Nikita Sergeevich Markin, Ivan Sergeevich Gordeev, Hong En Fu, Sergey Igorevich Ivannikov, Yeon Beom Kim, Alexey Yurievich Samardak, Alexander Sergeevich Samardak, Young Keun Kim, Alexey Vyacheslavovich Ognev
As the global incidence of cancer escalates, there exists an urgent necessity for innovative therapeutic modalities. While radiation therapy is indispensable in oncology, it faces significant challenges in achieving an optimal equilibrium between tumour ablation and the preservation of surrounding healthy tissues. Noteworthy advancements such as intensity-modulated radiation therapy (IMRT) and three-dimensional conformal radiation therapy (3D-CRT) have enhanced the precision of treatment; however, their efficacy is still constrained by the accuracy of tumour delineation. The utilization of radiosensitizers, with a particular emphasis on metal nanoparticles, presents a promising avenue for augmenting the susceptibility of neoplastic cells to ionizing radiation. This research examines the potential of core-shell-satellite Fe3O4-SiO2-Au nanoparticles as effective radiosensitizers. By investigating the interaction of individual nanoparticles situated within a water phantom of 20 micrometers in diameter with monochromatic photon beams at energies of 50, 100, and 150 keV, we analyse how variations in the structural composition of Au nanoparticles and their concentrations within these multifaceted nanoparticles influence the efficacy of radiation therapy, employing Monte Carlo simulations corroborated by the general-purpose radiation transport code PHITS. Our investigation aspires to refine nanoparticle-based methodologies to enhance cancer treatment outcomes, potentially facilitating the development of more targeted therapeutic interventions that minimize adverse effects while improving patient survival rates.
{"title":"Secondary electron dynamics in core–shell–satellite nanoparticles: a computational strategy for targeted cancer treatment","authors":"Nikita Sergeevich Markin, Ivan Sergeevich Gordeev, Hong En Fu, Sergey Igorevich Ivannikov, Yeon Beom Kim, Alexey Yurievich Samardak, Alexander Sergeevich Samardak, Young Keun Kim, Alexey Vyacheslavovich Ognev","doi":"10.1039/d5nr00270b","DOIUrl":"https://doi.org/10.1039/d5nr00270b","url":null,"abstract":"As the global incidence of cancer escalates, there exists an urgent necessity for innovative therapeutic modalities. While radiation therapy is indispensable in oncology, it faces significant challenges in achieving an optimal equilibrium between tumour ablation and the preservation of surrounding healthy tissues. Noteworthy advancements such as intensity-modulated radiation therapy (IMRT) and three-dimensional conformal radiation therapy (3D-CRT) have enhanced the precision of treatment; however, their efficacy is still constrained by the accuracy of tumour delineation. The utilization of radiosensitizers, with a particular emphasis on metal nanoparticles, presents a promising avenue for augmenting the susceptibility of neoplastic cells to ionizing radiation. This research examines the potential of core-shell-satellite Fe<small><sub>3</sub></small>O<small><sub>4</sub></small>-SiO<small><sub>2</sub></small>-Au nanoparticles as effective radiosensitizers. By investigating the interaction of individual nanoparticles situated within a water phantom of 20 micrometers in diameter with monochromatic photon beams at energies of 50, 100, and 150 keV, we analyse how variations in the structural composition of Au nanoparticles and their concentrations within these multifaceted nanoparticles influence the efficacy of radiation therapy, employing Monte Carlo simulations corroborated by the general-purpose radiation transport code PHITS. Our investigation aspires to refine nanoparticle-based methodologies to enhance cancer treatment outcomes, potentially facilitating the development of more targeted therapeutic interventions that minimize adverse effects while improving patient survival rates.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"15 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857220","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}
Jinhua Wu, Zhang Liang, Hao Sun, Ying Cui, Cun-Zheng Ning
Erbium (Er) based NaYF4 nanoparticles (ENPs) are important for many applications including imaging, communications, and biosensing, especially at high Er concentrations. The rate equations (REs) are foundational for understanding various transitions in ENPs. However, the REs and various coefficients are determined only at the classical Er-composition of ~2% and Ytterbium at ~20% where upconversion processes were included only. This paper aims to determine coefficients of the REs through systematic characterizations at the full range of Er levels (5%, 50%, 75%, and 100%), where both up- and down-conversions are important and a careful calibration of visible and near-infrared emission bands is required. The parameter values of the REs are then curve-fitted to obtain their values for arbitrary Er concentration. We found that the non-radiative transitions and energy-transfer processes increase quadratically with Er concentration. We discovered the non-radiative transition from 4I11/2 to 4I13/2 increases with Er concentration and is orders of magnitude faster than other decay processes, exhibiting the highest down-conversion at 100% of Er. Our study explains why high-Er nanoparticles typically show weak upconversion emissions. Our results establish the REs for arbitrary Er-concentration for the first time and can be used more generally for designing ENPs and understanding complex nonlinear processes.
