Editor’s Choice Articles

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

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Article

20 pages, 20699 KiB  
Article
Biomolecular Adsorprion at ZnS Nanomaterials: A Molecular Dynamics Simulation Study of the Adsorption Preferences, Effects of the Surface Curvature and Coating
by Roja Rahmani and Alexander P. Lyubartsev
Nanomaterials 2023, 13(15), 2239; https://doi.org/10.3390/nano13152239 - 02 Aug 2023
Cited by 1 | Viewed by 1017
Abstract
The understanding of interactions between nanomaterials and biological molecules is of primary importance for biomedical applications of nanomaterials, as well as for the evaluation of their possible toxic effects. Here, we carried out extensive molecular dynamics simulations of the adsorption properties of about [...] Read more.
The understanding of interactions between nanomaterials and biological molecules is of primary importance for biomedical applications of nanomaterials, as well as for the evaluation of their possible toxic effects. Here, we carried out extensive molecular dynamics simulations of the adsorption properties of about 30 small molecules representing biomolecular fragments at ZnS surfaces in aqueous media. We computed adsorption free energies and potentials of mean force of amino acid side chain analogs, lipids, and sugar fragments to ZnS (110) crystal surface and to a spherical ZnS nanoparticle. Furthermore, we investigated the effect of poly-methylmethacrylate (PMMA) coating on the adsorption preferences of biomolecules to ZnS. We found that only a few anionic molecules: aspartic and glutamic acids side chains, as well as the anionic form of cysteine show significant binding to pristine ZnS surface, while other molecules show weak or no binding. Spherical ZnS nanoparticles show stronger binding of these molecules due to binding at the edges between different surface facets. Coating of ZnS by PMMA changes binding preferences drastically: the molecules that adsorb to a pristine ZnS surface do not adsorb on PMMA-coated surfaces, while some others, particularly hydrophobic or aromatic amino-acids, show high binding affinity due to binding to the coating. We investigate further the hydration properties of the ZnS surface and relate them to the binding preferences of biomolecules. Full article
(This article belongs to the Section Theory and Simulation of Nanostructures)
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19 pages, 3494 KiB  
Article
Hard-Shelled Glycol Chitosan Nanoparticles for Dual MRI/US Detection of Drug Delivery/Release: A Proof-of-Concept Study
by Simona Baroni, Monica Argenziano, Francesca La Cava, Marco Soster, Francesca Garello, David Lembo, Roberta Cavalli and Enzo Terreno
Nanomaterials 2023, 13(15), 2227; https://doi.org/10.3390/nano13152227 - 01 Aug 2023
Cited by 2 | Viewed by 954
Abstract
This paper describes a novel nanoformulation for dual MRI/US in vivo monitoring of drug delivery/release. The nanosystem was made of a perfluoropentane core coated with phospholipids stabilized by glycol chitosan crosslinked with triphosphate ions, and it was co-loaded with the prodrug prednisolone phosphate [...] Read more.
This paper describes a novel nanoformulation for dual MRI/US in vivo monitoring of drug delivery/release. The nanosystem was made of a perfluoropentane core coated with phospholipids stabilized by glycol chitosan crosslinked with triphosphate ions, and it was co-loaded with the prodrug prednisolone phosphate (PLP) and the structurally similar MRI agent Gd-DTPAMA-CHOL. Importantly, the in vitro release of PLP and Gd-DTPAMA-CHOL from the nanocarrier showed similar profiles, validating the potential impact of the MRI agent as an imaging reporter for the drug release. On the other hand, the nanobubbles were also detectable by US imaging both in vitro and in vivo. Therefore, the temporal evolution of both MRI and US contrast after the administration of the proposed nanosystem could report on the delivery and the release kinetics of the transported drug in a given lesion. Full article
(This article belongs to the Section Biology and Medicines)
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12 pages, 2756 KiB  
Article
Atomic-Layer Engineering of La2−xSrxCuO4—La2−xSrxZnO4 Heterostructures
by Xiaotao Xu, Xi He, Anthony T. Bollinger, Xiaoyan Shi and Ivan Božović
Nanomaterials 2023, 13(15), 2207; https://doi.org/10.3390/nano13152207 - 29 Jul 2023
Viewed by 784
Abstract
The fabrication of trilayer superconductor-insulator-superconductor (SIS) Josephson junctions with high-temperature superconductor (HTS) electrodes requires atomically perfect interfaces. Therefore, despite great interest and efforts, this remained a challenge for over three decades. Here, we report the discovery of a new family of metastable materials, [...] Read more.
The fabrication of trilayer superconductor-insulator-superconductor (SIS) Josephson junctions with high-temperature superconductor (HTS) electrodes requires atomically perfect interfaces. Therefore, despite great interest and efforts, this remained a challenge for over three decades. Here, we report the discovery of a new family of metastable materials, La2−xSrxZnO4 (LSZO), synthesized by atomic-layer-by-layer molecular beam epitaxy (ALL-MBE). We show that LSZO is insulating and epitaxially compatible with an HTS compound, La2−xSrxCuO4 (LSCO). Since the “parent” compound La2ZnO4 (LZO) is easier to grow, here we focus on this material as our insulating layer. Growing LZO at very low temperatures to reduce cation interdiffusion makes LSCO/LZO interfaces atomically sharp. We show that in LSCO/LZO/LSCO trilayers, the superconducting properties of the LSCO electrodes remain undiminished, unlike in previous attempts with insulator barriers made of other materials. This opens prospects to produce high-quality HTS tunnel junctions. Full article
(This article belongs to the Special Issue Recent Advances in Nanowires and Superconductors)
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15 pages, 2982 KiB  
Article
Unraveling the Mechanisms of Ch-SeNP Cytotoxicity against Cancer Cells: Insights from Targeted and Untargeted Metabolomics
by Hector Estevez, Estefania Garcia-Calvo, Maria L. Mena, Roberto Alvarez-Fernandez Garcia and Jose L. Luque-Garcia
Nanomaterials 2023, 13(15), 2204; https://doi.org/10.3390/nano13152204 - 29 Jul 2023
Cited by 2 | Viewed by 1101
Abstract
Although chitosan-stabilized selenium nanoparticles (Ch-SeNPs) have emerged as a promising chemical form of selenium for anticancer purposes, gathering more profound knowledge related to molecular dysfunctions contributes significantly to the promotion of their evolution as a chemotherapeutic drug. In this sense, metabolites are the [...] Read more.
Although chitosan-stabilized selenium nanoparticles (Ch-SeNPs) have emerged as a promising chemical form of selenium for anticancer purposes, gathering more profound knowledge related to molecular dysfunctions contributes significantly to the promotion of their evolution as a chemotherapeutic drug. In this sense, metabolites are the end products in the flow of gene expression and, thus, the most sensitive to changes in the physiological state of a biological system. Therefore, metabolomics provides a functional readout of the biochemical activity and cell state. In the present study, we evaluated alterations in the metabolomes of HepG2 cells after the exposure to Ch-SeNPs to elucidate the biomolecular mechanisms involved in their therapeutic effect. A targeted metabolomic approach was conducted to evaluate the levels of four of the main energy-related metabolites (adenosine triphosphate (ATP); adenosine diphosphate (ADP); nicotinamide adenine dinucleotide (NAD+); and 1,4-dihydronicotinamide adenine dinucleotide (NADH)), revealing alterations as a result of exposure to Ch-SeNPs related to a shortage in the energy supply system in the cell. In addition, an untargeted metabolomic experiment was performed, which allowed for the study of alterations in the global metabolic profile as a consequence of Ch-SeNP exposure. The results indicate that the TCA cycle and glycolytic pathways were impaired, while alternative pathways such as glutaminolysis and cysteine metabolism were upregulated. Additionally, increased fructose levels suggested the induction of hypoxia-like conditions. These findings highlight the potential of Ch-SeNPs to disrupt cancer cell metabolism and provide insights into the mechanisms underlying their antitumor effects. Full article
(This article belongs to the Special Issue Biomedical Applications of Metallic Nanoparticles)
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12 pages, 2283 KiB  
Article
Overcoming the Fermi-Level Pinning Effect in the Nanoscale Metal and Silicon Interface
by Zih-Chun Su and Ching-Fuh Lin
Nanomaterials 2023, 13(15), 2193; https://doi.org/10.3390/nano13152193 - 28 Jul 2023
Viewed by 1956
Abstract
Silicon-based photodetectors are attractive as low-cost and environmentally friendly optical sensors. Also, their compatibility with complementary metal-oxide-semiconductor (CMOS) technology is advantageous for the development of silicon photonics systems. However, extending optical responsivity of silicon-based photodetectors to the mid-infrared (mid-IR) wavelength range remains challenging. [...] Read more.
Silicon-based photodetectors are attractive as low-cost and environmentally friendly optical sensors. Also, their compatibility with complementary metal-oxide-semiconductor (CMOS) technology is advantageous for the development of silicon photonics systems. However, extending optical responsivity of silicon-based photodetectors to the mid-infrared (mid-IR) wavelength range remains challenging. In developing mid-IR infrared Schottky detectors, nanoscale metals are critical. Nonetheless, one key factor is the Fermi-level pinning effect at the metal/silicon interface and the presence of metal-induced gap states (MIGS). Here, we demonstrate the utilization of the passivated surface layer on semiconductor materials as an insulating material in metal-insulator-semiconductor (MIS) contacts to mitigate the Fermi-level pinning effect. The removal of Fermi-level pinning effectively reduces the Schottky barrier height by 12.5% to 16%. The demonstrated devices exhibit a high responsivity of up to 234 μA/W at a wavelength of 2 μm, 48.2 μA/W at 3 μm, and 1.75 μA/W at 6 μm. The corresponding detectivities at 2 and 3 μm are 1.17 × 108 cm Hz1/2 W−1 and 2.41 × 107 cm Hz1/2 W−1, respectively. The expanded sensing wavelength range contributes to the application development of future silicon photonics integration platforms. Full article
(This article belongs to the Section Nanoelectronics, Nanosensors and Devices)
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16 pages, 75254 KiB  
Article
Electric Field-Induced Nano-Assembly Formation: First Evidence of Silicon Superclusters with a Giant Permanent Dipole Moment
by Fatme Jardali, Jacqueline Tran, Frédéric Liège, Ileana Florea, Mohamed E. Leulmi and Holger Vach
Nanomaterials 2023, 13(15), 2169; https://doi.org/10.3390/nano13152169 - 26 Jul 2023
Cited by 1 | Viewed by 947
Abstract
The outstanding properties of silicon nanoparticles have been extensively investigated during the last few decades. Experimental evidence and applications of their theoretically predicted permanent electric dipole moment, however, have only been reported for silicon nanoclusters (SiNCs) for a size of about one to [...] Read more.
The outstanding properties of silicon nanoparticles have been extensively investigated during the last few decades. Experimental evidence and applications of their theoretically predicted permanent electric dipole moment, however, have only been reported for silicon nanoclusters (SiNCs) for a size of about one to two nanometers. Here, we have explored the question of whether suitable plasma conditions could lead to much larger silicon clusters with significantly stronger permanent electric dipole moments. A pulsed plasma approach was used for SiNC production and surface deposition. The absorption spectra of the deposited SiNCs were recorded using enhanced darkfield hyperspectral microscopy and compared to time-dependent DFT calculations. Atomic force microscopy and transmission electron microscopy observations completed our study, showing that one-to-two-nanometer SiNCs can, indeed, be used to assemble much larger ”superclusters” with a size of tens of nanometers. These superclusters possess extremely high permanent electric dipole moments that can be exploited to orient and guide these clusters with external electric fields, opening the path to the controlled architecture of silicon nanostructures. Full article
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19 pages, 9316 KiB  
Article
In Situ Ultra-Small- and Small-Angle X-ray Scattering Study of ZnO Nanoparticle Formation and Growth through Chemical Bath Deposition in the Presence of Polyvinylpyrrolidone
by Karina Abitaev, Petia Atanasova, Joachim Bill, Natalie Preisig, Ivan Kuzmenko, Jan Ilavsky, Yun Liu and Thomas Sottmann
Nanomaterials 2023, 13(15), 2180; https://doi.org/10.3390/nano13152180 - 26 Jul 2023
Viewed by 1177
Abstract
ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle [...] Read more.
ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth. Full article
(This article belongs to the Special Issue Nanomaterials for Chemical Engineering (Volume II))
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10 pages, 3407 KiB  
Article
The Atomic Observation of the Structural Change Process in Pt Networks in Air Using Environmental Cell Scanning Transmission Electron Microscopy
by Masaki Takeguchi, Toshiaki Takei and Kazutaka Mitsuishi
Nanomaterials 2023, 13(15), 2170; https://doi.org/10.3390/nano13152170 - 26 Jul 2023
Cited by 1 | Viewed by 782
Abstract
The structural change in Pt networks composed of multiple chain connections among grains was observed in air at 1 atm using atomic-resolution environmental cell scanning transmission electron microscopy. An aberration-corrected incident electron probe with a wide convergence angle made it possible to increase [...] Read more.
The structural change in Pt networks composed of multiple chain connections among grains was observed in air at 1 atm using atomic-resolution environmental cell scanning transmission electron microscopy. An aberration-corrected incident electron probe with a wide convergence angle made it possible to increase the depth resolution that contributes to enhancing the signal-to-noise ratio of Pt network samples in air in an environmental cell, resulting in the achievement of atomic-resolution imaging. The exposure of the Pt networks to gas molecules under Brownian motion, stimulated by electron beams in the air, increases the collision probability between gas molecules and Pt networks, and the Pt networks are more intensely stressed from all directions than in a situation without electron irradiation. By increasing the electron beam dose rate, the structural change of the Pt networks became significant. Dynamic observation on an atomic scale suggested that the structural change of the networks was not attributed to the surface atomic-diffusion-induced step motion but mainly caused by the movement and deformation of unstable grains and grain boundaries. The oxidized surface layers may be one of the factors hindering the surface atomic step motion, mitigating the change in the size of the grains and grain boundaries. Full article
(This article belongs to the Special Issue Transmission Electron Microscopy for Nanomaterials Research Advances)
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12 pages, 5793 KiB  
Article
Preparation of Ce-MnOx Composite Oxides via Coprecipitation and Their Catalytic Performance for CO Oxidation
by Junsheng Yang, Jie Li, Jiangang Kang, Wenkang Liu, Yijian Kuang, Hua Tan, Zhensen Yu, Liu Yang, Xuejin Yang, Kui Yu and Yiquan Fan
Nanomaterials 2023, 13(15), 2158; https://doi.org/10.3390/nano13152158 - 25 Jul 2023
Viewed by 1012
Abstract
Ce-MnOx composite oxide catalysts with different proportions were prepared using the coprecipitation method, and the CO-removal ability of the catalysts with the tested temperature range of 60–140 °C was investigated systematically. The effect of Ce and Mn ratios on the catalytic oxidation [...] Read more.
Ce-MnOx composite oxide catalysts with different proportions were prepared using the coprecipitation method, and the CO-removal ability of the catalysts with the tested temperature range of 60–140 °C was investigated systematically. The effect of Ce and Mn ratios on the catalytic oxidation performance of CO was investigated using X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), H2 temperature programmed reduction (H2-TPR), CO-temperature programmed desorption (CO-TPD), and in situ infrared spectra. The experimental results reveal that under the same test conditions, the CO conversion rate of pure Mn3O4 reaches 95.4% at 170 °C. Additionally, at 140 °C, the Ce-MnOx series composite oxide catalyst converts CO at a rate of over 96%, outperforming single-phase Mn3O4 in terms of catalytic performance. With the decrement in Ce content, the performance of Ce-MnOx series composite oxide catalysts first increase and then decrease. The Ce MnOx catalyst behaves best when Ce:Mn = 1:1, with a CO conversion rate of 99.96% at 140 °C and 91.98% at 100 °C. Full article
(This article belongs to the Special Issue Nanocatalysts for Air Purification)
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23 pages, 9294 KiB  
Article
Phase-Selective Epitaxy of Trigonal and Orthorhombic Bismuth Thin Films on Si (111)
by Abdur Rehman Jalil, Xiao Hou, Peter Schüffelgen, Jin Hee Bae, Elmar Neumann, Gregor Mussler, Lukasz Plucinski and Detlev Grützmacher
Nanomaterials 2023, 13(14), 2143; https://doi.org/10.3390/nano13142143 - 24 Jul 2023
Viewed by 1306
Abstract
Over the past three decades, the growth of Bi thin films has been extensively explored due to their potential applications in various fields such as thermoelectrics, ferroelectrics, and recently for topological and neuromorphic applications, too. Despite significant research efforts in these areas, achieving [...] Read more.
Over the past three decades, the growth of Bi thin films has been extensively explored due to their potential applications in various fields such as thermoelectrics, ferroelectrics, and recently for topological and neuromorphic applications, too. Despite significant research efforts in these areas, achieving reliable and controllable growth of high-quality Bi thin-film allotropes has remained a challenge. Previous studies have reported the growth of trigonal and orthorhombic phases on various substrates yielding low-quality epilayers characterized by surface morphology. In this study, we present a systematic growth investigation, enabling the high-quality growth of Bi epilayers on Bi-terminated Si (111) 1 × 1 surfaces using molecular beam epitaxy. Our work yields a phase map that demonstrates the realization of trigonal, orthorhombic, and pseudocubic thin-film allotropes of Bi. In-depth characterization through X-ray diffraction (XRD) techniques and scanning transmission electron microscopy (STEM) analysis provides a comprehensive understanding of phase segregation, phase stability, phase transformation, and phase-dependent thickness limitations in various Bi thin-film allotropes. Our study provides recipes for the realization of high-quality Bi thin films with desired phases, offering opportunities for the scalable refinement of Bi into quantum and neuromorphic devices and for revisiting technological proposals for this versatile material platform from the past 30 years. Full article
(This article belongs to the Special Issue Topological Materials in Low Dimensions)
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14 pages, 2350 KiB  
Article
Acute Aquatic Toxicity to Zebrafish and Bioaccumulation in Marine Mussels of Antimony Tin Oxide Nanoparticles
by Ivone Pinheiro, Monica Quarato, Antonio Moreda-Piñeiro, Ana Vieira, Virginie Serin, David Neumeyer, Nicolas Ratel-Ramond, Sébastien Joulié, Alain Claverie, Miguel Spuch-Calvar, Miguel A. Correa-Duarte, Alexandre Campos, José Carlos Martins, Pilar Bermejo-Barrera, Marisa P. Sarriá, Laura Rodriguez-Lorenzo and Begoña Espiña
Nanomaterials 2023, 13(14), 2112; https://doi.org/10.3390/nano13142112 - 20 Jul 2023
Viewed by 1052
Abstract
Antimony tin oxide (Sb2O5/SnO2) is effective in the absorption of infrared radiation for applications, such as skylights. As a nanoparticle (NP), it can be incorporated into films or sheets providing infrared radiation attenuation while allowing for a [...] Read more.
Antimony tin oxide (Sb2O5/SnO2) is effective in the absorption of infrared radiation for applications, such as skylights. As a nanoparticle (NP), it can be incorporated into films or sheets providing infrared radiation attenuation while allowing for a transparent final product. The acute toxicity exerted by commercial Sb2O5/SnO2 (ATO) NPs was studied in adults and embryos of zebrafish (Danio rerio). Our results suggest that these NPs do not induce an acute toxicity in zebrafish, either adults or embryos. However, some sub-lethal parameters were altered: heart rate and spontaneous movements. Finally, the possible bioaccumulation of these NPs in the aquacultured marine mussel Mytilus sp. was studied. A quantitative analysis was performed using single particle inductively coupled plasma mass spectrometry (sp-ICP-MS). The results indicated that, despite being scarce (2.31 × 106 ± 9.05 × 105 NPs/g), there is some accumulation of the ATO NPs in the mussel. In conclusion, commercial ATO NPs seem to be quite innocuous to aquatic organisms; however, the fact that some of the developmental parameters in zebrafish embryos are altered should be considered for further investigation. More in-depth analysis of these NPs transformations in the digestive tract of humans is needed to assess whether their accumulation in mussels presents an actual risk to humans. Full article
(This article belongs to the Special Issue Ecotoxicology and Risk Assessment of Engineered Nanomaterials)
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14 pages, 15522 KiB  
Article
Influence of Solvents and Adsorption of Organic Molecules on the Properties of CVD Synthesized 2D MoS2
by Antun Lovro Brkić, Antonio Supina, Davor Čapeta, Lucija Dončević, Lucija Ptiček, Šimun Mandić, Livio Racané and Ida Delač
Nanomaterials 2023, 13(14), 2115; https://doi.org/10.3390/nano13142115 - 20 Jul 2023
Viewed by 997
Abstract
We present a simple method for modification of 2D materials by drop-casting of the organic molecule in solution on the 2D material under ambient conditions. Specifically, we investigated the adsorption of 6-(4,5-Dihydro-1H-imidazol-3-ium-2-yl)-2-(naphthalene-2-yl)benzothiazole methanesulfonate (L63MS) organic molecule on 2D MoS2. [...] Read more.
We present a simple method for modification of 2D materials by drop-casting of the organic molecule in solution on the 2D material under ambient conditions. Specifically, we investigated the adsorption of 6-(4,5-Dihydro-1H-imidazol-3-ium-2-yl)-2-(naphthalene-2-yl)benzothiazole methanesulfonate (L63MS) organic molecule on 2D MoS2. To better understand the effect of the organic molecule on the 2D material, we also investigated the impact of solvents alone on the materials’ properties. The MoS2 samples were synthesized using ambient pressure chemical vapor deposition. Atomic force microscopy, Raman spectroscopy, photoluminescence spectroscopy and optical microscopy were used to characterize the samples. The measurements were performed after synthesis, after the drop-casting of solvents and after the drop-casting of organic molecule solutions. Our results indicate that the used organic molecule effectively adsorbs on and prompts discernible changes in the (opto)electronic properties of the 2D material. These changes encompass variations in the Raman spectra shape, alterations in the photoluminescence (PL) signal characteristics and modifications in excitonic properties. Such alterations can be linked to various phenomena including doping, bandgap modifications, introduction or healing of defects and that the solvent plays a crucial role in the process. Our study provides insights into the modification of 2D materials under ambient conditions and highlights the importance of solvent selection in the process. Full article
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13 pages, 4704 KiB  
Article
Sub-THz Vibrational Dynamics in Ordered Mesoporous Silica Nanoparticles
by Eduardo Hernando Abad, Frédéric Bouyer, Laroussi Chaabane, Alan Zerrouki, Jérémie Margueritat and Lucien Saviot
Nanomaterials 2023, 13(14), 2078; https://doi.org/10.3390/nano13142078 - 15 Jul 2023
Cited by 1 | Viewed by 1000
Abstract
The vibrational dynamics in the sub-THz range of mesoporous silica nanoparticles (MSNs) having ordered cylindrical mesopores was investigated. MCM-41 and SBA-15 particles were synthesized, and their structure was determined using scanning electron microscopy (SEM), low-angle X-ray diffraction (XRD), N2 physisorption analyses, and [...] Read more.
