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 authors, or important in this field. 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
Environmentally Benign Formation of Nickel Hexacyanoferrate-Derived Mesoframes for Heterogeneous Catalysis
Nanomaterials 2021, 11(10), 2756; https://doi.org/10.3390/nano11102756 - 18 Oct 2021
Abstract
The tetramethylammonium hydroxide (TMAH)-controlled alkaline etching of nickel hexacyanoferrate (NiHCF) mesocrystals is explored. The alkaline etching enables the formation of hollow framework structures with an increased surface area, the exposure of active Ni and Fe sites and the retention of morphology. The ambient [...] Read more.
The tetramethylammonium hydroxide (TMAH)-controlled alkaline etching of nickel hexacyanoferrate (NiHCF) mesocrystals is explored. The alkaline etching enables the formation of hollow framework structures with an increased surface area, the exposure of active Ni and Fe sites and the retention of morphology. The ambient reaction conditions enable the establishment of a sustainable production. Our work reveals novel perspectives on the eco-friendly synthesis of hollow and colloidal superstructures for the efficient degradation of the organic contaminants rhodamine-B and bisphenol-A. In the case of peroxomonosulfate (PMS)-mediated bisphenol-A degradation, the rate constant of the etched mesoframes was 10,000 times higher indicating their significant catalytic activity. Full article
(This article belongs to the Section Inorganic Materials and Metal-Organic Frameworks)
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Article
Promising Bialkali Bismuthides Cs(Na, K)2Bi for High-Performance Nanoscale Electromechanical Devices: Prediction of Mechanical and Anisotropic Elastic Properties under Hydrostatic Tension and Compression and Tunable Auxetic Properties
Nanomaterials 2021, 11(10), 2739; https://doi.org/10.3390/nano11102739 - 16 Oct 2021
Abstract
Using first-principles calculations, we predict highly stable cubic bialkali bismuthides Cs(Na, K)2Bi with several technologically important mechanical and anisotropic elastic properties. We investigate the mechanical and anisotropic elastic properties under hydrostatic tension and compression. At zero pressure, CsK2Bi is [...] Read more.
Using first-principles calculations, we predict highly stable cubic bialkali bismuthides Cs(Na, K)2Bi with several technologically important mechanical and anisotropic elastic properties. We investigate the mechanical and anisotropic elastic properties under hydrostatic tension and compression. At zero pressure, CsK2Bi is characterized by elastic anisotropy with maximum and minimum stiffness along the directions of [111] and [100], respectively. Unlike CsK2Bi, CsNa2Bi exhibits almost isotropic elastic behavior at zero pressure. We found that hydrostatic tension and compression change the isotropic and anisotropic mechanical responses of these compounds. Moreover, the auxetic nature of the CsK2Bi compound is tunable under pressure. This compound transforms into a material with a positive Poisson’s ratio under hydrostatic compression, while it holds a large negative Poisson’s ratio of about −0.45 along the [111] direction under hydrostatic tension. An auxetic nature is not observed in CsNa2Bi, and Poisson’s ratio shows completely isotropic behavior under hydrostatic compression. A directional elastic wave velocity analysis shows that hydrostatic pressure effectively changes the propagation pattern of the elastic waves of both compounds and switches the directions of propagation. Cohesive energy, phonon dispersion, and Born–Huang conditions show that these compounds are thermodynamically, mechanically, and dynamically stable, confirming the practical feasibility of their synthesis. The identified mechanisms for controlling the auxetic and anisotropic elastic behavior of these compounds offer a vital feature for designing and developing high-performance nanoscale electromechanical devices. Full article
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Article
Characterization of Gold Nanorods Conjugated with Synthetic Glycopolymers Using an Analytical Approach Based on spICP-SFMS and EAF4-MALS
Nanomaterials 2021, 11(10), 2720; https://doi.org/10.3390/nano11102720 - 15 Oct 2021
Abstract
A new comprehensive analytical approach based on single-particle inductively coupled plasma-sector field mass spectrometry (spICP-SFMS) and electrical asymmetric-flow field-flow-fractionation combined with multi-angle light scattering detection (EAF4-MALS) has been examined for the characterization of galactosamine-terminated poly(N-hydroxyethyl acrylamide)-coated gold nanorods (GNRs) in two different degrees [...] Read more.
A new comprehensive analytical approach based on single-particle inductively coupled plasma-sector field mass spectrometry (spICP-SFMS) and electrical asymmetric-flow field-flow-fractionation combined with multi-angle light scattering detection (EAF4-MALS) has been examined for the characterization of galactosamine-terminated poly(N-hydroxyethyl acrylamide)-coated gold nanorods (GNRs) in two different degrees of polymerization (DP) by tuning the feed ratio (short: DP 35; long: DP 60). spICP-SFMS provided information on the particle number concentration, size and size distribution of the GNRs, and was found to be useful as an orthogonal method for fast characterization of GNRs. Glycoconjugated GNRs were separated and characterized via EAF4-MALS in terms of their size and charge and compared to the bare GNRs. In contrast to spICP-SFMS, EAF4-MALS was also able of providing an estimate of the thickness of the glycopolymer coating on the GNRs surface. Full article
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Article
Use of Carbon Nanoparticles to Improve Soil Fertility, Crop Growth and Nutrient Uptake by Corn (Zea mays L.)
Nanomaterials 2021, 11(10), 2717; https://doi.org/10.3390/nano11102717 - 14 Oct 2021
Cited by 1
Abstract
The use of carbon nanoparticles (CNPs) as a fertilizer synergist to enhance crop growth has attracted increasing interest. However, current understanding about plant growth and soil response to CNPs is limited. In the present study, we investigated the effects of CNPs at different [...] Read more.
The use of carbon nanoparticles (CNPs) as a fertilizer synergist to enhance crop growth has attracted increasing interest. However, current understanding about plant growth and soil response to CNPs is limited. In the present study, we investigated the effects of CNPs at different application rates on soil properties, the plant growth and nutrient use efficiency (NUE) of corn (Zea mays L.) in two agricultural soils (Spodosol and Alfisol). The results showed that CNPs affected corn growth in a dose-dependent manner, augmenting and retarding growth at low and at high concentrations, respectively. The amendment at the optimal rate of 200 mg CNPs kg−1 significantly enhanced corn growth as indicated by improved plant height, biomass yield, nutrient uptake and nutrient use efficiency, which could be explained by the higher availability of phosphorus and nitrogen in the amended soils. The application of CNPs largely stimulated soil urease activity irrespectively of soil types. However, the responses of dehydrogenase and phosphatase to CNPs were dose dependent; their activity significantly increased with the increasing application rates of CNPs up to 200 mg kg−1 but declined at higher rates (>400 mg kg−1). These findings have important implications in the field application of CNPs for enhancing nutrient use efficiency and crop production in tropical/subtropical regions. Full article
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Article
Mesoporous Zn/MgO Hexagonal Nano-Plates as a Catalyst for Camelina Oil Biodiesel Synthesis
Nanomaterials 2021, 11(10), 2690; https://doi.org/10.3390/nano11102690 - 13 Oct 2021
Abstract
A novel mesoporous Zn/MgO hexagonal-nano-plate catalyst was synthesized by a simple template-free hydrothermal method and applied in the base-catalyzed transesterification of Camelina oil for biodiesel synthesis. The Zn/MgO catalyst calcinated at 873 K exhibited the highest catalytic activity with a yield of 88.7%. [...] Read more.
A novel mesoporous Zn/MgO hexagonal-nano-plate catalyst was synthesized by a simple template-free hydrothermal method and applied in the base-catalyzed transesterification of Camelina oil for biodiesel synthesis. The Zn/MgO catalyst calcinated at 873 K exhibited the highest catalytic activity with a yield of 88.7%. This catalytic reaction was performed using 3% w/w of the catalyst with a methanol-to-oil molar ratio of 24:1 at 393 K in 8 h. The excellent catalytic performance is possibly attributed to its favorable textural features with relatively high surface area (69.1 m2 g−1) and appropriate size of the mesopores (10.4 nm). In addition, the as-synthesized catalyst demonstrated a greater basic sites density than single mesoporous MgO, which might have been promoted by the addition of Zn, leading to a synergetic interaction that enhanced its catalytic activity. This catalytic system demonstrated high stability for five catalytic runs and catalytic activity with over 84% yield. Full article
(This article belongs to the Special Issue Nanotechnologies and Nanomaterials: Selected Papers from CCMR)
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Article
Ammonium Ion Enhanced V2O5-WO3/TiO2 Catalysts for Selective Catalytic Reduction with Ammonia
Nanomaterials 2021, 11(10), 2677; https://doi.org/10.3390/nano11102677 - 12 Oct 2021
Abstract
Selective catalytic reduction (SCR) is the most efficient NOX removal technology, and the vanadium-based catalyst is mainly used in SCR technology. The vanadium-based catalyst showed higher NOX removal performance in the high-temperature range but catalytic efficiency decreased at lower temperatures, following [...] Read more.
Selective catalytic reduction (SCR) is the most efficient NOX removal technology, and the vanadium-based catalyst is mainly used in SCR technology. The vanadium-based catalyst showed higher NOX removal performance in the high-temperature range but catalytic efficiency decreased at lower temperatures, following exposure to SOX because of the generation of ammonium sulfate on the catalyst surface. To overcome these limitations, we coated an NH4+ layer on a vanadium-based catalyst. After silane coating the V2O5-WO3/TiO2 catalyst by vapor evaporation, the silanized catalyst was heat treated under NH3 gas. By decomposing the silane on the surface, an NH4+ layer was formed on the catalyst surface through a substitution reaction. We observed high NOX removal efficiency over a wide temperature range by coating an NH4+ layer on a vanadium-based catalyst. This layer shows high proton conductivity, which leads to the reduction of vanadium oxides and tungsten oxide; additionally, the NOX removal performance was improved over a wide temperature range. These findings provide a new mothed to develop SCR catalyst with high efficiency at a wide temperature range. Full article
(This article belongs to the Special Issue Nanomaterials for Energy Conversion and Catalytic Applications)
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Article
New Insights into the Reactivity of Detonation Nanodiamonds during the First Stages of Graphitization
Nanomaterials 2021, 11(10), 2671; https://doi.org/10.3390/nano11102671 - 11 Oct 2021
Abstract
The present study aims to compare the early stages of graphitization of the same DND source for two annealing atmospheres (primary vacuum, argon at atmospheric pressure) in an identical set-up. DND samples are finely characterized by a combination of complementary techniques (FTIR, Raman, [...] Read more.