基于铒（Er）的 NaYF4 纳米粒子（ENPs）在成像、通信和生物传感等许多应用中都非常重要，尤其是在高浓度铒的情况下。速率方程（REs）是理解 ENPs 中各种转变的基础。然而，REs 和各种系数仅在经典的铒浓度约为 2% 和镱浓度约为 20% 时确定，其中仅包括上转换过程。本文旨在通过对全部铒含量范围（5%、50%、75% 和 100%）的系统表征来确定 REs 的系数，其中上转换和下转换都很重要，并且需要对可见光和近红外发射波段进行仔细校准。然后对 RE 的参数值进行曲线拟合，以获得任意 Er 浓度下的参数值。我们发现，非辐射跃迁和能量转移过程随 Er 浓度的增加而呈二次方增加。我们发现，从 4I11/2 到 4I13/2 的非辐射跃迁随 Er 浓度的增加而增加，其速度比其他衰变过程快几个数量级，在 Er 浓度为 100% 时表现出最高的下转换率。我们的研究解释了为什么高 Er 纳米粒子通常表现出微弱的上转换发射。我们的研究结果首次建立了任意 Er 浓度的 REs，可更广泛地用于设计 ENPs 和理解复杂的非线性过程。
{"title":"Determination of the rate equations for erbium nanoparticles at arbitrary concentrations and drastically enhanced non-radiative transitions.","authors":"Jinhua Wu, Zhang Liang, Hao Sun, Ying Cui, Cun-Zheng Ning","doi":"10.1039/d4nr04815f","DOIUrl":"https://doi.org/10.1039/d4nr04815f","url":null,"abstract":"Erbium (Er) based NaYF4 nanoparticles (ENPs) are important for many applications including imaging, communications, and biosensing, especially at high Er concentrations. The rate equations (REs) are foundational for understanding various transitions in ENPs. However, the REs and various coefficients are determined only at the classical Er-composition of ~2% and Ytterbium at ~20% where upconversion processes were included only. This paper aims to determine coefficients of the REs through systematic characterizations at the full range of Er levels (5%, 50%, 75%, and 100%), where both up- and down-conversions are important and a careful calibration of visible and near-infrared emission bands is required. The parameter values of the REs are then curve-fitted to obtain their values for arbitrary Er concentration. We found that the non-radiative transitions and energy-transfer processes increase quadratically with Er concentration. We discovered the non-radiative transition from 4I11/2 to 4I13/2 increases with Er concentration and is orders of magnitude faster than other decay processes, exhibiting the highest down-conversion at 100% of Er. Our study explains why high-Er nanoparticles typically show weak upconversion emissions. Our results establish the REs for arbitrary Er-concentration for the first time and can be used more generally for designing ENPs and understanding complex nonlinear processes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"2 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857226","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}
Organic-inorganic lead halide perovskite nanocrystals (NCs) have evolved as a superior material for various optoelectronic and sensing applications. The ultrapure green emission, high luminescent intensity, narrow emission spectra, and exceptional stability at high temperatures of FAPbBr3 make them suitable for lighting and sensing technologies. Very little research has been explored on photophysical properties, stability improvement, and applications on FA-based NCs. Herein, we represent a room-temperature synthesis of FA1-xCsxPbBr3 NCs, then encapsulated with a layered (OcA)2PbBr4 shell to enhance the NCs' stability and luminescence intensity. Though 10% Cs-doped FAPbBr3 NCs showed maximum emission intensity, we coated (OcA)2PbBr4 shells around 20% Cs-doped FAPbBr3 NCs for their highest stability. The nonlinear optical properties of the NCs dominated by the thermal lens effect reveal reverse saturable absorption and self-focusing effects with higher χ(3) values in the order of 10-6 e.s.u. The core@shell NCs were tested as temperature sensors, demonstrating a maximum relative sensitivity of 3.31 %-K-1. Further, these NCs were embedded in PMMA microfibers to improve flexibility and stability. These fluorescent microfibers offered excellent water stability for about four months while dipped in water. Finally, the fibers were tested as a fluorescent source to fabricate down-converted green LED, which unveils a CCT value of ~8161 K and a maximum efficiency of ~85 Lm/W. This research unlocks new possibilities for FA-based NCs for efficient temperature sensing, flexible futuristic displays, and optical limiting applications.