The vibrational dynamics in the sub-THz range of mesoporous silica nanoparticles (MSNs) having ordered cylindrical mesopores was investigated. MCM-41 and SBA-15 particles were synthesized, and their structure was determined using scanning electron microscopy (SEM), low-angle X-ray diffraction (XRD), N2 physisorption analyses, and Raman scattering. Brillouin scattering measurements are reported and enabled determining the stiffness of the silica walls (speed of sound) using finite element calculations for the ordered mesoporous structure. The relevance of this approach is discussed based on the comparison between the numerical and experimental results and previous works reported in the literature. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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12 pages, 6422 KiB  
Article
Synthesis of Multiple Emission Carbon Dots from Dihydroxybenzoic Acid via Decarboxylation Process
by Pengfei Li, Jijian Xu, Ziye Shen, Wenning Liu, Li An, Dan Qu, Xiayan Wang and Zaicheng Sun
Nanomaterials 2023, 13(14), 2062; https://doi.org/10.3390/nano13142062 - 13 Jul 2023
Cited by 1 | Viewed by 1149
Abstract
Carbon dots (CDs), as a new zero-dimensional carbon-based nanomaterial with desirable optical properties, exhibit great potential for many application fields. However, the preparation technique of multiple emission CDs with high yield is difficult and complex. Therefore, exploring the large-scale and straightforward synthesis of [...] Read more.
Carbon dots (CDs), as a new zero-dimensional carbon-based nanomaterial with desirable optical properties, exhibit great potential for many application fields. However, the preparation technique of multiple emission CDs with high yield is difficult and complex. Therefore, exploring the large-scale and straightforward synthesis of multicolor CDs from a simple carbon source is necessary. In this work, the solvent-free method prepares a series of multicolor emission CDs from dihydroxybenzoic acid (DHBA). The maximum emission wavelengths are 408, 445, 553, 580, and 610 nm, respectively, covering the visible light region. The 2,4- and 2,6-CDs possess the longer emission wavelength caused by the 2,4-, and 2,6-DHBA easily undergo decarboxylation to form the larger sp2 domain graphitized structure. These CDs incorporated with g-C3N4 can significantly improve the photocatalytic water-splitting hydrogen production rate by extending the visible light absorption and enhancing the charge separation efficiency. The long-wavelength emission CDs can further enhance photocatalytic activity primarily by improving visible light absorption efficiency. Full article
(This article belongs to the Special Issue Nano-Composites for Photo- and Electrocatalysis and Its Application)
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17 pages, 5222 KiB  
Article
Incorporation/Enrichment of 3D Bioprinted Constructs by Biomimetic Nanoparticles: Tuning Printability and Cell Behavior in Bone Models
by Tiziana Fischetti, Giorgia Borciani, Sofia Avnet, Katia Rubini, Nicola Baldini, Gabriela Graziani and Elisa Boanini
Nanomaterials 2023, 13(14), 2040; https://doi.org/10.3390/nano13142040 - 10 Jul 2023
Cited by 1 | Viewed by 1044
Abstract
Reproducing in vitro a model of the bone microenvironment is a current need. Preclinical in vitro screening, drug discovery, as well as pathophysiology studies may benefit from in vitro three-dimensional (3D) bone models, which permit high-throughput screening, low costs, and high reproducibility, overcoming [...] Read more.
Reproducing in vitro a model of the bone microenvironment is a current need. Preclinical in vitro screening, drug discovery, as well as pathophysiology studies may benefit from in vitro three-dimensional (3D) bone models, which permit high-throughput screening, low costs, and high reproducibility, overcoming the limitations of the conventional two-dimensional cell cultures. In order to obtain these models, 3D bioprinting offers new perspectives by allowing a combination of advanced techniques and inks. In this context, we propose the use of hydroxyapatite nanoparticles, assimilated to the mineral component of bone, as a route to tune the printability and the characteristics of the scaffold and to guide cell behavior. To this aim, both stoichiometric and Sr-substituted hydroxyapatite nanocrystals are used, so as to obtain different particle shapes and solubility. Our findings show that the nanoparticles have the desired shape and composition and that they can be embedded in the inks without loss of cell viability. Both Sr-containing and stoichiometric hydroxyapatite crystals permit enhancing the printing fidelity of the scaffolds in a particle-dependent fashion and control the swelling behavior and ion release of the scaffolds. Once Saos-2 cells are encapsulated in the scaffolds, high cell viability is detected until late time points, with a good cellular distribution throughout the material. We also show that even minor modifications in the hydroxyapatite particle characteristics result in a significantly different behavior of the scaffolds. This indicates that the use of calcium phosphate nanocrystals and structural ion-substitution is a promising approach to tune the behavior of 3D bioprinted constructs. Full article
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15 pages, 8835 KiB  
Article
Nanosurface Texturing for Enhancing the Antibacterial Effect of Biodegradable Metal Zinc: Surface Modifications
by Enmao Xiang, Corey S. Moran, Sašo Ivanovski and Abdalla Abdal-hay
Nanomaterials 2023, 13(13), 2022; https://doi.org/10.3390/nano13132022 - 07 Jul 2023
Cited by 4 | Viewed by 1231
Abstract
Zinc (Zn) as a biodegradable metal has attracted research interest for bone reconstruction, with the aim of eliminating the need for a second removal surgery and minimizing the implant-to-bone transfer of stress-shielding to maintain bone regeneration. In addition, Zn has been shown to [...] Read more.
Zinc (Zn) as a biodegradable metal has attracted research interest for bone reconstruction, with the aim of eliminating the need for a second removal surgery and minimizing the implant-to-bone transfer of stress-shielding to maintain bone regeneration. In addition, Zn has been shown to have antibacterial properties, particularly against Gram-negative bacteria, and is often used as a surface coating to inhibit bacterial growth and biofilm formation. However, the antibacterial property of Zn is still suboptimal in part due to low Zn ion release during degradation that has to be further improved in order to meet clinical requirements. This work aims to perform an innovative one-step surface modification using a nitric acid treatment to accelerate Zn ion release by increasing surface roughness, thereby endowing an effective antimicrobial property and biofilm formation inhibition. The antibacterial performance against Staphylococci aureus was evaluated by assessing biofilm formation and adhesion using quantitative assays. The surface roughness of acid-treated Zn (Ra ~ 30 nm) was significantly higher than polished Zn (Ra ~ 3 nm) and corresponded with the marked inhibition of bacterial biofilm, and this is likely due to the increased surface contact area and Zn ion accumulation. Overall, surface modification due to nitric acid etching appears to be an effective technique that can produce unique morphological surface structures and enhance the antibacterial properties of biodegradable Zn-based materials, thus increasing the translation potential toward multiple biomedical applications. Full article
(This article belongs to the Special Issue Nanostructured Biomaterials for Tissue Repair and Anti-infection)
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9 pages, 2352 KiB  
Article
Methods for Obtaining One Single Larmor Frequency, Either v1 or v2, in the Coherent Spin Dynamics of Colloidal Quantum Dots
by Meizhen Jiang, Yuanyuan Zhang, Rongrong Hu, Yumeng Men, Lin Cheng, Pan Liang, Tianqing Jia, Zhenrong Sun and Donghai Feng
Nanomaterials 2023, 13(13), 2006; https://doi.org/10.3390/nano13132006 - 05 Jul 2023
Cited by 2 | Viewed by 938
Abstract
The coexistence of two spin components with different Larmor frequencies in colloidal CdSe and CdS quantum dots (QDs) leads to the entanglement of spin signals, complicating the analysis of dynamic processes and hampering practical applications. Here, we explored several methods, including varying the [...] Read more.
The coexistence of two spin components with different Larmor frequencies in colloidal CdSe and CdS quantum dots (QDs) leads to the entanglement of spin signals, complicating the analysis of dynamic processes and hampering practical applications. Here, we explored several methods, including varying the types of hole acceptors, air or anaerobic atmosphere and laser repetition rates, in order to facilitate the obtention of one single Larmor frequency in the coherent spin dynamics using time-resolved ellipticity spectroscopy at room temperature. In an air or nitrogen atmosphere, manipulating the photocharging processes by applying different types of hole acceptors, e.g., Li[Et3BH] and 1-octanethiol (OT), can lead to pure spin components with one single Larmor frequency. For as-grown QDs, low laser repetition rates favor the generation of the higher Larmor frequency spin component individually, while the lower Larmor frequency spin component can be enhanced by increasing the laser repetition rates. We hope that the explored methods can inspire further investigations of spin dynamics and related photophysical processes in colloidal nanostructures. Full article
(This article belongs to the Special Issue Semiconductor Quantum Dots: Synthesis, Properties and Applications)
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12 pages, 4597 KiB  
Article
Towards All-Non-Vacuum-Processed Photovoltaic Systems: A Water-Based Screen-Printed Cu(In,Ga)Se2 Photoabsorber with a 6.6% Efficiency
by Bruna F. Gonçalves, Viviana Sousa, José Virtuoso, Evgeny Modin, Oleg I. Lebedev, Gabriela Botelho, Sascha Sadewasser, Laura M. Salonen, Senentxu Lanceros-Méndez and Yury V. Kolen’ko
Nanomaterials 2023, 13(13), 1920; https://doi.org/10.3390/nano13131920 - 23 Jun 2023
Cited by 1 | Viewed by 1190
Abstract
During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se2 chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to [...] Read more.
During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se2 chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to be effective solutions. This work combined printing, coating, and chemical bath deposition processes of photoabsorber, buffer, and transparent conductive layers for the development of solution-processed photovoltaic systems. Using a sustainable approach, all inks were formulated using water and ethanol as solvents. Screen printing of the photoabsorber on fluorine-doped tin-oxide-coated glass followed by selenization, chemical bath deposition of the cadmium sulfide buffer, and final sputtering of the intrinsic zinc oxide and aluminum-doped zinc oxide top conductive layers delivered a 6.6% maximum efficiency solar cell, a record for screen-printed Cu(In,Ga)Se2 solar cells. On the other hand, the all-non-vacuum-processed device with spray-coated intrinsic zinc-oxide- and tin-doped indium oxide top conductive layers delivered a 2.2% efficiency. The given approaches represent relevant steps towards the fabrication of sustainable and efficient Cu(In,Ga)Se2 solar cells. Full article
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16 pages, 4852 KiB  
Article
Single-Charge Tunneling in Codoped Silicon Nanodevices
by Daniel Moraru, Tsutomu Kaneko, Yuta Tamura, Taruna Teja Jupalli, Rohitkumar Shailendra Singh, Chitra Pandy, Luminita Popa and Felicia Iacomi
Nanomaterials 2023, 13(13), 1911; https://doi.org/10.3390/nano13131911 - 22 Jun 2023
Cited by 1 | Viewed by 1426
Abstract
Silicon (Si) nano-electronics is advancing towards the end of the Moore’s Law, as gate lengths of just a few nanometers have been already reported in state-of-the-art transistors. In the nanostructures that act as channels in transistors or depletion layers in pn diodes, the [...] Read more.
Silicon (Si) nano-electronics is advancing towards the end of the Moore’s Law, as gate lengths of just a few nanometers have been already reported in state-of-the-art transistors. In the nanostructures that act as channels in transistors or depletion layers in pn diodes, the role of dopants becomes critical, since the transport properties depend on a small number of dopants and/or on their random distribution. Here, we present the possibility of single-charge tunneling in codoped Si nanodevices formed in silicon-on-insulator films, in which both phosphorus (P) donors and boron (B) acceptors are introduced intentionally. For highly doped pn diodes, we report band-to-band tunneling (BTBT) via energy states in the depletion layer. These energy states can be ascribed to quantum dots (QDs) formed by the random distribution of donors and acceptors in such a depletion layer. For nanoscale silicon-on-insulator field-effect transistors (SOI-FETs) doped heavily with P-donors and also counter-doped with B-acceptors, we report current peaks and Coulomb diamonds. These features are ascribed to single-electron tunneling (SET) via QDs in the codoped nanoscale channels. These reports provide new insights for utilizing codoped silicon nanostructures for fundamental applications, in which the interplay between donors and acceptors can enhance the functionalities of the devices. Full article
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20 pages, 6507 KiB  
Article
From Synthesis to Clinical Trial: Novel Bioinductive Calcium Deficient HA/β-TCP Bone Grafting Nanomaterial
by Oleg Mishchenko, Anna Yanovska, Oksana Sulaieva, Roman Moskalenko, Mykola Pernakov, Yevheniia Husak, Viktoriia Korniienko, Volodymyr Deineka, Oleksii Kosinov, Olga Varakuta, Simonas Ramanavicius, Suren Varzhapetjan, Almira Ramanaviciene, Dzanna Krumina, Gundega Knipše, Arunas Ramanavicius and Maksym Pogorielov
Nanomaterials 2023, 13(12), 1876; https://doi.org/10.3390/nano13121876 - 17 Jun 2023
Viewed by 1309
Abstract
Maxillary sinus augmentation is a commonly used procedure for the placement of dental implants. However, the use of natural and synthetic materials in this procedure has resulted in postoperative complications ranging from 12% to 38%. To address this issue, we developed a novel [...] Read more.