The present study aims to compare the early stages of graphitization of the same DND source for two annealing atmospheres (primary vacuum, argon at atmospheric pressure) in an identical set-up. DND samples are finely characterized by a combination of complementary techniques (FTIR, Raman, XPS, HR-TEM) to highlight the induced modifications for temperature up to 1100 °C. The annealing atmosphere has a significant impact on the graphitization kinetics with a higher fraction of sp2-C formed under vacuum compared to argon for the same temperature. Whatever the annealing atmosphere, carbon hydrogen bonds are created at the DND surface during annealing according to FTIR. A “nano effect”, specific to the <10 nm size of DND, exalts the extreme surface chemistry in XPS analysis. According to HR-TEM images, the graphitization is limited to the first outer shell even for DND annealed at 1100 °C under vacuum. Full article
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Article
Physical Surface Modification of Carbon-Nanotube/Polydimethylsiloxane Composite Electrodes for High-Sensitivity DNA Detection
Nanomaterials 2021, 11(10), 2661; https://doi.org/10.3390/nano11102661 - 10 Oct 2021
Cited by 1
Abstract
The chemical modification of electrode surfaces has attracted significant attention for lowering the limit of detection or for improving the recognition of biomolecules; however, the chemical processes are complex, dangerous, and difficult to control. Therefore, instead of the chemical process, we physically modified [...] Read more.
The chemical modification of electrode surfaces has attracted significant attention for lowering the limit of detection or for improving the recognition of biomolecules; however, the chemical processes are complex, dangerous, and difficult to control. Therefore, instead of the chemical process, we physically modified the surface of carbon-nanotube/polydimethylsiloxane composite electrodes by dip coating them with functionalized multi-walled carbon nanotubes (F-MWCNTs). These electrodes are used as working electrodes in electrochemistry, where they act as a recognition layer for sequence-specific DNA sensing through π–π interactions. The F-MWCNT-modified electrodes showed a limit of detection of 19.9 fM, which was 1250 times lower than that of pristine carbon/polydimethylsiloxane electrodes in a previous study, with a broad linear range of 1–1000 pM. The physically modified electrode was very stable during the electrode regeneration process after DNA detection. Our method paves the way for utilizing physical modification to significantly lower the limit of detection of a biosensor system as an alternative to chemical processes. Full article
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Article
Ingested Engineered Nanomaterials Affect the Expression of Mucin Genes—An In Vitro-In Vivo Comparison
Nanomaterials 2021, 11(10), 2621; https://doi.org/10.3390/nano11102621 - 06 Oct 2021
Abstract
The increasing use of engineered nanomaterials (ENM) in food has fueled the development of intestinal in vitro models for toxicity testing. However, ENM effects on intestinal mucus have barely been addressed, although its crucial role for intestinal health is evident. We investigated the [...] Read more.
The increasing use of engineered nanomaterials (ENM) in food has fueled the development of intestinal in vitro models for toxicity testing. However, ENM effects on intestinal mucus have barely been addressed, although its crucial role for intestinal health is evident. We investigated the effects of ENM on mucin expression and aimed to evaluate the suitability of four in vitro models of increasing complexity compared to a mouse model exposed through feed pellets. We assessed the gene expression of the mucins MUC1, MUC2, MUC5AC, MUC13 and MUC20 and the chemokine interleukin-8 in pre-confluent and confluent HT29-MTX-E12 cells, in stable and inflamed triple cultures of Caco-2, HT29-MTX-E12 and THP-1 cells, and in the ileum of mice following exposure to TiO2, Ag, CeO2 or SiO2. All ENM had shared and specific effects. CeO2 downregulated MUC1 in confluent E12 cells and in mice. Ag induced downregulation of Muc2 in mice. Overall, the in vivo data were consistent with the findings in the stable triple cultures and the confluent HT29-MTX-E12 cells but not in pre-confluent cells, indicating the higher relevance of advanced models for hazard assessment. The effects on MUC1 and MUC2 suggest that specific ENM may lead to an elevated susceptibility towards intestinal infections and inflammations. Full article
(This article belongs to the Special Issue Advances in Toxicity of Nanoparticles)
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Article
Highly Efficient and Controllable Methodology of the Cd0.25Zn0.75Se/ZnS Core/Shell Quantum Dots Synthesis
Nanomaterials 2021, 11(10), 2616; https://doi.org/10.3390/nano11102616 - 05 Oct 2021
Abstract
The surface of any binary or multi-component nanocrystal has imperfections and defects. The number of surface defects depends both on the nature of the nanomaterial and on the method of its preparation. One of the possibilities to confine the number of surface defects [...] Read more.
The surface of any binary or multi-component nanocrystal has imperfections and defects. The number of surface defects depends both on the nature of the nanomaterial and on the method of its preparation. One of the possibilities to confine the number of surface defects is the epitaxial growth of the shell, which leads to a change in the physical properties while maintaining the morphology of the core. To form a shell of the desired thickness, an accurate calculation of the amount of its precursors is substantial to avoid the appearance of individual crystals consisting of the shell material. This study aimed to develop an effective calculation method for the theoretical amount of precursors required for the formation of a ZnS shell on the surface of a Cd0.25Zn0.75Se core, followed by the practical implementation of theoretical calculations and characterization of the prepared nanomaterials. This method allows the complete control of the masses and volumes of the initial reagents, which will in turn prevent undesirable nucleation of nuclei consisting of the shell material. In the synthesis of Cd0.25Zn0.75Se/ZnS core/shell quantum dots (QDs), the sources of chalcogens were substituted seleno- and thioureas, which are capable of not only supplanting modern toxic sources of sulfur and selenium but also allowing one to perform the controlled synthesis of highly photoluminescent QDs with a low number of surface defects. The result of this shell overcoating method was an impetuous augmentation in the photoluminescence quantum yield (PL QY up to 83%), uniformity in size and shape, and a high yield of nanomaterials. The developed synthetic technique of core/shell QDs provides a controlled growth of the shell on the core surface, which makes it possible to transfer this method to an industrial scale. Full article
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Article
Thermophysical Properties of NH3/IL+ Carbon Nanomaterial Solutions
Nanomaterials 2021, 11(10), 2612; https://doi.org/10.3390/nano11102612 - 04 Oct 2021
Abstract
This study proposes the use of new working fluids, refrigerant/IL+ carbon nanomaterials (CNMs), in absorption systems as an alternative to conventional working fluids. In this regard, the thermophysical properties of ammonia and carbon nanomaterials (graphene and single-wall carbon nanotubes) dispersed into [BMIM [...] Read more.
This study proposes the use of new working fluids, refrigerant/IL+ carbon nanomaterials (CNMs), in absorption systems as an alternative to conventional working fluids. In this regard, the thermophysical properties of ammonia and carbon nanomaterials (graphene and single-wall carbon nanotubes) dispersed into [BMIM]BF4 ionic liquid are theoretically investigated. The thermophysical properties of NH3/IL+ CNMs solutions are computed for weight fractions of NH3 in the range of 0.018–0.404 and temperatures between 293 and 388 K. In addition, two weight fractions of CNMs are considered: 0.005 and 0.01, respectively. Our results indicate that by adding a small amount of nanomaterial to the ionic liquid, the solution’s thermal conductivity is enhanced, while its viscosity and specific heat are reduced. Correlations of the thermal conductivity, viscosity, specific heat, and density of the NH3/IL+ CNMs solutions are proposed. Full article
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Article
Facile and Sensitive Detection of Nitrogen-Containing Organic Bases with Near Infrared C-Dots Derived Assays
Nanomaterials 2021, 11(10), 2607; https://doi.org/10.3390/nano11102607 - 03 Oct 2021
Abstract
In this article, we have designed both colorimetric (including solution and test paper type) and spectral sensors (including UV-vis and PL type) for the quick and sensitive detection of general nitrogen-containing organic bases (NCOBs); the limit of detection could reach as low as [...] Read more.
In this article, we have designed both colorimetric (including solution and test paper type) and spectral sensors (including UV-vis and PL type) for the quick and sensitive detection of general nitrogen-containing organic bases (NCOBs); the limit of detection could reach as low as 0.50 nM. NCOBs included 11 examples, covering aliphatic and aromatic amines, five- and six-membered heterocyclics, fused-ring heterocyclics, amino acids, and antibiotics. Furthermore, the assays demonstrated high reliability in sensing NCOBs and excellent ability to distinguish NCOBs from oxygen and sulfur containing organics. The assays developed could find important applications for the detection of NCOBs in the fields of biomedicine, chemistry, and agriculture. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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Article
How to Make a Cocktail of Palladium Catalysts with Cola and Alcohol: Heteroatom Doping vs. Nanoscale Morphology of Carbon Supports
Nanomaterials 2021, 11(10), 2599; https://doi.org/10.3390/nano11102599 - 02 Oct 2021
Abstract
Sparkling drinks such as cola can be considered an affordable and inexpensive starting material consisting of carbohydrates and sulfur- and nitrogen-containing organic substances in phosphoric acid, which makes them an excellent precursor for the production of heteroatom-doped carbon materials. In this study, heteroatom-doped [...] Read more.
Sparkling drinks such as cola can be considered an affordable and inexpensive starting material consisting of carbohydrates and sulfur- and nitrogen-containing organic substances in phosphoric acid, which makes them an excellent precursor for the production of heteroatom-doped carbon materials. In this study, heteroatom-doped carbon materials were successfully prepared in a quick and simple manner using direct carbonization of regular cola and diet cola. The low content of carbon in diet cola allowed reaching a higher level of phosphorus in the prepared carbon material, as well as obtaining additional doping with nitrogen and sulfur due to the presence of sweeteners and caffeine. Effects of carbon support doping with phosphorus, nitrogen and sulfur, as well as of changes in textural properties by ball milling, on the catalytic activity of palladium catalysts were investigated in the Suzuki–Miyaura and Mizoroki–Heck reactions. Contributions of the heteroatom doping and specific surface area of the carbon supports to the increased activity of supported catalysts were discussed. Additionally, the possibility of these reactions to proceed in 40% potable ethanol was studied. Moreover, transformation of various palladium particles (complexes and nanoparticles) in the reaction medium was detected by mass spectrometry and transmission electron microscopy, which evidenced the formation of a cocktail of catalysts in a commercial 40% ethanol/water solution. Full article
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Article
Revealing the Effect of Synthesis Conditions on the Structural, Optical, and Antibacterial Properties of Cerium Oxide Nanoparticles
Nanomaterials 2021, 11(10), 2596; https://doi.org/10.3390/nano11102596 - 01 Oct 2021
Abstract
Cerium oxide nanoparticles were prepared by a precipitation method using Ce(IV) sulphate as precursor dispersed in glycerol with varying synthesis parameters such as temperature or precipitating agent. The structural and morphological characteristics of the obtained nanoparticles were investigated by X-ray diffraction, transmission electron [...] Read more.
