Lipid nanoparticles (LNPs) have gained significant attention because of the clinical success of Onpattro drug and mRNA vaccines. Two major challenges remain are (i) designing LNPs for gene therapy targeting non-liver tissues and (ii) overcoming inefficient endosomal escape of conventional LNPs. Cationic LNPs have been reported to shift the organ tropism, but their endosomal escape yet to be evaluated. Here, we investigated the fusion dynamics of cationic LNPs with model membranes at the single-particle level. We found that the membrane fusion occurs through a unique mass transfer pathway, involving a one-step transition that forms a metastable intermediate which fully coalesces with the target membrane. A moderately high concentration (31 mol%) of the cationic lipid (DOTAP), combined with either DOPE or DSPC+cholesterol helper lipids, accelerates the fusion kinetics by reducing the lag time. The enhanced fusogenicity of these compositions aligns with the bulk-phase lipid mixing results. Endosomal localization and eGFP expression upon gene delivery in a range of mammalian cell lines confirm effective endosomal escape of DOPE- or DSPC+cholesterol-rich cationic LNPs. Overall, these findings represent a step toward designing optimal cationic LNP candidates for efficient gene delivery to organs beyond the liver.
{"title":"Helper Lipids Accelerate the Mass Transfer of Cationic Lipid Nanoparticles Resulting in an Efficient Gene Delivery","authors":"Anurag Sharma, Khushika Khushika, Monika Chaudhary, Pritam Jana, Nagma Parveen","doi":"10.1039/d5nr03142g","DOIUrl":"https://doi.org/10.1039/d5nr03142g","url":null,"abstract":"Lipid nanoparticles (LNPs) have gained significant attention because of the clinical success of Onpattro drug and mRNA vaccines. Two major challenges remain are (i) designing LNPs for gene therapy targeting non-liver tissues and (ii) overcoming inefficient endosomal escape of conventional LNPs. Cationic LNPs have been reported to shift the organ tropism, but their endosomal escape yet to be evaluated. Here, we investigated the fusion dynamics of cationic LNPs with model membranes at the single-particle level. We found that the membrane fusion occurs through a unique mass transfer pathway, involving a one-step transition that forms a metastable intermediate which fully coalesces with the target membrane. A moderately high concentration (31 mol%) of the cationic lipid (DOTAP), combined with either DOPE or DSPC+cholesterol helper lipids, accelerates the fusion kinetics by reducing the lag time. The enhanced fusogenicity of these compositions aligns with the bulk-phase lipid mixing results. Endosomal localization and eGFP expression upon gene delivery in a range of mammalian cell lines confirm effective endosomal escape of DOPE- or DSPC+cholesterol-rich cationic LNPs. Overall, these findings represent a step toward designing optimal cationic LNP candidates for efficient gene delivery to organs beyond the liver.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"54 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689034","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
João Marcos T. Palheta, André Luis de Oliveira Batista, E. M. Flores, Celso Ricardo Caldeira Rêgo, Alexandre Silva Santos, Diego Guedes-Sobrinho, Alexandre Cavalheiro Dias, Maurício Jeomar Piotrowski
In this work, we performed a computational screening of group IV transition-metal dihalide monolayers in the recently proposed 1T'' phase. We have thoroughly examined the structural, electronic, optical, and excitonic characteristics, using density functional theory with both the generalized gradient approximation (PBE) and hybrid (HSE06) exchange-correlation approaches including spin–orbit coupling, complemented by Wannier-function–based tight-binding and Bethe–Salpeter equation analyses; as well as phonon dispersion calculations and ab initio molecular dynamics to shed light on the material stability. Out of the nine candidate systems, only 1T'' ZrCl2, HfCl2, and HfBr2 were found to be dynamically and thermally stable, with semiconducting behavior observed exclusively for HfCl2. From a detailed analysis of this compound, we have revealed pronounced excitonic effects, with a binding energy of 275 meV, strong optical anisotropy, and broadband absorption covering the infrared, visible, and ultraviolet ranges. Moreover, efficiencies of up to 20% were obtained by evaluating the 1T''-HfCl2 photovoltaic performance using the spectroscopic limited maximum efficiency and the Shockley-Queisser limit. These results highlight 1T''- HfCl2 as a promising two-dimensional semiconductor for optoelectronic and solar energy applications.