Maxillary sinus augmentation is a commonly used procedure for the placement of dental implants. However, the use of natural and synthetic materials in this procedure has resulted in postoperative complications ranging from 12% to 38%. To address this issue, we developed a novel calcium deficient HA/β-TCP bone grafting nanomaterial using a two-step synthesis method with appropriate structural and chemical parameters for sinus lifting applications. We demonstrated that our nanomaterial exhibits high biocompatibility, enhances cell proliferation, and stimulates collagen expression. Furthermore, the degradation of β-TCP in our nanomaterial promotes blood clot formation, which supports cell aggregation and new bone growth. In a clinical trial involving eight cases, we observed the formation of compact bone tissue 8 months after the operation, allowing for the successful installation of dental implants without any early postoperative complications. Our results suggest that our novel bone grafting nanomaterial has the potential to improve the success rate of maxillary sinus augmentation procedures. Full article
(This article belongs to the Special Issue New Insights in Nanomaterials for Dental Diseases Management)
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18 pages, 25736 KiB  
Article
Machine Learning Electron Density Prediction Using Weighted Smooth Overlap of Atomic Positions
by Siddarth K. Achar, Leonardo Bernasconi and J. Karl Johnson
Nanomaterials 2023, 13(12), 1853; https://doi.org/10.3390/nano13121853 - 13 Jun 2023
Cited by 3 | Viewed by 2814
Abstract
Having access to accurate electron densities in chemical systems, especially for dynamical systems involving chemical reactions, ion transport, and other charge transfer processes, is crucial for numerous applications in materials chemistry. Traditional methods for computationally predicting electron density data for such systems include [...] Read more.
Having access to accurate electron densities in chemical systems, especially for dynamical systems involving chemical reactions, ion transport, and other charge transfer processes, is crucial for numerous applications in materials chemistry. Traditional methods for computationally predicting electron density data for such systems include quantum mechanical (QM) techniques, such as density functional theory. However, poor scaling of these QM methods restricts their use to relatively small system sizes and short dynamic time scales. To overcome this limitation, we have developed a deep neural network machine learning formalism, which we call deep charge density prediction (DeepCDP), for predicting charge densities by only using atomic positions for molecules and condensed phase (periodic) systems. Our method uses the weighted smooth overlap of atomic positions to fingerprint environments on a grid-point basis and map it to electron density data generated from QM simulations. We trained models for bulk systems of copper, LiF, and silicon; for a molecular system, water; and for two-dimensional charged and uncharged systems, hydroxyl-functionalized graphane, with and without an added proton. We showed that DeepCDP achieves prediction R2 values greater than 0.99 and mean squared error values on the order of 105e2 Å6 for most systems. DeepCDP scales linearly with system size, is highly parallelizable, and is capable of accurately predicting the excess charge in protonated hydroxyl-functionalized graphane. We demonstrate how DeepCDP can be used to accurately track the location of charges (protons) by computing electron densities at a few selected grid points in the materials, thus significantly reducing the computational cost. We also show that our models can be transferable, allowing prediction of electron densities for systems on which it has not been trained but that contain a subset of atomic species on which it has been trained. Our approach can be used to develop models that span different chemical systems and train them for the study of large-scale charge transport and chemical reactions. Full article
(This article belongs to the Special Issue First-Principle Calculation Study of Nanomaterials)
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19 pages, 6390 KiB  
Article
The True Nature of Tricalcium Phosphate Used as Food Additive (E341(iii))
by Youssef El Moussaoui, Hélène Terrisse, Sophie Quillard, Marie-Hélène Ropers and Bernard Humbert
Nanomaterials 2023, 13(12), 1823; https://doi.org/10.3390/nano13121823 - 08 Jun 2023
Cited by 1 | Viewed by 1950
Abstract
Tricalcium phosphate (TCP) is a food additive, labeled E341(iii), used in powdered food preparation, such as baby formula. In the United States, calcium phosphate nano-objects were identified in baby formula extractions. Our goal is to determine whether the TCP food additive, as is [...] Read more.
Tricalcium phosphate (TCP) is a food additive, labeled E341(iii), used in powdered food preparation, such as baby formula. In the United States, calcium phosphate nano-objects were identified in baby formula extractions. Our goal is to determine whether the TCP food additive, as is used in Europe, can be classified as a nanomaterial. The physicochemical properties of TCP were characterized. Three different samples (from a chemical company and two manufacturers) were thoroughly characterized according to the recommendations of the European Food Safety Authority. A commercial TCP food additive was identified as actually being hydroxyapatite (HA). It presents itself in the form of particles of different shapes (either needle-like, rod, or pseudo-spherical), which were demonstrated in this paper to be of a nanometric dimension: E341(iii) is thus a nanomaterial. In water, HA particles sediment rapidly as agglomerates or aggregates over a pH of 6 and are progressively dissolved in acidic media (pH < 5) until the complete dissolution at a pH of 2. Consequently, since TCP may be considered as a nanomaterial on the European market, it raises the question of its potential persistency in the gastrointestinal tract. Full article
(This article belongs to the Special Issue Nanomaterials for Food Science and Technology)
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13 pages, 7668 KiB  
Article
The Influence of Catechols on the Magnetization of Iron Oxide Nanoparticles
by Stanislav Čampelj, Matic Pobrežnik, Tomas Landovsky, Janez Kovač, Layla Martin-Samos, Vera Hamplova and Darja Lisjak
Nanomaterials 2023, 13(12), 1822; https://doi.org/10.3390/nano13121822 - 08 Jun 2023
Viewed by 1280
Abstract
In this study, MNPs were functionalized with pyrocatechol (CAT), pyrogallol (GAL), caffeic acid (CAF), and nitrodopamine (NDA) at pH 8 and pH 11. The functionalization of the MNPs was successful, except in the case of NDA at pH 11. The thermogravimetric analyses indicated [...] Read more.
In this study, MNPs were functionalized with pyrocatechol (CAT), pyrogallol (GAL), caffeic acid (CAF), and nitrodopamine (NDA) at pH 8 and pH 11. The functionalization of the MNPs was successful, except in the case of NDA at pH 11. The thermogravimetric analyses indicated that the surface concentration of the catechols was between 1.5 and 3.6 molecules/nm2. The saturation magnetizations (Ms) of the functionalized MNPs were higher than the starting material. XPS analyses showed only the presence of Fe(III) ions on the surface, thus refuting the idea of the Fe being reduced and magnetite being formed on the surfaces of the MNPs. Density functional theory (DFT) calculations were performed for two modes of adsorption of CAT onto two model surfaces: plain and adsorption via condensation. The total magnetization of both adsorption modes remained the same, indicating that the adsorption of the catechols does not affect the Ms. The analyses of the size and the size distribution showed an increase in the average size of the MNPs during the functionalization process. This increase in the average size of the MNPs and the reduction in the fraction of the smallest (i.e., <10 nm) MNPs explained the increase in the Ms values. Full article
(This article belongs to the Topic Functional Surface Modifications of Nanostructures)
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13 pages, 3826 KiB  
Article
Transport Characteristics of Silicon Multi-Quantum-Dot Transistor Analyzed by Means of Experimental Parametrization Based on Single-Hole Tunneling Model
by Youngmin Lee, Hyewon Jun, Seoyeon Park, Deuk Young Kim and Sejoon Lee
Nanomaterials 2023, 13(11), 1809; https://doi.org/10.3390/nano13111809 - 05 Jun 2023
Viewed by 1125
Abstract
The transport characteristics of a gate-all-around Si multiple-quantum-dot (QD) transistor were studied by means of experimental parametrization using theoretical models. The device was fabricated by using the e-beam lithographically patterned Si nanowire channel, in which the ultrasmall QDs were self-created along the [...] Read more.
The transport characteristics of a gate-all-around Si multiple-quantum-dot (QD) transistor were studied by means of experimental parametrization using theoretical models. The device was fabricated by using the e-beam lithographically patterned Si nanowire channel, in which the ultrasmall QDs were self-created along the Si nanowire due to its volumetric undulation. Owing to the large quantum-level spacings of the self-formed ultrasmall QDs, the device clearly exhibited both Coulomb blockade oscillation (CBO) and negative differential conductance (NDC) characteristics at room temperature. Furthermore, it was also observed that both CBO and NDC could evolve along the extended blockade region within wide gate and drain bias voltage ranges. By analyzing the experimental device parameters using the simple theoretical single-hole-tunneling models, the fabricated QD transistor was confirmed as comprising the double-dot system. Consequently, based on the analytical energy-band diagram, we found that the formation of ultrasmall QDs with imbalanced energetic natures (i.e., imbalanced quantum energy states and their imbalanced capacitive-coupling strengths between the two dots) could lead to effective CBO/NDC evolution in wide bias voltage ranges. Full article
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11 pages, 6504 KiB  
Article
Precision Tailoring Quasi-BIC Resonance of a-Si:H Metasurfaces
by Athira Kuppadakkath, Ángela Barreda, Lilit Ghazaryan, Tobias Bucher, Kirill Koshelev, Thomas Pertsch, Adriana Szeghalmi, Duk Choi, Isabelle Staude and Falk Eilenberger
Nanomaterials 2023, 13(11), 1810; https://doi.org/10.3390/nano13111810 - 05 Jun 2023
Cited by 3 | Viewed by 1620
Abstract
The capability of tailoring the resonance wavelength of metasurfaces is important as it can alleviate the manufacturing precision required to produce the exact structure according to the design of the nanoresonators. Tuning of Fano resonances by applying heat has been theoretically predicted in [...] Read more.
The capability of tailoring the resonance wavelength of metasurfaces is important as it can alleviate the manufacturing precision required to produce the exact structure according to the design of the nanoresonators. Tuning of Fano resonances by applying heat has been theoretically predicted in the case of silicon metasurfaces. Here, we experimentally demonstrate the permanent tailoring of quasi-bound states in the continuum (quasi-BIC) resonance wavelength in an a-Si:H metasurface and quantitatively analyze the modification in the Q-factor with gradual heating. A gradual increment in temperature leads to a spectral shift in the resonance wavelength. With the support of ellipsometry measurements, the spectral shift resulting from the short-duration (ten minutes) heating is identified to be due to refractive index variations in the material rather than a geometric effect or amorphous/polycrystalline phase transition. In the case of quasi-BIC modes in the near-infrared, resonance wavelength could be adjusted from T = 350 °C to T = 550 °C without affecting the Q-factor considerably. Apart from the temperature-induced resonance trimming, large Q-factors can be attained at the highest analyzed temperature (T = 700 °C) in the near-infrared quasi-BIC modes. Resonance tailoring is just one of the possible applications of our results. We expect that our study is also insightful in the design of a-Si:H metasurfaces where large Q-factors are required at high temperatures. Full article
(This article belongs to the Special Issue Metasurfaces for Photonic Devices: Theory and Applications)
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15 pages, 3708 KiB  
Article
Construction of 2D/2D Mesoporous WO3/CeO2 Laminated Heterojunctions for Optimized Photocatalytic Performance
by Wenjie Wang, Decai Yang, Yifan Mou, Lijun Liao, Shijie Wang, Liping Guo, Xuepeng Wang, Zhenzi Li and Wei Zhou
Nanomaterials 2023, 13(11), 1798; https://doi.org/10.3390/nano13111798 - 04 Jun 2023
Cited by 2 | Viewed by 1275
Abstract
Photocatalytic elimination of antibiotics from the environment and drinking water is of great significance for human health. However, the efficiency of photoremoval of antibiotics such as tetracycline is severely limited by the prompt recombination of electron holes and slow charge migration efficacy. Fabrication [...] Read more.
