Cong Hong Nhat Nguyen, Dinh Truong Nguyen, Trung Hieu Le, Lam Son Le, Nga Hang Thi Phan, Thi-Thao-Van Nguyen, Nguyen Van Tiep, Ekaterina Korneeva, Anh Tuyen Luu, My Uyen Dao, Minh Tuan Nguyen Dinh, Chinh Chien Nguyen
Electrolytic glucose oxidation has garnered great interest in energy-saving hydrogen generation. However, high charge-transfer resistance and inefficient active centers have been recognized as the primary issues for poor electrochemical performance. In this study, for the first time, we offer a novel defect-rich CeO x /β-Ni(OH)2 composite nanosheet-decorated Ni foam electrocatalyst (denoted as Ce@NF-GA), synthesized via a unique hydrothermal approach under the co-participation of glycerol and acetic acid. The employed characterizations unveil a close CeO x /β-Ni(OH)2 interfacial contact and numerous surface defects (e.g., oxygen vacancies). Such features significantly result in a significant enhancement in the electrocatalytic glucose oxidation reaction. Indeed, the obtained Ce@NF-GA catalyst demands a low potential of 1.31 V to reach a current density of 10 mA cm-2. Additionally, Ce@NF-GA exhibited a high charge transportation capability and stability for 3 consecutive working cycles, corresponding to an outstanding Faradaic efficiency of ∼100% toward hydrogen production. The exploration of such novel material discloses a potential pathway for the utilization of Ce-based electrocatalysts for the energy-saving hydrogen production-coupled glucose oxidation reaction.
电解葡萄糖氧化在节能制氢方面引起了极大的兴趣。然而,高电荷转移电阻和低效的活性中心已被认为是电化学性能差的主要问题。在这项研究中,我们首次提供了一种新颖的富含缺陷的CeO x /β-Ni(OH)2复合纳米片装饰镍泡沫电催化剂(表示为Ce@NF-GA),该催化剂是在甘油和乙酸的共同参与下通过独特的水热方法合成的。所采用的表征揭示了紧密的CeO x /β-Ni(OH)2界面接触和许多表面缺陷(例如氧空位)。这些特性显著地增强了电催化葡萄糖氧化反应。事实上,获得的Ce@NF-GA催化剂需要1.31 V的低电位才能达到10 mA cm-2的电流密度。此外,Ce@NF-GA在连续3个工作循环中表现出高电荷传输能力和稳定性,对应于对氢气生产的出色的法拉第效率~ 100%。这种新型材料的探索为ce基电催化剂在节能制氢-偶联葡萄糖氧化反应中的应用开辟了一条潜在途径。
{"title":"CeO <sub><i>x</i></sub> -anchored β-Ni(OH)<sub>2</sub> nanosheets onto nickel foam for efficient energy-saving hydrogen production <i>via</i> an electrocatalytic glucose oxidation reaction.","authors":"Cong Hong Nhat Nguyen, Dinh Truong Nguyen, Trung Hieu Le, Lam Son Le, Nga Hang Thi Phan, Thi-Thao-Van Nguyen, Nguyen Van Tiep, Ekaterina Korneeva, Anh Tuyen Luu, My Uyen Dao, Minh Tuan Nguyen Dinh, Chinh Chien Nguyen","doi":"10.1039/d4na00892h","DOIUrl":"https://doi.org/10.1039/d4na00892h","url":null,"abstract":"<p><p>Electrolytic glucose oxidation has garnered great interest in energy-saving hydrogen generation. However, high charge-transfer resistance and inefficient active centers have been recognized as the primary issues for poor electrochemical performance. In this study, for the first time, we offer a novel defect-rich CeO <sub><i>x</i></sub> /β-Ni(OH)<sub>2</sub> composite nanosheet-decorated Ni foam electrocatalyst (denoted as Ce@NF-GA), synthesized <i>via</i> a unique hydrothermal approach under the co-participation of glycerol and acetic acid. The employed characterizations unveil a close CeO <sub><i>x</i></sub> /β-Ni(OH)<sub>2</sub> interfacial contact and numerous surface defects (<i>e.g.</i>, oxygen vacancies). Such features significantly result in a significant enhancement in the electrocatalytic glucose oxidation reaction. Indeed, the obtained Ce@NF-GA catalyst demands a low potential of 1.31 V to reach a current density of 10 mA cm<sup>-2</sup>. Additionally, Ce@NF-GA exhibited a high charge transportation capability and stability for 3 consecutive working cycles, corresponding to an outstanding Faradaic efficiency of ∼100% toward hydrogen production. The exploration of such novel material discloses a potential pathway for the utilization of Ce-based electrocatalysts for the energy-saving hydrogen production-coupled glucose oxidation reaction.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11694650/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142932257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Siavash Iravani, Atefeh Zarepour, Arezoo Khosravi and Ali Zarrabi
Recently, interest has surged in the environmental and biomedical applications of two-dimensional transition metal borides, commonly referred to as MBenes. These materials have emerged as promising candidates for energy storage devices, such as batteries and supercapacitors. Additionally, MBenes have shown remarkable catalytic activity due to their high surface area and tunable electronic properties. They exhibit significant promise in various catalytic applications, particularly in nitrogen reduction reactions (NRRs), electrocatalytic conversion of nitrogen oxides, and several electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Notably, MBenes have shown great potential in water treatment and pollutant removal applications, such as desalination and water purification. Their high water permeability, ion selectivity, and excellent stability make them suitable for efficient water treatment processes. On the other hand, MBenes are emerging as versatile materials with significant potential in various biomedical applications, particularly in biosensing, cancer therapy, and the treatment of neurodegenerative diseases. However, several challenges hinder their practical implementation in biomedical and environmental fields. One significant issue is the scalability of synthesis methods; producing MBenes in large quantities while maintaining high purity and uniformity is often complex and costly. Moreover, the stability of MBenes and their composites under different environmental and biological conditions raises concerns, as they may undergo degradation or lose their functional properties over time, which could limit their long-term effectiveness. Additionally, there is a need for comprehensive toxicity assessments to ensure the safety of MBenes in biomedical applications, particularly when interacting with human tissues or biological systems. This review aims to systematically investigate the environmental and biomedical applications of MBenes and their composites, emphasizing their unique characteristics and potential roles in addressing pressing global challenges. Furthermore, the review will identify and discuss the existing challenges and limitations in the operational performance of MBenes and their composites, providing a critical assessment of their current state in various applications.
