Harishchandra S Nishad, Shobhnath P Gupta, Aruna Ivaturi, Pravin Walke
The present study aims to probe morphological tuning of hydrated tungsten oxide (WO3-x·H2O) nanostructures and their electrochemical performance investigation for energy storage in supercapacitors. The WO3-x·H2O nanostructures have prepared via a single-step wet chemical method. Further, the morphological transition of WO3-x·H2O nanostructures from nanosheet-assembled nanoflowers (W1) to nanoribbons (W2) as a result of regulating the reaction time has achieved without disturbing the orthorhombic crystal structure. The morphological transformation from W1 to W2 exhibited decrease in crystallinity and other physical properties significantly affecting electrochemical behavior. Electrochemical investigations emphasized that W1 has higher specific capacitance of 70 F g-1 than W2 of 37 F g-1 at 1 A g-1. Moreover, an Aqueous Asymmetric Supercapacitor (AASC) device fabricated using WO3-x·H2O as the negative electrode. The device exhibited a specific capacitance of 40 F g-1 at 0.5 A g-1 with an energy density of 12.5 W h kg-1 and a power density of 3784 W kg-1. Additionally, it demonstrated excellent cycling stability with 97 % capacitance retention over 5000 cycles. These findings highlight the potential of morphology-controlled WO3-x·H2O nanostructures for advanced energy storage applications.
本研究旨在探讨水合氧化钨（WO3-x·H2O）纳米结构的形态调谐及其在超级电容器储能中的电化学性能研究。采用单步湿化学法制备了WO3-x·H2O纳米结构。此外，通过调节反应时间，WO3-x·H2O纳米结构从纳米片组装的纳米花（W1）转变为纳米带（W2），而不影响正交晶型结构。从W1到W2的形态转变显示出结晶度和其他物理性质的降低，显著影响了电化学行为。电化学研究强调W1在1 A g-1下比电容为70 F -1，高于W2的37 F -1。此外，以WO3-x·H2O为负极制备了水不对称超级电容器（AASC）器件。该器件在0.5 a g-1下的比电容为40 F -1，能量密度为12.5 W h kg-1，功率密度为3784 W kg-1。此外，它还表现出优异的循环稳定性，在5000次循环中保持97%的电容。这些发现突出了形态控制的WO3-x·H2O纳米结构在先进储能应用中的潜力。
{"title":"Probing the Influence of Morphological Transformation on the Electrochemical Properties of Hydrated Tungsten Oxide (WO3-x.H2O) for High-Rate Aqueous Asymmetric Supercapacitor","authors":"Harishchandra S Nishad, Shobhnath P Gupta, Aruna Ivaturi, Pravin Walke","doi":"10.1039/d5nr01658d","DOIUrl":"https://doi.org/10.1039/d5nr01658d","url":null,"abstract":"The present study aims to probe morphological tuning of hydrated tungsten oxide (WO3-x·H2O) nanostructures and their electrochemical performance investigation for energy storage in supercapacitors. The WO3-x·H2O nanostructures have prepared via a single-step wet chemical method. Further, the morphological transition of WO3-x·H2O nanostructures from nanosheet-assembled nanoflowers (W1) to nanoribbons (W2) as a result of regulating the reaction time has achieved without disturbing the orthorhombic crystal structure. The morphological transformation from W1 to W2 exhibited decrease in crystallinity and other physical properties significantly affecting electrochemical behavior. Electrochemical investigations emphasized that W1 has higher specific capacitance of 70 F g-1 than W2 of 37 F g-1 at 1 A g-1. Moreover, an Aqueous Asymmetric Supercapacitor (AASC) device fabricated using WO3-x·H2O as the negative electrode. The device exhibited a specific capacitance of 40 F g-1 at 0.5 A g-1 with an energy density of 12.5 W h kg-1 and a power density of 3784 W kg-1. Additionally, it demonstrated excellent cycling stability with 97 % capacitance retention over 5000 cycles. These findings highlight the potential of morphology-controlled WO3-x·H2O nanostructures for advanced energy storage applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"7 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652656","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}
Sangsoo Shin, Huijeong Jeong, Jiwoo Kim, Byeong Jin Kim, Jin Hong Lee, Sungyup Jung, Jaegeun Lee
Gas-phase decomposition of carbon precursor is a critical yet not fully understood step in the catalytic chemical vapor deposition growth of carbon nanotubes (CNTs). Here, we present a systematic investigation of how the thermal decomposition of C2H4 influences CNT growth. Using a custom-designed two-zone reactor with independently controlled preheating (decomposition) and CNT growth zones, we decoupled the effects of gas-phase decomposition from the growth temperature. A standard synthesis condition was first established using Bayesian Optimization, with the CNT growth zone temperature (Tg) fixed at 700 °C. CNTs were then synthesized at preheating zone temperature (Tp) of 500, 600, 700, 800, and 900 °C, while maintaining Tg at 700 °C under the standard condition. Carbon yield and IG/ID remained stable at 500, 600, and 700 °C but showed significant changes at 800 and 900 °C. To elucidate these variations, we analyzed the gas-phase composition at various temperatures using micro-GC. Significant change in the gas-phase composition was observed at above 700 °C, correlating with changes in carbon yield and crystallinity. Based on these results, we propose a mechanism by which differences in gas chemistry lead to changes in the carbon yield and the IG/ID ratio. This study provides valuable insight into the role of gas-phase decomposition in CNT growth and highlights the potential of tuning gas-phase chemistry for controlled growth of CNTs.
