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Impact of Ni Doping on the Microstructure and Mechanical Properties of TiB2 Films.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-31 DOI: 10.3390/nano15030229
Ying Wang, Xu Wang, Hailong Shang, Xiaotong Liu, Yu Qi, Xiaoben Qi, Ning Zhong

The TiB2 film exhibits exceptional hardness and chemical stability due to its unique crystal structure and robust covalent bonds, but it also demonstrates high brittleness and poor toughness, which restricts its practical applications in engineering. By appropriately incorporating metal dopants, the toughness of the ceramic matrix can be enhanced without compromising its inherent hardness. In this study, TiB2 films with different nickel contents (0-32.22 at.%) were fabricated through radio frequency magnetron sputtering. The microstructure, chemical composition, phase structure, and mechanical properties were analyzed using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and nanoindentation tester. The pure TiB2 film exhibited (0001) and (0002) peaks; however, the addition of nickel resulted in broadening of the (0001) peak and disappearance of the (0002) peak, and no crystalline nickel or other nickel-containing phases could be identified. It was found that the incorporation of nickel refines the grain structure of titanium diboride, with nickel present in an amorphous form at the boundaries of titanium diboride, thereby forming a wrapped structure. The enrichment of nickel at the grain boundary becomes more pronounced as the nickel content is further increased, which hinders the growth of TiB2 grains, resulting in the thinning of columnar crystals and formation of nanocrystalline in the film, and the coating hardness remains above 20 GPa, when the nickel content is less than 10.83 at.%. With the increase in nickel content, titanium diboride exhibited a tendency to form an amorphous structure, while nickel became increasingly enriched at the boundaries, and the coating hardness and elastic modulus decreased. The wrapped microstructure could absorb the energy generated by compressive shear stress through plastic deformation, which should be beneficial to improve the toughness of the coatings. The addition of nickel enhanced the adhesion between the film and substrate while reducing the friction coefficient of the film. Specifically, when the nickel content reached 4.26 at.%, a notable enhancement in both nanohardness and toughness was observed for nanocomposite films.

{"title":"Impact of Ni Doping on the Microstructure and Mechanical Properties of TiB<sub>2</sub> Films.","authors":"Ying Wang, Xu Wang, Hailong Shang, Xiaotong Liu, Yu Qi, Xiaoben Qi, Ning Zhong","doi":"10.3390/nano15030229","DOIUrl":"10.3390/nano15030229","url":null,"abstract":"<p><p>The TiB<sub>2</sub> film exhibits exceptional hardness and chemical stability due to its unique crystal structure and robust covalent bonds, but it also demonstrates high brittleness and poor toughness, which restricts its practical applications in engineering. By appropriately incorporating metal dopants, the toughness of the ceramic matrix can be enhanced without compromising its inherent hardness. In this study, TiB<sub>2</sub> films with different nickel contents (0-32.22 at.%) were fabricated through radio frequency magnetron sputtering. The microstructure, chemical composition, phase structure, and mechanical properties were analyzed using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and nanoindentation tester. The pure TiB<sub>2</sub> film exhibited (0001) and (0002) peaks; however, the addition of nickel resulted in broadening of the (0001) peak and disappearance of the (0002) peak, and no crystalline nickel or other nickel-containing phases could be identified. It was found that the incorporation of nickel refines the grain structure of titanium diboride, with nickel present in an amorphous form at the boundaries of titanium diboride, thereby forming a wrapped structure. The enrichment of nickel at the grain boundary becomes more pronounced as the nickel content is further increased, which hinders the growth of TiB<sub>2</sub> grains, resulting in the thinning of columnar crystals and formation of nanocrystalline in the film, and the coating hardness remains above 20 GPa, when the nickel content is less than 10.83 at.%. With the increase in nickel content, titanium diboride exhibited a tendency to form an amorphous structure, while nickel became increasingly enriched at the boundaries, and the coating hardness and elastic modulus decreased. The wrapped microstructure could absorb the energy generated by compressive shear stress through plastic deformation, which should be beneficial to improve the toughness of the coatings. The addition of nickel enhanced the adhesion between the film and substrate while reducing the friction coefficient of the film. Specifically, when the nickel content reached 4.26 at.%, a notable enhancement in both nanohardness and toughness was observed for nanocomposite films.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820867/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409242","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}
引用次数: 0
Spontaneous Emission Mediated by Moiré Hyperbolic Metasurfaces.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-31 DOI: 10.3390/nano15030228
Yuying Liu, Zhanrong Yang, Tongbiao Wang, Jianrong Yang, Tianbao Yu, Qinghua Liao