{"title":"Stable 1T'' HfCl2 monolayer with strong excitonic effects and promising solar harvesting efficiency","authors":"João Marcos T. Palheta, André Luis de Oliveira Batista, E. M. Flores, Celso Ricardo Caldeira Rêgo, Alexandre Silva Santos, Diego Guedes-Sobrinho, Alexandre Cavalheiro Dias, Maurício Jeomar Piotrowski","doi":"10.1039/d5nr04047g","DOIUrl":"https://doi.org/10.1039/d5nr04047g","url":null,"abstract":"In this work, we performed a computational screening of group IV transition-metal dihalide monolayers in the recently proposed 1T'' phase. We have thoroughly examined the structural, electronic, optical, and excitonic characteristics, using density functional theory with both the generalized gradient approximation (PBE) and hybrid (HSE06) exchange-correlation approaches including spin–orbit coupling, complemented by Wannier-function–based tight-binding and Bethe–Salpeter equation analyses; as well as phonon dispersion calculations and <em>ab initio</em> molecular dynamics to shed light on the material stability. Out of the nine candidate systems, only 1T'' ZrCl<small><sub>2</sub></small>, HfCl<small><sub>2</sub></small>, and HfBr<small><sub>2</sub></small> were found to be dynamically and thermally stable, with semiconducting behavior observed exclusively for HfCl<small><sub>2</sub></small>. From a detailed analysis of this compound, we have revealed pronounced excitonic effects, with a binding energy of 275 meV, strong optical anisotropy, and broadband absorption covering the infrared, visible, and ultraviolet ranges. Moreover, efficiencies of up to 20% were obtained by evaluating the 1T''-HfCl<small><sub>2</sub></small> photovoltaic performance using the spectroscopic limited maximum efficiency and the Shockley-Queisser limit. These results highlight 1T''- HfCl<small><sub>2</sub></small> as a promising two-dimensional semiconductor for optoelectronic and solar energy applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"26 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Waterborne pathogens are among the most significant threats to public health, underscoring the need for advanced disinfection methods. Conventional methods often produce harmful disinfection by-products and demand high energy. As an emerging solution, electrochemical membrane filtration technology provides effective microbial disinfection. Due to its excellent electrical conductivity, large surface area, and mechanical strength, graphene shows enhanced disinfection performance. Bimetallic nanoparticles, such as nickel-manganese oxide (NiMnO3), demonstrate synergistic physicochemical properties compared to their monometallic counterparts. This work focuses on fabricating and characterizing laser-induced graphene (LIG)-NiMnO3 composites to act as electroconductive surfaces. The LIG-NiMnO3 composite combines the redox and catalytic properties of nickel and manganese oxides, enhancing both electrochemical and antimicrobial efficiency. Bimetallic composites were synthesized with varying concentrations of NiMnO3 at 1%, 5%, and 10% embedded into LIG, with the 10% nanoparticle concentration demonstrating optimal performance. The characterization of composites confirmed their structural integrity, morphology, and electrochemical properties. Electrochemical characterization revealed a charge density of 1.86 × 104 µC cm-2 for the 10% composite, a ~5.8-fold increase over pristine LIG, confirming significantly improved electrochemical performance. The charge density of the composite was ~2.1 times higher than the previously reported LIG composites, highlighting its superior electrochemical properties. The composite exhibited intense antimicrobial activity against microbes, including Escherichia coli and MS2 bacteriophage. In batch experiments, 6-log bacteria were removed within one hour, while viruses were inactivated within four hours of operation at 2.5V. In flow-through mode, the 10% composite filter, operating at 2.5V, demonstrated complete microbial removal. Our findings suggest that bimetallic NiMnO3 composites improve LIG electrochemical properties via the combined effects of electrical fields and chemically induced oxidant effects. Thus, the newly developed LIG-NiMnO3 composite exhibits excellent potential for environmental applications, including water and wastewater treatment, as well as disinfection.