{"title":"Influence of Ethylene Thermal Decomposition on Carbon Nanotube Growth: Insights from a Two-Zone Reactor Study","authors":"Sangsoo Shin, Huijeong Jeong, Jiwoo Kim, Byeong Jin Kim, Jin Hong Lee, Sungyup Jung, Jaegeun Lee","doi":"10.1039/d5nr02143j","DOIUrl":"https://doi.org/10.1039/d5nr02143j","url":null,"abstract":"Gas-phase decomposition of carbon precursor is a critical yet not fully understood step in the catalytic chemical vapor deposition growth of carbon nanotubes (CNTs). Here, we present a systematic investigation of how the thermal decomposition of C2H4 influences CNT growth. Using a custom-designed two-zone reactor with independently controlled preheating (decomposition) and CNT growth zones, we decoupled the effects of gas-phase decomposition from the growth temperature. A standard synthesis condition was first established using Bayesian Optimization, with the CNT growth zone temperature (Tg) fixed at 700 °C. CNTs were then synthesized at preheating zone temperature (Tp) of 500, 600, 700, 800, and 900 °C, while maintaining Tg at 700 °C under the standard condition. Carbon yield and IG/ID remained stable at 500, 600, and 700 °C but showed significant changes at 800 and 900 °C. To elucidate these variations, we analyzed the gas-phase composition at various temperatures using micro-GC. Significant change in the gas-phase composition was observed at above 700 °C, correlating with changes in carbon yield and crystallinity. Based on these results, we propose a mechanism by which differences in gas chemistry lead to changes in the carbon yield and the IG/ID ratio. This study provides valuable insight into the role of gas-phase decomposition in CNT growth and highlights the potential of tuning gas-phase chemistry for controlled growth of CNTs.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652622","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}
Guanjun Liu, Yan Liu, Meng Zhang, Danyang Zhao, Ping Liu, Lu Wang, Lizhi Li, Meiling Yan
The rise of hydrogen energy places stringent demands on the mechanical strength and thermal conductivity of polyamide 6 (PA6) liners used in hydrogen storage tanks. However, the presence of weak interfaces in PA6 composites significantly hinders the efficient transfer of the intrinsic mechanical and thermal conductivity properties of the reinforcing phases. In this work, hydroxyl-functionalized carbon nanotubes (CNT-OH) were covalently grafted onto graphene oxide (GO) to construct a hybrid nanofiller, which was subsequently surface-functionalized with hexamethylene diisocyanate (HDI), yielding a reactive nanofiller (fGO+CNT-OH+HDI) rich in isocyanate groups. This functionalized nanofiller served as an activator during the in situ anionic ring-opening polymerization of ε-caprolactam, enabling the fabrication of PA6 composites with strengthened nanofiller/nanofiller and nanofiller/matrix interfacial interactions. Owing to the synergistic reinforcement from the hybrid nanofiller and its uniform dispersion driven by in situ polymerization, the resulting composite containing only 0.2 wt% fGO+CNT-OH+HDI exhibited outstanding mechanical performance, with a 36.3% increase in tensile strength and an exceptional elongation at break of 130.86%. In addition, the thermal conductivity was improved by 46.3%. This interfacial engineering strategy provides a promising pathway toward the development of high-performance liner materials for reliable and safe hydrogen energy applications.