We investigate the spontaneous emission of a quantum emitter (QE) placed near the twisted hyperbolic metasurfaces (HMTSs) made of graphene strips. We demonstrate that the spontaneous emission can be enhanced distinctly due to the existence of moiré hyperbolic plasmon polaritons (HPPs) supported by the twisted HMTSs. Moreover, the spontaneous emission decay rate can be efficiently modulated by the chemical potential of graphene, the thickness of the dielectric spacer, and the twist angle between two HMTSs. The maximum spontaneous emission is achieved when topological transition occurs. The spontaneous emission will be enhanced as the thickness of the dielectric spacer increases for most cases. In particular, the twisted HMTSs make it possible to flexibly modify the spontaneous emission through the external field. The findings in this work not only extend past studies of twisted photonic structures but also have important applications in optical sensing and integrated photonics.

{"title":"Spontaneous Emission Mediated by Moiré Hyperbolic Metasurfaces.","authors":"Yuying Liu, Zhanrong Yang, Tongbiao Wang, Jianrong Yang, Tianbao Yu, Qinghua Liao","doi":"10.3390/nano15030228","DOIUrl":"10.3390/nano15030228","url":null,"abstract":"<p><p>We investigate the spontaneous emission of a quantum emitter (QE) placed near the twisted hyperbolic metasurfaces (HMTSs) made of graphene strips. We demonstrate that the spontaneous emission can be enhanced distinctly due to the existence of moiré hyperbolic plasmon polaritons (HPPs) supported by the twisted HMTSs. Moreover, the spontaneous emission decay rate can be efficiently modulated by the chemical potential of graphene, the thickness of the dielectric spacer, and the twist angle between two HMTSs. The maximum spontaneous emission is achieved when topological transition occurs. The spontaneous emission will be enhanced as the thickness of the dielectric spacer increases for most cases. In particular, the twisted HMTSs make it possible to flexibly modify the spontaneous emission through the external field. The findings in this work not only extend past studies of twisted photonic structures but also have important applications in optical sensing and integrated photonics.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820464/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409110","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}
引用次数: 0
Growth of ZnO Nanoparticles Using Microwave Hydrothermal Method-Search for Defect-Free Particles.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-31 DOI: 10.3390/nano15030230
Julita Rosowska, Jarosław Kaszewski, Marcin Krajewski, Artur Małolepszy, Bartłomiej S Witkowski, Łukasz Wachnicki, Lev-Ivan Bulyk, Piotr Sybilski, Marek Godlewski, Michał M Godlewski

This study investigated the influence of chemical reagent selection on the properties of ZnO nanoparticles synthesized using the microwave-assisted hydrothermal method to control the intensities of near-band-edge (NBE) and defect-related deep-level (DLE) emissions. Two zinc precursors-zinc nitrate and zinc chloride-along with three different precipitating agents (NaOH, KOH, and NH4OH) were used. ZnO nanoparticles from the ZnCl2 precursor exhibited two orders of magnitude higher NBE/DLE intensity ratio compared to those obtained from zinc nitrate characterized by a higher contribution from defect-related emissions. Chlorine ions in ZnO nanoparticles play a key role in passivating defects by forming V0-Cl2 complexes, quenching luminescence associated with oxygen vacancies (V0). Thermal treatment in a nitrogen atmosphere enhanced defect-related luminescence, possibly due to chlorine atom diffusion. This study highlights a successful synthesis of ZnO nanoparticles with low defect-related luminescence (DLE) achieved via the microwave-assisted hydrothermal method, a result rarely reported in the literature. The results emphasize the importance of reagent selection in controlling the morphology and optical properties, especially the defect density of ZnO nanoparticles. Optimizing these properties is crucial for biomedical applications such as bioimaging, antibacterial treatments, and photocatalysis.

