the existing lithium‐ion battery industry as sodium‐ion batteries gain traction as a potential low‐cost, drop‐in replacement. However, achieving relevant energy density with a suitable cycle life remains a challenge for sodium layered oxides. At high operating potentials, several competing degradation mechanisms prevent P2‐type Na<jats:sub>2/3</jats:sub>Ni<jats:sub>1/3</jats:sub>Mn<jats:sub>2/3</jats:sub>O<jats:sub>2</jats:sub> (≈550 Wh kg<jats:sup>−1</jats:sup>) from achieving meaningful cycle life—with bulk structural instability and surface reactivity being the primary retractors. Herein, the issue of particle cracking is addressed through detailed synthesis methods of “single‐crystal” materials. By comparison to a polycrystalline baseline, the single‐crystal materials quantify the capacity loss due to isolation of active material caused by intergranular particle cracking. The single crystal materials are then employed in cells with an advanced, “localized saturated electrolyte” (LSE) to demonstrate the magnitude of capacity loss due to electrolyte decomposition at the cathode surface. Mitigation of the surface reactivity through the LSE electrolyte effectively demonstrates the elevated importance of surface reactivity at high voltages despite the onset of egregious particle cracking. This work aims to guide future research into understanding molten‐salt assisted syntheses and advance the debate on surface versus bulk degradation.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553460","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}
Haiyin Liu, Moore Z. Chen, Thomas Payne, Christopher J.H. Porter, Colin W. Pouton, Angus P.R. Johnston
The development of lipid nanoparticles (LNP) holds great promise for vaccine and therapeutic applications. However, ineffective transport of nucleic acid cargo from endosomes to the cytosol, termed “endosomal escape,” has remained a bottleneck to achieving greater LNP efficacy. Poor understanding of the mechanisms of endosomal escape and a lack of suitable techniques to assess the efficiency of escape have also impeded progress in this field. To address this gap, a modified SNAPSwitch/SNAP‐tag assay is developed to compare the cytosolic delivery capabilities of various LNP formulations, comparing ionizable lipids used in major commercial LNP products. The results show that all the LNP formulations tested exhibited low (<10%) endosomal escape efficiency. Interestingly, a limited correlation is found between the amount of mRNA delivery to the cytosol and protein expression. While endosomal escape of mRNA LNP cargo is necessary for protein expression, subcellular processes after delivery to the cytosol play a critical role in maximising protein expression. These findings challenge existing paradigms and reveal critical parameters for optimizing nucleic acid delivery and therapeutic effectiveness of next‐generation LNP.
{"title":"Beyond the Endosomal Bottleneck: Understanding the Efficiency of mRNA/LNP Delivery","authors":"Haiyin Liu, Moore Z. Chen, Thomas Payne, Christopher J.H. Porter, Colin W. Pouton, Angus P.R. Johnston","doi":"10.1002/adfm.202404510","DOIUrl":"https://doi.org/10.1002/adfm.202404510","url":null,"abstract":"The development of lipid nanoparticles (LNP) holds great promise for vaccine and therapeutic applications. However, ineffective transport of nucleic acid cargo from endosomes to the cytosol, termed “endosomal escape,” has remained a bottleneck to achieving greater LNP efficacy. Poor understanding of the mechanisms of endosomal escape and a lack of suitable techniques to assess the efficiency of escape have also impeded progress in this field. To address this gap, a modified SNAP<jats:sub>Switch</jats:sub>/SNAP‐tag assay is developed to compare the cytosolic delivery capabilities of various LNP formulations, comparing ionizable lipids used in major commercial LNP products. The results show that all the LNP formulations tested exhibited low (<10%) endosomal escape efficiency. Interestingly, a limited correlation is found between the amount of mRNA delivery to the cytosol and protein expression. While endosomal escape of mRNA LNP cargo is necessary for protein expression, subcellular processes after delivery to the cytosol play a critical role in maximising protein expression. These findings challenge existing paradigms and reveal critical parameters for optimizing nucleic acid delivery and therapeutic effectiveness of next‐generation LNP.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553462","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}
Rare earth elements (REEs) are vital in high‐tech industries and defense due to their strategic significance. Crafting an efficient membranes channel for REE separation poses a significant challenge. Employing 2‐methylimidazole‐hydrolyzed OH−, dopamine polymerization is initiated and then Zn2+ coordinates with 2‐methylimidazole on PDA surfaces. The confined symbiotic reaction yields 2D vertical heterojunctions of GO/ZIF‐8/PDA (G/Z/P). During separation, partially dehydrated smaller hydrated lanthanide ions preferentially access interlayers, expanding and stabilizing the interlayer space by coordinating with PDA, thus excluding larger hydrated scandium ions from the membranes. Some scandium ions entering interlayer channels are sequestered by N in size‐matched ZIF‐8 pores. This distinctive mechanism facilitates selective scandium separation from other REEs (other REEs/Sc selectivity ≈68.73), achieving nearly complete Sc3+ rejection in a single step. The methodology offers unprecedented insights into precise nano‐space material synthesis, indicating promising strides in advancing scandium production.