{"title":"Environmental and biomedical applications of 2D transition metal borides (MBenes): recent advancements","authors":"Siavash Iravani, Atefeh Zarepour, Arezoo Khosravi and Ali Zarrabi","doi":"10.1039/D4NA00867G","DOIUrl":"10.1039/D4NA00867G","url":null,"abstract":"<p >Recently, interest has surged in the environmental and biomedical applications of two-dimensional transition metal borides, commonly referred to as MBenes. These materials have emerged as promising candidates for energy storage devices, such as batteries and supercapacitors. Additionally, MBenes have shown remarkable catalytic activity due to their high surface area and tunable electronic properties. They exhibit significant promise in various catalytic applications, particularly in nitrogen reduction reactions (NRRs), electrocatalytic conversion of nitrogen oxides, and several electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Notably, MBenes have shown great potential in water treatment and pollutant removal applications, such as desalination and water purification. Their high water permeability, ion selectivity, and excellent stability make them suitable for efficient water treatment processes. On the other hand, MBenes are emerging as versatile materials with significant potential in various biomedical applications, particularly in biosensing, cancer therapy, and the treatment of neurodegenerative diseases. However, several challenges hinder their practical implementation in biomedical and environmental fields. One significant issue is the scalability of synthesis methods; producing MBenes in large quantities while maintaining high purity and uniformity is often complex and costly. Moreover, the stability of MBenes and their composites under different environmental and biological conditions raises concerns, as they may undergo degradation or lose their functional properties over time, which could limit their long-term effectiveness. Additionally, there is a need for comprehensive toxicity assessments to ensure the safety of MBenes in biomedical applications, particularly when interacting with human tissues or biological systems. This review aims to systematically investigate the environmental and biomedical applications of MBenes and their composites, emphasizing their unique characteristics and potential roles in addressing pressing global challenges. Furthermore, the review will identify and discuss the existing challenges and limitations in the operational performance of MBenes and their composites, providing a critical assessment of their current state in various applications.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 3","pages":" 670-699"},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11656904/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. T. T. Huong, N. T. Sa, N. T. M. Thuy, P. V. Hao, N. H. Thao, N. T. Hien and N. X. Ca
This article studies the synthesis, as well as the structural, vibrational, and optical properties of Eu3+-doped ZnO quantum dots (QDs) and investigates the energy transfer mechanism from the ZnO host to Eu3+ ions using Reisfeld's approximation. Eu3+-doped ZnO QDs at varying concentrations (0–7%) were successfully prepared using a wet chemical method. The successful doping of Eu3+ ions into the ZnO host lattice, as well as the composition and valence states of the elements present in the sample, were confirmed through X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. XRD results demonstrated the crystalline nature of the ZnO QDs, revealing their wurtzite (WZ) structure with no secondary phases. XPS analysis provided further confirmation of the presence of Eu3+ ions within the ZnO host, with clear signals corresponding to the Zn, O, and Eu elements. The valence states of Eu were verified as trivalent (Eu3+), confirming the successful doping of Eu3+ ions, as evidenced by the characteristic Eu 3d peaks in the XPS spectra. Raman spectroscopy (RS) was employed to analyze the vibrational modes, revealing shifts in ZnO lattice vibrations due to Eu3+ incorporation, indicating strong coupling between Eu3+ ions and the ZnO host. Optical properties were studied using UV-Vis absorption, photoluminescence (PL) spectroscopy, and PL decay spectroscopy, showing a significant enhancement of red emission, attributed to the 5D0 → 7F2 transition of Eu3+ ions under UV excitation. Using Judd–Ofelt (JO) analysis, the intensity parameters (Ω2, Ω4, Ω6) were derived, providing insights into the asymmetry of the Eu3+ ion's local environment and the radiative transition probabilities. Energy transfer processes between the ZnO host and Eu3+ dopants were examined, showing efficient sensitization of Eu3+ through excitation of the ZnO host, with an optimal Eu3+ doping level maximizing luminescence. Eu3+-doped ZnO QDs, which emit in the visible light region and are non-toxic, have great potential for applications in photonic devices, light-emitting diodes, and bioimaging.