{"title":"Bimetallic NiMnO3 -Embedded Laser-Induced Graphene: A High-Performance Catalytic Filter for Electrochemical Pathogen Inactivation","authors":"Arnab Ghosh, Akhila Manoharan Nair, Swatantra Pratap Singh","doi":"10.1039/d5nr03544a","DOIUrl":"https://doi.org/10.1039/d5nr03544a","url":null,"abstract":"Waterborne pathogens are among the most significant threats to public health, underscoring the need for advanced disinfection methods. Conventional methods often produce harmful disinfection by-products and demand high energy. As an emerging solution, electrochemical membrane filtration technology provides effective microbial disinfection. Due to its excellent electrical conductivity, large surface area, and mechanical strength, graphene shows enhanced disinfection performance. Bimetallic nanoparticles, such as nickel-manganese oxide (NiMnO3), demonstrate synergistic physicochemical properties compared to their monometallic counterparts. This work focuses on fabricating and characterizing laser-induced graphene (LIG)-NiMnO3 composites to act as electroconductive surfaces. The LIG-NiMnO3 composite combines the redox and catalytic properties of nickel and manganese oxides, enhancing both electrochemical and antimicrobial efficiency. Bimetallic composites were synthesized with varying concentrations of NiMnO3 at 1%, 5%, and 10% embedded into LIG, with the 10% nanoparticle concentration demonstrating optimal performance. The characterization of composites confirmed their structural integrity, morphology, and electrochemical properties. Electrochemical characterization revealed a charge density of 1.86 × 104 µC cm-2 for the 10% composite, a ~5.8-fold increase over pristine LIG, confirming significantly improved electrochemical performance. The charge density of the composite was ~2.1 times higher than the previously reported LIG composites, highlighting its superior electrochemical properties. The composite exhibited intense antimicrobial activity against microbes, including Escherichia coli and MS2 bacteriophage. In batch experiments, 6-log bacteria were removed within one hour, while viruses were inactivated within four hours of operation at 2.5V. In flow-through mode, the 10% composite filter, operating at 2.5V, demonstrated complete microbial removal. Our findings suggest that bimetallic NiMnO3 composites improve LIG electrochemical properties via the combined effects of electrical fields and chemically induced oxidant effects. Thus, the newly developed LIG-NiMnO3 composite exhibits excellent potential for environmental applications, including water and wastewater treatment, as well as disinfection.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"4 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiamin Tian, Fangren Shen, Yitian Gu, Zidong Cai, Chao Feng, Qin Hu, Shuang Zhao, Qizhi Li, Lei Yang, Changrun Cai, Haolin Hu, Wei Zeng, David Zhou, Hongyan Liu, Kuang-Tse Ho
The performance of GaN-based high-electron-mobility transistors (HEMTs) hinges on the two-dimensional electron gas (2DEG) concentration induced by polarization fields at heterojunction interfaces. The AlN interlayer, critical for optimizing interfaces and 2DEG transport, requires atomic-scale understanding of its thickness-dependent polarization modulation, especially at sub-nanoscales (<1 nm). Using four-dimensional scanning transmission electron microscopy, polarization fields at AlGaN/AlN/GaN interfaces with 0.5 nm and 1 nm AlN interlayers are characterized. The sample with a 1 nm interlayer reveals two opposite electric fields, while the sample with a 0.5 nm interlayer exhibits only one unidirectional field. Geometric phase analysis reveals strain transfer in the sample with a 0.5 nm interlayer, with tensile (rather than compressive) strain at the AlGaN lower interface. Quantitative analyses further demonstrate stronger polarization fields and higher negative polarization charge density on the upper interface of GaN in the sample with a 1 nm interlayer, corresponding to lower onresistance (higher 2DEG concentration) in HEMTs. This work establishes atomic-scale correlations among AlN thickness, strain, and polarization fields, uncovers subnanoscale critical size effects, and guides high-performance HEMT design.