{"title":"Covalently bonded graphene oxide-carbon nanotube hybrid nanofillers for achieving high-performance polyamide 6 composites with superior mechanical properties and thermal conductivity","authors":"Guanjun Liu, Yan Liu, Meng Zhang, Danyang Zhao, Ping Liu, Lu Wang, Lizhi Li, Meiling Yan","doi":"10.1039/d5nr02405f","DOIUrl":"https://doi.org/10.1039/d5nr02405f","url":null,"abstract":"The rise of hydrogen energy places stringent demands on the mechanical strength and thermal conductivity of polyamide 6 (PA6) liners used in hydrogen storage tanks. However, the presence of weak interfaces in PA6 composites significantly hinders the efficient transfer of the intrinsic mechanical and thermal conductivity properties of the reinforcing phases. In this work, hydroxyl-functionalized carbon nanotubes (CNT-OH) were covalently grafted onto graphene oxide (GO) to construct a hybrid nanofiller, which was subsequently surface-functionalized with hexamethylene diisocyanate (HDI), yielding a reactive nanofiller (fGO+CNT-OH+HDI) rich in isocyanate groups. This functionalized nanofiller served as an activator during the in situ anionic ring-opening polymerization of ε-caprolactam, enabling the fabrication of PA6 composites with strengthened nanofiller/nanofiller and nanofiller/matrix interfacial interactions. Owing to the synergistic reinforcement from the hybrid nanofiller and its uniform dispersion driven by in situ polymerization, the resulting composite containing only 0.2 wt% fGO+CNT-OH+HDI exhibited outstanding mechanical performance, with a 36.3% increase in tensile strength and an exceptional elongation at break of 130.86%. In addition, the thermal conductivity was improved by 46.3%. This interfacial engineering strategy provides a promising pathway toward the development of high-performance liner materials for reliable and safe hydrogen energy applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"9 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652654","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}
Aurora Rizzo, Ermelinda M. S. Maçôas, Tayebeh Ameri, Renjie Chen, Raghvendra Singh Yadav
A graphical abstract is available for this content
此内容的图形摘要可用
{"title":"Introduction to the Nanoscale and Nanoscale Advances joint themed collection: Synthesis, physical properties and applications of advanced nanocrystalline materials","authors":"Aurora Rizzo, Ermelinda M. S. Maçôas, Tayebeh Ameri, Renjie Chen, Raghvendra Singh Yadav","doi":"10.1039/d5nr90127h","DOIUrl":"https://doi.org/10.1039/d5nr90127h","url":null,"abstract":"A graphical abstract is available for this content","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"24 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652657","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}
Kamoliddin Mehmonov, Aziza Ergasheva, S. Mehdi Vaez Allaei, Erik C. Neyts, Umedjon Khalilov
The growing demand for high-modulus, high-strength, and lightweight materials has spurred interest in carbynes; however, their catalytic synthesis mechanisms remain largely unexplored. In this study, we use reactive molecular dynamics simulations to investigate the catalytic synthesis of endohedral carbynes within double-walled carbon nanotubes, comparing the distinct roles of Ni and Pt catalysts. Our findings indicate that Ni catalysts are more effective, promoting a stable, self-propagating chain growth mechanism with the potential for extreme lengths. In contrast, Pt catalysts exhibit higher energy barriers, resulting in fragmented, metallic carbyne-like structures; a finding which provides a mechanistic explanation for experimentally observed metalated carbynes. This study not only identifies an efficient catalyst for carbyne synthesis but also suggests a new route to novel encapsulated materials, advancing the rational design of nanocarbons for demanding applications.ich facilitates carbon feedstock attachment. In contrast, Pt catalysts present higher energy barriers, leading to fragmented, metallic carbyne-like structures due to less-controlled carbon bonding. This study identifies an efficient catalyst for efficient carbyne synthesis and offers valuable insights into the distinct mechanisms of carbyne formation, paving the way for developing advanced nanocarbon materials for demanding applications.