{"title":"Synergistic Nanoarchitectonics: Precision Membrane Engineering for Rare Earth Selective Separation","authors":"Zixiao Lv, Xin Zhang, Qifeng Gao, Chuanxi Wen, Yuqi He, HongXin Tan, Lijuan Qian, Wei Qi, Ximeng Chen, Zhan Li","doi":"10.1002/adfm.202409274","DOIUrl":"https://doi.org/10.1002/adfm.202409274","url":null,"abstract":"Rare earth elements (REEs) are vital in high‐tech industries and defense due to their strategic significance. Crafting an efficient membranes channel for REE separation poses a significant challenge. Employing 2‐methylimidazole‐hydrolyzed OH<jats:sup>−</jats:sup>, dopamine polymerization is initiated and then Zn<jats:sup>2+</jats:sup> coordinates with 2‐methylimidazole on PDA surfaces. The confined symbiotic reaction yields 2D vertical heterojunctions of GO/ZIF‐8/PDA (G/Z/P). During separation, partially dehydrated smaller hydrated lanthanide ions preferentially access interlayers, expanding and stabilizing the interlayer space by coordinating with PDA, thus excluding larger hydrated scandium ions from the membranes. Some scandium ions entering interlayer channels are sequestered by N in size‐matched ZIF‐8 pores. This distinctive mechanism facilitates selective scandium separation from other REEs (other REEs/Sc selectivity ≈68.73), achieving nearly complete Sc<jats:sup>3+</jats:sup> rejection in a single step. The methodology offers unprecedented insights into precise nano‐space material synthesis, indicating promising strides in advancing scandium production.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553371","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}
Owing to the adverse influences of irreversible oxidation, the development of MXene‐based materials, especially those with satisfactory performance and longevity for aqueous energy storage, continues to suffer severe challenges. Herein, the strategy of targeted passivation‐supported defect‐lock‐oxygen is conceived, whereby engineered the V2CTx material for controllable partial oxidation with enhanced regioselectivity. When the material works, inside the intrinsic defects, the outward diffusion of oxidation is confined by the Lewis bases around the defects, which allows for the controllable progress of oxidation. The defect‐locked oxygen oxidizes the exposed carbon, thus forming sufficient amorphous carbons for enhancing the capacitive‐type adsorption of K‐ions. Then the oxidized defects enabled the fast kinetics via the cross‐layer transport of K‐ions. Benefiting from the strategy, the electrode assembly V2CTx‐RTIL (V2CTx equipped with room temperature ionic liquid) exhibits high capacity, good rate capability, and ultra‐longevity compared with those of the MXene materials so far reported. This work presents the first strategy of targeted passivation‐supported defect‐lock‐oxygen for high‐rate capability and super long‐cycling aqueous K+ storage and hopefully would provide the inspiration for the future design of novel electrodes.
由于不可逆氧化的不利影响，MXene 基材料的开发，尤其是那些性能和寿命令人满意的水性储能材料的开发，仍然面临严峻挑战。在此，我们构思了有针对性的钝化-支持缺陷-锁氧策略，从而设计出具有增强区域选择性的可控部分氧化的 V2CTx 材料。材料工作时，在固有缺陷内部，氧化的向外扩散受到缺陷周围路易斯碱的限制，从而实现了可控的氧化过程。被缺陷锁住的氧气会氧化暴露在外的碳，从而形成足够的无定形碳，以增强对 K 离子的电容式吸附。然后，氧化缺陷通过 K 离子的跨层传输实现了快速动力学。得益于这一策略，V2CTx-RTIL（配备室温离子液体的 V2CTx）电极组件与迄今报道的 MXene 材料相比，具有高容量、良好的速率能力和超长寿命。这项工作首次提出了定向钝化-支持缺陷-锁氧的策略，以实现高倍率能力和超长循环的水性 K+ 储存，希望能为未来新型电极的设计提供启发。
{"title":"Defect‐Driven Oxidation Enabled V2CTx MXene with Ultralong‐Cycling and High‐Rate Capability in Aqueous K+ Storage","authors":"Yujing Liu, Qi Liu, Chengyao Zhao, Liping Liu, Zhongqiu Liu, Anguo Ying, Zhibin Pang, Xuping Sun, Pu Chen, Guang Chen","doi":"10.1002/adfm.202407497","DOIUrl":"https://doi.org/10.1002/adfm.202407497","url":null,"abstract":"Owing to the adverse influences of irreversible oxidation, the development of MXene‐based materials, especially those with satisfactory performance and longevity for aqueous energy storage, continues to suffer severe challenges. Herein, the strategy of targeted passivation‐supported defect‐lock‐oxygen is conceived, whereby engineered the V<jats:sub>2</jats:sub>CT<jats:sub>x</jats:sub> material for controllable partial oxidation with enhanced regioselectivity. When the material works, inside the intrinsic defects, the outward diffusion of oxidation is confined by the Lewis bases around the defects, which allows for the controllable progress of oxidation. The defect‐locked oxygen oxidizes the exposed carbon, thus forming sufficient amorphous carbons for enhancing the capacitive‐type adsorption of K‐ions. Then the oxidized defects enabled the fast kinetics via the cross‐layer transport of K‐ions. Benefiting from the strategy, the electrode assembly V<jats:sub>2</jats:sub>CT<jats:sub>x</jats:sub>‐RTIL (V<jats:sub>2</jats:sub>CT<jats:sub>x</jats:sub> equipped with room temperature ionic liquid) exhibits high capacity, good rate capability, and ultra‐longevity compared with those of the MXene materials so far reported. This work presents the first strategy of targeted passivation‐supported defect‐lock‐oxygen for high‐rate capability and super long‐cycling aqueous K<jats:sup>+</jats:sup> storage and hopefully would provide the inspiration for the future design of novel electrodes.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553456","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}