Cerium oxide nanoparticles were prepared by a precipitation method using Ce(IV) sulphate as precursor dispersed in glycerol with varying synthesis parameters such as temperature or precipitating agent. The structural and morphological characteristics of the obtained nanoparticles were investigated by X-ray diffraction, transmission electron microscopy, and diffuse reflectance spectroscopy. The crystallite size of the nanoparticles varied between 13 and 17 nm. The presence of Ce3+ and Ce4+ was proved by XPS data in the CeO2 samples and the conservation of the fluorite structure was evinced by X-ray diffractograms with a contraction of the lattice parameter, regardless of the size of the nanoparticle. From diffuse reflectance spectra, two band gap energy values for the direct transition were observed. Depending on the synthesis condition, the red shift of gap energy and the blue shift of Urbach energy with increasing content of Ce3+ were ascertained. The antibacterial tests revealed that the cerium oxide nanoparticles show good antimicrobial activity towards the common pathogens Escherichia coli and Staphylococcus aureus. Full article
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Article
Facile In Situ Synthesis of ZnO Flower-like Hierarchical Nanostructures by the Microwave Irradiation Method for Multifunctional Textile Coatings
Nanomaterials 2021, 11(10), 2574; https://doi.org/10.3390/nano11102574 - 30 Sep 2021
Abstract
ZnO nanoparticle-based multifunctional coatings were prepared by a simple, time-saving microwave method. Arginine and ammonia were used as precipitation agents, and zinc acetate dehydrate was used as a zinc precursor. Under the optimized conditions, flower-like morphologies of ZnO aggregates were obtained. The prepared [...] Read more.
ZnO nanoparticle-based multifunctional coatings were prepared by a simple, time-saving microwave method. Arginine and ammonia were used as precipitation agents, and zinc acetate dehydrate was used as a zinc precursor. Under the optimized conditions, flower-like morphologies of ZnO aggregates were obtained. The prepared nanopowders were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and UV/Visible spectroscopy. The developed in situ synthesis with microwave irradiation enabled significant ZnO nanoparticle deposition on cotton fabrics, without additional steps. The functionalized textiles were tested as a photocatalyst in methylene blue (MB) photodegradation and showed good self-cleaning and UV-blocking properties. The coated cotton fabrics exhibited good antibacterial properties against common microbial trains (Staphylococcus aureus, Escherichia coli, and Candida albicans), together with self-cleaning and photocatalytic efficiency in organic dye degradation. The proposed microwave-assisted in situ synthesis of ZnO nanocoatings on textiles shows high potential as a rapid, efficient, environmentally friendly, and scalable method to fabricate functional fabrics. Full article
(This article belongs to the Special Issue Microwave Technology and Nanomaterials: Synthesis and Application)
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Article
Monolayer-Scale GaN/AlN Multiple Quantum Wells for High Power e-Beam Pumped UV-Emitters in the 240–270 nm Spectral Range
Nanomaterials 2021, 11(10), 2553; https://doi.org/10.3390/nano11102553 - 29 Sep 2021
Abstract
Monolayer (ML)-scale GaN/AlN multiple quantum well (MQW) structures for electron-beam-pumped ultraviolet (UV) emitters are grown on c-sapphire substrates by using plasma-assisted molecular beam epitaxy under controllable metal-rich conditions, which provides the spiral growth of densely packed atomically smooth hillocks without metal droplets. [...] Read more.
Monolayer (ML)-scale GaN/AlN multiple quantum well (MQW) structures for electron-beam-pumped ultraviolet (UV) emitters are grown on c-sapphire substrates by using plasma-assisted molecular beam epitaxy under controllable metal-rich conditions, which provides the spiral growth of densely packed atomically smooth hillocks without metal droplets. These structures have ML-stepped terrace-like surface topology in the entire QW thickness range from 0.75–7 ML and absence of stress at the well thickness below 2 ML. Satisfactory quantum confinement and mitigating the quantum-confined Stark effect in the stress-free MQW structures enable one to achieve the relatively bright UV cathodoluminescence with a narrow-line (~15 nm) in the sub-250-nm spectral range. The structures with many QWs (up to 400) exhibit the output optical power of ~1 W at 240 nm, when pumped by a standard thermionic-cathode (LaB6) electron gun at an electron energy of 20 keV and a current of 65 mA. This power is increased up to 11.8 W at an average excitation energy of 5 µJ per pulse, generated by the electron gun with a ferroelectric plasma cathode at an electron-beam energy of 12.5 keV and a current of 450 mA. Full article
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Article
Evaporation of Methylammonium Iodide in Thermal Deposition of MAPbI3
Nanomaterials 2021, 11(10), 2532; https://doi.org/10.3390/nano11102532 - 28 Sep 2021
Cited by 1
Abstract
Thermal evaporation is an important technique for fabricating methylammonium lead iodide (MAPbI3), but the process is complicated by the need to co-evaporate methylammonium iodide (MAI) and PbI2. In this work, the effect of water vapor during the thermal deposition [...] Read more.
Thermal evaporation is an important technique for fabricating methylammonium lead iodide (MAPbI3), but the process is complicated by the need to co-evaporate methylammonium iodide (MAI) and PbI2. In this work, the effect of water vapor during the thermal deposition of MAPbI3 was investigated under high vacuum. The evaporation process was monitored with a residual gas analyzer (RGA), and the film quality was examined with X-ray photoelectron spectroscopy (XPS). The investigations showed that during evaporation, MAI decomposed while PbI2 evaporated as a whole compound. It was found that the residual water vapor reacted with one of the MAI-dissociated products. The higher iodine ratio suggests that the real MAI flux was higher than the reading from the QCM. The XPS analysis demonstrated that the residual water vapor may alter the elemental ratios of C, N, and I in thermally deposited MAPbI3. Morphologic properties were investigated with atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). It was observed that a sample grown with high water vapor pressure had a roughened surface and poor film quality. Therefore, an evaporation environment with water vapor pressure below 10−8 Torr is needed to fabricate high quality perovskite films. Full article
(This article belongs to the Special Issue Hybrid Perovskite Thin Film)
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Article
Hydroxyapatite Particles from Simulated Body Fluids with Different pH and Their Effects on Mesenchymal Stem Cells
Nanomaterials 2021, 11(10), 2517; https://doi.org/10.3390/nano11102517 - 27 Sep 2021
Abstract
Bone-like hydroxyapatite (HAp) has been prepared by biomimetic synthesis using simulated body fluid (SBF), mimicking inorganic ion concentrations in human plasma, or 1.5SBF that has 1.5-times higher ion concentrations than SBF. In this study, the controllable preparations of HAp particles from 1.5SBF with [...] Read more.
Bone-like hydroxyapatite (HAp) has been prepared by biomimetic synthesis using simulated body fluid (SBF), mimicking inorganic ion concentrations in human plasma, or 1.5SBF that has 1.5-times higher ion concentrations than SBF. In this study, the controllable preparations of HAp particles from 1.5SBF with different pH values were examined. The particles obtained as precipitates from 1.5SBF showed different morphologies and crystallinities depending on the pH of 1.5SBF. Micro-sized particles at pH 7.4 of 1.5SBF had a higher Ca/P ratio and crystallinity as compared with nano-sized particles at pH 8.0 and pH 8.4 of 1.5SBF. However, a mixture of micro-sized and nano-sized particles was obtained from pH 7.7 of 1.5SBF. When Ca2+ concentrations in 1.5SBF during mineralization were monitored, the concentration at pH 7.4 drastically decreased from 12 to 24 h. At higher pH, such as 8.0 and 8.4, the Ca2+ concentrations decreased during pH adjustment and slightly decreased even after 48 h. In this investigation at pH 7.7, the Ca2+ concentrations were higher than pH 8.0 and 8.4.Additionally, cytotoxicity of the obtained precipitates to mesenchymal stem cells was lower than that of synthetic HAp. Controllable preparation HAp particles from SBF has potential applications in the construction of building components of cell scaffolds. Full article
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Article
Electronic Transport Mechanisms Correlated to Structural Properties of a Reduced Graphene Oxide Sponge
Nanomaterials 2021, 11(10), 2503; https://doi.org/10.3390/nano11102503 - 26 Sep 2021
Abstract
We report morpho-structural properties and charge conduction mechanisms of a foamy “graphene sponge”, having a density as low as ≈0.07 kg/m3 and a carbon to oxygen ratio C:O ≃ 13:1. The spongy texture analysed by scanning electron microscopy is made of irregularly-shaped [...] Read more.
We report morpho-structural properties and charge conduction mechanisms of a foamy “graphene sponge”, having a density as low as ≈0.07 kg/m3 and a carbon to oxygen ratio C:O ≃ 13:1. The spongy texture analysed by scanning electron microscopy is made of irregularly-shaped millimetres-sized small flakes, containing small crystallites with a typical size of ≃16.3 nm. A defect density as high as ≃2.6 × 1011 cm2 has been estimated by the Raman intensity of D and G peaks, dominating the spectrum from room temperature down to ≃153 K. Despite the high C:O ratio, the graphene sponge exhibits an insulating electrical behavior, with a raise of the resistance value at ≃6 K up to 5 orders of magnitude with respect to the room temperature value. A variable range hopping (VRH) conduction, with a strong 2D character, dominates the charge carriers transport, from 300 K down to 20 K. At T < 20 K, graphene sponge resistance tends to saturate, suggesting a temperature-independent quantum tunnelling. The 2D-VRH conduction originates from structural disorder and is consistent with hopping of charge carriers between sp2 defects in the plane, where sp3 clusters related to oxygen functional groups act as potential barriers. Full article
(This article belongs to the Special Issue Carbon-Based Materials: Growth, Characterization, and Applications)
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Article
Flower-Like Dual-Defective Z-Scheme Heterojunction g-C3N4/ZnIn2S4 High-Efficiency Photocatalytic Hydrogen Evolution and Degradation of Mixed Pollutants
Nanomaterials 2021, 11(10), 2483; https://doi.org/10.3390/nano11102483 - 24 Sep 2021
Abstract
Graphitic carbon nitride (g-C3N4) with a porous nano-structure, nitrogen vacancies, and oxygen-doping was prepared by the calcination method. Then, it was combined with ZnIn2S4 nanosheets containing zinc vacancies to construct a three-dimensional (3D) flower-like Z-scheme heterojunction [...] Read more.