{"title":"Driving Catalytic Carbyne Formation within Endohedral DWCNTs: The role of Ni vs Pt","authors":"Kamoliddin Mehmonov, Aziza Ergasheva, S. Mehdi Vaez Allaei, Erik C. Neyts, Umedjon Khalilov","doi":"10.1039/d5nr01919b","DOIUrl":"https://doi.org/10.1039/d5nr01919b","url":null,"abstract":"The growing demand for high-modulus, high-strength, and lightweight materials has spurred interest in carbynes; however, their catalytic synthesis mechanisms remain largely unexplored. In this study, we use reactive molecular dynamics simulations to investigate the catalytic synthesis of endohedral carbynes within double-walled carbon nanotubes, comparing the distinct roles of Ni and Pt catalysts. Our findings indicate that Ni catalysts are more effective, promoting a stable, self-propagating chain growth mechanism with the potential for extreme lengths. In contrast, Pt catalysts exhibit higher energy barriers, resulting in fragmented, metallic carbyne-like structures; a finding which provides a mechanistic explanation for experimentally observed metalated carbynes. This study not only identifies an efficient catalyst for carbyne synthesis but also suggests a new route to novel encapsulated materials, advancing the rational design of nanocarbons for demanding applications.ich facilitates carbon feedstock attachment. In contrast, Pt catalysts present higher energy barriers, leading to fragmented, metallic carbyne-like structures due to less-controlled carbon bonding. This study identifies an efficient catalyst for efficient carbyne synthesis and offers valuable insights into the distinct mechanisms of carbyne formation, paving the way for developing advanced nanocarbon materials for demanding applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"52 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652659","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}
Alexei V. Prokhorov, Anton S. Chernikov, Gleb Celikov, Alexander V. Shesterikov, Mikhail Yu. Gubin, Ivan S. Kazantsev, Alexander V. Syuy, Artem A. Pelyovin, Anton A. Popov, Olga A. Shalygina, Kirill S. Khorkov, Dmitry A. Kochuev, Dmitry S. Kitkov, Aleksey V Arsenin, Valentyn Volkov
Laser synthesis of nanoparticles in a liquid has already opened a new page in the history of development of the in-test-tube methods for fabrication of nanomaterials. A fascinating continuation of the topic is the synthesis of quantum-sized nanostructures with complex topology/morphology, when the initial materials for their fabrication are strongly anisotropic van der Waals (vdW) and 2D materials. Two aspects determine the photoluminescent properties of such nanostructures at once: the dependence of the emission wavelength is determined by the size quantization effects as in conventional semiconductors, while the photoluminescence intensity is resulted from the dependence of relative positions of the energy bands on the number of layers in nanostructure. In this work, the progress on the development of straightforward laser and auxiliary ultrasonic methods for the synthesis of quantum-sized photoluminescent nanostructures from WS2 powder is reported. By combining various solvents and different treatment times, the possibility of tuning the photoluminescence spectra of the obtained 2D WS2 flakes and quantum dots over a wide spectral range is demonstrated.
{"title":"Tunable photoluminescence on 2D WS2 quantum dots","authors":"Alexei V. Prokhorov, Anton S. Chernikov, Gleb Celikov, Alexander V. Shesterikov, Mikhail Yu. Gubin, Ivan S. Kazantsev, Alexander V. Syuy, Artem A. Pelyovin, Anton A. Popov, Olga A. Shalygina, Kirill S. Khorkov, Dmitry A. Kochuev, Dmitry S. Kitkov, Aleksey V Arsenin, Valentyn Volkov","doi":"10.1039/d5nr01924a","DOIUrl":"https://doi.org/10.1039/d5nr01924a","url":null,"abstract":"Laser synthesis of nanoparticles in a liquid has already opened a new page in the history of development of the in-test-tube methods for fabrication of nanomaterials. A fascinating continuation of the topic is the synthesis of quantum-sized nanostructures with complex topology/morphology, when the initial materials for their fabrication are strongly anisotropic van der Waals (vdW) and 2D materials. Two aspects determine the photoluminescent properties of such nanostructures at once: the dependence of the emission wavelength is determined by the size quantization effects as in conventional semiconductors, while the photoluminescence intensity is resulted from the dependence of relative positions of the energy bands on the number of layers in nanostructure. In this work, the progress on the development of straightforward laser and auxiliary ultrasonic methods for the synthesis of quantum-sized photoluminescent nanostructures from WS<small><sub>2</sub></small> powder is reported. By combining various solvents and different treatment times, the possibility of tuning the photoluminescence spectra of the obtained 2D WS<small><sub>2</sub></small> flakes and quantum dots over a wide spectral range is demonstrated.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"53 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652658","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}