{"title":"Thickness-Dependent Polarization Modulation at AlN Interlayers in GaN Heterostructures Revealed by Atomic-Scale 4D-STEM","authors":"Jiamin Tian, Fangren Shen, Yitian Gu, Zidong Cai, Chao Feng, Qin Hu, Shuang Zhao, Qizhi Li, Lei Yang, Changrun Cai, Haolin Hu, Wei Zeng, David Zhou, Hongyan Liu, Kuang-Tse Ho","doi":"10.1039/d5nr03637b","DOIUrl":"https://doi.org/10.1039/d5nr03637b","url":null,"abstract":"The performance of GaN-based high-electron-mobility transistors (HEMTs) hinges on the two-dimensional electron gas (2DEG) concentration induced by polarization fields at heterojunction interfaces. The AlN interlayer, critical for optimizing interfaces and 2DEG transport, requires atomic-scale understanding of its thickness-dependent polarization modulation, especially at sub-nanoscales (<1 nm). Using four-dimensional scanning transmission electron microscopy, polarization fields at AlGaN/AlN/GaN interfaces with 0.5 nm and 1 nm AlN interlayers are characterized. The sample with a 1 nm interlayer reveals two opposite electric fields, while the sample with a 0.5 nm interlayer exhibits only one unidirectional field. Geometric phase analysis reveals strain transfer in the sample with a 0.5 nm interlayer, with tensile (rather than compressive) strain at the AlGaN lower interface. Quantitative analyses further demonstrate stronger polarization fields and higher negative polarization charge density on the upper interface of GaN in the sample with a 1 nm interlayer, corresponding to lower onresistance (higher 2DEG concentration) in HEMTs. This work establishes atomic-scale correlations among AlN thickness, strain, and polarization fields, uncovers subnanoscale critical size effects, and guides high-performance HEMT design.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"138 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Su Hyun Park, Gyeong Min Seo, Jeong Wook Kim, Yun Ho Lee, Gyubin Lee, Hong Jae Lee, Byoung Don Kong
We report a scalable, thermodynamically guided method for synthesizing germanium quantum dots embedded in a silicon oxide matrix with nanometer-scale precision. By engineering the oxidation and annealing conditions of silicon–germanium alloy layers, we achieve spatially confined, crystalline germanium quantum dots as small as 9.2 nanometers with tunneling oxide thicknesses down to 3.2 nanometers—suitable for room-temperature quantum confinement. Molecular dynamics simulations across a range of germanium compositions predict the agglomeration behaviour and size evolution of the quantum dots, while an analytical model enables predictive tuning of quantum dot dimensions and oxide thickness based on initial alloy composition. Experimental validation using scanning transmission electron microscopy, X-ray diffraction, and photoluminescence confirms crystallinity and size-dependent optical emission in the visible range. In contrast to earlier nanocrystal memory systems that relied on randomly distributed germanium precipitates embedded deep in thick oxide, our method enables precise formation of shallow, single-layer quantum dots with controlled geometry. These findings establish a robust platform for room-temperature quantum dot electronics, combining tunable confinement and compatibility with integrated circuit architectures.
{"title":"Scalable Synthesis of Spatially Confined Ge Quantum Dots with Tunable Quantum Confinement","authors":"Su Hyun Park, Gyeong Min Seo, Jeong Wook Kim, Yun Ho Lee, Gyubin Lee, Hong Jae Lee, Byoung Don Kong","doi":"10.1039/d5nr04252f","DOIUrl":"https://doi.org/10.1039/d5nr04252f","url":null,"abstract":"We report a scalable, thermodynamically guided method for synthesizing germanium quantum dots embedded in a silicon oxide matrix with nanometer-scale precision. By engineering the oxidation and annealing conditions of silicon–germanium alloy layers, we achieve spatially confined, crystalline germanium quantum dots as small as 9.2 nanometers with tunneling oxide thicknesses down to 3.2 nanometers—suitable for room-temperature quantum confinement. Molecular dynamics simulations across a range of germanium compositions predict the agglomeration behaviour and size evolution of the quantum dots, while an analytical model enables predictive tuning of quantum dot dimensions and oxide thickness based on initial alloy composition. Experimental validation using scanning transmission electron microscopy, X-ray diffraction, and photoluminescence confirms crystallinity and size-dependent optical emission in the visible range. In contrast to earlier nanocrystal memory systems that relied on randomly distributed germanium precipitates embedded deep in thick oxide, our method enables precise formation of shallow, single-layer quantum dots with controlled geometry. These findings establish a robust platform for room-temperature quantum dot electronics, combining tunable confinement and compatibility with integrated circuit architectures.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"36 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Doping in transition metal chalcogenides (TMCs) has emerged as a prominent method for tuning various properties with potential optoelectronics applications. The prime focus of the current study lies on the enhancement of photo detectivity, photo response ability through Sb doping into Bi2Se3 films under heat treatment. The Sb/Bi2Se3 heterostructure film formation is checked through cross-sectional FESEM (Field Emission Scanning Electron Microscope), which also showed the intermixing of the two layers upon annealing. The enhanced crystallinity, as probed from X-ray diffraction (XRD), modified the microstructure (probed by Raman spectroscopy) and surface morphology (noticed from FESEM image). The developed phases from XRD data were identified through HRTEM and SAED patterns. The element's existence in the film before and after annealing was verified through EDS data. The optical changes in the films were detected from UV-visible spectroscopy. The reduction in transmittance resulted in increased absorbance and decreased optical gap. The energy gap reduced from 1.419 (heterostructure) to 1.065 eV (mixed layer) by heat treatment, which caused 3.043 to 3.313 increment in refractive index. There is a two-fold enhancement in nonlinear parameters in terms of nonlinear refractive index and third-order nonlinearity upon annealing. The increased contact angle value upon annealing signifies the enhanced hydrophobicity in the annealed films. The photo response efficiency increased from 5.82 × 10-7AW-1(as-prepared) to 6.7 × 10-1 AW-1, and detectivity increased from 1.31 × 107 Jones (as-prepared) to 1.04 × 109 Jones with 250 °C annealing. The nA to mA transition in photo current upon annealing at 250 °C increased the photoconductivity. The resulting experimental data enable such types of films for advanced visible light photodetectors with future optoelectronic devices with high energy efficiency and sensitivity.