{"title":"Nonlinear Optical Properties of Stable Cs-doped FAPbBr3 Core@Shell Layered Perovskite Nanocrystals: Superior Temperature Sensing and Flexible Fiber-Based Pure Green LEDs","authors":"Ashutosh Mohapatra, Smaranika Ray, Prabhukrupa Chinmay Kumar, Rajat Kumar Das, Pragalbh Kashyap, Saikat Bhaumik","doi":"10.1039/d4nr04309j","DOIUrl":"https://doi.org/10.1039/d4nr04309j","url":null,"abstract":"Organic-inorganic lead halide perovskite nanocrystals (NCs) have evolved as a superior material for various optoelectronic and sensing applications. The ultrapure green emission, high luminescent intensity, narrow emission spectra, and exceptional stability at high temperatures of FAPbBr3 make them suitable for lighting and sensing technologies. Very little research has been explored on photophysical properties, stability improvement, and applications on FA-based NCs. Herein, we represent a room-temperature synthesis of FA1-xCsxPbBr3 NCs, then encapsulated with a layered (OcA)2PbBr4 shell to enhance the NCs' stability and luminescence intensity. Though 10% Cs-doped FAPbBr3 NCs showed maximum emission intensity, we coated (OcA)2PbBr4 shells around 20% Cs-doped FAPbBr3 NCs for their highest stability. The nonlinear optical properties of the NCs dominated by the thermal lens effect reveal reverse saturable absorption and self-focusing effects with higher χ(3) values in the order of 10-6 e.s.u. The core@shell NCs were tested as temperature sensors, demonstrating a maximum relative sensitivity of 3.31 %-K-1. Further, these NCs were embedded in PMMA microfibers to improve flexibility and stability. These fluorescent microfibers offered excellent water stability for about four months while dipped in water. Finally, the fibers were tested as a fluorescent source to fabricate down-converted green LED, which unveils a CCT value of ~8161 K and a maximum efficiency of ~85 Lm/W. This research unlocks new possibilities for FA-based NCs for efficient temperature sensing, flexible futuristic displays, and optical limiting applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"67 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857218","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}
Protonic ceramic fuel cells offer a promising route to effectively generate electricity from various fuels at reduced temperatures. However, the viability of this technology is impeded by the sluggish kinetics of the oxygen reduction reaction at the cathode. Recently, triple ionic–electronic conductors have shown their promise as cathode materials with improved catalytic activity because of their enhanced mixed electron and ionic conductivities that can maximise the active sites for the reaction. This review examines the transport mechanism of holes, oxygen ions, and protons within triple ionic–electronic conductors. This review highlights the equilibrium among these charge carriers and their requirement for specific cationic environments to facilitate rapid transport. As a result, triple ionic–electronic conductors need to balance the transport of these charges to realise optimum oxygen reduction reaction activity. The review further identifies the transport of oxygen ions or protons as the current limiting factor in triple ionic–electronic conductors. This review concludes by emphasizing the importance of understanding the role of ionic transport in the oxygen reduction reaction to enhance the performance of triple ionic–electronic conductors.