Hady Ahmed Ibrahim Hamza, Veronica Schifano, Giorgia Colciago, Marco Aldo Ortenzi, Anna Maria Ferretti, Gabriele Di Carlo, Maria Vittoria Dozzi, riccardo vago, Francesca Tessore, Daniela Maggioni
The development of effective drug delivery systems represents a significant advancement in cancer treatment. Anisotropic, natural, and cost-effective nano-vectors, such as Halloysite nanotubes (HNT), can be utilized for this purpose. In this study, we loaded the HNT with the apolar photosensitizers (PS) 5,10,15,20-tetrakis(perfluorophenyl)porphyrin (H2TPPF20) and its Zn(II) complex (ZnTPPF20) to produce singlet oxygen for photodynamic therapy (PDT). The loading was achieved through repeated vacuum/N2 cycles using both pristine HNT and HNT modified with tetradecylphosphonic acid (HNT-TDP) to promote the uptake of the lipophilic PS in the inner lumen. To slow the release of PS from HNT, the nanotubes were treated with dextrin. The ability of the free base and Zn perfluorinated porphyrins to produce singlet oxygen (1O2) was confirmed by irradiating the samples with a low-power visible LED emitter (23 mW/cm2), showing a 1O2 quantum yield of 22 % and 34 %, respectively, in ethanol. The characterization of the nanocomposite is not trivial, so we employed a wide range of analytical techniques to investigate the material thoroughly, particularly the location of PS within the HNT. All nano-hybrids were analyzed by Attenuated Total Reflectance Infrared (ATR-FTIR), Diffuse Reflectance (DRS) and solid-state emission spectroscopies. Thermogravimetric analysis (TGA) was used to determine the loading capacity of HNT. To better understand the interactions between the PS and the nanoclay, we compared all the loaded HNT samples with mechanically mixed HNT and solid H2TPPF20 or ZnTPPF20 samples, where the interaction with the HNT inner lumen is assumed to be absent. We measured the release kinetics using UV-vis spectroscopy, observing a delayed release of the PS. Finally, we firstly studied the cellular uptake of pristine HNT and a loaded sample (HNT-TDP-H2TPPF20-dextrin) by confocal microscopy by three distinct tumor cell lines. The cytotoxicity on PC3, 5637 and UMUC3 cells was then assessed as reduction of cell viability both on cells left in the dark and irradiated with a visible light emitting LED (1.3 mW/cm2), ascertaining the ability to induce cell death especially after light administration.
{"title":"Halloysite nanotubes as a vector for hydrophobic perfluorinated porphyrin-based photosensitizers for singlet oxygen generation","authors":"Hady Ahmed Ibrahim Hamza, Veronica Schifano, Giorgia Colciago, Marco Aldo Ortenzi, Anna Maria Ferretti, Gabriele Di Carlo, Maria Vittoria Dozzi, riccardo vago, Francesca Tessore, Daniela Maggioni","doi":"10.1039/d5nr01078k","DOIUrl":"https://doi.org/10.1039/d5nr01078k","url":null,"abstract":"The development of effective drug delivery systems represents a significant advancement in cancer treatment. Anisotropic, natural, and cost-effective nano-vectors, such as Halloysite nanotubes (HNT), can be utilized for this purpose. In this study, we loaded the HNT with the apolar photosensitizers (PS) 5,10,15,20-tetrakis(perfluorophenyl)porphyrin (H<small><sub>2</sub></small>TPPF<small><sub>20</sub></small>) and its Zn(II) complex (ZnTPPF<small><sub>20</sub></small>) to produce singlet oxygen for photodynamic therapy (PDT). The loading was achieved through repeated vacuum/N<small><sub>2</sub></small> cycles using both pristine HNT and HNT modified with tetradecylphosphonic acid (HNT-TDP) to promote the uptake of the lipophilic PS in the inner lumen. To slow the release of PS from HNT, the nanotubes were treated with dextrin. The ability of the free base and Zn perfluorinated porphyrins to produce singlet oxygen (<small><sup>1</sup></small>O<small><sub>2</sub></small>) was confirmed by irradiating the samples with a low-power visible LED emitter (23 mW/cm<small><sup>2</sup></small>), showing a <small><sup>1</sup></small>O<small><sub>2</sub></small> quantum yield of 22 % and 34 %, respectively, in ethanol. The characterization of the nanocomposite is not trivial, so we employed a wide range of analytical techniques to investigate the material thoroughly, particularly the location of PS within the HNT. All nano-hybrids were analyzed by Attenuated Total Reflectance Infrared (ATR-FTIR), Diffuse Reflectance (DRS) and solid-state emission spectroscopies. Thermogravimetric analysis (TGA) was used to determine the loading capacity of HNT. To better understand the interactions between the PS and the nanoclay, we compared all the loaded HNT samples with mechanically mixed HNT and solid H<small><sub>2</sub></small>TPPF<small><sub>20</sub></small> or ZnTPPF<small><sub>20</sub></small> samples, where the interaction with the HNT inner lumen is assumed to be absent. We measured the release kinetics using UV-vis spectroscopy, observing a delayed release of the PS. Finally, we firstly studied the cellular uptake of pristine HNT and a loaded sample (HNT-TDP-H<small><sub>2</sub></small>TPPF<small><sub>20</sub></small>-dextrin) by confocal microscopy by three distinct tumor cell lines. The cytotoxicity on PC3, 5637 and UMUC3 cells was then assessed as reduction of cell viability both on cells left in the dark and irradiated with a visible light emitting LED (1.3 mW/cm<small><sup>2</sup></small>), ascertaining the ability to induce cell death especially after light administration.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"96 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144645257","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}