{"title":"Enhanced Photoresponsivity, Detectivity by Sb Doping into Bi2Se3 Thin Films for Visible Light Photodetectors","authors":"Gouttam Mallick, Prabhukrupa Chinmay Kumar, Ramakanta Naik, Rajib Biswal","doi":"10.1039/d5nr04502a","DOIUrl":"https://doi.org/10.1039/d5nr04502a","url":null,"abstract":"Doping in transition metal chalcogenides (TMCs) has emerged as a prominent method for tuning various properties with potential optoelectronics applications. The prime focus of the current study lies on the enhancement of photo detectivity, photo response ability through Sb doping into Bi2Se3 films under heat treatment. The Sb/Bi2Se3 heterostructure film formation is checked through cross-sectional FESEM (Field Emission Scanning Electron Microscope), which also showed the intermixing of the two layers upon annealing. The enhanced crystallinity, as probed from X-ray diffraction (XRD), modified the microstructure (probed by Raman spectroscopy) and surface morphology (noticed from FESEM image). The developed phases from XRD data were identified through HRTEM and SAED patterns. The element's existence in the film before and after annealing was verified through EDS data. The optical changes in the films were detected from UV-visible spectroscopy. The reduction in transmittance resulted in increased absorbance and decreased optical gap. The energy gap reduced from 1.419 (heterostructure) to 1.065 eV (mixed layer) by heat treatment, which caused 3.043 to 3.313 increment in refractive index. There is a two-fold enhancement in nonlinear parameters in terms of nonlinear refractive index and third-order nonlinearity upon annealing. The increased contact angle value upon annealing signifies the enhanced hydrophobicity in the annealed films. The photo response efficiency increased from 5.82 × 10-7AW-1(as-prepared) to 6.7 × 10-1 AW-1, and detectivity increased from 1.31 × 107 Jones (as-prepared) to 1.04 × 109 Jones with 250 °C annealing. The nA to mA transition in photo current upon annealing at 250 °C increased the photoconductivity. The resulting experimental data enable such types of films for advanced visible light photodetectors with future optoelectronic devices with high energy efficiency and sensitivity.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"21 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
P Chinnappan Santhosh, Suresh Jayakumar, A V Radhamani
Engineering a two-in-one multifunctional device that couples energy conversion and storage offers a smarter strategy to address the current global energy crisis while reducing reliance on grid electricity. Photo-rechargeable supercapacitors are perfect devices for the storage of light-induced electrochemical energy, garnering increasing attention as the next-generation energy storage technology. This study presents a novel 2D/1D g-C3N4/MnO2-based photocathode architecture, reported for the first time, for the fabrication of a solid-state photo-rechargeable supercapacitor device. Here, g-C3N4 functions as the light-capturing component, while MnO2 acts as the primary charge-storing element for the device. Photoluminescence (PL) results confirm that the MnO2/g-C3N4 S-scheme architecture promotes efficient photoexcited charge separation and suppresses their recombination. Upon light illumination, the optimized device exhibits a ∼23% enhancement in areal capacitance, compared to its performance in the dark at 0.7 mA cm-2. Under light exposure, the fabricated device retains double its areal capacitance after 600 cycles and achieves 100% retention after 2000 cycles under dark conditions, highlighting its outstanding cycling stability. This remarkable performance is ascribed to the presence of oxygen vacancy-mediated trap states in MnO2, which reduce charge carrier recombination during light illumination and facilitate charge transfer kinetics. The proposed S-scheme charge transfer mechanism is further validated by the combined evidence from Scanning Kelvin Probe (SKP) and Mott-Schottky measurements. These findings emphasize the promise of the g-C3N4/MnO2 S-scheme heterojunction for efficient light-assisted energy storage, making a significant advancement for an emerging class of materials. As the proof-of-concept, the device powered a red LED for 33 s in the dark and for up to 43 s under light illumination.