Graphitic carbon nitride (g-C3N4) with a porous nano-structure, nitrogen vacancies, and oxygen-doping was prepared by the calcination method. Then, it was combined with ZnIn2S4 nanosheets containing zinc vacancies to construct a three-dimensional (3D) flower-like Z-scheme heterojunction (pCN-N/ZIS-Z), which was used for photocatalytic hydrogen evolution and the degradation of mixed pollutants. The constructed Z-scheme heterojunction improved the efficiency of photogenerated charges separation and migration, and the large surface area and porous characteristics provided more active sites. Doping and defect engineering can change the bandgap structure to improve the utilization of visible light, and can also capture photogenerated electrons to inhibit recombination, so as to promote the use of photogenerated electron-hole pairs in the photocatalytic redox process. Heterojunction and defect engineering synergized to form a continuous and efficient conductive operation framework, which achieves the hydrogen production of pCN-N/ZIS-Z (9189.8 µmol·h−1·g−1) at 58.9 times that of g-C3N4 (155.9 µmol·h−1·g−1), and the degradation rates of methyl orange and metronidazole in the mixed solution were 98.7% and 92.5%, respectively. Our research provides potential ideas for constructing a green and environmentally friendly Z-scheme heterojunction catalyst based on defect engineering to address the energy crisis and environmental restoration. Full article
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Article
Molecular Junctions Enhancing Thermal Transport within Graphene Polymer Nanocomposite: A Molecular Dynamics Study
Nanomaterials 2021, 11(10), 2480; https://doi.org/10.3390/nano11102480 - 23 Sep 2021
Cited by 1
Abstract
Thermal conductivity of polymer-based (nano)composites is typically limited by thermal resistances occurring at the interfaces between the polymer matrix and the conductive particles as well as between particles themselves. In this work, the adoption of molecular junctions between thermally conductive graphene foils is [...] Read more.
Thermal conductivity of polymer-based (nano)composites is typically limited by thermal resistances occurring at the interfaces between the polymer matrix and the conductive particles as well as between particles themselves. In this work, the adoption of molecular junctions between thermally conductive graphene foils is addressed, aiming at the reduction of the thermal boundary resistance and eventually lead to an efficient percolation network within the polymer nanocomposite. This system was computationally investigated at the atomistic scale, using classical Molecular Dynamics, applied the first time to the investigation of heat transfer trough molecular junctions within a realistic environment for a polymer nanocomposite. A series of Molecular Dynamics simulations were conducted to investigate the thermal transport efficiency of molecular junctions in polymer tight contact, to quantify the contribution of molecular junctions when graphene and the molecular junctions are surrounded by polydimethylsiloxane (PDMS) molecules. A strong dependence of the thermal conductance was found in PDMS/graphene model, with best performances obtained with short and conformationally rigid molecular junctions. Furthermore, the adoption of the molecular linkers was found to contribute additionally to the thermal transport provided by the surrounding polymer matrix, demonstrating the possibility of exploiting molecular junctions in composite materials. Full article
(This article belongs to the Special Issue Thermal Transport in Nanoscale)
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Article
Effects of Nanoplastics on the Dinoflagellate Amphidinium carterae Hulburt from the Perspectives of Algal Growth, Oxidative Stress and Hemolysin Production
Nanomaterials 2021, 11(10), 2471; https://doi.org/10.3390/nano11102471 - 22 Sep 2021
Abstract
Recently, the effects of nanoplastics (NPs) on aquatic organisms have attracted much attention; however, research on the toxicity of NPs to microalgae has been insufficient. In the present study, the effects of polystyrene nanoplastics (nano-PS, 50 nm) on growth inhibition, chlorophyll content, oxidative [...] Read more.
Recently, the effects of nanoplastics (NPs) on aquatic organisms have attracted much attention; however, research on the toxicity of NPs to microalgae has been insufficient. In the present study, the effects of polystyrene nanoplastics (nano-PS, 50 nm) on growth inhibition, chlorophyll content, oxidative stress, and algal toxin production of the marine toxigenic dinoflagellate Amphidinium carterae Hulburt were investigated. Chlorophyll synthesis was promoted by nano-PS on day 2 but was inhibited on day 4; high concentrations of nano-PS (≥50 mg/L) significantly inhibited the growth of A. carterae. Moreover, despite the combined effect of superoxide dismutase (SOD) and glutathione (GSH), high reactive oxygen species (ROS) level and malondialdehyde (MDA) content were still induced by nano-PS (≥50 mg/L), indicating severe lipid peroxidation. In addition, the contents of extracellular and intracellular hemolytic toxins in nano-PS groups were significantly higher than those in control groups on days 2 and 8, except that those of extracellular hemolytic toxins in the 100 mg/L nano-PS group decreased on day 8 because of severe adsorption of hemolytic toxins to the nano-PS. Hence, the effects of nano-PS on A. carterae are closely linked to nano-PS concentration and surface properties and exposure time. These findings provide a deep understanding of the complex effects of NPs on toxigenic microalgae and present valuable data for assessing their environmental risks. Full article
(This article belongs to the Special Issue Nanomaterials Ecotoxicity Evaluation)
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Article
Fast Fabrication of Solid-State Nanopores for DNA Molecule Analysis
Nanomaterials 2021, 11(9), 2450; https://doi.org/10.3390/nano11092450 - 20 Sep 2021
Abstract
Solid-state nanopores have been developed as a prominent tool for single molecule analysis in versatile applications. Although controlled dielectric breakdown (CDB) is the most accessible method for a single nanopore fabrication, it is still necessary to improve the fabrication efficiency and avoid the [...] Read more.
Solid-state nanopores have been developed as a prominent tool for single molecule analysis in versatile applications. Although controlled dielectric breakdown (CDB) is the most accessible method for a single nanopore fabrication, it is still necessary to improve the fabrication efficiency and avoid the generation of multiple nanopores. In this work, we treated the SiNx membranes in the air–plasma before the CDB process, which shortened the time-to-pore-formation by orders of magnitude. λ-DNA translocation experiments validated the functionality of the pore and substantiated the presence of only a single pore on the membrane. Our fabricated pore could also be successfully used to detect short single-stranded DNA (ssDNA) fragments. Using to ionic current signals, ssDNA fragments with different lengths could be clearly distinguished. These results will provide a valuable reference for the nanopore fabrication and DNA analysis. Full article
(This article belongs to the Special Issue New Trends of Bio- and Chemo- Sensors with Nanomaterials)
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Article
Preparation of Network-Structured Carbon Nanofiber Mats Based on PAN Blends Using Electrospinning and Hot-Pressing Methods for Supercapacitor Applications
Nanomaterials 2021, 11(9), 2447; https://doi.org/10.3390/nano11092447 - 20 Sep 2021
Abstract
In this work, we prepared network-structured carbon nanofibers using polyacrylonitrile blends (PAN150 and PAN85) with different molecular weights (150,000 and 85,000 g mol−1) as precursors through electrospinning/hot-pressing methods and stabilization/carbonization processes. The obtained PAN150/PAN85 polymer nanofibers (PNFs; PNF-73, PNF-64 and PNF-55) [...] Read more.
In this work, we prepared network-structured carbon nanofibers using polyacrylonitrile blends (PAN150 and PAN85) with different molecular weights (150,000 and 85,000 g mol−1) as precursors through electrospinning/hot-pressing methods and stabilization/carbonization processes. The obtained PAN150/PAN85 polymer nanofibers (PNFs; PNF-73, PNF-64 and PNF-55) with different weight ratios of 70/30, 60/40 and 50/50 (w/w) provided good mechanical and electrochemical properties due to the formation of physically bonded network structures between the blended PAN nanofibers during the hot-processing/stabilization processes. The resulting carbonized PNFs (cPNFs; cPNF-73, cPNF-64, and cPNF-55) were utilized as anode materials for supercapacitor applications. cPNF-73 exhibited a good specific capacitance of 689 F g−1 at 1 A g−1 in a three-electrode set-up compared to cPNF-64 (588 F g−1 at 1 A g−1) and cPNF-55 (343 F g−1 at 1 A g−1). In addition, an asymmetric hybrid cPNF-73//NiCo2O4 supercapacitor device also showed a good specific capacitance of 428 F g−1 at 1 A g−1 compared to cPNF-64 (400 F g−1 at 1 A g−1) and cPNF-55 (315 F g−1 at 1 A g−1). The cPNF-73-based device showed a good energy density of 1.74 W h kg−1 (0.38 W kg−1) as well as an excellent cyclic stability (83%) even after 2000 continuous charge–discharge cycles at a current density of 2 A g−1. Full article
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Article
Modulation of Conductivity and Contact Resistance of RuO2 Nanosheets via Metal Nano-Particles Surface Decoration
Nanomaterials 2021, 11(9), 2444; https://doi.org/10.3390/nano11092444 - 19 Sep 2021
Abstract
We studied the variation in electrical conductivity of exfoliated RuO2 nanosheets and the modulation in the contact resistance of individual nanosheet devices using charge transfer doping effects based on surface metal nanoparticle decorations. The electrical conductivity in the monolayer and bilayer RuO [...] Read more.
We studied the variation in electrical conductivity of exfoliated RuO2 nanosheets and the modulation in the contact resistance of individual nanosheet devices using charge transfer doping effects based on surface metal nanoparticle decorations. The electrical conductivity in the monolayer and bilayer RuO2 nanosheets gradually increased due to the surface decoration of Cu, and subsequently Ag, nanoparticles. We obtained contact resistances between the nanosheet and electrodes using the four-point and two-point probe techniques. Moreover, the contact resistances decreased during the surface decoration processes. We established that the surface decoration of metal nanoparticles is a suitable method for external contact engineering and the modulation of the internal properties of nanomaterials. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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Article
Phase Behavior and Composition Distribution of Multiphase Hydrocarbon Binary Mixtures in Heterogeneous Nanopores: A Molecular Dynamics Simulation Study
Nanomaterials 2021, 11(9), 2431; https://doi.org/10.3390/nano11092431 - 18 Sep 2021
Abstract
In this study, molecular dynamics (MD) simulation is used to investigate the phase behavior and composition distribution of an ethane/heptane binary mixture in heterogeneous oil-wet graphite nanopores with pore size distribution. The pore network system consists of two different setups of connected bulk [...] Read more.