{"title":"Progress in understanding triple ionic–electronic conduction in perovskite oxides for protonic ceramic fuel cell applications","authors":"Desheng Feng, Zhonghua Zhu, Dan Li, Mengran Li","doi":"10.1039/d4nr05513f","DOIUrl":"https://doi.org/10.1039/d4nr05513f","url":null,"abstract":"Protonic ceramic fuel cells offer a promising route to effectively generate electricity from various fuels at reduced temperatures. However, the viability of this technology is impeded by the sluggish kinetics of the oxygen reduction reaction at the cathode. Recently, triple ionic–electronic conductors have shown their promise as cathode materials with improved catalytic activity because of their enhanced mixed electron and ionic conductivities that can maximise the active sites for the reaction. This review examines the transport mechanism of holes, oxygen ions, and protons within triple ionic–electronic conductors. This review highlights the equilibrium among these charge carriers and their requirement for specific cationic environments to facilitate rapid transport. As a result, triple ionic–electronic conductors need to balance the transport of these charges to realise optimum oxygen reduction reaction activity. The review further identifies the transport of oxygen ions or protons as the current limiting factor in triple ionic–electronic conductors. This review concludes by emphasizing the importance of understanding the role of ionic transport in the oxygen reduction reaction to enhance the performance of triple ionic–electronic conductors.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"68 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857222","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}
Arkadiusz Zarzycki, Marcin Perzanowski, Michal Krupinski, Marta Marszalek
Local surface curvature and effects associated with a large surface-to-volume ratio are of great importance in thin films and can influence the character of temperature-induced phase transitions. In particular, these effects have a substantial influence on the transformation of thin multilayers into nano-alloys where the introduction of template-assisted patterning can shift the transformation temperature, induce a crystallographic texture, and change the phase composition. In this work, we study the phase transformations in patterned Fe/Pd multilayers leading to the formation of FePd alloys. We used two different template-assisted patterning methods, nanosphere lithography and anodization process, to study the influence of film morphology along with local curvature on the transformation process, structure, and magnetism of the resulting alloy. We combined Mössbauer spectroscopy, X-ray diffraction, SEM imaging, and magnetometry to track these changes at short- and long-range scales. We show that film morphology is one of the most important factors determining the physical properties of the alloy formed after thermal treatment. It allows for patterning-controlled solid-state dewetting and rearrangement of atoms that in turn governs the phase transformation as well as structural and magnetic properties. We identified two counter-effective processes responsible for FePd L10 phase formation, the effect of patterning-induced interatomic diffusion and the patterning-limited diffusion radius.
{"title":"Phase transformations and magnetism in patterned FePd thin films","authors":"Arkadiusz Zarzycki, Marcin Perzanowski, Michal Krupinski, Marta Marszalek","doi":"10.1039/d5nr00545k","DOIUrl":"https://doi.org/10.1039/d5nr00545k","url":null,"abstract":"Local surface curvature and effects associated with a large surface-to-volume ratio are of great importance in thin films and can influence the character of temperature-induced phase transitions. In particular, these effects have a substantial influence on the transformation of thin multilayers into nano-alloys where the introduction of template-assisted patterning can shift the transformation temperature, induce a crystallographic texture, and change the phase composition. In this work, we study the phase transformations in patterned Fe/Pd multilayers leading to the formation of FePd alloys. We used two different template-assisted patterning methods, nanosphere lithography and anodization process, to study the influence of film morphology along with local curvature on the transformation process, structure, and magnetism of the resulting alloy. We combined Mössbauer spectroscopy, X-ray diffraction, SEM imaging, and magnetometry to track these changes at short- and long-range scales. We show that film morphology is one of the most important factors determining the physical properties of the alloy formed after thermal treatment. It allows for patterning-controlled solid-state dewetting and rearrangement of atoms that in turn governs the phase transformation as well as structural and magnetic properties. We identified two counter-effective processes responsible for FePd L1<small><sub>0</sub></small> phase formation, the effect of patterning-induced interatomic diffusion and the patterning-limited diffusion radius.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"7 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857217","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}
Tuan-Hoang Tran, Raul D. Rodriguez, Aura Garcia, Qiang Ma, Tao Zhang, Ranran Wang, Evgeniya Sheremet
Molybdenum disulfide (MoS2) is a promising 2D material for (photo)catalysis. However, its performance in (photo)catalytic applications is usually limited by a small amount of catalytically active defects. Here, we developed a novel large-scale, rapid, green, low-cost photoetching technique to transform multilayer MoS2 into a few-layer MoS2 with high defect density and simultaneous spatial functionalization of MoS2 with magnetic nanostructures using a photo-driven Fenton reaction. The photoetching process and resulting nanostructures were characterized by optical microscopy, atomic force microscopy, photoluminescence, and Raman spectroscopy. We elucidated the reaction mechanism driven by the Fenton reaction in which photogenerated charge carriers in MoS2 play a dual role: reducing Fe3+ and Cu2+ ions and generating hydrogen peroxide (H2O2) from water and dissolved O2. In this Fenton reaction, Fe2+ ions react with H2O2 to generate hydroxyl (˙OH) radicals, oxidizing MoS2 and forming metal oxide nanostructures at the reaction sites. This dual pathway, triggered by MoS2 photon absorption even at low-intensity illumination, ensures in situ generation of Fenton reactants (Fe2+ and H2O2), generating ˙OH, to achieve on-demand thinning and functionalization of MoS2 in a single step. Electron paramagnetic resonance spectroscopy confirmed the generation of ˙OH radicals as the main reactive oxygen species. This photochemical approach enables the photo-driven creation and growth of defects from submicrometer regions up to a dozen micrometers, both at native defects and predefined defective region seeds, by photochemical processing of MoS2 in FeCl3 and CuSO4 solutions. The presence of metal oxide nanostructures on MoS2 was verified using magnetic force microscopy, scanning electron microscopy with elemental mapping by energy dispersive X-ray spectroscopy and Raman spectroscopy. The simultaneous photoetching and metal oxide deposition improves the catalytic performance of MoS2 in the electrical hydrogen evolution reaction, evidenced by a potential shift from −0.7 V (graphite electrode) to −0.47 V (MoS2 sample photoetched in FeCl3 solution under a halogen lamp illumination) at a current density of 10 mA cm−2.