{"title":"Eu3+-doped ZnO quantum dots: structure, vibration characteristics, optical properties, and energy transfer process","authors":"T. T. T. Huong, N. T. Sa, N. T. M. Thuy, P. V. Hao, N. H. Thao, N. T. Hien and N. X. Ca","doi":"10.1039/D4NA00858H","DOIUrl":"10.1039/D4NA00858H","url":null,"abstract":"<p >This article studies the synthesis, as well as the structural, vibrational, and optical properties of Eu<small><sup>3+</sup></small>-doped ZnO quantum dots (QDs) and investigates the energy transfer mechanism from the ZnO host to Eu<small><sup>3+</sup></small> ions using Reisfeld's approximation. Eu<small><sup>3+</sup></small>-doped ZnO QDs at varying concentrations (0–7%) were successfully prepared using a wet chemical method. The successful doping of Eu<small><sup>3+</sup></small> ions into the ZnO host lattice, as well as the composition and valence states of the elements present in the sample, were confirmed through X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. XRD results demonstrated the crystalline nature of the ZnO QDs, revealing their wurtzite (WZ) structure with no secondary phases. XPS analysis provided further confirmation of the presence of Eu<small><sup>3+</sup></small> ions within the ZnO host, with clear signals corresponding to the Zn, O, and Eu elements. The valence states of Eu were verified as trivalent (Eu<small><sup>3+</sup></small>), confirming the successful doping of Eu<small><sup>3+</sup></small> ions, as evidenced by the characteristic Eu 3d peaks in the XPS spectra. Raman spectroscopy (RS) was employed to analyze the vibrational modes, revealing shifts in ZnO lattice vibrations due to Eu<small><sup>3+</sup></small> incorporation, indicating strong coupling between Eu<small><sup>3+</sup></small> ions and the ZnO host. Optical properties were studied using UV-Vis absorption, photoluminescence (PL) spectroscopy, and PL decay spectroscopy, showing a significant enhancement of red emission, attributed to the <small><sup>5</sup></small>D<small><sub>0</sub></small> → <small><sup>7</sup></small>F<small><sub>2</sub></small> transition of Eu<small><sup>3+</sup></small> ions under UV excitation. Using Judd–Ofelt (JO) analysis, the intensity parameters (<em>Ω</em><small><sub>2</sub></small>, <em>Ω</em><small><sub>4</sub></small>, <em>Ω</em><small><sub>6</sub></small>) were derived, providing insights into the asymmetry of the Eu<small><sup>3+</sup></small> ion's local environment and the radiative transition probabilities. Energy transfer processes between the ZnO host and Eu<small><sup>3+</sup></small> dopants were examined, showing efficient sensitization of Eu<small><sup>3+</sup></small> through excitation of the ZnO host, with an optimal Eu<small><sup>3+</sup></small> doping level maximizing luminescence. Eu<small><sup>3+</sup></small>-doped ZnO QDs, which emit in the visible light region and are non-toxic, have great potential for applications in photonic devices, light-emitting diodes, and bioimaging.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 3","pages":" 909-921"},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11664421/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, we present a comprehensive investigation into the electronic properties and contact behavior of γ-GeSe/Ga2SSe heterostructures using first-principles calculations. Two stacking configurations, γ-GeSe/SGa2Se and γ-GeSe/SeGa2S, are explored, both exhibiting semiconducting behavior with type-II and type-I band alignments, respectively. Notably, our results show that the band alignment transition in these heterostructures can occur spontaneously by simply altering the stacking configuration, eliminating the need for external factors. Additionally, the electronic properties of these heterostructures are highly tunable with an applied electric field, further enabling transitions between type-I and type-II alignments. Specifically, a positive electric field induces a transition from type-II to type-I alignment in the γ-GeSe/SGa2Se heterostructure, while a negative field drives the reverse transition in the γ-GeSe/SeGa2S heterostructure. Our findings underscore the potential of γ-GeSe/Ga2SSe heterostructures for diverse applications, where the tunability of electronic properties is crucial for optimizing device performance.