Photocatalytic elimination of antibiotics from the environment and drinking water is of great significance for human health. However, the efficiency of photoremoval of antibiotics such as tetracycline is severely limited by the prompt recombination of electron holes and slow charge migration efficacy. Fabrication of low-dimensional heterojunction composites is an efficient method for shortening charge carrier migration distance and enhancing charge transfer efficiency. Herein, 2D/2D mesoporous WO3/CeO2 laminated Z-scheme heterojunctions were successfully prepared using a two-step hydrothermal process. The mesoporous structure of the composites was proved by nitrogen sorption isotherms, in which sorption-desorption hysteresis was observed. The intimate contact and charge transfer mechanism between WO3 nanoplates and CeO2 nanosheets was investigated using high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy measurements, respectively. Photocatalytic tetracycline degradation efficiency was noticeably promoted by the formation of 2D/2D laminated heterojunctions. The improved photocatalytic activity could be attributed to the formation of Z-scheme laminated heterostructure and 2D morphology favoring spatial charge separation, confirmed by various characterizations. The optimized 5WO3/CeO2 (5 wt.% WO3) composites can degrade more than 99% of tetracycline in 80 min, achieving a peak TC photodegradation efficiency of 0.0482 min−1, which is approximately 3.4 times that of pristine CeO2. A Z-scheme mechanism is proposed for photocatalytic tetracycline by from WO3/CeO2 Z-scheme laminated heterojunctions based on the experimental results. Full article
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26 pages, 8534 KiB  
Article
Size Matters? A Comprehensive In Vitro Study of the Impact of Particle Size on the Toxicity of ZnO
by Montserrat Mitjans, Laura Marics, Marc Bilbao, Adriana S. Maddaleno, Juan José Piñero and M. Pilar Vinardell
Nanomaterials 2023, 13(11), 1800; https://doi.org/10.3390/nano13111800 - 04 Jun 2023
Cited by 1 | Viewed by 1365
Abstract
This study describes a comparative in vitro study of the toxicity behavior of zinc oxide (ZnO) nanoparticles and micro-sized particles. The study aimed to understand the impact of particle size on ZnO toxicity by characterizing the particles in different media, including cell culture [...] Read more.
This study describes a comparative in vitro study of the toxicity behavior of zinc oxide (ZnO) nanoparticles and micro-sized particles. The study aimed to understand the impact of particle size on ZnO toxicity by characterizing the particles in different media, including cell culture media, human plasma, and protein solutions (bovine serum albumin and fibrinogen). The particles and their interactions with proteins were characterized in the study using a variety of methods, including atomic force microscopy (AFM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). Hemolytic activity, coagulation time, and cell viability assays were used to assess ZnO toxicity. The results highlight the complex interactions between ZnO NPs and biological systems, including their aggregation behavior, hemolytic activity, protein corona formation, coagulation effects, and cytotoxicity. Additionally, the study indicates that ZnO nanoparticles are not more toxic than micro-sized particles, and the 50 nm particle results were, in general, the least toxic. Furthermore, the study found that, at low concentrations, no acute toxicity was observed. Overall, this study provides important insights into the toxicity behavior of ZnO particles and highlights that no direct relationship between nanometer size and toxicity can be directly attributed. Full article
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22 pages, 7173 KiB  
Article
Comparative Study of the U(VI) Adsorption by Hybrid Silica-Hyperbranched Poly(ethylene imine) Nanoparticles and Xerogels
by Michael Arkas, Konstantinos Giannakopoulos, Evangelos P. Favvas, Sergios Papageorgiou, George V. Theodorakopoulos, Artemis Giannoulatou, Michail Vardavoulias, Dimitrios A. Giannakoudakis, Konstantinos S. Triantafyllidis, Efthalia Georgiou and Ioannis Pashalidis
Nanomaterials 2023, 13(11), 1794; https://doi.org/10.3390/nano13111794 - 02 Jun 2023
Cited by 3 | Viewed by 1411
Abstract
Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to [...] Read more.
Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities, and MW of the organic matrix, was investigated to determine the optimum formulation for water purification under these conditions. This was attained with the aid of UV-visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential, liquid nitrogen (LN2) porosimetry, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Results highlighted that both adsorbents have extraordinary sorption capacities. Xerogels are cost-effective since they approximate the performance of nanoparticles with much less organic content. Both adsorbents could be used in the form of dispersions. The xerogels, though, are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor gel-forming solution, producing composite purification devices. Full article
(This article belongs to the Special Issue Nanoscale Materials for Water Purification and Catalysis)
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15 pages, 3945 KiB  
Article
Calculation of Self, Corrected, and Transport Diffusivities of Isopropyl Alcohol in UiO-66
by Chinmay V. Mhatre, Jacob J. Wardzala, Priyanka B. Shukla, Mayank Agrawal and J. Karl Johnson
Nanomaterials 2023, 13(11), 1793; https://doi.org/10.3390/nano13111793 - 02 Jun 2023
Cited by 2 | Viewed by 1617
Abstract
The UiO-6x family of metal-organic frameworks has been extensively studied for applications in chemical warfare agent (CWA) capture and destruction. An understanding of intrinsic transport phenomena, such as diffusion, is key to understanding experimental results and designing effective materials for CWA capture. However, [...] Read more.
The UiO-6x family of metal-organic frameworks has been extensively studied for applications in chemical warfare agent (CWA) capture and destruction. An understanding of intrinsic transport phenomena, such as diffusion, is key to understanding experimental results and designing effective materials for CWA capture. However, the relatively large size of CWAs and their simulants makes diffusion in the small-pored pristine UiO-66 very slow and hence impractical to study directly with direct molecular simulations because of the time scales required. We used isopropanol (IPA) as a surrogate for CWAs to investigate the fundamental diffusion mechanisms of a polar molecule within pristine UiO-66. IPA can form hydrogen bonds with the μ3-OH groups bound to the metal oxide clusters in UiO-66, similar to some CWAs, and can be studied by direct molecular dynamics simulations. We report self, corrected, and transport diffusivities of IPA in pristine UiO-66 as a function of loading. Our calculations highlight the importance of the accurate modeling of the hydrogen bonding interactions on diffusivities, with about an order of magnitude decrease in diffusion coefficients when the hydrogen bonding between IPA and the μ3-OH groups is included. We found that a fraction of the IPA molecules have very low mobility during the course of a simulation, while a small fraction are highly mobile, exhibiting mean square displacements far greater than the ensemble average. Full article
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15 pages, 6194 KiB  
Article
Zinc Oxide Nanoparticles—Solution-Based Synthesis and Characterizations
by Khagendra P. Bhandari, Dhurba R. Sapkota, Manoj K. Jamarkattel, Quenton Stillion and Robert W. Collins
Nanomaterials 2023, 13(11), 1795; https://doi.org/10.3390/nano13111795 - 02 Jun 2023
Cited by 3 | Viewed by 2416
Abstract
Zinc oxide (ZnO) nanoparticles have shown great potential because of their versatile and promising applications in different fields, including solar cells. Various methods of synthesizing ZnO materials have been reported. In this work, controlled synthesis of ZnO nanoparticles was achieved via a simple, [...] Read more.
Zinc oxide (ZnO) nanoparticles have shown great potential because of their versatile and promising applications in different fields, including solar cells. Various methods of synthesizing ZnO materials have been reported. In this work, controlled synthesis of ZnO nanoparticles was achieved via a simple, cost-effective, and facile synthetic method. Using transmittance spectra and film thickness of ZnO, the optical band gap energies were calculated. For as-synthesized and annealed ZnO films, the bandgap energies were found to be 3.40 eV and 3.30 eV, respectively. The nature of the optical transition indicates that the material is a direct bandgap semiconductor. Spectroscopic ellipsometry (SE) analysis was used to extract dielectric functions where the onset of optical absorption of ZnO was observed at lower photon energy due to annealing of the nanoparticle film. Similarly, X-ray diffraction (XRD) and scanning electron microscopy (SEM) data revealed that the material is pure and crystalline in nature, with the average crystallite size of ~9 nm. Full article
(This article belongs to the Topic Nanomaterials for Energy and Environmental Applications)
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12 pages, 5167 KiB  
Article
Enhanced Photoluminescence and Random Lasing Emission in TiO2-Decorated FAPbBr3 Thin Films
by Xiaohong Liu, Caixia Xu and Hongquan Zhao
Nanomaterials 2023, 13(11), 1761; https://doi.org/10.3390/nano13111761 - 30 May 2023
Viewed by 1410
Abstract
Herein, titanium-dioxide-decorated organic formamidinium lead bromide perovskite thin films grown by the one-step spin-coating method are studied. TiO2 nanoparticles are widespread in FAPbBr3 thin films, which changes the optical properties of the perovskite thin films effectively. Obvious reductions in the absorption [...] Read more.
Herein, titanium-dioxide-decorated organic formamidinium lead bromide perovskite thin films grown by the one-step spin-coating method are studied. TiO2 nanoparticles are widespread in FAPbBr3 thin films, which changes the optical properties of the perovskite thin films effectively. Obvious reductions in the absorption and enhancements in the intensity of the photoluminescence spectra are observed. Over 6 nm, a blueshift of the photoluminescence emission peaks is observed due to 5.0 mg/mL TiO2 nanoparticle decoration in the thin films, which originates from the variation in the grain sizes of the perovskite thin films. Light intensity redistributions in perovskite thin films are measured by using a home-built confocal microscope, and the multiple scattering and weak localization of light are analyzed based on the scattering center of TiO2 nanoparticle clusters. Furthermore, random lasing emission with sharp emission peaks is achieved in the scattering perovskite thin films with a full width at the half maximum of 2.1 nm. The multiple scattering of light, the random reflection and reabsorption of light, and the coherent interaction of light within the TiO2 nanoparticle clusters play important roles in random lasing. This work could be used to improve the efficiency of photoluminescence and random lasing emissions, and it is promising in high-performance optoelectrical devices. Full article
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12 pages, 6609 KiB  
Article
One-Step Electrochemical Dealloying of 3D Bi-Continuous Micro-Nanoporous Bismuth Electrodes and CO2RR Performance
by Wenqin Lai, Yating Liu, Mingming Zeng, Dongmei Han, Min Xiao, Shuanjin Wang, Shan Ren and Yuezhong Meng
Nanomaterials 2023, 13(11), 1767; https://doi.org/10.3390/nano13111767 - 30 May 2023
Cited by 1 | Viewed by 1169
Abstract
The rapid development of electrochemical CO2 reduction offers a promising route to convert intermittent renewable energy into products of high value-added fuels or chemical feedstocks. However, low faradaic efficiency, low current density, and a narrow potential range still limit the large-scale application [...] Read more.