{"title":"Photoactivated defect engineering and nanostructure functionalization of MoS2 via a photochemical Fenton process","authors":"Tuan-Hoang Tran, Raul D. Rodriguez, Aura Garcia, Qiang Ma, Tao Zhang, Ranran Wang, Evgeniya Sheremet","doi":"10.1039/d4nr05278a","DOIUrl":"https://doi.org/10.1039/d4nr05278a","url":null,"abstract":"Molybdenum disulfide (MoS<small><sub>2</sub></small>) is a promising 2D material for (photo)catalysis. However, its performance in (photo)catalytic applications is usually limited by a small amount of catalytically active defects. Here, we developed a novel large-scale, rapid, green, low-cost photoetching technique to transform multilayer MoS<small><sub>2</sub></small> into a few-layer MoS<small><sub>2</sub></small> with high defect density and simultaneous spatial functionalization of MoS<small><sub>2</sub></small> with magnetic nanostructures using a photo-driven Fenton reaction. The photoetching process and resulting nanostructures were characterized by optical microscopy, atomic force microscopy, photoluminescence, and Raman spectroscopy. We elucidated the reaction mechanism driven by the Fenton reaction in which photogenerated charge carriers in MoS<small><sub>2</sub></small> play a dual role: reducing Fe<small><sup>3+</sup></small> and Cu<small><sup>2+</sup></small> ions and generating hydrogen peroxide (H<small><sub>2</sub></small>O<small><sub>2</sub></small>) from water and dissolved O<small><sub>2</sub></small>. In this Fenton reaction, Fe<small><sup>2+</sup></small> ions react with H<small><sub>2</sub></small>O<small><sub>2</sub></small> to generate hydroxyl (˙OH) radicals, oxidizing MoS<small><sub>2</sub></small> and forming metal oxide nanostructures at the reaction sites. This dual pathway, triggered by MoS<small><sub>2</sub></small> photon absorption even at low-intensity illumination, ensures <em>in situ</em> generation of Fenton reactants (Fe<small><sup>2+</sup></small> and H<small><sub>2</sub></small>O<small><sub>2</sub></small>), generating ˙OH, to achieve on-demand thinning and functionalization of MoS<small><sub>2</sub></small> in a single step. Electron paramagnetic resonance spectroscopy confirmed the generation of ˙OH radicals as the main reactive oxygen species. This photochemical approach enables the photo-driven creation and growth of defects from submicrometer regions up to a dozen micrometers, both at native defects and predefined defective region seeds, by photochemical processing of MoS<small><sub>2</sub></small> in FeCl<small><sub>3</sub></small> and CuSO<small><sub>4</sub></small> solutions. The presence of metal oxide nanostructures on MoS<small><sub>2</sub></small> was verified using magnetic force microscopy, scanning electron microscopy with elemental mapping by energy dispersive X-ray spectroscopy and Raman spectroscopy. The simultaneous photoetching and metal oxide deposition improves the catalytic performance of MoS<small><sub>2</sub></small> in the electrical hydrogen evolution reaction, evidenced by a potential shift from −0.7 V (graphite electrode) to −0.47 V (MoS<small><sub>2</sub></small> sample photoetched in FeCl<small><sub>3</sub></small> solution under a halogen lamp illumination) at a current density of 10 mA cm<small><sup>−2</sup></small>.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"12 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857219","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}
Vikas Kumar Jha, Kranti Salgaonkar, Avishek Saha, Chinnakonda S. Gopinath, E. Siva Subramaniam Iyer
The ever-increasing demand for sustainable solutions for eliminating environmental pollutants, solar energy harvesting, water splitting, etc., has led to the design and development of novel materials to achieve the desired result. In this regard, structurally and electronically integrated (SEI) BiVO4-TiO2 (SEI-BVT) with abundant heterojunctions have emerged as promising entity for efficient charge separation, which in turn enhanced artificial photosynthesis (APS) activity. The present work adopted a unique synthetic strategy by SILAR to fabricate SEI-BVT from ionic precursors (Bi3+ and VO43-) into the pores of TiO2, exhibiting benchmark APS efficiency than the individual components. This preparation results in approximately 180 trillions of uniformly distributed heterojunctions in 1 mg/cm2 of SEI-BVT photoanode material. Charge carriers in SEI-BVT and BiVO4 are similar; however, the recombination is highly hindered