{"title":"Stacking-dependent and electric field-driven electronic properties and band alignment transitions in γ-GeSe/Ga2SSe heterostructures: a first-principles study","authors":"Nguyen V. Vinh, D. V. Lu and K. D. Pham","doi":"10.1039/D4NA00830H","DOIUrl":"10.1039/D4NA00830H","url":null,"abstract":"<p >In this work, we present a comprehensive investigation into the electronic properties and contact behavior of γ-GeSe/Ga<small><sub>2</sub></small>SSe heterostructures using first-principles calculations. Two stacking configurations, γ-GeSe/SGa<small><sub>2</sub></small>Se and γ-GeSe/SeGa<small><sub>2</sub></small>S, are explored, both exhibiting semiconducting behavior with type-II and type-I band alignments, respectively. Notably, our results show that the band alignment transition in these heterostructures can occur spontaneously by simply altering the stacking configuration, eliminating the need for external factors. Additionally, the electronic properties of these heterostructures are highly tunable with an applied electric field, further enabling transitions between type-I and type-II alignments. Specifically, a positive electric field induces a transition from type-II to type-I alignment in the γ-GeSe/SGa<small><sub>2</sub></small>Se heterostructure, while a negative field drives the reverse transition in the γ-GeSe/SeGa<small><sub>2</sub></small>S heterostructure. Our findings underscore the potential of γ-GeSe/Ga<small><sub>2</sub></small>SSe heterostructures for diverse applications, where the tunability of electronic properties is crucial for optimizing device performance.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 3","pages":" 790-799"},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11635631/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142829438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gilded wall paintings such as those in Petra-Jordan undergo deterioration processes such as delamination and loss of the gold layer. The aim of this work is to produce a functioning long-lasting adhesive that compensates for binder and gold loss while stabilising the gold layer. Polymer-stabilised gold nanoparticles (AuNPs) as a conservation material for gilded heritage paintings (Nano Gold Gel (NGG)) were synthesised using two facile and affordable synthesis approaches. AuNPs enhance the stability of the adhesive polymer over time and introduce mass conservation to the gold layer. Two natural polymers and one synthetic polymer, frequently used in conservation as adhesives, were used as reducing agents and stabilisers for the nanoparticles. The chemical alteration of the polymers and the Au-polymer interaction at the molecular level were investigated with FTIR spectroscopy, while the chemical environment of gold was investigated with X-ray absorption spectroscopy (XANES/EXAFS). The synthesized NGG was applied on the replica samples to reattach the gold layer to its support. Characterisation results indicate that the formation of AuNPs stabilised by the three polymers did not alter the chemical structure of the polymers. The applied NGG successfully achieved re-adhesion and exhibited appropriate optical and chemical properties for use as a conservation material.
{"title":"A new conservation material for gold in heritage wall paintings: polymer-stabilized nanogold gels (NGGs).","authors":"Maram Na'es, Lars Lühl, Birgit Kanngießer","doi":"10.1039/d4na00877d","DOIUrl":"10.1039/d4na00877d","url":null,"abstract":"<p><p>Gilded wall paintings such as those in Petra-Jordan undergo deterioration processes such as delamination and loss of the gold layer. The aim of this work is to produce a functioning long-lasting adhesive that compensates for binder and gold loss while stabilising the gold layer. Polymer-stabilised gold nanoparticles (AuNPs) as a conservation material for gilded heritage paintings (Nano Gold Gel (NGG)) were synthesised using two facile and affordable synthesis approaches. AuNPs enhance the stability of the adhesive polymer over time and introduce mass conservation to the gold layer. Two natural polymers and one synthetic polymer, frequently used in conservation as adhesives, were used as reducing agents and stabilisers for the nanoparticles. The chemical alteration of the polymers and the Au-polymer interaction at the molecular level were investigated with FTIR spectroscopy, while the chemical environment of gold was investigated with X-ray absorption spectroscopy (XANES/EXAFS). The synthesized NGG was applied on the replica samples to reattach the gold layer to its support. Characterisation results indicate that the formation of AuNPs stabilised by the three polymers did not alter the chemical structure of the polymers. The applied NGG successfully achieved re-adhesion and exhibited appropriate optical and chemical properties for use as a conservation material.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11667577/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142895791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A magnetic-biopolymer composite of carboxymethyl cellulose (CMC), designated as Fe3O4@CMC, was synthesized featuring remarkable stability and an active surface with a green biosynthetic method. This composite was engineered to serve as a substrate for stabilizing silver nanoparticles (Ag NPs) with enhanced functional properties. The catalytic efficacy of the nanocatalyst, incorporating Ag NPs at concentrations of 3%, 7%, and 10%, was evaluated for the reduction of the toxic compound 4-nitrophenol to the beneficial 4-aminophenol. Among the tested configurations, the formulation containing 10% silver nanoparticles, in conjunction with Euphorbia plant extract as a bioreducing agent, exhibited the highest reduction efficiency and favorable reaction kinetics, rendering it the optimal choice. The apparent rate constant (Kapp) was assessed by fine-tuning the catalyst parameters, while the reaction mechanism was further elucidated by adjusting the concentrations of NaBH4 and 4-nitrophenol. Notably, the catalyst demonstrated good stability over five consecutive reduction cycles and could be easily retrieved from the reaction mixture using an external magnet.