In this study, molecular dynamics (MD) simulation is used to investigate the phase behavior and composition distribution of an ethane/heptane binary mixture in heterogeneous oil-wet graphite nanopores with pore size distribution. The pore network system consists of two different setups of connected bulk and a 5-nm pore in the middle; and the bulk connected to 5-nm and 2-nm pores. Our results show that nanopore confinement influences the phase equilibrium of the multicomponent hydrocarbon mixtures and this effect is stronger for smaller pores. We recognized multiple adsorbed layers of hydrocarbon molecules near the pore surface. However, for smaller pores, adsorption is dominant so that, for the 2-nm pore, most of the hydrocarbon molecules are in the adsorbed phase. The MD simulation results revealed that the overall composition of the hydrocarbon mixture is a function of pore size. This has major implications for macro-scale unconventional reservoir simulation, as it suggests that heterogenous shale nanopores would host fluids with different compositions depending on the pore size. The results of this paper suggest that modifications should be made to the calculation of overall composition of reservoir fluids in shale nanopores, as using only one overall composition for the entire heterogenous reservoir can result in significant error in recovery estimations. Full article
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Article
A Novel Carbon-Assisted Chemical Vapor Deposition Growth of Large-Area Uniform Monolayer MoS2 and WS2
Nanomaterials 2021, 11(9), 2423; https://doi.org/10.3390/nano11092423 - 17 Sep 2021
Abstract
Monolayer MoS2 can be used for various applications such as flexible optoelectronics and electronics due to its exceptional optical and electronic properties. For these applications, large-area synthesis of high-quality monolayer MoS2 is highly desirable. However, the conventional chemical vapor deposition (CVD) [...] Read more.
Monolayer MoS2 can be used for various applications such as flexible optoelectronics and electronics due to its exceptional optical and electronic properties. For these applications, large-area synthesis of high-quality monolayer MoS2 is highly desirable. However, the conventional chemical vapor deposition (CVD) method using MoO3 and S powder has shown limitations in synthesizing high-quality monolayer MoS2 over a large area on a substrate. In this study, we present a novel carbon cloth-assisted CVD method for large-area uniform synthesis of high-quality monolayer MoS2. While the conventional CVD method produces thick MoS2 films in the center of the substrate and forms MoS2 monolayers at the edge of the thick MoS2 films, our carbon cloth-assisted CVD method uniformly grows high-quality monolayer MoS2 in the center of the substrate. The as-synthesized monolayer MoS2 was characterized in detail by Raman/photoluminescence spectroscopy, atomic force microscopy, and transmission electron microscopy. We reveal the growth process of monolayer MoS2 initiated from MoS2 seeds by synthesizing monolayer MoS2 with varying reaction times. In addition, we show that the CVD method employing carbon powder also produces uniform monolayer MoS2 without forming thick MoS2 films in the center of the substrate. This confirms that the large-area growth of monolayer MoS2 using the carbon cloth-assisted CVD method is mainly due to reducing properties of the carbon material, rather than the effect of covering the carbon cloth. Furthermore, we demonstrate that our carbon cloth-assisted CVD method is generally applicable to large-area uniform synthesis of other monolayer transition metal dichalcogenides, including monolayer WS2. Full article
(This article belongs to the Special Issue New Growth Mechanisms for Synthesizing Various Novel Nanostructures)
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Article
Improved Sensitivity of Surface-Enhanced Raman Scattering with Gold Nanoparticles-Insulator-Metal Sandwich Layers on Flat Sapphire Substrate
Nanomaterials 2021, 11(9), 2416; https://doi.org/10.3390/nano11092416 - 16 Sep 2021
Abstract
Surface-enhanced Raman scattering (SERS) as a high sensitivity analytical method for molecule detection has attracted much attention in recent research. In this work, we demonstrated an improved SERS substrate, which has the gold nanoparticles randomly distributed on a SiO2 interception layer over [...] Read more.
Surface-enhanced Raman scattering (SERS) as a high sensitivity analytical method for molecule detection has attracted much attention in recent research. In this work, we demonstrated an improved SERS substrate, which has the gold nanoparticles randomly distributed on a SiO2 interception layer over a gold thin film layer on the flat sapphire substrate (AuNP/SiO2/Au/Sapphire), over the dispersed gold nanoparticles on a silicon substrate (AuNP/Si), for detection of R6G (1 × 10−6 M) in a Raman microscope. The fabrication of sandwich layers on top of the sapphire substrate involves evaporation of a gold mirror as thick as 100 nm, plasma enhanced chemical vapor deposition of the silica insulator layer 10 nm thick, and evaporation of a thin gold layer 10 nm thick for forming gold nanoparticles. For comparison, a gold thin film with a thickness of 5 nm and 10 nm was evaporated on a silicon substrate, respectively (AuNP/Si), as the reference SERS substrates in the experiment. The AuNP/SiO2/Au/Sapphire substrate demonstrated improved sensitivity in detection of molecules in Raman microscopy, which can enable the molecules to be recognizable at a low laser power as 8.5 × 10−3 mW, 0.017 mW, 0.085 mW, and 0.17 mW for ultrashort exposure time. The simulation of AuNP/SiO2/Au/Sapphire substrate and AuNP/Si substrate, based on the finite-difference time-domain (FDTD) method, explained the improved sensitivity for detection of R6G molecules from the view of classical electromagnetics, and it suggested the optimized size for the gold nanoparticles and the optimized laser wavelength for Raman microscopy for further research. Full article
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Article
Acetone-Sensitive Thin Films Comprising Coal Fly Ash Na-X Zeolites and Sol–Gel Nb2O5 Matrix
Nanomaterials 2021, 11(9), 2399; https://doi.org/10.3390/nano11092399 - 15 Sep 2021
Abstract
In this study, thin composite films of a sol–gel Nb2O5 matrix doped with coal fly ash Na-X zeolites were deposited by the spin-coating method. Fly ash of lignite coal collected from the electrostatic precipitators of one of the biggest TPPs [...] Read more.
In this study, thin composite films of a sol–gel Nb2O5 matrix doped with coal fly ash Na-X zeolites were deposited by the spin-coating method. Fly ash of lignite coal collected from the electrostatic precipitators of one of the biggest TPPs in Bulgaria was used as a raw material for obtaining zeolites. Zeolite Na-X was synthesized by ultrasonic-assisted double stage fusion-hydrothermal alkaline conversion of coal fly ash. In order to improve the optical quality and sensing properties of the deposited thin films, synthesized zeolites were wet-milled for 60, 120, and 540 s prior to film deposition. The surface morphology of zeolite powders was studied both by scanning electron microscopy and transmission electron microscopy, while their porosity was investigated by N2-physisorption. Refractive index, extinction coefficient, and thickness of the films were determined through fitting of their reflectance spectra. The sensing ability of thin films towards acetone vapors was tested by measuring the reflectance spectra prior to and during exposure to the analyte, and the change in the reflection coefficient ∆R of the films was calculated. The influence of milling time of zeolites on the sensing and optical properties of the films was assumed and confirmed. Full article
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Article
Fluorinated Boron-Based Anions for Higher Voltage Li Metal Battery Electrolytes
Nanomaterials 2021, 11(9), 2391; https://doi.org/10.3390/nano11092391 - 14 Sep 2021
Abstract
Lithium metal batteries (LMBs) require an electrolyte with high ionic conductivity as well as high thermal and electrochemical stability that can maintain a stable solid electrolyte interphase (SEI) layer on the lithium metal anode surface. The borate anions tetrakis(trifluoromethyl)borate ([B(CF3)4 [...] Read more.
Lithium metal batteries (LMBs) require an electrolyte with high ionic conductivity as well as high thermal and electrochemical stability that can maintain a stable solid electrolyte interphase (SEI) layer on the lithium metal anode surface. The borate anions tetrakis(trifluoromethyl)borate ([B(CF3)4]), pentafluoroethyltrifluoroborate ([(C2F5)BF3]), and pentafluoroethyldifluorocyanoborate ([(C2F5)BF2(CN)]) have shown excellent physicochemical properties and electrochemical stability windows; however, the suitability of these anions as high-voltage LMB electrolytes components that can stabilise the Li anode is yet to be determined. In this work, density functional theory calculations show high reductive stability limits and low anion–cation interaction strengths for Li[B(CF3)4], Li[(C2F5)BF3], and Li[(C2F5)BF2(CN)] that surpass popular sulfonamide salts. Specifically, Li[B(CF3)4] has a calculated oxidative stability limit of 7.12 V vs. Li+/Li0 which is significantly higher than the other borate and sulfonamide salts (≤6.41 V vs. Li+/Li0). Using ab initio molecular dynamics simulations, this study is the first to show that these borate anions can form an advantageous LiF-rich SEI layer on the Li anode at room (298 K) and elevated (358 K) temperatures. The interaction of the borate anions, particularly [B(CF3)4], with the Li+ and Li anode, suggests they are suitable inclusions in high-voltage LMB electrolytes that can stabilise the Li anode surface and provide enhanced ionic conductivity. Full article
(This article belongs to the Special Issue Advanced Materials for Lithium (and Post-Lithium) Batteries)
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Article
Antibacterial Biodegradable Films Based on Alginate with Silver Nanoparticles and Lemongrass Essential Oil–Innovative Packaging for Cheese
Nanomaterials 2021, 11(9), 2377; https://doi.org/10.3390/nano11092377 - 13 Sep 2021
Abstract
Replacing the petroleum-based materials in the food industry is one of the main objectives of the scientists and decision makers worldwide. Biodegradable packaging will help diminish the environmental impact of human activity. Improving such biodegradable packaging materials by adding antimicrobial activity will not [...] Read more.