The rapid development of electrochemical CO2 reduction offers a promising route to convert intermittent renewable energy into products of high value-added fuels or chemical feedstocks. However, low faradaic efficiency, low current density, and a narrow potential range still limit the large-scale application of CO2RR electrocatalysts. Herein, monolith 3D bi-continuous nanoporous bismuth (np-Bi) electrodes are fabricated via a simple one-step electrochemical dealloying strategy from Pb-Bi binary alloy. The unique bi-continuous porous structure ensures highly effective charge transfer; meanwhile, the controllable millimeter-sized geometric porous structure enables easy catalyst adjustment to expose highly suitable surface curvatures with abundant reactive sites. This results in a high selectivity of 92.6% and superior potential window (400 mV, selectivity > 88%) for the electrochemical reduction of carbon dioxide to formate. Our scalable strategy provides a feasible pathway for mass-producing high-performance and versatile CO2 electrocatalysts. Full article
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15 pages, 2658 KiB  
Article
High-Performance Perovskite Solar Cells and Modules Fabricated by Slot-Die Coating with Nontoxic Solvents
by Chia-Feng Li, Hung-Che Huang, Shih-Han Huang, Yu-Hung Hsiao, Priyanka Chaudhary, Chun-Yu Chang, Feng-Yu Tsai, Wei-Fang Su and Yu-Ching Huang
Nanomaterials 2023, 13(11), 1760; https://doi.org/10.3390/nano13111760 - 29 May 2023
Cited by 2 | Viewed by 1798
Abstract
Energy shortage has become a global issue in the twenty-firt century, as energy consumption grows at an alarming rate as the fossil fuel supply exhausts. Perovskite solar cells (PSCs) are a promising photovoltaic technology that has grown quickly in recent years. Its power [...] Read more.
Energy shortage has become a global issue in the twenty-firt century, as energy consumption grows at an alarming rate as the fossil fuel supply exhausts. Perovskite solar cells (PSCs) are a promising photovoltaic technology that has grown quickly in recent years. Its power conversion efficiency (PCE) is comparable to that of traditional silicon-based solar cells, and scale-up costs can be substantially reduced due to its utilization of solution-processable fabrication. Nevertheless, most PSCs research uses hazardous solvents, such as dimethylformamide (DMF) and chlorobenzene (CB), which are not suitable for large-scale ambient operations and industrial production. In this study, we have successfully deposited all of the layers of PSCs, except the top metal electrode, under ambient conditions using a slot-die coating process and nontoxic solvents. The fully slot-die coated PSCs exhibited PCEs of 13.86% and 13.54% in a single device (0.09 cm2) and mini-module (0.75 cm2), respectively. Full article
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21 pages, 14746 KiB  
Article
Enhancing Functionalization of Health Care Textiles with Gold Nanoparticle-Loaded Hydroxyapatite Composites
by Bárbara Vieira, Jorge Padrão, Cátia Alves, Carla Joana Silva, Helena Vilaça and Andrea Zille
Nanomaterials 2023, 13(11), 1752; https://doi.org/10.3390/nano13111752 - 27 May 2023
Viewed by 1368
Abstract
Hospitals and nursing home wards are areas prone to the propagation of infections and are of particular concern regarding the spreading of dangerous viruses and multidrug-resistant bacteria (MDRB). MDRB infections comprise approximately 20% of cases in hospitals and nursing homes. Healthcare textiles, such [...] Read more.
Hospitals and nursing home wards are areas prone to the propagation of infections and are of particular concern regarding the spreading of dangerous viruses and multidrug-resistant bacteria (MDRB). MDRB infections comprise approximately 20% of cases in hospitals and nursing homes. Healthcare textiles, such as blankets, are ubiquitous in hospitals and nursing home wards and may be easily shared between patients/users without an adequate pre-cleaning process. Therefore, functionalizing these textiles with antimicrobial properties may considerably reduce the microbial load and prevent the propagation of infections, including MDRB. Blankets are mainly comprised of knitted cotton (CO), polyester (PES), and cotton-polyester (CO–PES). These fabrics were functionalized with novel gold-hydroxyapatite nanoparticles (AuNPs-HAp) that possess antimicrobial properties, due to the presence of the AuNPs’ amine and carboxyl groups, and low propensity to display toxicity. For optimal functionalization of the knitted fabrics, two pre-treatments, four different surfactants, and two incorporation processes were evaluated. Furthermore, exhaustion parameters (time and temperature) were subjected to a design of experiments (DoE) optimization. The concentration of AuNPs-HAp in the fabrics and their washing fastness were critical factors assessed through color difference (ΔE). The best performing knitted fabric was half bleached CO, functionalized using a surfactant combination of Imerol® Jet-B (surfactant A) and Luprintol® Emulsifier PE New (surfactant D) through exhaustion at 70 °C for 10 min. This knitted CO displayed antibacterial properties even after 20 washing cycles, showing its potential to be used in comfort textiles within healthcare environments. Full article
(This article belongs to the Section Nanocomposite Materials)
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15 pages, 1247 KiB  
Article
The Key Role of Non-Local Screening in the Environment-Insensitive Exciton Fine Structures of Transition-Metal Dichalcogenide Monolayers
by Wei-Hua Li, Jhen-Dong Lin, Ping-Yuan Lo, Guan-Hao Peng, Ching-Yu Hei, Shao-Yu Chen and Shun-Jen Cheng
Nanomaterials 2023, 13(11), 1739; https://doi.org/10.3390/nano13111739 - 26 May 2023
Cited by 4 | Viewed by 1977
Abstract
In this work, we present a comprehensive theoretical and computational investigation of exciton fine structures of WSe2-monolayers, one of the best-known two-dimensional (2D) transition-metal dichalcogenides (TMDs), in various dielectric-layered environments by solving the first-principles-based Bethe–Salpeter equation. While the physical and electronic [...] Read more.
In this work, we present a comprehensive theoretical and computational investigation of exciton fine structures of WSe2-monolayers, one of the best-known two-dimensional (2D) transition-metal dichalcogenides (TMDs), in various dielectric-layered environments by solving the first-principles-based Bethe–Salpeter equation. While the physical and electronic properties of atomically thin nanomaterials are normally sensitive to the variation of the surrounding environment, our studies reveal that the influence of the dielectric environment on the exciton fine structures of TMD-MLs is surprisingly limited. We point out that the non-locality of Coulomb screening plays a key role in suppressing the dielectric environment factor and drastically shrinking the fine structure splittings between bright exciton (BX) states and various dark-exciton (DX) states of TMD-MLs. The intriguing non-locality of screening in 2D materials can be manifested by the measurable non-linear correlation between the BX-DX splittings and exciton-binding energies by varying the surrounding dielectric environments. The revealed environment-insensitive exciton fine structures of TMD-ML suggest the robustness of prospective dark-exciton-based optoelectronics against the inevitable variation of the inhomogeneous dielectric environment. Full article
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15 pages, 3159 KiB  
Article
High-Dose Exposure to Polymer-Coated Iron Oxide Nanoparticles Elicits Autophagy-Dependent Ferroptosis in Susceptible Cancer Cells
by Thanpisit Lomphithak, Selin Helvacioglu, Ilaria Armenia, Sandeep Keshavan, Jesús G. Ovejero, Giovanni Baldi, Costanza Ravagli, Valeria Grazú and Bengt Fadeel
Nanomaterials 2023, 13(11), 1719; https://doi.org/10.3390/nano13111719 - 24 May 2023
Cited by 4 | Viewed by 1795
Abstract
Ferroptosis, a form of iron-dependent, lipid peroxidation-driven cell death, has been extensively investigated in recent years, and several studies have suggested that the ferroptosis-inducing properties of iron-containing nanomaterials could be harnessed for cancer treatment. Here we evaluated the potential cytotoxicity of iron oxide [...] Read more.
Ferroptosis, a form of iron-dependent, lipid peroxidation-driven cell death, has been extensively investigated in recent years, and several studies have suggested that the ferroptosis-inducing properties of iron-containing nanomaterials could be harnessed for cancer treatment. Here we evaluated the potential cytotoxicity of iron oxide nanoparticles, with and without cobalt functionalization (Fe2O3 and Fe2O3@Co-PEG), using an established, ferroptosis-sensitive fibrosarcoma cell line (HT1080) and a normal fibroblast cell line (BJ). In addition, we evaluated poly (ethylene glycol) (PEG)-poly(lactic-co-glycolic acid) (PLGA)-coated iron oxide nanoparticles (Fe3O4-PEG-PLGA). Our results showed that all the nanoparticles tested were essentially non-cytotoxic at concentrations up to 100 μg/mL. However, when the cells were exposed to higher concentrations (200–400 μg/mL), cell death with features of ferroptosis was observed, and this was more pronounced for the Co-functionalized nanoparticles. Furthermore, evidence was provided that the cell death triggered by the nanoparticles was autophagy-dependent. Taken together, the exposure to high concentrations of polymer-coated iron oxide nanoparticles triggers ferroptosis in susceptible human cancer cells. Full article
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12 pages, 2731 KiB  
Article
A Flexible Piezocapacitive Pressure Sensor with Microsphere-Array Electrodes
by Shu Ying, Jiean Li, Jinrong Huang, Jia-Han Zhang, Jing Zhang, Yongchang Jiang, Xidi Sun, Lijia Pan and Yi Shi
Nanomaterials 2023, 13(11), 1702; https://doi.org/10.3390/nano13111702 - 23 May 2023
Cited by 5 | Viewed by 2907
Abstract
Flexible pressure sensors that emulate the sensation and characteristics of natural skins are of great importance in wearable medical devices, intelligent robots, and human–machine interfaces. The microstructure of the pressure-sensitive layer plays a significant role in the sensor’s overall performance. However, microstructures usually [...] Read more.
Flexible pressure sensors that emulate the sensation and characteristics of natural skins are of great importance in wearable medical devices, intelligent robots, and human–machine interfaces. The microstructure of the pressure-sensitive layer plays a significant role in the sensor’s overall performance. However, microstructures usually require complex and costly processes such as photolithography or chemical etching for fabrication. This paper proposes a novel approach that combines self-assembled technology to prepare a high-performance flexible capacitive pressure sensor with a microsphere-array gold electrode and a nanofiber nonwoven dielectric material. When subjected to pressure, the microsphere structures of the gold electrode deform via compressing the medium layer, leading to a significant increase in the relative area between the electrodes and a corresponding change in the thickness of the medium layer, as simulated in COMSOL simulations and experiments, which presents high sensitivity (1.807 kPa−1). The developed sensor demonstrates excellent performance in detecting signals such as slight object deformations and human finger bending. Full article
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15 pages, 3886 KiB  
Article
Peroxidase-Mimicking Ir-Te Nanorods for Photoconversion-Combined Multimodal Cancer Therapy
by Gyeonghye Yim, Seounghun Kang, Subean Kim and Hongje Jang
Nanomaterials 2023, 13(11), 1706; https://doi.org/10.3390/nano13111706 - 23 May 2023
Viewed by 1333
Abstract
Owing to multiple physicochemical properties, the combination of hybrid elemental compositions of nanoparticles can be widely utilized for a variety of applications. To combine pristine tellurium nanorods, which act as a sacrificing template, with another element, iridium–tellurium nanorods (IrTeNRs) were synthesized via the [...] Read more.
Owing to multiple physicochemical properties, the combination of hybrid elemental compositions of nanoparticles can be widely utilized for a variety of applications. To combine pristine tellurium nanorods, which act as a sacrificing template, with another element, iridium–tellurium nanorods (IrTeNRs) were synthesized via the galvanic replacement technique. Owing to the coexistence of iridium and tellurium, IrTeNRs exhibited unique properties, such as peroxidase-like activity and photoconversion. Additionally, the IrTeNRs demonstrated exceptional colloidal stability in complete media. Based on these properties, the IrTeNRs were applied to in vitro and in vivo cancer therapy, allowing for the possibility of multiple therapeutic methodologies. The enzymatic therapy was enabled by the peroxidase-like activity that generated reactive oxygen species, and the photoconversion under 473, 660 and 808 nm laser irradiation induced cancer cell apoptosis via photothermal and photodynamic therapy. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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10 pages, 536 KiB  
Article
Cone-Shell Quantum Structures in Electric and Magnetic Fields as Switchable Traps for Photoexcited Charge Carriers
by Christian Heyn, Leonardo Ranasinghe, Ahmed Alshaikh and Carlos A. Duque
Nanomaterials 2023, 13(10), 1696; https://doi.org/10.3390/nano13101696 - 22 May 2023
Viewed by 879
Abstract
The optical emission of cone-shell quantum structures (CSQS) under vertical electric (F) and magnetic (B) fields is studied by means of simulations. A CSQS has a unique shape, where an electric field induces the transformation of the hole probability [...] Read more.