设计一种结合能量转换和存储的二合一多功能设备，为解决当前的全球能源危机提供了一种更明智的策略，同时减少了对电网电力的依赖。光可充电超级电容器是存储光致电化学能量的理想器件，作为下一代储能技术日益受到关注。本研究首次提出了一种基于g-C3N4/ mno2的新型2D/1D光电阴极结构，用于制造固态光可充电超级电容器器件。在这里，g-C3N4作为光捕获组件，而MnO2作为设备的主要电荷存储元素。光致发光（PL）结果证实MnO2/g- c3n4s结构促进了有效的光激发电荷分离并抑制了它们的重组。在光照下，优化后的器件的面电容比在0.7 mA cm-2的黑暗环境下的性能提高了约23%。在光照条件下，该器件在600次循环后仍能保持2倍的面电容，在黑暗条件下，在2000次循环后仍能保持100%的面电容，突出了其出色的循环稳定性。这种显著的性能归因于二氧化锰中氧空位介导的陷阱态的存在，这减少了光照下载流子的重组，促进了电荷转移动力学。扫描开尔文探针（SKP）和Mott-Schottky测量结果进一步验证了S-scheme电荷转移机制。这些发现强调了g-C3N4/MnO2 s方案异质结用于高效光辅助储能的前景，为新兴材料类别取得了重大进展。作为概念验证，该设备在黑暗中为红色LED供电33秒，在光照下可达43秒。
{"title":"Engineered S-scheme g-C<sub>3</sub>N<sub>4</sub>/MnO<sub>2</sub> heterostructures for integrated photo-rechargeable supercapacitors with enhanced energy storage performance.","authors":"P Chinnappan Santhosh, Suresh Jayakumar, A V Radhamani","doi":"10.1039/d5nr03958d","DOIUrl":"https://doi.org/10.1039/d5nr03958d","url":null,"abstract":"<p><p>Engineering a two-in-one multifunctional device that couples energy conversion and storage offers a smarter strategy to address the current global energy crisis while reducing reliance on grid electricity. Photo-rechargeable supercapacitors are perfect devices for the storage of light-induced electrochemical energy, garnering increasing attention as the next-generation energy storage technology. This study presents a novel 2D/1D g-C<sub>3</sub>N<sub>4</sub>/MnO<sub>2</sub>-based photocathode architecture, reported for the first time, for the fabrication of a solid-state photo-rechargeable supercapacitor device. Here, g-C<sub>3</sub>N<sub>4</sub> functions as the light-capturing component, while MnO<sub>2</sub> acts as the primary charge-storing element for the device. Photoluminescence (PL) results confirm that the MnO<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> S-scheme architecture promotes efficient photoexcited charge separation and suppresses their recombination. Upon light illumination, the optimized device exhibits a ∼23% enhancement in areal capacitance, compared to its performance in the dark at 0.7 mA cm<sup>-2</sup>. Under light exposure, the fabricated device retains double its areal capacitance after 600 cycles and achieves 100% retention after 2000 cycles under dark conditions, highlighting its outstanding cycling stability. This remarkable performance is ascribed to the presence of oxygen vacancy-mediated trap states in MnO<sub>2</sub>, which reduce charge carrier recombination during light illumination and facilitate charge transfer kinetics. The proposed S-scheme charge transfer mechanism is further validated by the combined evidence from Scanning Kelvin Probe (SKP) and Mott-Schottky measurements. These findings emphasize the promise of the g-C<sub>3</sub>N<sub>4</sub>/MnO<sub>2</sub> S-scheme heterojunction for efficient light-assisted energy storage, making a significant advancement for an emerging class of materials. As the proof-of-concept, the device powered a red LED for 33 s in the dark and for up to 43 s under light illumination.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" ","pages":""},"PeriodicalIF":5.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145675790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jürgen Pfeffermann, Rohit Yadav, Toma N Glasnov, Oliver Thorn-Seshold, Peter Pohl
We report a molecular strategy for precise, reversible, and noninvasive photoregulation of ion-selective membrane transport. Embedding azobenzene-containing photolipids into bilayers enables nanoscale control over the interaction and mobility of small-molecule ion carriers. Photoisomerization alone produces only minor changes in baseline conductance, consistent with the limited influence of small bilayer thickness variations on ion permeability, yet it elicits striking responses in the presence of mobile carriers. A newly designed protonophore exhibits proton-selective currents that increase by up to 200-fold under UV illumination and revert to baseline within milliseconds upon blue light. These effects cannot be explained by thickness or fluidity changes. Instead, they arise from light-dependent interactions between azobenzene moieties and the carrier that increase the membrane-bound carrier concentration and lower the effective barrier for transbilayer permeation via interfacial dipole and packing modulation. Because this mechanism relies entirely on chemical design—without genetic modification—and is compatible with photoswitches operating at longer wavelengths, it establishes a versatile framework for dynamic, light-driven control of ion transport in biological membranes and synthetic nanosystems.