Replacing the petroleum-based materials in the food industry is one of the main objectives of the scientists and decision makers worldwide. Biodegradable packaging will help diminish the environmental impact of human activity. Improving such biodegradable packaging materials by adding antimicrobial activity will not only extend the shelf life of foodstuff, but will also eliminate some health hazards associated with food borne diseases, and by diminishing the food spoilage will decrease the food waste. The objective of this research was to obtain innovative antibacterial films based on a biodegradable polymer, namely alginate. Films were characterized by environmental scanning electron microscopy (ESEM), Fourier-transform infrared spectroscopy (FTIR) and microscopy, complex thermal analysis (TG-DSC-FTIR), UV-Vis and fluorescence spectroscopy. Water vapor permeability and swelling behavior were also determined. As antimicrobial agents, we used silver spherical nanoparticles (Ag NPs) and lemongrass essential oil (LGO), which were found to act in a synergic way. The obtained films exhibited strong antibacterial activity against tested strains, two Gram-positive (Bacillus cereus and Staphylococcus aureus) and two Gram-negative (Escherichia coli and Salmonella Typhi). Best results were obtained against Bacillus cereus. The tests indicate that the antimicrobial films can be used as packaging, preserving the color, surface texture, and softness of cheese for 14 days. At the same time, the color of the films changed (darkened) as a function of temperature and light presence, a feature that can be used to monitor the storage conditions for sensitive food. Full article
(This article belongs to the Special Issue Food Packaging Bionanocomposites)
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Article
Amino-Functionalized Fe3O4@SiO2 Core-Shell Magnetic Nanoparticles for Dye Adsorption
Nanomaterials 2021, 11(9), 2371; https://doi.org/10.3390/nano11092371 - 12 Sep 2021
Abstract
Fe3O4@SiO2 core-shell nanoparticles (NPs) were synthesized with the co-precipitation method and functionalized with NH2 amino-groups. The nanoparticles were characterized by X-ray, FT-IR spectroscopy, transmission electron microscopy, selected area electron diffraction, and vibrating sample magnetometry. The magnetic core [...] Read more.
Fe3O4@SiO2 core-shell nanoparticles (NPs) were synthesized with the co-precipitation method and functionalized with NH2 amino-groups. The nanoparticles were characterized by X-ray, FT-IR spectroscopy, transmission electron microscopy, selected area electron diffraction, and vibrating sample magnetometry. The magnetic core of all the nanoparticles was shown to be nanocrystalline with the crystal parameters corresponding only to the Fe3O4 phase covered with a homogeneous amorphous silica (SiO2) shell of about 6 nm in thickness. The FT-IR spectra confirmed the appearance of chemical bonds at amino functionalization. The magnetic measurements revealed unusually high saturation magnetization of the initial Fe3O4 nanoparticles, which was presumably associated with the deviations in the Fe ion distribution between the tetrahedral and octahedral positions in the nanocrystals as compared to the bulk stoichiometric magnetite. The fluorescent spectrum of eosin Y-doped NPs dispersed in water solution was obtained and a red shift and line broadening (in comparison with the dye molecules being free in water) were revealed and explained. Most attention was paid to the adsorption properties of the nanoparticles with respect to three dyes: methylene blue, Congo red, and eosin Y. The kinetic data showed that the adsorption processes were associated with the pseudo-second order mechanism for all three dyes. The equilibrium data were more compatible with the Langmuir isotherm and the maximum adsorption capacity was reached for Congo red. Full article
(This article belongs to the Section Nanocomposite Materials)
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Article
Solid State Photoreduction of Silver on Mesoporous Silica to Enhance Antifungal Activity
Nanomaterials 2021, 11(9), 2340; https://doi.org/10.3390/nano11092340 - 09 Sep 2021
Abstract
A solid-state Ultraviolet-photoreduction process of silver cations to produce Ag0 nanostructures on a mesoporous silica is presented as an innovative method for the preparation of efficient environmental anti-fouling agents. Mesoporous silica powder, contacted with AgNO3, is irradiated at 366 nm, [...] Read more.
A solid-state Ultraviolet-photoreduction process of silver cations to produce Ag0 nanostructures on a mesoporous silica is presented as an innovative method for the preparation of efficient environmental anti-fouling agents. Mesoporous silica powder, contacted with AgNO3, is irradiated at 366 nm, where silica surface defects absorb. The detailed characterization of the materials enables us to document the silica assisted photo-reduction. The appearance of a Visible (Vis) band centered at 470 nm in the extinction spectra, due to the surface plasmon resonance of Ag0 nanostructures, and the morphology changes observed in transmission electron microscopy (TEM) images, associated with the increase of Ag/O ratio in energy dispersive X-ray (EDX) analysis, indicate the photo-induced formation of Ag0. The data demonstrate that the photo-induced reduction of silver cation occurs in the solid state and takes place through the activation of silica defects. The activation of the materials after UV-processing is then tested, evaluating their antimicrobial activity using an environmental filamentous fungus, Aspergillus niger. The treatment doubled inhibitory capacity in terms of minimal inhibitory concentration (MIC) and biofilm growth. The antimicrobial properties of silver–silica nanocomposites are investigated when dispersed in a commercial sealant; the nanocomposites show excellent dispersion in the silicon and improve its anti-fouling capacity. Full article
(This article belongs to the Special Issue Metallic and Metal Oxide Nanoparticles and Their Applications)
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Article
Pd-C Catalytic Thin Films Prepared by Magnetron Sputtering for the Decomposition of Formic Acid
Nanomaterials 2021, 11(9), 2326; https://doi.org/10.3390/nano11092326 - 07 Sep 2021
Abstract
Formic acid is an advantageous liquid organic hydrogen carrier. It is relatively nontoxic and can be synthesized by the reaction of CO2 with sustainable hydrogen or by biomass decomposition. As an alternative to more widely studied powdery catalysts, supported Pd-C catalytic thin [...] Read more.
Formic acid is an advantageous liquid organic hydrogen carrier. It is relatively nontoxic and can be synthesized by the reaction of CO2 with sustainable hydrogen or by biomass decomposition. As an alternative to more widely studied powdery catalysts, supported Pd-C catalytic thin films with controlled nanostructure and compositions were newly prepared in this work by magnetron sputtering on structured supports and tested for the formic acid decomposition reaction. A two-magnetron configuration (carbon and tailored Pd-C targets) was used to achieve a reduction in Pd consumption and high catalyst surface roughness and dispersion by increasing the carbon content. Activity and durability tests were carried out for the gas phase formic acid decomposition reaction on SiC foam monoliths coated with the Pd-C films and the effects of column width, surface roughness and thermal pre-reduction time were investigated. Activity of 5.04 molH2·gPd−1·h−1 and 92% selectivity to the dehydrogenation reaction were achieved at 300 °C for the catalyst with a lower column width and higher carbon content and surface roughness. It was also found that deactivation occurs when Pd is sintered due to the elimination of carbon and/or the segregation and agglomeration of Pd upon cycling. Magnetron sputtering deposition appears as a promising and scalable route for the one-step preparation of Pd-C catalytic films by overcoming the different deposition characteristics of Pd and C with an appropriate experimental design. Full article
(This article belongs to the Special Issue Nanostructures for Surfaces, Catalysis and Sensing)
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Article
Bayesian Data Assimilation of Temperature Dependence of Solid–Liquid Interfacial Properties of Nickel
Nanomaterials 2021, 11(9), 2308; https://doi.org/10.3390/nano11092308 - 06 Sep 2021
Abstract
Temperature dependence of solid–liquid interfacial properties during crystal growth in nickel was investigated by ensemble Kalman filter (EnKF)-based data assimilation, in which the phase-field simulation was combined with atomic configurations of molecular dynamics (MD) simulation. Negative temperature dependence was found in the solid–liquid [...] Read more.
Temperature dependence of solid–liquid interfacial properties during crystal growth in nickel was investigated by ensemble Kalman filter (EnKF)-based data assimilation, in which the phase-field simulation was combined with atomic configurations of molecular dynamics (MD) simulation. Negative temperature dependence was found in the solid–liquid interfacial energy, the kinetic coefficient, and their anisotropy parameters from simultaneous estimation of four parameters. On the other hand, it is difficult to obtain a concrete value for the anisotropy parameter of solid–liquid interfacial energy since this factor is less influential for the MD simulation of crystal growth at high undercooling temperatures. The present study is significant in shedding light on the high potential of Bayesian data assimilation as a novel methodology of parameter estimation of practical materials an out of equilibrium condition. Full article
(This article belongs to the Special Issue Thermal, Mechanical and Radiation Stability of Nanostructured Metals)
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Article
Marble Waste Sludges as Effective Nanomaterials for Cu (II) Adsorption in Aqueous Media
Nanomaterials 2021, 11(9), 2305; https://doi.org/10.3390/nano11092305 - 05 Sep 2021
Abstract
This study evaluated the waste generated by a Spanish marble-producing company as adsorbent for the removal of copper (Cu [II]) from aqueous media. Six marble waste sludge samples were studied, and the following operational parameters were analyzed in discontinuous regime, including pollutant concentration, [...] Read more.
This study evaluated the waste generated by a Spanish marble-producing company as adsorbent for the removal of copper (Cu [II]) from aqueous media. Six marble waste sludge samples were studied, and the following operational parameters were analyzed in discontinuous regime, including pollutant concentration, pH, temperature, nature of aqueous medium, and ionic strength. The applicability of the adsorbent material was assessed with experiments in both continuous and discontinuous regimes under close-to-real-life conditions. A pseudo-second order model yielded a better fit to the kinetic data. Application of the intraparticle diffusion model revealed two well-differentiated adsorption stages, in which the external material transfer is negligible and intraparticle diffusion is the controlling stage. The equilibrium study was better fitted to a Freundlich-type isotherm, predicting elevated maximum adsorption values (22.7 mg g−1) at a relatively low initial Cu (II) concentration (25 ppm), yielding a highly favorable chemisorption process (n >> 1). X-ray fluorescence study identified calcite (CaCO3) as the main component of marble waste sludges. According to X-ray diffraction analysis, Cu (II) ion adsorption occurred by intercalation of the metallic cation between CaCO3 layers and by the formation of surface complexes such as CaCO3 and Cu2(CO3)(OH)2. Cu (II) was more effectively removed at medium pH, lower temperature, and lower ionic strength of the aqueous medium. The salinity and dissolved organic matter in surface, ground-, and waste-waters negatively affected the Cu (II) removal process in both continuous and discontinuous regimes by competing for active adsorption sites. These findings demonstrate the applicability and effectiveness of marble-derived waste sludges as low-cost and readily available adsorbents for the treatment of waters polluted by Cu (II) under close-to-real-life conditions. Full article
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Article
MHD Williamson Nanofluid Flow over a Slender Elastic Sheet of Irregular Thickness in the Presence of Bioconvection
Nanomaterials 2021, 11(9), 2297; https://doi.org/10.3390/nano11092297 - 03 Sep 2021
Abstract
Bioconvection phenomena for MHD Williamson nanofluid flow over an extending sheet of irregular thickness are investigated theoretically, and non-uniform viscosity and thermal conductivity depending on temperature are taken into account. The magnetic field of uniform strength creates a magnetohydrodynamics effect. The basic formulation [...] Read more.