{"title":"Growth of ZnO Nanoparticles Using Microwave Hydrothermal Method-Search for Defect-Free Particles.","authors":"Julita Rosowska, Jarosław Kaszewski, Marcin Krajewski, Artur Małolepszy, Bartłomiej S Witkowski, Łukasz Wachnicki, Lev-Ivan Bulyk, Piotr Sybilski, Marek Godlewski, Michał M Godlewski","doi":"10.3390/nano15030230","DOIUrl":"10.3390/nano15030230","url":null,"abstract":"<p><p>This study investigated the influence of chemical reagent selection on the properties of ZnO nanoparticles synthesized using the microwave-assisted hydrothermal method to control the intensities of near-band-edge (NBE) and defect-related deep-level (DLE) emissions. Two zinc precursors-zinc nitrate and zinc chloride-along with three different precipitating agents (NaOH, KOH, and NH<sub>4</sub>OH) were used. ZnO nanoparticles from the ZnCl<sub>2</sub> precursor exhibited two orders of magnitude higher NBE/DLE intensity ratio compared to those obtained from zinc nitrate characterized by a higher contribution from defect-related emissions. Chlorine ions in ZnO nanoparticles play a key role in passivating defects by forming V<sub>0</sub>-Cl<sub>2</sub> complexes, quenching luminescence associated with oxygen vacancies (V<sub>0</sub>). Thermal treatment in a nitrogen atmosphere enhanced defect-related luminescence, possibly due to chlorine atom diffusion. This study highlights a successful synthesis of ZnO nanoparticles with low defect-related luminescence (DLE) achieved via the microwave-assisted hydrothermal method, a result rarely reported in the literature. The results emphasize the importance of reagent selection in controlling the morphology and optical properties, especially the defect density of ZnO nanoparticles. Optimizing these properties is crucial for biomedical applications such as bioimaging, antibacterial treatments, and photocatalysis.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11821158/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409238","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}
引用次数: 0
New Nanobioceramics Based on Hydroxyapatite for Biomedical Applications: Stability and Properties.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030224
Carmen Steluta Ciobanu, Daniela Predoi, Simona Liliana Iconaru, Catalin Constantin Negrila, Damien Leduc, Liliana Ghegoiu, Coralia Bleotu, Mounsif Ech Cherif El Kettani, Roxana Trusca, Philippe Zelmar, Mihai Valentin Predoi

In this work, we report for the first time the development and complex characterization of new bioceramics based on hydroxyapatite (HAp, Ca10(PO4)6(OH)2). On the other hand, the lyophilization process was used for the first time in this research. The samples were obtained by a modified coprecipitation method and were dried by lyophilization (lyophilized hydroxyapatite (HApLF) and lyophilized zinc-doped hydroxyapatite (5ZnHApLF)). Valuable information about the HApLF and 5ZnHApLF stability was obtained through nondestructive ultrasound measurements. The X-ray diffraction (XRD) studies revealed the phase and the effects of the incorporation of Zn ions into the HAp structure. The chemical composition of the samples was evaluated by energy dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS). Information about the functional groups present in the HApLF and 5ZnHApLF was obtained using Fourier Transform Infrared Spectroscopy (FTIR) studies. The morphology of HApLF and 5ZnHApLF pellets was observed by scanning electron microscopy (SEM). The surface topography of HApLF and 5ZnHApLF pellets was studied with the aid of atomic force microscopy (AFM). Details regarding the roughness of the samples were also obtained using AFM topographies and SEM images. A complementary study was also carried out on a larger analysis surface using a Scanning Acoustic Microscope (SAM). The SAM was used for the first time to analyze the surface of HAp and 5ZnHAp pellets. The biological properties of the HApLF and 5ZnHApLF pellets was investigated with the aid of MG63 and human gingival fibroblasts (HGF-1) cell lines. The results of the cell viability assay highlighted that both the HApLF and 5ZnHApLF pellets exhibited good biological activity. Moreover, SEM and AFM studies were conducted in order to emphasize the development of MG63 and HGF-1 cells on the pellet's surface. Both SEM and AFM images depicted that the pellets' surface favored the cell attachment and development of MG63 and HGF-1 cells. Furthermore, the antimicrobial properties of the HApLF and 5ZnHApLF were evaluated against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, and Candida albicans ATCC 10231. The results of the antimicrobial assays highlighted that the 5ZnHApLF exhibited a strong antimicrobial activity against the tested microbial strains. The results of the biological assays suggested that the samples show great potential for being used in the development of novel materials for biomedical applications.