{"title":"Controlled bioreduction of silver ions to nanosized particles on a porous magnetic-biopolymer of carboxymethyl cellulose, Fe<sub>3</sub>O<sub>4</sub>/CMC-Ag NPs, serving as a sustainable nanocatalyst.","authors":"Mojtaba Azizi, Mahdi Jafari, Sadegh Rostamnia","doi":"10.1039/d4na00866a","DOIUrl":"10.1039/d4na00866a","url":null,"abstract":"<p><p>A magnetic-biopolymer composite of carboxymethyl cellulose (CMC), designated as Fe<sub>3</sub>O<sub>4</sub>@CMC, was synthesized featuring remarkable stability and an active surface with a green biosynthetic method. This composite was engineered to serve as a substrate for stabilizing silver nanoparticles (Ag NPs) with enhanced functional properties. The catalytic efficacy of the nanocatalyst, incorporating Ag NPs at concentrations of 3%, 7%, and 10%, was evaluated for the reduction of the toxic compound 4-nitrophenol to the beneficial 4-aminophenol. Among the tested configurations, the formulation containing 10% silver nanoparticles, in conjunction with Euphorbia plant extract as a bioreducing agent, exhibited the highest reduction efficiency and favorable reaction kinetics, rendering it the optimal choice. The apparent rate constant (<i>K</i> <sub>app</sub>) was assessed by fine-tuning the catalyst parameters, while the reaction mechanism was further elucidated by adjusting the concentrations of NaBH<sub>4</sub> and 4-nitrophenol. Notably, the catalyst demonstrated good stability over five consecutive reduction cycles and could be easily retrieved from the reaction mixture using an external magnet.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11726232/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142984172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carbon dot (CD)-based theranostics offers a promising approach for breast cancer (BC) treatment, integrating ultra-localized chemo-photothermal effects to address chemoresistance and enhance therapeutic control. Herein, the development of a targeted theranostic nanosystem for the chemo-phototherapy of breast cancer is described. Fluorescent and biocompatible CDs were passivated with 1,2-bis(3-aminopropylamino)ethane (bAPAE) and decorated with the targeting agent folic acid (FA) through conjugation with a PEG spacer. This yielded CDs-bAPAE-PEG-FA, hydrophilic nanocarriers (12 nm) with a high drug interaction surface. Fluorescence analysis confirmed their utility as bioimaging probes, while NIR light stimulation demonstrated good photothermal conversion. Doxorubicin-loaded CDs (CDs-bAPAE-PEG-FA/Dox) showed an on-demand NIR-boosted drug release, increased by 50% after localized NIR exposure, while in vitro studies on BC cells MCF-7 and MDA-MB-231 demonstrated NIR-enhanced antitumor efficacy, providing the opportunity to realize selective and remote-controlled synergistic therapy. Furthermore, uptake investigations highlighted the imaging potential of CDs and efficient internalization of doxorubicin, emphasizing FA's role in receptor-mediated specific targeting. Data suggest that CDs-bAPAE-PEG-FA/Dox could perform efficient image-guided and selective BC therapy, enhancing the therapeutic outcomes.