Bioconvection phenomena for MHD Williamson nanofluid flow over an extending sheet of irregular thickness are investigated theoretically, and non-uniform viscosity and thermal conductivity depending on temperature are taken into account. The magnetic field of uniform strength creates a magnetohydrodynamics effect. The basic formulation of the model developed in partial differential equations which are later transmuted into ordinary differential equations by employing similarity variables. To elucidate the influences of controlling parameters on dependent quantities of physical significance, a computational procedure based on the Runge–Kutta method along shooting technique is coded in MATLAB platform. This is a widely used procedure for the solution of such problems because it is efficient with fifth-order accuracy and cost-effectiveness. The enumeration of the results reveals that Williamson fluid parameter λ, variable viscosity parameter Λμ and wall thickness parameter ς impart reciprocally decreasing effect on fluid velocity whereas these parameters directly enhance the fluid temperature. The fluid temperature is also improved with Brownian motion parameter Nb and thermophoresis parameter Nt. The boosted value of Brownian motion Nb and Lewis number Le reduce the concentration of nanoparticles. The higher inputs of Peclet number Pe and bioconvection Lewis number Lb decline the bioconvection distribution. The velocity of non-Newtonian (Williamson nanofluid) is less than the viscous nanofluid but temperature behaves oppositely. Full article
(This article belongs to the Special Issue New Frontiers in Nanofluids)
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Communication
Structural Insight into La0.5Ca0.5Mn0.5Co0.5O3 Decomposition in the Methane Combustion Process
Nanomaterials 2021, 11(9), 2283; https://doi.org/10.3390/nano11092283 - 02 Sep 2021
Abstract
Perovskite-like solid solution La0.5Ca0.5Mn0.5Co0.5O3 was tested during the total methane combustion reaction. During the reaction, there is a noticeable decrease in methane conversion, the rate of catalyst deactivation increasing with an increase in temperature. [...] Read more.
Perovskite-like solid solution La0.5Ca0.5Mn0.5Co0.5O3 was tested during the total methane combustion reaction. During the reaction, there is a noticeable decrease in methane conversion, the rate of catalyst deactivation increasing with an increase in temperature. The in situ XRD and HRTEM methods show that the observed deactivation occurs as a result of the segregation of calcite and cobalt oxide particles on the perovskite surface. According to the TGA, the observed drop in catalytic activity is also associated with a large loss of oxygen from the perovskite structure. Full article
(This article belongs to the Special Issue Synthesis of Nanocomposites and Catalysis Applications)
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Article
Flexible Layered-Graphene Charge Modulation for Highly Stable Triboelectric Nanogenerator
Nanomaterials 2021, 11(9), 2276; https://doi.org/10.3390/nano11092276 - 01 Sep 2021
Abstract
The continuous quest to enhance the output performance of triboelectric nanogenerators (TENGs) based on the surface charge density of the tribolayer has motivated researchers to harvest mechanical energy efficiently. Most of the previous work focused on the enhancement of negative triboelectric charges. The [...] Read more.
The continuous quest to enhance the output performance of triboelectric nanogenerators (TENGs) based on the surface charge density of the tribolayer has motivated researchers to harvest mechanical energy efficiently. Most of the previous work focused on the enhancement of negative triboelectric charges. The enhancement of charge density over positive tribolayer has been less investigated. In this work, we developed a layer-by-layer assembled multilayer graphene-based TENG to enhance the charge density by creatively introducing a charge trapping layer (CTL) Al2O3 in between the positive triboelectric layer and conducting electrode to construct an attractive flexible TENG. Based on the experimental results, the optimized three layers of graphene TENG (3L-Gr-TENG) with CTL showed a 30-fold enhancement in output power compared to its counterpart, 3L-Gr-TENG without CTL. This remarkably enhanced performance can be ascribed to the synergistic effect between the optimized graphene layers with high dielectric CTL. Moreover, the device exhibited outstanding stability after continuous operation of >2000 cycles. Additionally, the device was capable of powering 20 green LEDs and sufficient to power an electronic timer with rectifying circuits. This research provides a new insight to improve the charge density of Gr-TENGs as energy harvesters for next-generation flexible electronics. Full article
(This article belongs to the Special Issue Multifunctional Nanomaterials for Energy Applications)
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Article
Laser-Induced Modification of Hydrogenated Detonation Nanodiamonds in Ethanol
Nanomaterials 2021, 11(9), 2251; https://doi.org/10.3390/nano11092251 - 31 Aug 2021
Abstract
Apart from the frequently used high-temperature annealing of detonation nanodiamonds (DNDs) in an inert environment, laser irradiation of DNDs in a liquid can be effectively used for onion-like carbon (OLC) formation. Here, we used fully de-aggregated hydrogenated DNDs (H-DNDs) dispersed in ethanol, which [...] Read more.
Apart from the frequently used high-temperature annealing of detonation nanodiamonds (DNDs) in an inert environment, laser irradiation of DNDs in a liquid can be effectively used for onion-like carbon (OLC) formation. Here, we used fully de-aggregated hydrogenated DNDs (H-DNDs) dispersed in ethanol, which were irradiated for up to 60 min using a 532 nm NdYAG laser with an energy of 150 mJ in a pulse (5 J/cm2) at a pulse duration of 10 ns and a repetition rate of 10 Hz. We investigated the DND surface chemistry, zeta potential, and structure as a function of laser irradiation time. Infrared spectroscopy revealed a monotonical decrease in the C–Hx band intensities and an increase of the C–O and C=O features. Transmission electron microscopy (TEM) revealed the formation of OLC, as well as a gradual loss of nanoparticle character, with increasing irradiation time. Surprisingly, for samples irradiated up to 40 min, the typical and unchanged DND Raman spectrum was recovered after their annealing in air at 450 °C for 300 min. This finding indicates the inhomogeneous sp3 to sp2 carbon transformation during laser irradiation, as well as the insensitivity of DND Raman spectra to surface chemistry, size, and transient structural changes. Full article
(This article belongs to the Special Issue Synthesis, Functionalization and Applications of Nanocarbons)
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Article
Effect of Silver Modification on the Photoactivity of Titania Coatings with Different Pore Structures
Nanomaterials 2021, 11(9), 2240; https://doi.org/10.3390/nano11092240 - 30 Aug 2021
Abstract
Nanostructured photoactive systems are promising for applications such as air and water purification, including self-cleaning coatings. In this study, mesoporous TiO2 sol-gel coatings with different pore structures were prepared and modified with silver by two methods: the “mixing” method by adding AgNO [...] Read more.
Nanostructured photoactive systems are promising for applications such as air and water purification, including self-cleaning coatings. In this study, mesoporous TiO2 sol-gel coatings with different pore structures were prepared and modified with silver by two methods: the “mixing” method by adding AgNO3 to the precursor sol, and the “impregnation” method by immersing the samples in AgNO3 solution (0.03 and 1 M) followed by heat treatment. Our aim was to investigate the effects that silver modification has on the functional properties (e.g., those that are important for self-cleaning coatings). Transmittance, band gap energy, refractive index, porosity and thickness values were determined from UV-Vis spectroscopy measurements. Silver content and structure of the silver modified samples were characterized by X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, High-resolution transmission electron microscopy and Energy Dispersive X-ray Spectrometry elemental mapping measurements. Wettability properties, including photoinduced wettability conversion behavior were investigated by water contact angle measurements. Photoactivity was studied under both UV and visible light with rhodamine 6G and methylene blue dye molecules, at the liquid–solid and air–solid interfaces modeling the operating conditions of self-cleaning coatings. Samples made with “impregnation” method showed better functional properties, in spite of their significantly lower silver content. The pore structure influenced the Ag content achieved by the “impregnation” method, and consequently affected their photoactivity. Full article
(This article belongs to the Special Issue Latest Developments in Photocatalytic Materials and Processes)
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Article
Preparation of Metal Nitride Particles Using Arc Discharge in Liquid Nitrogen
Nanomaterials 2021, 11(9), 2214; https://doi.org/10.3390/nano11092214 - 28 Aug 2021
Abstract
A simple process to synthesize metal nitride particles was proposed using submerged arc discharge plasma in liquid nitrogen. Gibbs standard free energy was considered for the selection of the nitride-forming materials. In this study, titanium (Ti) and aluminum (Al) electrodes were used as [...] Read more.
A simple process to synthesize metal nitride particles was proposed using submerged arc discharge plasma in liquid nitrogen. Gibbs standard free energy was considered for the selection of the nitride-forming materials. In this study, titanium (Ti) and aluminum (Al) electrodes were used as raw materials for nitride particle preparation. Liquid nitrogen acted as a dielectric medium as well as a nitridation source in this process. A copper electrode was also used as a non-reactive material for comparison with the reactive Ti and Al electrodes. As the operating conditions of the experiments, the arc discharge current was varied from 5 A (low-power mode) to 30 A (high-power mode). The formation of titanium nitride (TiN) and aluminum nitride (AlN) was confirmed in the particles prepared in all experimental conditions by X-ray powder diffraction (XRD). The observation using a field emission scanning electron microscope (FE-SEM) and a field emission transmission electron microscope (FE-TEM) indicated that the synthesized TiN particles showed a cubic morphology, whereas AlN particles containing unreacted Al showed a spherical morphology. The experiments using different metal electrode configurations showed that the anode generated most of the particles in this process. Based on the obtained results, a particle formation mechanism was proposed. Full article
(This article belongs to the Special Issue Plasma Based Nanomaterials and Their Applications)
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Article
Oxygen Concentration Effect on Conductive Bridge Random Access Memory of InWZnO Thin Film
Nanomaterials 2021, 11(9), 2204; https://doi.org/10.3390/nano11092204 - 27 Aug 2021
Abstract
In this study, the influence of oxygen concentration in InWZnO (IWZO), which was used as the switching layer of conductive bridge random access memory, (CBRAM) is investigated. With different oxygen flow during the sputtering process, the IWZO film can be fabricated with different [...] Read more.