The optical emission of cone-shell quantum structures (CSQS) under vertical electric (F) and magnetic (B) fields is studied by means of simulations. A CSQS has a unique shape, where an electric field induces the transformation of the hole probability density from a disk into a quantum-ring with a tunable radius. The present study addresses the influence of an additional magnetic field. A common description for the influence of a B-field on charge carriers confined in a quantum dot is the Fock-Darwin model, which introduces the angular momentum quantum number l to describe the splitting of the energy levels. For a CSQS with the hole in the quantum ring state, the present simulations demonstrate a B-dependence of the hole energy which substantially deviates from the prediction of the Fock-Darwin model. In particular, the energy of exited states with a hole lh> 0 can become lower than the ground state energy with lh= 0. Because for the lowest-energy state the electron le is always zero, states with lh> 0 are optically dark due to selection rules. This allows switching from a bright state (lh= 0) to a dark state (lh> 0) or vice versa by changing the strength of the F or B field. This effect can be very interesting for trapping photoexcited charge carriers for a desired time. Furthermore, the influence of the CSQS shape on the fields required for the bright to dark state transition is investigated. Full article
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15 pages, 10906 KiB  
Article
Multi-Scale Femtosecond-Laser Texturing for Photothermal Efficiency Enhancement on Solar Absorbers Based on TaB2 Ceramics
by Elisa Sani, Diletta Sciti, Simone Failla, Cesare Melandri, Alessandro Bellucci, Stefano Orlando and Daniele M. Trucchi
Nanomaterials 2023, 13(10), 1692; https://doi.org/10.3390/nano13101692 - 21 May 2023
Cited by 3 | Viewed by 1134
Abstract
Tantalum boride is an ultra-refractory and ultra-hard ceramic known so far for its favorable high-temperature thermo-mechanical properties and also characterized by a low spectral emittance, making it interesting for novel high-temperature solar absorbers for Concentrating Solar Power. In this work, we investigated two [...] Read more.
Tantalum boride is an ultra-refractory and ultra-hard ceramic known so far for its favorable high-temperature thermo-mechanical properties and also characterized by a low spectral emittance, making it interesting for novel high-temperature solar absorbers for Concentrating Solar Power. In this work, we investigated two types of TaB2 sintered products with different porosities, and on each of them, we realized four femtosecond laser treatments differing in the accumulated laser fluence. The treated surfaces were then characterized by SEM-EDS, roughness analysis, and optical spectrometry. We show that, depending on laser processing parameters, the multi-scale surface textures produced by femtosecond laser machining can greatly increase the solar absorptance, while the spectral emittance increase is significantly lower. These combined effects result in increased photothermal efficiency of the absorber, with interesting perspectives for the application of these ceramics in Concentrating Solar Power and Concentrating Solar Thermal. To the best of our knowledge, this is the first demonstration of successful photothermal efficiency enhancement of ultra-hard ceramics using laser machining. Full article
(This article belongs to the Special Issue Novel Nanomaterials for Renewable Energies and Technical Applications)
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12 pages, 3294 KiB  
Article
Effect of High-Energy Ball Milling, Capping Agents and Alkalizer on Capacitance of Nanostructured FeOOH Anodes
by Chengwei Zhang and Igor Zhitomirsky
Nanomaterials 2023, 13(10), 1693; https://doi.org/10.3390/nano13101693 - 21 May 2023
Viewed by 1186
Abstract
This investigation is motivated by interest in nanostructured FeOOH anodes for aqueous asymmetric supercapacitors operating in Na2SO4 electrolyte. The research goal is the fabrication of anodes with high active mass loading of 40 mg cm−2, high capacitance and [...] Read more.
This investigation is motivated by interest in nanostructured FeOOH anodes for aqueous asymmetric supercapacitors operating in Na2SO4 electrolyte. The research goal is the fabrication of anodes with high active mass loading of 40 mg cm−2, high capacitance and low resistance. The influence of high-energy ball milling (HEBM), capping agents and alkalizer on the nanostructure and capacitive properties is investigated. HEBM promotes the crystallization of FeOOH, which results in capacitance reduction. Capping agents from the catechol family, such as tetrahydroxy-1,4-benzoquinone (THB) and gallocyanine (GC), facilitate the fabrication of FeOOH nanoparticles, eliminate the formation of micron size particles and allow the fabrication of anodes with enhanced capacitance. The analysis of testing results provided insight into the influence of the chemical structure of the capping agents on nanoparticle synthesis and dispersion. The feasibility of a conceptually new strategy for the synthesis of FeOOH nanoparticles is demonstrated, which is based on the use of polyethylenimine as an organic alkalizer-dispersant. The capacitances of materials prepared using different nanotechnology strategies are compared. The highest capacitance of 6.54 F cm−2 is obtained using GC as a capping agent. The obtained electrodes are promising for applications as anodes for asymmetric supercapacitors. Full article
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14 pages, 2653 KiB  
Article
Photoelectrochemical Selective Oxidation of Glycerol to Glyceraldehyde with Bi-Based Metal–Organic-Framework-Decorated WO3 Photoanode
by Yoonsung Jung, Seungkyu Kim, Hojoong Choi, Yunseul Kim, Jun Beom Hwang, Donghyeon Lee, Yejoon Kim, Jun-Cheol Park, Dong-Yu Kim and Sanghan Lee
Nanomaterials 2023, 13(10), 1690; https://doi.org/10.3390/nano13101690 - 21 May 2023
Cited by 3 | Viewed by 2347
Abstract
The conversion of glycerol to high-value-added products via photoelectrochemical (PEC) oxidation has emerged as a promising approach for utilizing a sustainable and clean energy source with environmental and economic benefits. Moreover, the energy requirement for glycerol to produce hydrogen is lower than that [...] Read more.
The conversion of glycerol to high-value-added products via photoelectrochemical (PEC) oxidation has emerged as a promising approach for utilizing a sustainable and clean energy source with environmental and economic benefits. Moreover, the energy requirement for glycerol to produce hydrogen is lower than that for pure water splitting. In this study, we propose the use of WO3 nanostructures decorated with Bi-based metal–organic frameworks (Bi-MOFs) as the photoanode for glycerol oxidation with simultaneous hydrogen production. The WO3-based electrodes selectively converted glycerol to glyceraldehyde, a high-value-added product, with remarkable selectivity. The Bi-MOF-decorated WO3 nanorods enhanced the surface charge transfer and adsorption properties, thereby improving the photocurrent density and production rate (1.53 mA/cm2 and 257 mmol/m2·h at 0.8 VRHE). The photocurrent was maintained for 10 h, ensuring stable glycerol conversion. Furthermore, at 1.2 VRHE, the average production rate of glyceraldehyde reached 420 mmol/m2·h, with a selectivity of 93.6% between beneficial oxidized products over the photoelectrode. This study provides a practical approach for the conversion of glycerol to glyceraldehyde via the selective oxidation of WO3 nanostructures and demonstrates the potential of Bi-MOFs as a promising cocatalyst for PEC biomass valorization. Full article
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14 pages, 3450 KiB  
Article
Research on an Optimized Quarter-Wavelength Resonator-Based Triboelectric Nanogenerator for Efficient Low-Frequency Acoustic Energy Harvesting
by Xiu Xiao, Ling Liu, Ziyue Xi, Hongyong Yu, Wenxiang Li, Qunyi Wang, Cong Zhao, Yue Huang and Minyi Xu
Nanomaterials 2023, 13(10), 1676; https://doi.org/10.3390/nano13101676 - 19 May 2023
Cited by 5 | Viewed by 1517
Abstract
Sound wave is an extensively existing mechanical wave, especially in marine and industrial plants where low-frequency acoustic waves are ubiquitous. The effective collection and utilization of sound waves provide a fresh new approach to supply power for the distributed nodes of the rapidly [...] Read more.
Sound wave is an extensively existing mechanical wave, especially in marine and industrial plants where low-frequency acoustic waves are ubiquitous. The effective collection and utilization of sound waves provide a fresh new approach to supply power for the distributed nodes of the rapidly developing Internet of Things technology. In this paper, a novel acoustic triboelectric nanogenerator (QWR-TENG) was proposed for efficient low-frequency acoustic energy harvesting. QWR-TENG consisted of a quarter-wavelength resonant tube, a uniformly perforated aluminum film, an FEP membrane, and a conductive carbon nanotube coating. Simulation and experimental studies showed that QWR-TENG has two resonance peaks in the low-frequency range, which effectively extends the response bandwidth of acoustic–electrical conversion. The structural optimized QWR-TENG has excellent electrical output performance, and the maximum output voltage, short-circuit current and transferred charge are 255 V, 67 μA, and 153 nC, respectively, under the acoustic frequency of 90 Hz and sound pressure level of 100 dB. On this basis, a conical energy concentrator was introduced to the entrance of the acoustic tube, and a composite quarter-wavelength resonator-based triboelectric nanogenerator (CQWR-TENG) was designed to further enhance the electrical output. Results showed that the maximum output power and the power density per unit pressure of CQWR-TENG reached 13.47 mW and 2.27 WPa−1m−2, respectively. Application demonstrations indicated that QWR/CQWR-TENG has good capacitor charging performance and is expected to realize power supply for distributed sensor nodes and other small electrical devices. Full article
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13 pages, 6329 KiB  
Article
Monolithic MXene Aerogels Encapsulated Phase Change Composites with Superior Photothermal Conversion and Storage Capability
by Yan Wang, Fuqiang Wang, Changrui Shi, Hongsheng Dong, Yongchen Song, Jiafei Zhao and Zheng Ling
Nanomaterials 2023, 13(10), 1661; https://doi.org/10.3390/nano13101661 - 17 May 2023
Cited by 2 | Viewed by 1493
Abstract
The inherently intermittent feature of solar energy requires reliable energy conversion and storage systems for utilizing the most abundant solar energy. Phase change materials are potential solutions to store a large amount of heat produced by solar light. However, few of the phase [...] Read more.
The inherently intermittent feature of solar energy requires reliable energy conversion and storage systems for utilizing the most abundant solar energy. Phase change materials are potential solutions to store a large amount of heat produced by solar light. However, few of the phase change materials have the ability to efficiently convert solar energy into heat; additionally, phase change materials need to be encapsulated in porous substrates for enhancing their leaking resistance and photo-to-thermal performance. In this work, monolithic MXene aerogels, fabricated by Al3+ cross-linking and freeze-drying, were used as the encapsulation and photothermal materials. The composites phase change materials of MXene/polyethylene glycol can be made with a large polyethylene glycol loading above 90 wt% with the maximum of 97 wt%, owing to the large porosity of MXene aerogels. The low content of MXene has a limited impact on the phase transition temperature and enthalpy of polyethylene glycol, with an enthalpy retention rate ranging from 89.2 to 96.5% for 90–97 wt% polyethylene glycol loadings. MXene aerogels greatly improve the leaking resistance of polyethylene glycol above its melting point of 60 °C, even at 100 °C. The composites phase change materials also show outstanding cycling stability for 500 cycles of heat storage and release, retaining 97.7% of the heat storage capability. The optimized composite phase change material has a solar energy utilization of 93.5%, being superior to most of the reported results. Our strategy produces promising composite phase change materials for solar energy utilization using the MXene aerogels as the encapsulation and photothermal materials. Full article
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10 pages, 3049 KiB  
Article
Optical and Electrical Analyses of Solar Cells with a Radial PN Junction and Incorporating an Innovative NW Design That Mimics ARC Layers
by Francisco J. Cabrera-España and B. M. Azizur Rahman
Nanomaterials 2023, 13(10), 1649; https://doi.org/10.3390/nano13101649 - 16 May 2023
Viewed by 975
Abstract
The implementation of a texturing pattern on the surface of a solar cell is well known for reducing reflection, thus increasing the absorption of sunlight by the solar cell. Nanowires (NWs) that are large in their height have been widely used for this [...] Read more.