when SEI-BVT heterojunctions are formed in the former. Our earlier work demonstrated 31-38% solar-to-fuel efficiency (STFE) with BiVO4-TiO2 for APS in the presence of Pd-nanocube co-catalyst. The emphasis of the current manuscript is to explore the dynamics of the light-induced processes in these heterojunctions to understand the interfacial charge transfer process. Femtosecond transient absorption (TA) spectroscopy has been employed to monitor the excited state dynamics. Our results show that new trap states have evolved under light illumination, which are significantly long-lived and hinder charge recombination, and consequently enhancing STFE. A significantly large number of charge carriers exhibit a lifetime of >> 6 ns with visible light photons, at least up to 720 nm, which is higher than the band-gap absorption onset at 490 nm for SEI-BVT than bulk BiVO4. The rate of formation of charge carriers are significantly affected in the heterojunctions.
{"title":"Enhanced mid-visible light absorption and long-lived charge carriers in electronically and structurally integrated BiVO4-TiO2 photoanode for efficient artificial photosynthesis applications","authors":"Vikas Kumar Jha, Kranti Salgaonkar, Avishek Saha, Chinnakonda S. Gopinath, E. Siva Subramaniam Iyer","doi":"10.1039/d5nr00723b","DOIUrl":"https://doi.org/10.1039/d5nr00723b","url":null,"abstract":"The ever-increasing demand for sustainable solutions for eliminating environmental pollutants, solar energy harvesting, water splitting, etc., has led to the design and development of novel materials to achieve the desired result. In this regard, structurally and electronically integrated (SEI) BiVO4-TiO2 (SEI-BVT) with abundant heterojunctions have emerged as promising entity for efficient charge separation, which in turn enhanced artificial photosynthesis (APS) activity. The present work adopted a unique synthetic strategy by SILAR to fabricate SEI-BVT from ionic precursors (Bi3+ and VO43-) into the pores of TiO2, exhibiting benchmark APS efficiency than the individual components. This preparation results in approximately 180 trillions of uniformly distributed heterojunctions in 1 mg/cm2 of SEI-BVT photoanode material. Charge carriers in SEI-BVT and BiVO4 are similar; however, the recombination is highly hindered when SEI-BVT heterojunctions are formed in the former. Our earlier work demonstrated 31-38% solar-to-fuel efficiency (STFE) with BiVO4-TiO2 for APS in the presence of Pd-nanocube co-catalyst. The emphasis of the current manuscript is to explore the dynamics of the light-induced processes in these heterojunctions to understand the interfacial charge transfer process. Femtosecond transient absorption (TA) spectroscopy has been employed to monitor the excited state dynamics. Our results show that new trap states have evolved under light illumination, which are significantly long-lived and hinder charge recombination, and consequently enhancing STFE. A significantly large number of charge carriers exhibit a lifetime of >> 6 ns with visible light photons, at least up to 720 nm, which is higher than the band-gap absorption onset at 490 nm for SEI-BVT than bulk BiVO4. The rate of formation of charge carriers are significantly affected in the heterojunctions.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"64 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857223","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}
Atomically precise gold nanoclusters (AuNCs) are nanomolecular species with unique optoelectronic properties, both at the individual and assembled levels. Here, we demonstrate the precise ligand engineer-ing of AuNCs, enabling the controlled grafting of single-stranded oligonucleotides onto atomically defined AuNCs of different sizes (Au₁₈ and Au₂₅), which emit in the NIR-I (600–800 nm) and NIR-II (900–1300 nm) spectral windows, respectively. These biofunctionalized AuNCs, which can be considered nanomo-lecular building blocks, were thoroughly characterized using complementary analytical and optical tech-niques, including absorption and fluorescence spectroscopy, mass spectrometry, liquid chromatography, and gel electrophoresis. Through selective DNA hybridization, we successfully assembled AuNC dimers, trimers, and AuNC-dye nanosystems with high reproducibility and yield. This work lays the foundation for the design of AuNC-DNA superstructures with potential applications in optoelectronics, sensing, and nanomedicine.