{"title":"Optical control of carrier-mediated ion transport by photoswitchable lipids","authors":"Jürgen Pfeffermann, Rohit Yadav, Toma N Glasnov, Oliver Thorn-Seshold, Peter Pohl","doi":"10.1039/d5nr04234h","DOIUrl":"https://doi.org/10.1039/d5nr04234h","url":null,"abstract":"We report a molecular strategy for precise, reversible, and noninvasive photoregulation of ion-selective membrane transport. Embedding azobenzene-containing photolipids into bilayers enables nanoscale control over the interaction and mobility of small-molecule ion carriers. Photoisomerization alone produces only minor changes in baseline conductance, consistent with the limited influence of small bilayer thickness variations on ion permeability, yet it elicits striking responses in the presence of mobile carriers. A newly designed protonophore exhibits proton-selective currents that increase by up to 200-fold under UV illumination and revert to baseline within milliseconds upon blue light. These effects cannot be explained by thickness or fluidity changes. Instead, they arise from light-dependent interactions between azobenzene moieties and the carrier that increase the membrane-bound carrier concentration and lower the effective barrier for transbilayer permeation via interfacial dipole and packing modulation. Because this mechanism relies entirely on chemical design—without genetic modification—and is compatible with photoswitches operating at longer wavelengths, it establishes a versatile framework for dynamic, light-driven control of ion transport in biological membranes and synthetic nanosystems.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"13 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Poly(amino acids), protein analogues with amide backbones, have garnered wide attention due to their biodegradability, and their tunable physicochemical properties. However, the absence of an efficient polymerization strategy that combines simplified procedures with kinetic control for synthesizing poly(amino acids) remains a critical technical bottleneck, hindering their practical applications in advanced materials science. On-surface synthesis under ultra-high vacuum (UHV) conditions emerges as a promising avenue to overcome these challenges. In this review, we systematically review the design of monomer, synthetic methodologies, and network structures of surface-confined polyamides, emphasizing the pivotal roles of substrate engineering and monomer design in governing polymerization outcomes. We first elucidate the formation of surface-confined amide bonds and polyamide chains on noble metal substrates, involving acyl chloride-amine coupling for constructing one-dimensional linear polyamides and two-dimensional (2D) porous polyamide networks, and direct dehydration condensation of carboxyl and amino species. Additionally, we explore oligomerization pathways of natural amino acids, exemplified by the nickel-catalyzed formation of oligoprolines on Au(111) surface. Looking forward, we propose that 2D materials, featuring tunable phase structures and versatile electronic properties, offer a transformative alternative to conventional metal substrates with limited modifiability. Meanwhile, natural amino acids, endowed with their diverse functional side groups, present unique opportunities for synthesizing structurally complex polymer networks. By synergistically optimizing substrate properties and monomer structures, and harnessing advanced surface synthesis techniques, we aim to establish robust strategies for the substrate-confined catalytic precision synthesis of poly(amino acids). These advances are anticipated to unlock innovative applications in molecular electronics, nanoscale templating, and bio-inspired functional materials.