{"title":"New Nanobioceramics Based on Hydroxyapatite for Biomedical Applications: Stability and Properties.","authors":"Carmen Steluta Ciobanu, Daniela Predoi, Simona Liliana Iconaru, Catalin Constantin Negrila, Damien Leduc, Liliana Ghegoiu, Coralia Bleotu, Mounsif Ech Cherif El Kettani, Roxana Trusca, Philippe Zelmar, Mihai Valentin Predoi","doi":"10.3390/nano15030224","DOIUrl":"10.3390/nano15030224","url":null,"abstract":"<p><p>In this work, we report for the first time the development and complex characterization of new bioceramics based on hydroxyapatite (HAp, Ca<sub>10</sub>(PO<sub>4</sub>)<sub>6</sub>(OH)<sub>2</sub>). On the other hand, the lyophilization process was used for the first time in this research. The samples were obtained by a modified coprecipitation method and were dried by lyophilization (lyophilized hydroxyapatite (HApLF) and lyophilized zinc-doped hydroxyapatite (5ZnHApLF)). Valuable information about the HApLF and 5ZnHApLF stability was obtained through nondestructive ultrasound measurements. The X-ray diffraction (XRD) studies revealed the phase and the effects of the incorporation of Zn ions into the HAp structure. The chemical composition of the samples was evaluated by energy dispersive X-ray analysis (EDS) and X-ray photoelectron spectroscopy (XPS). Information about the functional groups present in the HApLF and 5ZnHApLF was obtained using Fourier Transform Infrared Spectroscopy (FTIR) studies. The morphology of HApLF and 5ZnHApLF pellets was observed by scanning electron microscopy (SEM). The surface topography of HApLF and 5ZnHApLF pellets was studied with the aid of atomic force microscopy (AFM). Details regarding the roughness of the samples were also obtained using AFM topographies and SEM images. A complementary study was also carried out on a larger analysis surface using a Scanning Acoustic Microscope (SAM). The SAM was used for the first time to analyze the surface of HAp and 5ZnHAp pellets. The biological properties of the HApLF and 5ZnHApLF pellets was investigated with the aid of MG63 and human gingival fibroblasts (HGF-1) cell lines. The results of the cell viability assay highlighted that both the HApLF and 5ZnHApLF pellets exhibited good biological activity. Moreover, SEM and AFM studies were conducted in order to emphasize the development of MG63 and HGF-1 cells on the pellet's surface. Both SEM and AFM images depicted that the pellets' surface favored the cell attachment and development of MG63 and HGF-1 cells. Furthermore, the antimicrobial properties of the HApLF and 5ZnHApLF were evaluated against <i>Escherichia coli</i> ATCC 25922, <i>Staphylococcus aureus</i> ATCC 25923, and <i>Candida albicans</i> ATCC 10231. The results of the antimicrobial assays highlighted that the 5ZnHApLF exhibited a strong antimicrobial activity against the tested microbial strains. The results of the biological assays suggested that the samples show great potential for being used in the development of novel materials for biomedical applications.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820604/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409298","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}
引用次数: 0
A Highly Spatiotemporal Resolved Pyrometry for Combustion Temperature Measurement of Single Microparticles Applied in Powder-Fueled Ramjets.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030223
Zhangtao Wang, Xunjie Lin, Xuefeng Huang, Houye Huang, Minqi Zhang, Qinnan Yu, Chao Cui, Shengji Li

It is vital to measure combustion temperature to define combustion models accurately. For single fuel particles in powder-fueled ramjets, their size distribution ranges from submicron to submillimeter, and their burn time is short to millisecond order. Moreover, the radiation intensity of different types of fuel particles significantly oscillated with several orders of magnitude. Current temperature measurement technology is facing this challenge. This paper proposes a highly spatiotemporal resolved pyrometry to measure the combustion temperature of fuel particles by coupling single-point photomultiplier tube (PMT)-based and two-dimensional complementary metal oxide semiconductor (CMOS)-based photoelectric devices. Both the offline calibration by blackbody furnace and online calibration by standard lamp confirmed the measurement accuracy of the pyrometry. Then, the pyrometry was used to measure the combustion temperature of fuel particles including micro-Al, nano-Al, micro-Mg, nano-B, and micro-B4C. The temperature evolution and distribution of burning fuel particles were complementarily obtained, especially the interfacial flame temperature near the particle surface. Based on the obtained combustion temperature, the combustion characteristics and the energy release efficiencies among these fuels were evaluated and compared in detail, which are helpful to recognize, in depth, the combustion behavior and reveal the combustion mechanism of fuel particles in powder-fueled ramjets.