基于碳点(CD)的治疗为乳腺癌(BC)的治疗提供了一种很有前途的方法,结合超局部化疗-光热效应来解决化疗耐药问题并加强治疗控制。本文描述了一种靶向治疗纳米系统用于乳腺癌的化学光疗。采用1,2-双(3-氨基丙基氨基)乙烷(bAPAE)钝化荧光CDs,并通过PEG间隔剂偶联靶向剂叶酸(FA)修饰CDs。这产生了CDs-bAPAE-PEG-FA,一种具有高药物相互作用表面的亲水纳米载体(12 nm)。荧光分析证实了它们作为生物成像探针的实用性,而近红外光刺激显示出良好的光热转换。多柔比星负载cd (cd - bapae - peg - fa /Dox)显示出按需NIR促进的药物释放,在局部NIR暴露后增加50%,而在BC细胞MCF-7和MDA-MB-231的体外研究显示NIR增强的抗肿瘤功效,为实现选择性和远程控制的协同治疗提供了机会。此外,摄取研究强调了CDs的成像潜力和阿霉素的有效内化,强调了FA在受体介导的特异性靶向中的作用。数据表明,CDs-bAPAE-PEG-FA/Dox可以进行有效的图像引导和选择性BC治疗,提高治疗效果。
{"title":"Targeted NIR-triggered doxorubicin release using carbon dots–poly(ethylene glycol)–folate conjugates for breast cancer treatment†","authors":"Paola Varvarà, Nicolò Mauro and Gennara Cavallaro","doi":"10.1039/D4NA00834K","DOIUrl":"10.1039/D4NA00834K","url":null,"abstract":"<p >Carbon dot (CD)-based theranostics offers a promising approach for breast cancer (BC) treatment, integrating ultra-localized chemo-photothermal effects to address chemoresistance and enhance therapeutic control. Herein, the development of a targeted theranostic nanosystem for the chemo-phototherapy of breast cancer is described. Fluorescent and biocompatible CDs were passivated with 1,2-bis(3-aminopropylamino)ethane (bAPAE) and decorated with the targeting agent folic acid (FA) through conjugation with a PEG spacer. This yielded CDs-bAPAE-PEG-FA, hydrophilic nanocarriers (12 nm) with a high drug interaction surface. Fluorescence analysis confirmed their utility as bioimaging probes, while NIR light stimulation demonstrated good photothermal conversion. Doxorubicin-loaded CDs (CDs-bAPAE-PEG-FA/Dox) showed an on-demand NIR-boosted drug release, increased by 50% after localized NIR exposure, while <em>in vitro</em> studies on BC cells MCF-7 and MDA-MB-231 demonstrated NIR-enhanced antitumor efficacy, providing the opportunity to realize selective and remote-controlled synergistic therapy. Furthermore, uptake investigations highlighted the imaging potential of CDs and efficient internalization of doxorubicin, emphasizing FA's role in receptor-mediated specific targeting. Data suggest that CDs-bAPAE-PEG-FA/Dox could perform efficient image-guided and selective BC therapy, enhancing the therapeutic outcomes.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 3","pages":" 862-875"},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11660423/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142877465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shasvat Rathod, Monika Snowdon, Matthew Peres Tino and Peng Peng
Flexible and wearable devices play a pivotal role in the realm of smart portable electronics due to their diverse applications in healthcare monitoring, soft robotics, human–machine interfaces, and artificial intelligence. Nonetheless, the extensive integration of intelligent wearable sensors into mass production faces challenges within a resource-limited environment, necessitating low-cost manufacturing, high reliability, stability, and multi-functionality. In this study, a cost-effective fiber laser direct writing method (fLDW) was illustrated to create highly responsive and robust flexible sensors. These sensors integrate laser-induced graphene (LiG) with mixed metal oxides on a flexible polyimide film. fLDW simplifies the synthesis of graphene, functionalization of carbon structures into graphene oxides and reduced graphene oxides, and deposition of metal-oxide nanoparticles within a single experimental laser writing setup. The preparation and surface modification of dense oxygenated graphene networks and semiconducting metal oxide nanoparticles (CuOx, ZnOx, FeOx) enables rapid fabrication of LiG/MOx composite sensors with the ability to detect and differentiate various stimuli, including visible light, UV light, temperature, humidity, and magnetic fluxes. Further, this in situ customizability of fLDW-produced sensors allows for tunable sensitivity, response time, recovery time, and selectivity. The normalized current gain of resistive LiG/MOx sensors can be controlled between −2.7 to 3.5, with response times ranging from 0.02 to 15 s, and recovery times from 0.04 to 6 s. Furthermore, the programmable properties showed great endurance after 200 days in air and extended bend cycles. Collectively, these LiG/MOx sensors stand as a testament to the effectiveness of fLDW in economically mass-producing flexible and wearable electronic devices to meet the explicit demands of the Internet of Things.