{"title":"On-surface polymerization of natural amino acids: substrate engineering and monomer design","authors":"Yinuo Zhu, Miao Zhou, Tianchao Niu","doi":"10.1039/d5nr04579g","DOIUrl":"https://doi.org/10.1039/d5nr04579g","url":null,"abstract":"Poly(amino acids), protein analogues with amide backbones, have garnered wide attention due to their biodegradability, and their tunable physicochemical properties. However, the absence of an efficient polymerization strategy that combines simplified procedures with kinetic control for synthesizing poly(amino acids) remains a critical technical bottleneck, hindering their practical applications in advanced materials science. On-surface synthesis under ultra-high vacuum (UHV) conditions emerges as a promising avenue to overcome these challenges. In this review, we systematically review the design of monomer, synthetic methodologies, and network structures of surface-confined polyamides, emphasizing the pivotal roles of substrate engineering and monomer design in governing polymerization outcomes. We first elucidate the formation of surface-confined amide bonds and polyamide chains on noble metal substrates, involving acyl chloride-amine coupling for constructing one-dimensional linear polyamides and two-dimensional (2D) porous polyamide networks, and direct dehydration condensation of carboxyl and amino species. Additionally, we explore oligomerization pathways of natural amino acids, exemplified by the nickel-catalyzed formation of oligoprolines on Au(111) surface. Looking forward, we propose that 2D materials, featuring tunable phase structures and versatile electronic properties, offer a transformative alternative to conventional metal substrates with limited modifiability. Meanwhile, natural amino acids, endowed with their diverse functional side groups, present unique opportunities for synthesizing structurally complex polymer networks. By synergistically optimizing substrate properties and monomer structures, and harnessing advanced surface synthesis techniques, we aim to establish robust strategies for the substrate-confined catalytic precision synthesis of poly(amino acids). These advances are anticipated to unlock innovative applications in molecular electronics, nanoscale templating, and bio-inspired functional materials.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The heteroleptic gold nanoclusters [Au13(dppe)5(PA)2]3+ (dppe = 1,2-bis(diphenylphosphino)ethane; PA– = phenylacetylide) and [Au38(PPh3)4(PA)20]2+ underwent the removal of PA− and a [Au(PA)2]− staple unit, respectively, via reaction with the Lewis acid, scandium trifluoromethanesulfonate Sc(OTf)3. The surface-exposed [Au37(PPh3)4(PA)18]3+ obtained from the Au38 nanocluster self-assembled into a dimer with two di-isocyanide linker molecules. This non-thermal strategy provides a foundation for the targeted synthesis of novel AuNCs with well-defined naked sites that can act as selective catalysts or building blocks for assembled materials.
{"title":"Sc(OTf)3-Induced, Selective Removal of Alkynyl Ligands from Heteroleptic Au13 and Au38 Nanoclusters","authors":"Zengguang Huang, Shinjiro Takano, Tatsuya Tsukuda","doi":"10.1039/d5nr03977k","DOIUrl":"https://doi.org/10.1039/d5nr03977k","url":null,"abstract":"The heteroleptic gold nanoclusters [Au<small><sub>13</sub></small>(dppe)<small><sub>5</sub></small>(PA)<small><sub>2</sub></small>]<small><sup>3+</sup></small> (dppe = 1,2-bis(diphenylphosphino)ethane; PA<small><sup>–</sup></small> = phenylacetylide) and [Au<small><sub>38</sub></small>(PPh<small><sub>3</sub></small>)<small><sub>4</sub></small>(PA)<small><sub>20</sub></small>]<small><sup>2+</sup></small> underwent the removal of PA<small><sup>−</sup></small> and a [Au(PA)<small><sub>2</sub></small>]<small><sup>−</sup></small> staple unit, respectively, via reaction with the Lewis acid, scandium trifluoromethanesulfonate Sc(OTf)<small><sub>3</sub></small>. The surface-exposed [Au<small><sub>37</sub></small>(PPh<small><sub>3</sub></small>)<small><sub>4</sub></small>(PA)<small><sub>18</sub></small>]<small><sup>3+</sup></small> obtained from the Au<small><sub>38</sub></small> nanocluster self-assembled into a dimer with two di-isocyanide linker molecules. This non-thermal strategy provides a foundation for the targeted synthesis of novel AuNCs with well-defined naked sites that can act as selective catalysts or building blocks for assembled materials.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"2 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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