{"title":"A Highly Spatiotemporal Resolved Pyrometry for Combustion Temperature Measurement of Single Microparticles Applied in Powder-Fueled Ramjets.","authors":"Zhangtao Wang, Xunjie Lin, Xuefeng Huang, Houye Huang, Minqi Zhang, Qinnan Yu, Chao Cui, Shengji Li","doi":"10.3390/nano15030223","DOIUrl":"10.3390/nano15030223","url":null,"abstract":"<p><p>It is vital to measure combustion temperature to define combustion models accurately. For single fuel particles in powder-fueled ramjets, their size distribution ranges from submicron to submillimeter, and their burn time is short to millisecond order. Moreover, the radiation intensity of different types of fuel particles significantly oscillated with several orders of magnitude. Current temperature measurement technology is facing this challenge. This paper proposes a highly spatiotemporal resolved pyrometry to measure the combustion temperature of fuel particles by coupling single-point photomultiplier tube (PMT)-based and two-dimensional complementary metal oxide semiconductor (CMOS)-based photoelectric devices. Both the offline calibration by blackbody furnace and online calibration by standard lamp confirmed the measurement accuracy of the pyrometry. Then, the pyrometry was used to measure the combustion temperature of fuel particles including micro-Al, nano-Al, micro-Mg, nano-B, and micro-B<sub>4</sub>C. The temperature evolution and distribution of burning fuel particles were complementarily obtained, especially the interfacial flame temperature near the particle surface. Based on the obtained combustion temperature, the combustion characteristics and the energy release efficiencies among these fuels were evaluated and compared in detail, which are helpful to recognize, in depth, the combustion behavior and reveal the combustion mechanism of fuel particles in powder-fueled ramjets.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820064/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409204","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}
引用次数: 0
Microfluidic-Assisted Silk Nanoparticles Co-Loaded with Epirubicin and Copper Sulphide: A Synergistic Photothermal-Photodynamic Chemotherapy Against Breast Cancer.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030221
Zijian Gao, Muhamad Hawari Mansor, Faith Howard, Jordan MacInnes, Xiubo Zhao, Munitta Muthana

Phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), has emerged as a promising non-invasive cancer treatment, addressing issues like drug resistance and systemic toxicity common in conventional breast cancer therapies. Recent research has shown that copper sulphide (CuS) nanoparticles and polydopamine (PDA) exhibit exceptional photothermal conversion efficiency under 808 nm near-infrared (NIR) laser irradiation, making them valuable for cancer phototherapy. However, the effectiveness of PDT is limited in hypoxic tumour environments, which are common in many breast cancer types, due to its reliance on local oxygen levels. Moreover, single-modality approaches, including phototherapy, often prove insufficient for complete tumour elimination, despite their therapeutic strength. In this paper, a microfluidic-assisted approach was used to create multifunctional silk-based nanoparticles (SFNPs) encapsulating the chemotherapeutic drug Epirubicin (EPI), the PTT/PDT agent CuS, and the heat-activated, oxygen-independent alkyl radical generator AIPH for combined chemotherapy, PTT, and PDT, with a polydopamine (PDA) coating for enhanced photothermal effects and surface-bound folic acid (FA) for targeted delivery in breast cancer treatment. The synthesised CuS-EPI-AIPH@SF-PDA-FA nanoparticles achieved a controlled size of 378 nm, strong NIR absorption, and high photothermal conversion efficiency. Under 808 nm NIR irradiation, these nanoparticles selectively triggered the release of alkyl radicals and EPI, improving intracellular drug levels and effectively killing various breast cancer cell lines while demonstrating low toxicity to non-cancerous cells. We demonstrate that novel core-shell CuS-EPI-AIPH@SF-PDA-FA NPs have been successfully designed as a multifunctional nanoplatform integrating PTT, PDT, and chemotherapy for targeted, synergistic breast cancer treatment.