柔性可穿戴设备在医疗保健监测、软机器人、人机界面和人工智能等领域有着广泛的应用,因此在智能便携式电子产品领域发挥着举足轻重的作用。然而,在资源有限的环境中,将智能可穿戴传感器广泛集成到大规模生产中面临着挑战,需要低成本制造、高可靠性、稳定性和多功能性。在本研究中,我们展示了一种具有成本效益的光纤激光直写方法(fLDW),用于制造反应灵敏、坚固耐用的柔性传感器。这些传感器在柔性聚酰亚胺薄膜上集成了激光诱导石墨烯(LiG)和混合金属氧化物。fLDW 简化了石墨烯的合成、将碳结构功能化为石墨烯氧化物和还原石墨烯氧化物以及在单一激光写入实验装置中沉积金属氧化物纳米颗粒的过程。高密度含氧石墨烯网络和半导体金属氧化物纳米颗粒(CuO x、ZnO x、FeO x)的制备和表面改性使 LiG/MO x 复合传感器得以快速制造,并能检测和区分各种刺激,包括可见光、紫外线、温度、湿度和磁通量。此外,fLDW 生产的传感器的这种原位定制性允许对灵敏度、响应时间、恢复时间和选择性进行调整。电阻式 LiG/MO x 传感器的归一化电流增益可控制在 -2.7 到 3.5 之间,响应时间为 0.02 到 15 秒,恢复时间为 0.04 到 6 秒。总之,这些 LiG/MO x 传感器证明了 fLDW 在经济地大规模生产柔性可穿戴电子设备以满足物联网明确需求方面的有效性。
{"title":"Laser writing of metal-oxide doped graphene films for tunable sensor applications†","authors":"Shasvat Rathod, Monika Snowdon, Matthew Peres Tino and Peng Peng","doi":"10.1039/D4NA00463A","DOIUrl":"10.1039/D4NA00463A","url":null,"abstract":"<p >Flexible and wearable devices play a pivotal role in the realm of smart portable electronics due to their diverse applications in healthcare monitoring, soft robotics, human–machine interfaces, and artificial intelligence. Nonetheless, the extensive integration of intelligent wearable sensors into mass production faces challenges within a resource-limited environment, necessitating low-cost manufacturing, high reliability, stability, and multi-functionality. In this study, a cost-effective fiber laser direct writing method (fLDW) was illustrated to create highly responsive and robust flexible sensors. These sensors integrate laser-induced graphene (LiG) with mixed metal oxides on a flexible polyimide film. fLDW simplifies the synthesis of graphene, functionalization of carbon structures into graphene oxides and reduced graphene oxides, and deposition of metal-oxide nanoparticles within a single experimental laser writing setup. The preparation and surface modification of dense oxygenated graphene networks and semiconducting metal oxide nanoparticles (CuO<small><sub><em>x</em></sub></small>, ZnO<small><sub><em>x</em></sub></small>, FeO<small><sub><em>x</em></sub></small>) enables rapid fabrication of LiG/MO<small><sub><em>x</em></sub></small> composite sensors with the ability to detect and differentiate various stimuli, including visible light, UV light, temperature, humidity, and magnetic fluxes. Further, this <em>in situ</em> customizability of fLDW-produced sensors allows for tunable sensitivity, response time, recovery time, and selectivity. The normalized current gain of resistive LiG/MO<small><sub><em>x</em></sub></small> sensors can be controlled between −2.7 to 3.5, with response times ranging from 0.02 to 15 s, and recovery times from 0.04 to 6 s. Furthermore, the programmable properties showed great endurance after 200 days in air and extended bend cycles. Collectively, these LiG/MO<small><sub><em>x</em></sub></small> sensors stand as a testament to the effectiveness of fLDW in economically mass-producing flexible and wearable electronic devices to meet the explicit demands of the Internet of Things.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 3","pages":" 766-783"},"PeriodicalIF":4.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11632522/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142818500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhaolong Li, Kaiming Peng, Nannan Ji, Wenlong Zhang, Wenrou Tian and Zhenfei Gao
The interaction of microwave radiation with carbon-based materials induces rapid, instantaneous heating. When combined with the plasma excitation capabilities of microwaves, this property presents novel avenues for synthesizing carbon-based materials that require high temperatures and catalytic activity. This review investigates the response of carbon-based materials to microwave radiation, analyzes the dielectric loss mechanism responsible for heat generation, and details the microwave plasma excitation mechanisms employed in the synthesis and processing of carbon-based materials. Furthermore, the structure of microwave reactors is discussed, followed by a discussion of their diverse applications in both laboratory and industrial settings. Lastly, the review addresses the challenges associated with the practical implementation of microwave technology and explores future development prospects, with a particular focus on the application of microwaves in carbon-based material synthesis.