{"title":"Designing Atomically Precise Gold Nanocluster Architectures with DNA-Guided Self-Assembly and Biofunctionalization Approaches","authors":"Abdallah ALHALABI, Christine Saint-Pierre, Elisabetta Boeri Erba, Pierre-henri Elchinger, Harinderbir KAUR, Didier Gasparutto, Xavier Le Guevel","doi":"10.1039/d5nr00905g","DOIUrl":"https://doi.org/10.1039/d5nr00905g","url":null,"abstract":"Atomically precise gold nanoclusters (AuNCs) are nanomolecular species with unique optoelectronic properties, both at the individual and assembled levels. Here, we demonstrate the precise ligand engineer-ing of AuNCs, enabling the controlled grafting of single-stranded oligonucleotides onto atomically defined AuNCs of different sizes (Au₁₈ and Au₂₅), which emit in the NIR-I (600–800 nm) and NIR-II (900–1300 nm) spectral windows, respectively. These biofunctionalized AuNCs, which can be considered nanomo-lecular building blocks, were thoroughly characterized using complementary analytical and optical tech-niques, including absorption and fluorescence spectroscopy, mass spectrometry, liquid chromatography, and gel electrophoresis. Through selective DNA hybridization, we successfully assembled AuNC dimers, trimers, and AuNC-dye nanosystems with high reproducibility and yield. This work lays the foundation for the design of AuNC-DNA superstructures with potential applications in optoelectronics, sensing, and nanomedicine.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"11 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853343","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}
Muhammad Irfan Qadir, Gustavo Javier Chacón Rosales, Camila Ebersol, Gabriel Abarca, Pedro Henrique Ferreira Matias, Heibbe C. B. Oliveira, Renato Borges Pontes, Rafael Stieler, Jairton Dupont
Thermodynamic stability of nanoparticles necessitates the use of stabilizing agents to provide steric and electronic protection. Nevertheless, their activity and selectivity remain suboptimal under moderate reaction conditions. In this study, we present high-performance Pd nanoparticles with a distinctive Pd-phosphate surface that is akin to a “quasi nano-frustrated Lewis pair” architecture, where electron donation from ionophilic phosphine species enhances the electron density of the Pd NPs. Solid state NMR and XPS analyses disclose the strong coordination of phosphine species on Pd NPs. DFT calculations reveals the geometry and conformations of the coordinated phosphine, where one of the phenyl rings is nearly parallel to the facets of the nanoparticle, such interaction occurs through the six carbon atoms of the π system. We investigate the structure-activity relationships (SARs) exhibited by these NPs in the efficient semi-hydrogenation of phenylacetylene (TOF = 3.85 s⁻¹), 2-cyclohexen-1-one (TOF = 0.8 s⁻¹), and 1,3-cyclohexadiene (TOF = 12.82 s⁻¹) at 40°C and 2-4 bar H₂ in BMIm.NTF2 ionic liquid. The higher activity and selectivity are related to; (i) the formation of ionic liquid cages/membrane around NPs akin to catalytic active membranes that tune the diffusion affinity of reactants, reactive intermediates, and products to catalytic active sites, and (ii) the hindrance provided by the Pd-P bonds.