The implementation of a texturing pattern on the surface of a solar cell is well known for reducing reflection, thus increasing the absorption of sunlight by the solar cell. Nanowires (NWs) that are large in their height have been widely used for this purpose. Through rigorous numerical simulations, this work explores the benefits of short but index-matched NWs and how these designs are also affected by surface recombination. Additionally, this work further optimized power conversion efficiency (PCE) by placing two or three NWs of different heights and diameters on top of each other to mimic the performance of two-NW and three-NW ARC designs with PCEs of 16.8% and 17.55%, respectively, when a radial pn junction is considered. These are the highest reported so far for such a thin silicon solar cell. Furthermore, we also show how these designs were impacted by surface recombination velocity and compare these findings to simple NWs of different heights and diameters. Full article
(This article belongs to the Special Issue Recent Advances on Photovoltaics and Solar Cells)
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18 pages, 9066 KiB  
Article
Variation in Metal–Support Interaction with TiO2 Loading and Synthesis Conditions for Pt-Ti/SBA-15 Active Catalysts in Methane Combustion
by Mihaela Filip, Elena Maria Anghel, Vasile Rednic, Florica Papa, Simona Somacescu, Cornel Munteanu, Nicolae Aldea, Jing Zhang and Viorica Parvulescu
Nanomaterials 2023, 13(10), 1647; https://doi.org/10.3390/nano13101647 - 15 May 2023
Cited by 1 | Viewed by 1244
Abstract
The control of catalytic performance using synthesis conditions is one of the main goals of catalytic research. Two series of Pt-Ti/SBA-15 catalysts with different TiO2 percentages (n = 1, 5, 10, 30 wt.%) were obtained from tetrabutylorthotitanate (TBOT) and peroxotitanate (PT), [...] Read more.
The control of catalytic performance using synthesis conditions is one of the main goals of catalytic research. Two series of Pt-Ti/SBA-15 catalysts with different TiO2 percentages (n = 1, 5, 10, 30 wt.%) were obtained from tetrabutylorthotitanate (TBOT) and peroxotitanate (PT), as titania precursors and Pt impregnation. The obtained catalysts were characterized using X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM), N2 sorption, Raman, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), hydrogen temperature-programmed reduction (H2-TPR) and H2-chemisorption measurements. Raman spectroscopy showed framework titanium species in low TiO2 loading samples. The anatase phase was evidenced for samples with higher titania loading, obtained from TBOT, and a mixture of rutile and anatase for those synthesized by PT. The rutile phase prevails in rich TiO2 catalysts obtained from PT. Variable concentrations of Pt0 as a result of the stronger interaction of PtO with anatase and the weaker interaction with rutile were depicted using XPS. TiO2 loading and precursors influenced the concentration of Pt species, while the effect on Pt nanoparticles’ size and uniform distribution on support was insignificant. The Pt/PtO ratio and their concentration on the surface were the result of strong metal–support interaction, and this influenced catalytic performance in the complete oxidation of methane at a low temperature. The highest conversion was obtained for sample prepared from PT with 30% TiO2. Full article
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12 pages, 2144 KiB  
Article
Inductively Coupled Nonthermal Plasma Synthesis of Size-Controlled γ-Al2O3 Nanocrystals
by Zichang Xiong, Himashi P. Andaraarachchi, Jacob T. Held, Rick W. Dorn, Yong-Jin Jeong, Aaron Rossini and Uwe R. Kortshagen
Nanomaterials 2023, 13(10), 1627; https://doi.org/10.3390/nano13101627 - 12 May 2023
Viewed by 1147
Abstract
Gamma alumina (γ-Al2O3) is widely used as a catalyst and catalytic support due to its high specific surface area and porosity. However, synthesis of γ-Al2O3 nanocrystals is often a complicated process requiring high temperatures or additional [...] Read more.
Gamma alumina (γ-Al2O3) is widely used as a catalyst and catalytic support due to its high specific surface area and porosity. However, synthesis of γ-Al2O3 nanocrystals is often a complicated process requiring high temperatures or additional post-synthetic steps. Here, we report a single-step synthesis of size-controlled and monodisperse, facetted γ-Al2O3 nanocrystals in an inductively coupled nonthermal plasma reactor using trimethylaluminum and oxygen as precursors. Under optimized conditions, we observed phase-pure, cuboctahedral γ-Al2O3 nanocrystals with defined surface facets. Nuclear magnetic resonance studies revealed that nanocrystal surfaces are populated with AlO6, AlO5 and AlO4 units with clusters of hydroxyl groups. Nanocrystal size tuning was achieved by varying the total reactor pressure yielding particles as small as 3.5 nm, below the predicted thermodynamic stability limit for γ-Al2O3. Full article
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19 pages, 10429 KiB  
Article
Cell-Biological Response and Sub-Toxic Inflammatory Effects of Titanium Dioxide Particles with Defined Polymorphic Phase, Size, and Shape
by Marina Breisch, Mateusz Olejnik, Kateryna Loza, Oleg Prymak, Nina Rosenkranz, Jürgen Bünger, Christina Sengstock, Manfred Köller, Götz Westphal and Matthias Epple
Nanomaterials 2023, 13(10), 1621; https://doi.org/10.3390/nano13101621 - 12 May 2023
Viewed by 1126
Abstract
Six types of titanium dioxide particles with defined size, shape, and crystal structure (polymorphic form) were prepared: nanorods (70 × 25 nm2), rutile sub-microrods (190 × 40 nm2), rutile microspheres (620 nm), anatase nanospheres (100 nm), anatase microspheres (510 [...] Read more.
Six types of titanium dioxide particles with defined size, shape, and crystal structure (polymorphic form) were prepared: nanorods (70 × 25 nm2), rutile sub-microrods (190 × 40 nm2), rutile microspheres (620 nm), anatase nanospheres (100 nm), anatase microspheres (510 nm), and amorphous titania microspheres (620 nm). All particles were characterized by scanning electron microscopy, X-ray powder diffraction, dynamic light scattering, infrared spectroscopy, and UV spectroscopy. The sub-toxic cell-biological response to these particles by NR8383 macrophages was assessed. All particle types were taken up well by the cells. The cytotoxicity and the induction of reactive oxygen species (ROS) were negligible for all particles up to a dose of 100 µg mL−1, except for rutile microspheres which had a very rough surface in contrast to anatase and amorphous titania microspheres. The particle-induced cell migration assay (PICMA; based on chemotaxis) of all titanium dioxide particles was comparable to the effect of control silica nanoparticles (50 nm, uncoated, agglomerated) but did not show a trend with respect to particle size, shape, or crystal structure. The coating with carboxymethylcellulose (CMC) had no significant biological effect. However, the rough surface of rutile microspheres clearly induced pro-inflammatory cell reactions that were not predictable by the primary particle size alone. Full article
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19 pages, 5084 KiB  
Article
Green Nanoformulations of Polyvinylpyrrolidone-Capped Metal Nanoparticles: A Study at the Hybrid Interface with Biomimetic Cell Membranes and In Vitro Cell Models
by Alice Foti, Luana Calì, Salvatore Petralia and Cristina Satriano
Nanomaterials 2023, 13(10), 1624; https://doi.org/10.3390/nano13101624 - 12 May 2023
Cited by 1 | Viewed by 1559
Abstract
Noble metal nanoparticles (NP) with intrinsic antiangiogenic, antibacterial, and anti-inflammatory properties have great potential as potent chemotherapeutics, due to their unique features, including plasmonic properties for application in photothermal therapy, and their capability to slow down the migration/invasion speed of cancer cells and [...] Read more.
Noble metal nanoparticles (NP) with intrinsic antiangiogenic, antibacterial, and anti-inflammatory properties have great potential as potent chemotherapeutics, due to their unique features, including plasmonic properties for application in photothermal therapy, and their capability to slow down the migration/invasion speed of cancer cells and then suppress metastasis. In this work, gold (Au), silver (Ag), and palladium (Pd) NP were synthesized by a green redox chemistry method with the reduction of the metal salt precursor with glucose in the presence of polyvinylpyrrolidone (PVP) as stabilizing and capping agent. The physicochemical properties of the PVP-capped NP were investigated by UV-visible (UV-vis) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopies, dynamic light scattering (DLS), and atomic force microscopy (AFM), to scrutinize the optical features and the interface between the metal surface and the capping polymer, the hydrodynamic size, and the morphology, respectively. Biophysical studies with model cell membranes were carried out by using laser scanning confocal microscopy (LSM) with fluorescence recovery after photobleaching (FRAP) and fluorescence resonance energy transfer (FRET) techniques. To this purpose, artificial cell membranes of supported lipid bilayers (SLBs) made with 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphocholine (POPC) dye-labeled with 7-nitro-2-1,3-benzoxadiazol-4-yl (NBD, FRET donor) and/or lissamine rhodamine B sulfonyl (Rh, FRET acceptor) were prepared. Proof-of-work in vitro cellular experiments were carried out with prostate cancer cells (PC-3 line) in terms of cytotoxicity, cell migration (wound scratch assay), NP cellular uptake, and cytoskeleton actin perturbation. Full article
(This article belongs to the Special Issue Prospects of Bioinspired and Biomimetic Materials)
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20 pages, 8465 KiB  
Article
Zinc (Zn) Doping by Hydrothermal and Alkaline Heat-Treatment Methods on Titania Nanotube Arrays for Enhanced Antibacterial Activity
by Abhishek Bhattacharjee, Emma Goodall, Bruno Leandro Pereira, Paulo Soares and Ketul C. Popat
Nanomaterials 2023, 13(10), 1606; https://doi.org/10.3390/nano13101606 - 10 May 2023
Cited by 3 | Viewed by 1989
Abstract
Titanium (Ti) is a popular biomaterial for orthopedic implant applications due to its superior mechanical properties such as corrosion resistance and low modulus of elasticity. However, around 10% of these implants fail annually due to bacterial infection and poor osseointegration, resulting in severe [...] Read more.
Titanium (Ti) is a popular biomaterial for orthopedic implant applications due to its superior mechanical properties such as corrosion resistance and low modulus of elasticity. However, around 10% of these implants fail annually due to bacterial infection and poor osseointegration, resulting in severe pain and suffering for the patients. To improve their performance, nanoscale surface modification approaches and doping of trace elements on the surfaces can be utilized which may help in improving cell adhesion for better osseointegration while reducing bacterial infection. In this work, at first, titania (TiO2) nanotube arrays (NT) were fabricated on commercially available pure Ti surfaces via anodization. Then zinc (Zn) doping was conducted following two distinct methods: hydrothermal and alkaline heat treatment. Scanning electron microscopic (SEM) images of the prepared surfaces revealed unique surface morphologies, while energy dispersive X-ray spectroscopy (EDS) revealed Zn distribution on the surfaces. Contact angle measurements indicated that NT surfaces were superhydrophilic. X-ray photoelectron spectroscopy (XPS) provided the relative amount of Zn on the surfaces and indicated that hydrothermally treated surfaces had more Zn compared to the alkaline heat-treated surfaces. X-ray crystallography (XRD) and nanoindentation techniques provided the crystal structure and mechanical properties of the surfaces. While testing with adipose-derived stem cells (ADSC), the surfaces showed no apparent cytotoxicity to the cells. Finally, bacteria adhesion and morphology were evaluated on the surfaces after 6 h and 24 h of incubation. From the results, it was confirmed that NT surfaces doped with Zn drastically reduced bacteria adhesion compared to the Ti control. Zn-doped NT surfaces thus offer a potential platform for orthopedic implant application. Full article
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