Xiaozheng Liang, Quan Li, Yangjun Ren, Weimin Xie, Aidong Tang, Huaming Yang
The vast energy storage potential of polymer composite dielectrics in high pulse power sources stands in stark contrast to the unbalanced improvements in discharge energy density (Ud), charge–discharge efficiency (η), and dielectric strength (Eb) as reported currently. Herein, a multistage coupled interface engineering design is proposed: a novel gradient alternating dielectric buffer layer (G‐A‐DBL) is constructed, which consists of inorganic low‐k nanoclay aluminosilicate layer and high‐k ferroelectric layer assembled in a highly oriented alternation as a basic unit and gradient distribution in polymer matrix. This design achieves electric field confinement from the nanoscale to the macroscopic level and achieves an ultra‐balanced enhancement effect, resulting in a Ud of 28.5 J cm−3, an η of 80%, and an Eb of 676 kV mm−1. The universal charge retention ability of charge traps from aluminosilicate heterogeneous skeletons is demonstrated by combining density functional theory calculations and scanning probe measurements. The G‐A‐DBL design integrates traditional charge trapping, heterostructure formation, and gradient modulation, effectively suppressing the entire process of carrier excitation, transport, and before capture. This work advances the basic understanding of charge confinement within inorganic interface charge traps, demonstrating the most well‐balanced enhancement effect and potential for broad application across dielectric polymer nanocomposites.
聚合物复合电介质在高脉冲电源中具有巨大的储能潜力，但与之形成鲜明对比的是，目前所报道的放电能量密度（Ud）、充放电效率（η）和介电强度（Eb）的提高并不平衡。本文提出了一种多级耦合界面工程设计：构建了一种新型梯度交变介电缓冲层（G-A-DBL），该缓冲层由无机低 K 纳米钙钛矿铝硅酸盐层和高 K 铁电层以高度取向交替的方式组装而成，作为基本单元并梯度分布于聚合物基体中。这种设计实现了从纳米级到宏观级的电场限制，达到了超平衡增强效应，使 Ud 达到 28.5 J cm-3，η 达到 80%，Eb 达到 676 kV mm-1。通过结合密度泛函理论计算和扫描探针测量，证明了铝硅酸盐异质骨架电荷阱具有普遍的电荷保持能力。G-A-DBL 设计集成了传统的电荷捕获、异质结构形成和梯度调制，有效抑制了载流子激发、传输和捕获前的整个过程。这项工作推进了对无机界面电荷陷阱内电荷禁锢的基本理解，展示了最均衡的增强效应，并具有在介电聚合物纳米复合材料中广泛应用的潜力。
{"title":"Nanoclay Reinforced Polymer Composite Dielectrics for Ultra‐Balanced Electrostatic Energy Storage","authors":"Xiaozheng Liang, Quan Li, Yangjun Ren, Weimin Xie, Aidong Tang, Huaming Yang","doi":"10.1002/adfm.202408719","DOIUrl":"https://doi.org/10.1002/adfm.202408719","url":null,"abstract":"The vast energy storage potential of polymer composite dielectrics in high pulse power sources stands in stark contrast to the unbalanced improvements in discharge energy density (U<jats:sub>d</jats:sub>), charge–discharge efficiency (η), and dielectric strength (E<jats:sub>b</jats:sub>) as reported currently. Herein, a multistage coupled interface engineering design is proposed: a novel gradient alternating dielectric buffer layer (G‐A‐DBL) is constructed, which consists of inorganic low‐k nanoclay aluminosilicate layer and high‐k ferroelectric layer assembled in a highly oriented alternation as a basic unit and gradient distribution in polymer matrix. This design achieves electric field confinement from the nanoscale to the macroscopic level and achieves an ultra‐balanced enhancement effect, resulting in a U<jats:sub>d</jats:sub> of 28.5 J cm<jats:sup>−3</jats:sup>, an η of 80%, and an E<jats:sub>b</jats:sub> of 676 kV mm<jats:sup>−1</jats:sup>. The universal charge retention ability of charge traps from aluminosilicate heterogeneous skeletons is demonstrated by combining density functional theory calculations and scanning probe measurements. The G‐A‐DBL design integrates traditional charge trapping, heterostructure formation, and gradient modulation, effectively suppressing the entire process of carrier excitation, transport, and before capture. This work advances the basic understanding of charge confinement within inorganic interface charge traps, demonstrating the most well‐balanced enhancement effect and potential for broad application across dielectric polymer nanocomposites.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553370","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}
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