{"title":"Microfluidic-Assisted Silk Nanoparticles Co-Loaded with Epirubicin and Copper Sulphide: A Synergistic Photothermal-Photodynamic Chemotherapy Against Breast Cancer.","authors":"Zijian Gao, Muhamad Hawari Mansor, Faith Howard, Jordan MacInnes, Xiubo Zhao, Munitta Muthana","doi":"10.3390/nano15030221","DOIUrl":"10.3390/nano15030221","url":null,"abstract":"<p><p>Phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), has emerged as a promising non-invasive cancer treatment, addressing issues like drug resistance and systemic toxicity common in conventional breast cancer therapies. Recent research has shown that copper sulphide (CuS) nanoparticles and polydopamine (PDA) exhibit exceptional photothermal conversion efficiency under 808 nm near-infrared (NIR) laser irradiation, making them valuable for cancer phototherapy. However, the effectiveness of PDT is limited in hypoxic tumour environments, which are common in many breast cancer types, due to its reliance on local oxygen levels. Moreover, single-modality approaches, including phototherapy, often prove insufficient for complete tumour elimination, despite their therapeutic strength. In this paper, a microfluidic-assisted approach was used to create multifunctional silk-based nanoparticles (SFNPs) encapsulating the chemotherapeutic drug Epirubicin (EPI), the PTT/PDT agent CuS, and the heat-activated, oxygen-independent alkyl radical generator AIPH for combined chemotherapy, PTT, and PDT, with a polydopamine (PDA) coating for enhanced photothermal effects and surface-bound folic acid (FA) for targeted delivery in breast cancer treatment. The synthesised CuS-EPI-AIPH@SF-PDA-FA nanoparticles achieved a controlled size of 378 nm, strong NIR absorption, and high photothermal conversion efficiency. Under 808 nm NIR irradiation, these nanoparticles selectively triggered the release of alkyl radicals and EPI, improving intracellular drug levels and effectively killing various breast cancer cell lines while demonstrating low toxicity to non-cancerous cells. We demonstrate that novel core-shell CuS-EPI-AIPH@SF-PDA-FA NPs have been successfully designed as a multifunctional nanoplatform integrating PTT, PDT, and chemotherapy for targeted, synergistic breast cancer treatment.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820260/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409288","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}
引用次数: 0
Effect of Ammonium Salt on Conjugated Polyelectrolyte as an Interlayer for Organic-Inorganic Hybrid Perovskite Memristors.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030227
Eun Soo Shim, Ji Hyeon Lee, Ju Wan Park, Sun Woo Kim, Su Bin Park, Jea Woong Jo

Memristors are promising candidates for next-generation non-volatile memory devices, offering low power consumption and high-speed switching capabilities. However, conventional metal oxide-based memristors are constrained by fabrication complexity and high costs, limiting their commercial viability. Organic-inorganic hybrid perovskites (OIHPs), known for their facile solution processability and unique ionic-electronic conductivity, provide an attractive alternative. This study presents a conjugated polyelectrolyte (CPE), PhNa-1T, as an interlayer for OIHP memristors to enhance the high-resistance state (HRS) performance. A post-treatment process using n-octylammonium bromide (OABr) was further applied to optimize the interlayer properties. Devices treated with PhNa-1T/OABr achieved a significantly improved ON/OFF ratio of 2150, compared to 197 for untreated devices. Systematic characterization revealed that OABr treatment improved film morphology, reduced crystallite strain, and optimized energy level alignment, thereby reinforcing the Schottky barrier and minimizing current leakage. These findings highlight the potential of tailored interlayer engineering to improve OIHP-based memristor performance, offering promising prospects for applications in non-volatile memory technologies.

{"title":"Effect of Ammonium Salt on Conjugated Polyelectrolyte as an Interlayer for Organic-Inorganic Hybrid Perovskite Memristors.","authors":"Eun Soo Shim, Ji Hyeon Lee, Ju Wan Park, Sun Woo Kim, Su Bin Park, Jea Woong Jo","doi":"10.3390/nano15030227","DOIUrl":"10.3390/nano15030227","url":null,"abstract":"<p><p>Memristors are promising candidates for next-generation non-volatile memory devices, offering low power consumption and high-speed switching capabilities. However, conventional metal oxide-based memristors are constrained by fabrication complexity and high costs, limiting their commercial viability. Organic-inorganic hybrid perovskites (OIHPs), known for their facile solution processability and unique ionic-electronic conductivity, provide an attractive alternative. This study presents a conjugated polyelectrolyte (CPE), PhNa-1T, as an interlayer for OIHP memristors to enhance the high-resistance state (HRS) performance. A post-treatment process using <i>n</i>-octylammonium bromide (OABr) was further applied to optimize the interlayer properties. Devices treated with PhNa-1T/OABr achieved a significantly improved ON/OFF ratio of 2150, compared to 197 for untreated devices. Systematic characterization revealed that OABr treatment improved film morphology, reduced crystallite strain, and optimized energy level alignment, thereby reinforcing the Schottky barrier and minimizing current leakage. These findings highlight the potential of tailored interlayer engineering to improve OIHP-based memristor performance, offering promising prospects for applications in non-volatile memory technologies.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11819950/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143408879","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}
引用次数: 0
Comparison of Single Atoms vs. Sub-Nanoclusters as Co-Catalysts in Perovskites and Metal Oxides for Photocatalytic Technologies.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030226
Anastasia V Spyrou, Konstantinos Zodhiates, Yiannis Deligiannakis