{"title":"Advanced mechanisms and applications of microwave-assisted synthesis of carbon-based materials: a brief review","authors":"Zhaolong Li, Kaiming Peng, Nannan Ji, Wenlong Zhang, Wenrou Tian and Zhenfei Gao","doi":"10.1039/D4NA00701H","DOIUrl":"10.1039/D4NA00701H","url":null,"abstract":"<p >The interaction of microwave radiation with carbon-based materials induces rapid, instantaneous heating. When combined with the plasma excitation capabilities of microwaves, this property presents novel avenues for synthesizing carbon-based materials that require high temperatures and catalytic activity. This review investigates the response of carbon-based materials to microwave radiation, analyzes the dielectric loss mechanism responsible for heat generation, and details the microwave plasma excitation mechanisms employed in the synthesis and processing of carbon-based materials. Furthermore, the structure of microwave reactors is discussed, followed by a discussion of their diverse applications in both laboratory and industrial settings. Lastly, the review addresses the challenges associated with the practical implementation of microwave technology and explores future development prospects, with a particular focus on the application of microwaves in carbon-based material synthesis.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 2","pages":" 419-432"},"PeriodicalIF":4.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11629176/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142813818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuuki Sugawara, Yuto Nakase, Gopinathan M Anilkumar, Keigo Kamata and Takeo Yamaguchi
Metal phosphate-type compounds have been utilized in diverse applications, and their distinctive chemical properties have recently opened avenues for their use as catalysts. Metal phosphates have previously demonstrated significant electrocatalytic activity for the anodic oxygen evolution reaction (OER) in electrochemical water splitting. However, the critical factors influencing OER electrocatalysis on Ni-based phosphates have been insufficiently explored. We herein demonstrate nickel (Ni)-based phosphates—monoclinic Ni3(PO4)2, monoclinic Ni2P2O7, and monoclinic Ni2P4O12—as exemplary materials exhibiting outstanding OER activity in alkaline media. These Ni-based phosphates exhibit superior OER overpotentials compared to conventional Ni-based oxides (NiO) and phosphides (Ni2P). Additionally, their OER-specific activity surpasses that of the rare metal-based benchmark, IrO2, and previously reported state-of-the-art crystalline electrocatalysts comprising nonprecious metals. Long-term durability tests show that Ni3(PO4)2 maintains its OER activity even after 1000 repeated potential cycles while retaining its elemental composition and Raman spectrum. To understand the excellent OER activities of Ni-based phosphates, the atomic configurations within their crystals are examined. Remarkably, a clear correlation between Ni–O bond length and OER overpotentials is observed in both Ni-based phosphates and NiO, i.e., shorter Ni–O bond lengths are highly beneficial for the OER. Density functional theory (DFT) calculations revealed that the outstanding OER activities of Ni-based phosphates are facilitated by their favorable electronic orbitals, which strengthen the Ni–O bond and improve the adsorption of OER intermediates on Ni sites. This mechanism is substantiated by DFT calculations employing surface slab models, where the adsorption of OER intermediates on the surface of Ni-based phosphates is more energetically favorable than on the surface of NiO. Hence, Ni-based phosphates are promising OER electrocatalysts, and this study provides important guidelines to further improve Ni-based electrocatalysts.
{"title":"Oxygen evolution activity of nickel-based phosphates and effects of their electronic orbitals†","authors":"Yuuki Sugawara, Yuto Nakase, Gopinathan M Anilkumar, Keigo Kamata and Takeo Yamaguchi","doi":"10.1039/D4NA00794H","DOIUrl":"10.1039/D4NA00794H","url":null,"abstract":"<p >Metal phosphate-type compounds have been utilized in diverse applications, and their distinctive chemical properties have recently opened avenues for their use as catalysts. Metal phosphates have previously demonstrated significant electrocatalytic activity for the anodic oxygen evolution reaction (OER) in electrochemical water splitting. However, the critical factors influencing OER electrocatalysis on Ni-based phosphates have been insufficiently explored. We herein demonstrate nickel (Ni)-based phosphates—monoclinic Ni<small><sub>3</sub></small>(PO<small><sub>4</sub></small>)<small><sub>2</sub></small>, monoclinic Ni<small><sub>2</sub></small>P<small><sub>2</sub></small>O<small><sub>7</sub></small>, and monoclinic Ni<small><sub>2</sub></small>P<small><sub>4</sub></small>O<small><sub>12</sub></small>—as exemplary materials exhibiting outstanding OER activity in alkaline media. These Ni-based phosphates exhibit superior OER overpotentials compared to conventional Ni-based oxides (NiO) and phosphides (Ni<small><sub>2</sub></small>P). Additionally, their OER-specific activity surpasses that of the rare metal-based benchmark, IrO<small><sub>2</sub></small>, and previously reported state-of-the-art crystalline electrocatalysts comprising nonprecious metals. Long-term durability tests show that Ni<small><sub>3</sub></small>(PO<small><sub>4</sub></small>)<small><sub>2</sub></small> maintains its OER activity even after 1000 repeated potential cycles while retaining its elemental composition and Raman spectrum. To understand the excellent OER activities of Ni-based phosphates, the atomic configurations within their crystals are examined. Remarkably, a clear correlation between Ni–O bond length and OER overpotentials is observed in both Ni-based phosphates and NiO, <em>i.e.</em>, shorter Ni–O bond lengths are highly beneficial for the OER. Density functional theory (DFT) calculations revealed that the outstanding OER activities of Ni-based phosphates are facilitated by their favorable electronic orbitals, which strengthen the Ni–O bond and improve the adsorption of OER intermediates on Ni sites. This mechanism is substantiated by DFT calculations employing surface slab models, where the adsorption of OER intermediates on the surface of Ni-based phosphates is more energetically favorable than on the surface of NiO. Hence, Ni-based phosphates are promising OER electrocatalysts, and this study provides important guidelines to further improve Ni-based electrocatalysts.</p>","PeriodicalId":18806,"journal":{"name":"Nanoscale Advances","volume":" 2","pages":" 456-466"},"PeriodicalIF":4.6,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11626464/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142807060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}