Alejandro Casillas-Rubio, khouloud Hamraoui, Diego Méndez González, Marco Laurenti, Jorge Rubio Retama, Oscar G. Calderon, Sonia Melle
Accurate and reliable quantification of Förster Resonance Energy Transfer (FRET) is essential for the development of sensitive upconverting nanoparticle (UCNP)-based biosensors. While lifetime-based FRET measurements are generally considered robust, excitation conditions can significantly bias observed efficiencies. Here, we investigate how excitation pulse width and power influence lifetimederived FRET efficiency in core-shell β-NaYF4:Yb0.2@NaYF4:Yb0.2,Er0.02 UCNPs functionalized with Cy3 dyes. Time-resolved upconversion luminescence (UCL) measurements reveal that apparent FRET efficiencies decrease with increasing excitation pulse duration and power. These variations stem from excitation-induced changes in the UCL lifetime, arising from the complex dynamics that accompany the upconversion emission process. A dynamic rate equation model reproduces the experimental trends, confirming that excitation parameters alter emissive state kinetics and thus bias lifetime-based FRET measurements. Our findings identify excitation conditions as a hidden variable in UCNP-FRET experiments and underscore the need for standardized measurement protocols.
{"title":"Influence of Excitation Pulse Duration on the Efficiency of Upconversion Nanoparticle-Based FRET","authors":"Alejandro Casillas-Rubio, khouloud Hamraoui, Diego Méndez González, Marco Laurenti, Jorge Rubio Retama, Oscar G. Calderon, Sonia Melle","doi":"10.1039/d5nr01779c","DOIUrl":"https://doi.org/10.1039/d5nr01779c","url":null,"abstract":"Accurate and reliable quantification of Förster Resonance Energy Transfer (FRET) is essential for the development of sensitive upconverting nanoparticle (UCNP)-based biosensors. While lifetime-based FRET measurements are generally considered robust, excitation conditions can significantly bias observed efficiencies. Here, we investigate how excitation pulse width and power influence lifetimederived FRET efficiency in core-shell β-NaYF4:Yb0.2@NaYF4:Yb0.2,Er0.02 UCNPs functionalized with Cy3 dyes. Time-resolved upconversion luminescence (UCL) measurements reveal that apparent FRET efficiencies decrease with increasing excitation pulse duration and power. These variations stem from excitation-induced changes in the UCL lifetime, arising from the complex dynamics that accompany the upconversion emission process. A dynamic rate equation model reproduces the experimental trends, confirming that excitation parameters alter emissive state kinetics and thus bias lifetime-based FRET measurements. Our findings identify excitation conditions as a hidden variable in UCNP-FRET experiments and underscore the need for standardized measurement protocols.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"95 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144645402","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}
Ana Barragán, Goudappagouda, Manish Kumar, Diego Soler-Polo, Elena Pérez-Elvira, Andrés Pinar Solé, Alba García-Frutos, Zhiqiang Gao, Koen Lauwaet, José M. Gallego, Rodolfo Miranda, David Écija, Pavel Jelínek, Akimitsu Narita, José I. Urgel
Open-shell nanographenes (NGs), also known as molecular π-magnets, have recently garnered attention for their potential in spintronics and quantum computing. Tailoring of such NGs at the atomic level allows the control of their magnetic interactions. We report here the on-surface synthesis of a dibenzo-fused rhomboidal NG with predominant zigzag edges featuring an open-shell (antiferromagnetic) character and a high value of magnetic exchange coupling (MEC) on Au(111) surfaces. Scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc-AFM) confirm its chemical structure. Scanning tunneling spectroscopy (STS) measurements, complemented by state-of-the-art theoretical calculations, reveal the open-shell character of the NG, observed as singlet−triplet inelastic excitations. Furthermore, molecular chains consisting of these NGs were fabricated with tunable periodicities through the functionalization of the precursor, showing the absence of MEC between adjacent units, which provides deeper insights into the behavior of open-shell systems and preservation of individual magnetic entities within π-conjugated structures.