Adatoms as co-catalysts may play a key role in photocatalysis, yet control of their exact configuration remains challenging. Specifically, there is converging evidence that ultra-small structures may be optimal as co-catalysts; however, a comprehensive distinction between single atoms (SAs), sub-nanoclusters (SNCs), and quantum-sized small particles (QSSPs) has yet to be established. Herein, we present a critical review addressing these distinctions, along with challenges related to the controlled synthesis of SAs, SNCs, and QSSPs; their detection methods; and their functional benefits in photocatalysis. Our discussion focuses on perovskite oxides (e.g., such as ABO3, where A and B are cations) and metal oxides (MxOy, where M is a metal) decorated with adatoms, which demonstrate superior photocatalytic performance compared to their unmodified counterparts. Finally, we highlight cases of misinterpretation between SA, SNC, and QSSP configurations emerging from limitations in high-resolution detection techniques and synthesis methods.

{"title":"Comparison of Single Atoms vs. Sub-Nanoclusters as Co-Catalysts in Perovskites and Metal Oxides for Photocatalytic Technologies.","authors":"Anastasia V Spyrou, Konstantinos Zodhiates, Yiannis Deligiannakis","doi":"10.3390/nano15030226","DOIUrl":"10.3390/nano15030226","url":null,"abstract":"<p><p>Adatoms as co-catalysts may play a key role in photocatalysis, yet control of their exact configuration remains challenging. Specifically, there is converging evidence that ultra-small structures may be optimal as co-catalysts; however, a comprehensive distinction between single atoms (SAs), sub-nanoclusters (SNCs), and quantum-sized small particles (QSSPs) has yet to be established. Herein, we present a critical review addressing these distinctions, along with challenges related to the controlled synthesis of SAs, SNCs, and QSSPs; their detection methods; and their functional benefits in photocatalysis. Our discussion focuses on perovskite oxides (e.g., such as ABO<sub>3</sub>, where A and B are cations) and metal oxides (M<sub>x</sub>O<sub>y</sub>, where M is a metal) decorated with adatoms, which demonstrate superior photocatalytic performance compared to their unmodified counterparts. Finally, we highlight cases of misinterpretation between SA, SNC, and QSSP configurations emerging from limitations in high-resolution detection techniques and synthesis methods.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820212/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143408257","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}
引用次数: 0
Multi-Scale Modeling of Transport Properties in Cementitious Materials with GO Admixture.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030222
Bing Liu, Weichen Kang, Weixing Lian, Feng Xing, Hongfang Sun, Hongyan Ma

In coastal areas, the presence of concrete cracks provides pathways for hazardous ions to ingress from the exterior into the interior of concrete, while the migration of the ions further accelerates concrete deterioration and causes durability problems. The incorporation of graphene oxide (GO) into concrete can inhibit crack initiation and development starting at the nanoscale, improving the concrete microstructure, thereby affecting concrete's resistance to hazardous ion transport and the resulting deterioration. In this study, a multi-scale transport model for cementitious materials with a GO admixture was established to predict the resistance to hazardous ions. Based on the determination of hydration types and hydration kinetics, microstructure modeling was conducted at three scales, the sub-microscale, microscale, and mesoscale, upon which transport property simulations were performed. At the microscale, the effects of both the cement paste matrix and the interfacial transition zone (ITZ) were considered. Through the simulation, it was found that the addition of GO reduced the duration of the induction period and increased the rate of hydration development after the induction period. Moreover, the incorporation of GO could reduce the porosity of cementitious materials at all simulation scales at both early and later ages. At the microscale, it improved the pore structure of the cement matrix and ITZ by reducing large pores and increasing small pores. At all three simulation scales, GO could increase the diffusion tortuosity in hydration products, suppress ion transport, and improve the resistance to hazardous ions of cementitious materials.