{"title":"Surface palladium nanoparticles in ionic liquids modified with phosphorus ligands for enhanced catalytic semi-hydrogenation","authors":"Muhammad Irfan Qadir, Gustavo Javier Chacón Rosales, Camila Ebersol, Gabriel Abarca, Pedro Henrique Ferreira Matias, Heibbe C. B. Oliveira, Renato Borges Pontes, Rafael Stieler, Jairton Dupont","doi":"10.1039/d5nr00789e","DOIUrl":"https://doi.org/10.1039/d5nr00789e","url":null,"abstract":"Thermodynamic stability of nanoparticles necessitates the use of stabilizing agents to provide steric and electronic protection. Nevertheless, their activity and selectivity remain suboptimal under moderate reaction conditions. In this study, we present high-performance Pd nanoparticles with a distinctive Pd-phosphate surface that is akin to a “quasi nano-frustrated Lewis pair” architecture, where electron donation from ionophilic phosphine species enhances the electron density of the Pd NPs. Solid state NMR and XPS analyses disclose the strong coordination of phosphine species on Pd NPs. DFT calculations reveals the geometry and conformations of the coordinated phosphine, where one of the phenyl rings is nearly parallel to the facets of the nanoparticle, such interaction occurs through the six carbon atoms of the π system. We investigate the structure-activity relationships (SARs) exhibited by these NPs in the efficient semi-hydrogenation of phenylacetylene (TOF = 3.85 s⁻¹), 2-cyclohexen-1-one (TOF = 0.8 s⁻¹), and 1,3-cyclohexadiene (TOF = 12.82 s⁻¹) at 40°C and 2-4 bar H₂ in BMIm.NTF2 ionic liquid. The higher activity and selectivity are related to; (i) the formation of ionic liquid cages/membrane around NPs akin to catalytic active membranes that tune the diffusion affinity of reactants, reactive intermediates, and products to catalytic active sites, and (ii) the hindrance provided by the Pd-P bonds.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"1 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853303","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}
Jiahao Li, Yushuang Wei, Qin Lai, Xiangyang Li, Yu Wang, Xun Wang, Yinghua Chen, Hong Liu, Kai Yang, Bing Yuan
Resveratrol (RSV) is a natural polyphenolic compound known for its antioxidant, anti-inflammatory, anticancer, and cardioprotective properties. However, the limited water solubility and poor bioavailability of RSV significantly hinder its applications in the food and pharmaceutical industries. To address these challenges, we developed a facile, scalable, and specifically organic-solvent-free method to prepare highly stable and concentrated RSV nanoformulations. By utilizing an ethoxylated hydrogenated castor oil (EHCO) aqueous solution, we successfully dissolve RSV in water at concentrations up to 30 mg/mL. This RSV solution can subsequently be incorporated with hydrogenated lecithin S10 to formulate stable lipid nanoparticles (e.g., 140–180 nm). The entire process is performed under heating and stirring, eliminating the need for organic solvents and ensuring simplicity and high reproducibility. The resulting RSV-CO60@S10 nanoformulations exhibit relatively high encapsulation efficiency (with final RSV concentrations up to 30 mg/mL), long-term stability (exceeding 6 months), preserved antioxidant activity, and effective cellular internalization capabilities that alleviate oxidative stress. Additionally, these nanoparticles exhibit promising therapeutic efficacy on atopic dermatitis in mice. These findings offer valuable insights into the potential utilization of RSV across diverse applications.
{"title":"Efficacy of a resveratrol nanoformulation prepared by a facile solvent-free method","authors":"Jiahao Li, Yushuang Wei, Qin Lai, Xiangyang Li, Yu Wang, Xun Wang, Yinghua Chen, Hong Liu, Kai Yang, Bing Yuan","doi":"10.1039/d5nr00691k","DOIUrl":"https://doi.org/10.1039/d5nr00691k","url":null,"abstract":"Resveratrol (RSV) is a natural polyphenolic compound known for its antioxidant, anti-inflammatory, anticancer, and cardioprotective properties. However, the limited water solubility and poor bioavailability of RSV significantly hinder its applications in the food and pharmaceutical industries. To address these challenges, we developed a facile, scalable, and specifically organic-solvent-free method to prepare highly stable and concentrated RSV nanoformulations. By utilizing an ethoxylated hydrogenated castor oil (EHCO) aqueous solution, we successfully dissolve RSV in water at concentrations up to 30 mg/mL. This RSV solution can subsequently be incorporated with hydrogenated lecithin S10 to formulate stable lipid nanoparticles (e.g., 140–180 nm). The entire process is performed under heating and stirring, eliminating the need for organic solvents and ensuring simplicity and high reproducibility. The resulting RSV-CO60@S10 nanoformulations exhibit relatively high encapsulation efficiency (with final RSV concentrations up to 30 mg/mL), long-term stability (exceeding 6 months), preserved antioxidant activity, and effective cellular internalization capabilities that alleviate oxidative stress. Additionally, these nanoparticles exhibit promising therapeutic efficacy on atopic dermatitis in mice. These findings offer valuable insights into the potential utilization of RSV across diverse applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"33 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853514","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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