{"title":"Strong magnetic exchange coupling of a dibenzo-fused rhomboidal nanographene and its homocoupling with tunable periodicities on a metal surface","authors":"Ana Barragán, Goudappagouda, Manish Kumar, Diego Soler-Polo, Elena Pérez-Elvira, Andrés Pinar Solé, Alba García-Frutos, Zhiqiang Gao, Koen Lauwaet, José M. Gallego, Rodolfo Miranda, David Écija, Pavel Jelínek, Akimitsu Narita, José I. Urgel","doi":"10.1039/d5nr00957j","DOIUrl":"https://doi.org/10.1039/d5nr00957j","url":null,"abstract":"Open-shell nanographenes (NGs), also known as molecular π-magnets, have recently garnered attention for their potential in spintronics and quantum computing. Tailoring of such NGs at the atomic level allows the control of their magnetic interactions. We report here the on-surface synthesis of a dibenzo-fused rhomboidal NG with predominant zigzag edges featuring an open-shell (antiferromagnetic) character and a high value of magnetic exchange coupling (MEC) on Au(111) surfaces. Scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc-AFM) confirm its chemical structure. Scanning tunneling spectroscopy (STS) measurements, complemented by state-of-the-art theoretical calculations, reveal the open-shell character of the NG, observed as singlet−triplet inelastic excitations. Furthermore, molecular chains consisting of these NGs were fabricated with tunable periodicities through the functionalization of the precursor, showing the absence of MEC between adjacent units, which provides deeper insights into the behavior of open-shell systems and preservation of individual magnetic entities within π-conjugated structures.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"12 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144645255","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 grain size is an important structural parameter in polycrystalline materials contributing to the strength of the material and the ability to achieve a superplastic forming capability. Grain refinement is especially important because small grains lead to stronger materials and they provide more opportunities for attaining superplastic flow. Traditionally, the grain size was modified through the use of various thermo-mechanical treatments but this had a significant limitation because it was not possible to produce materials with grain sizes smaller than a few micrometers. The situation has changed over the last forty years with the demonstration that much smaller grain sizes may be produced by processing through the application of severe plastic deformation (SPD) where a high strain is imposed without causing any significant change in the overall dimensions of the sample. This report summarizes the principles of the main SPD processing techniques and then demonstrates the significance of producing submicrometer grain sizes.
{"title":"Recent advances in using severe plastic deformation for the processing of nanomaterials","authors":"Terence G Langdon","doi":"10.1039/d5nr01886b","DOIUrl":"https://doi.org/10.1039/d5nr01886b","url":null,"abstract":"The grain size is an important structural parameter in polycrystalline materials contributing to the strength of the material and the ability to achieve a superplastic forming capability. Grain refinement is especially important because small grains lead to stronger materials and they provide more opportunities for attaining superplastic flow. Traditionally, the grain size was modified through the use of various thermo-mechanical treatments but this had a significant limitation because it was not possible to produce materials with grain sizes smaller than a few micrometers. The situation has changed over the last forty years with the demonstration that much smaller grain sizes may be produced by processing through the application of severe plastic deformation (SPD) where a high strain is imposed without causing any significant change in the overall dimensions of the sample. This report summarizes the principles of the main SPD processing techniques and then demonstrates the significance of producing submicrometer grain sizes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"109 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652660","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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