{"title":"Multi-Scale Modeling of Transport Properties in Cementitious Materials with GO Admixture.","authors":"Bing Liu, Weichen Kang, Weixing Lian, Feng Xing, Hongfang Sun, Hongyan Ma","doi":"10.3390/nano15030222","DOIUrl":"10.3390/nano15030222","url":null,"abstract":"<p><p>In coastal areas, the presence of concrete cracks provides pathways for hazardous ions to ingress from the exterior into the interior of concrete, while the migration of the ions further accelerates concrete deterioration and causes durability problems. The incorporation of graphene oxide (GO) into concrete can inhibit crack initiation and development starting at the nanoscale, improving the concrete microstructure, thereby affecting concrete's resistance to hazardous ion transport and the resulting deterioration. In this study, a multi-scale transport model for cementitious materials with a GO admixture was established to predict the resistance to hazardous ions. Based on the determination of hydration types and hydration kinetics, microstructure modeling was conducted at three scales, the sub-microscale, microscale, and mesoscale, upon which transport property simulations were performed. At the microscale, the effects of both the cement paste matrix and the interfacial transition zone (ITZ) were considered. Through the simulation, it was found that the addition of GO reduced the duration of the induction period and increased the rate of hydration development after the induction period. Moreover, the incorporation of GO could reduce the porosity of cementitious materials at all simulation scales at both early and later ages. At the microscale, it improved the pore structure of the cement matrix and ITZ by reducing large pores and increasing small pores. At all three simulation scales, GO could increase the diffusion tortuosity in hydration products, suppress ion transport, and improve the resistance to hazardous ions of cementitious materials.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11821173/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409294","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}
引用次数: 0
Evaluating the In Situ Effects of Whole Protein Coronas on the Biosensing of Antibody-Immobilized Nanoparticles Using Two-Color Fluorescence Nanoparticle Tracking Analysis.
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-30 DOI: 10.3390/nano15030220
Heeju Joung, Gwi Ju Jang, Ji Yeon Jeong, Goeun Lim, Sang Yun Han

The formation of protein coronas around engineered nanoparticles (ENPs) in biological environments is critical in nanomedicine, as these coronas significantly influence the biological behavior of ENPs. Despite extensive research on protein coronas, understanding the in situ influence of whole (soft plus hard) protein coronas has remained challenging. In this study, we demonstrate a strategy to assess the in situ effects of whole coronas on the model biosensing of anti-IgG using IgG-conjugated gold nanoparticles (IgG-AuNPs) through fluorescence nanoparticle tracking analysis (F-NTA), which enables the selective tracking of fluorescent particles within complex media. In our approach, anti-IgG and IgG-AuNPs were labeled with distinct fluorescent dyes. The accordance in hydrodynamic diameter distributions observed at two different wavelengths verifies the successful capture of anti-IgG on the IgG-AuNPs. The counting of fluorescent anti-IgG within the size distribution allows for a quantitative assessment of biosensing efficiency. This method was applied to evaluate the effects of four protein coronas-human serum albumin, high-density lipoproteins, immunoglobulin G, and fibrinogen-as well as their mixture across varying incubation times and concentrations. The results suggest that the physical presence of whole protein coronas surrounding the IgG-AuNPs may assist the biosensing interaction in situ rather than screening it.

{"title":"Evaluating the In Situ Effects of Whole Protein Coronas on the Biosensing of Antibody-Immobilized Nanoparticles Using Two-Color Fluorescence Nanoparticle Tracking Analysis.","authors":"Heeju Joung, Gwi Ju Jang, Ji Yeon Jeong, Goeun Lim, Sang Yun Han","doi":"10.3390/nano15030220","DOIUrl":"10.3390/nano15030220","url":null,"abstract":"<p><p>The formation of protein coronas around engineered nanoparticles (ENPs) in biological environments is critical in nanomedicine, as these coronas significantly influence the biological behavior of ENPs. Despite extensive research on protein coronas, understanding the in situ influence of whole (soft plus hard) protein coronas has remained challenging. In this study, we demonstrate a strategy to assess the in situ effects of whole coronas on the model biosensing of anti-IgG using IgG-conjugated gold nanoparticles (IgG-AuNPs) through fluorescence nanoparticle tracking analysis (F-NTA), which enables the selective tracking of fluorescent particles within complex media. In our approach, anti-IgG and IgG-AuNPs were labeled with distinct fluorescent dyes. The accordance in hydrodynamic diameter distributions observed at two different wavelengths verifies the successful capture of anti-IgG on the IgG-AuNPs. The counting of fluorescent anti-IgG within the size distribution allows for a quantitative assessment of biosensing efficiency. This method was applied to evaluate the effects of four protein coronas-human serum albumin, high-density lipoproteins, immunoglobulin G, and fibrinogen-as well as their mixture across varying incubation times and concentrations. The results suggest that the physical presence of whole protein coronas surrounding the IgG-AuNPs may assist the biosensing interaction in situ rather than screening it.</p>","PeriodicalId":18966,"journal":{"name":"Nanomaterials","volume":"15 3","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11820540/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143409131","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}
引用次数: 0
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