In this study, the influence of oxygen concentration in InWZnO (IWZO), which was used as the switching layer of conductive bridge random access memory, (CBRAM) is investigated. With different oxygen flow during the sputtering process, the IWZO film can be fabricated with different oxygen concentrations and different oxygen vacancy distribution. In addition, the electrical characteristics of CBRAM device with different oxygen concentration are compared and further analyzed with an atomic force microscope and X-ray photoelectron spectrum. Furthermore, a stacking structure with different bilayer switching is also systematically discussed. Compared with an interchange stacking layer and other single layer memory, the CBRAM with specific stacking sequence of bilayer oxygen-poor/-rich IWZO (IWZOx/IWZOy, x < y) exhibits more stable distribution of a resistance state and also better endurance (more than 3 × 104 cycles). Meanwhile, the memory window of IWZOx/IWZOy can even be maintained over 104 s at 85 °C. Those improvements can be attributed to the oxygen vacancy distribution in switching layers, which may create a suitable environment for the conductive filament formation or rupture. Therefore, it is believed that the specific stacking bilayer IWZO CBRAM might further pave the way for emerging memory applications. Full article
(This article belongs to the Special Issue Nanomaterials for Electron Devices)
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Article
Effect of Artemisinin-Loaded Mesoporous Cerium-Doped Calcium Silicate Nanopowder on Cell Proliferation of Human Periodontal Ligament Fibroblasts
Nanomaterials 2021, 11(9), 2189; https://doi.org/10.3390/nano11092189 - 26 Aug 2021
Cited by 1
Abstract
Ion doping has rendered mesoporous structures important materials in the field of tissue engineering, as apart from drug carriers, they can additionally serve as regenerative materials. The purpose of the present study was the synthesis, characterization and evaluation of the effect of artemisinin [...] Read more.
Ion doping has rendered mesoporous structures important materials in the field of tissue engineering, as apart from drug carriers, they can additionally serve as regenerative materials. The purpose of the present study was the synthesis, characterization and evaluation of the effect of artemisinin (ART)-loaded cerium-doped mesoporous calcium silicate nanopowders (NPs) on the hemocompatibility and cell proliferation of human periodontal ligament fibroblasts (hPDLFs). Mesoporous NPs were synthesized in a basic environment via a surfactant assisted cooperative self-assembly process and were characterized using Scanning Electron Microscopy (SEM), X-ray Fluorescence Spectroscopy (XRF), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction Analysis (XRD) and N2 Porosimetry. The loading capacity of NPs was evaluated using Ultrahigh Performance Liquid Chromatography/High resolution Mass Spectrometry (UHPLC/HRMS). Their biocompatibility was evaluated with the MTT assay, and the analysis of reactive oxygen species was performed using the cell-permeable ROS-sensitive probe 2′,7′-dichlorodihydrofluorescein diacetate (H2DCFDA). The synthesized NPs presented a mesoporous structure with a surface area ranging from 1312 m2/g for undoped silica to 495 m2/g for the Ce-doped NPs, excellent bioactivity after a 1-day immersion in c-SBF, hemocompatibility and a high loading capacity (around 80%). They presented ROS scavenging properties, and both the unloaded and ART-loaded NPs significantly promoted cell proliferation even at high concentrations of NPs (125 μg/mL). The ART-loaded Ce-doped NPs with the highest amount of cerium slightly restricted cell proliferation after 7 days of culture, but the difference was not significant compared with the control untreated cells. Full article
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Article
Introduction of Rare-Earth Oxide Nanoparticles in CNT-Based Nanocomposites for Improved Detection of Underlying CNT Network
Nanomaterials 2021, 11(9), 2168; https://doi.org/10.3390/nano11092168 - 25 Aug 2021
Abstract
Epoxy resins for adhesive and structural applications are widely employed by various industries. The introduction of high aspect ratio nanometric conductive fillers, i.e., carbon nanotubes, are well studied and are known to improve the electrical properties of the bulk material by orders of [...] Read more.
Epoxy resins for adhesive and structural applications are widely employed by various industries. The introduction of high aspect ratio nanometric conductive fillers, i.e., carbon nanotubes, are well studied and are known to improve the electrical properties of the bulk material by orders of magnitude. This improved electrical conductivity has made carbon nanotube-based nanocomposites an attractive material for applications where their weight savings are at a premium. However, the analytical methods for validating carbon nanotube (CNT) nanofiller dispersion and for assuring that the properties they induce extend to the entire volume are destructive and inhibited by poor resolution between matrix and tube bundles. Herein, rare-earth oxide nanoparticles are synthesized on CNT walls for the purpose of increasing the contrast between their network and the surrounding matrix when studied by imaging techniques, alleviating these issues. The adherence of the synthesized nanoparticles to the CNT walls is documented via transmission electron microscopy. The crystalline phases generated during the various fabrication steps are determined using X-ray diffraction. Deep ultraviolet-induced fluorescence of the Eu:Y2O3-CNT nanostructures is verified. The impacts to nanocomposite electrical properties resulting from dopant introduction are characterized. The scanning electron microscopy imaging of CNT pulp and nanocomposites fabricated from untreated CNTs and Eu:Y2O3-CNTs are compared, resulting in improved contrast and detection of CNT bundles. The micro-CT scans of composites with similar results are presented for discussion. Full article
(This article belongs to the Special Issue Carbon-Based Nanocomposites)
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Article
Design, Synthesis, and Cytotoxicity Assessment of [64Cu]Cu-NOTA-Terpyridine Platinum Conjugate: A Novel Chemoradiotherapeutic Agent with Flexible Linker
Nanomaterials 2021, 11(9), 2154; https://doi.org/10.3390/nano11092154 - 24 Aug 2021
Abstract
Maximum benefits of chemoradiation therapy with platinum-based compounds are expected if the radiation and the drug are localized simultaneously in cancer cells. To optimize this concomitant effect, we developed the novel chemoradiotherapeutic agent [64Cu]Cu-NOTA-C3-TP by conjugating, via a short flexible alkyl [...] Read more.
Maximum benefits of chemoradiation therapy with platinum-based compounds are expected if the radiation and the drug are localized simultaneously in cancer cells. To optimize this concomitant effect, we developed the novel chemoradiotherapeutic agent [64Cu]Cu-NOTA-C3-TP by conjugating, via a short flexible alkyl chain spacer (C3), a terpyridine platinum (TP) moiety to a NOTA chelator complexed with copper-64 (64Cu). The decay of 64Cu produces numerous low-energy electrons, enabling the 64Cu-conjugate to deliver radiation energy close to TP, which intercalates into G-quadruplex DNA. Accordingly, the in vitro internalization kinetic and the cytotoxic activity of [64Cu]Cu-NOTA-C3-TP and its derivatives were investigated with colorectal cancer (HCT116) and normal human fibroblast (GM05757) cells. Radiolabeling by 64Cu results in a >55,000-fold increase of cytotoxic potential relative to [NatCu]Cu-NOTA-C3-TP at 72 h post administration, indicating a large additive effect between 64Cu and the TP drug. The internalization and nucleus accumulation of [64Cu]Cu-NOTA-C3-TP in the HCT116 cells were, respectively, 3.1 and 6.0 times higher than that for GM05757 normal human fibroblasts, which is supportive of the higher efficiency of the [64Cu]Cu-NOTA-C3-TP for HCT116 cancer cells. This work presents the first proof-of-concept study showing the potential use of the [64Cu]Cu-NOTA-C3-TP conjugate as a targeted chemoradiotherapeutic agent to treat colorectal cancer. Full article
(This article belongs to the Special Issue Recent Advances in Cancer Nanotechnology)
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Article
Unravelling the Role of Synthesis Conditions on the Structure of Zinc Oxide-Reduced Graphene Oxide Nanofillers
Nanomaterials 2021, 11(8), 2149; https://doi.org/10.3390/nano11082149 - 23 Aug 2021
Cited by 1
Abstract
The diversity of zinc oxide (ZnO) particles and derived composites applications is highly dependent on their structure, size, morphology, defect amounts, and/or presence of dopant molecules. In this work, ZnO nanostructures are grown in situ on graphene oxide (GO) sheets by an easily [...] Read more.
The diversity of zinc oxide (ZnO) particles and derived composites applications is highly dependent on their structure, size, morphology, defect amounts, and/or presence of dopant molecules. In this work, ZnO nanostructures are grown in situ on graphene oxide (GO) sheets by an easily implementable solvothermal method with simultaneous reduction of GO. The effect of two zinc precursors (zinc acetate (ZA) and zinc acetate dihydrate (ZAD)), NaOH concentration (0.5, 1 or 2 M), and concentration (1 and 12.5 mg/mL) and pH (pH = 1, 4, 8, and 12) of GO suspension were evaluated. While the ZnO particle morphology shows to be precursor dependent, the average particle size length decreases with lower NaOH concentration, as well as with the addition of a higher basicity and concentration of GO suspension. A lowered band gap and a higher specific surface area are obtained from the ZnO composites with higher amounts of GO suspension. Otherwise, the low concentration and the higher pH of GO suspension induce more lattice defects on the ZnO crystal structure. The role of the different condition parameters on the ZnO nanostructures and their interaction with graphene sheets was observed to tune the ZnO–rGO nanofiller properties for photocatalytic and antimicrobial activities. Full article
(This article belongs to the Special Issue Synthesis, Characteristics, and Applications of Nanocomposites)
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Article
Skin Sensitization Potential and Cellular ROS-Induced Cytotoxicity of Silica Nanoparticles
Nanomaterials 2021, 11(8), 2140; https://doi.org/10.3390/nano11082140 - 22 Aug 2021
Abstract
Nowadays, various industries using nanomaterials are growing rapidly, and in particular, as the commercialization and use of nanomaterials increase in the cosmetic field, the possibility of exposure of nanomaterials to the skin of product producers and consumers is increasing. Due to the unique [...] Read more.
Nowadays, various industries using nanomaterials are growing rapidly, and in particular, as the commercialization and use of nanomaterials increase in the cosmetic field, the possibility of exposure of nanomaterials to the skin of product producers and consumers is increasing. Due to the unique properties of nanomaterials with a very small size, they can act as hapten and induce immune responses and skin sensitization, so accurate identification of toxicity is required. Therefore, we selected silica nanomaterials used in various fields such as cosmetics and biomaterials and evaluated the skin sensitization potential step-by-step according to in-vitro and in-vivo alternative test methods. KeratinoSensTM cells of modified keratinocyte and THP-1 cells mimicking dendritic-cells were treated with silica nanoparticles, and their potential for skin sensitization and cytotoxicity were evaluated, respectively. We also confirmed the sensitizing ability of silica nanoparticles in the auricle-lymph nodes of BALB/C mice by in-vivo analysis. As a result, silica nanoparticles showed high protein binding and reactive oxygen species (ROS) mediated cytotoxicity, but no significant observation of skin sensitization indicators was observed. Although more studies are needed to elucidate the mechanism of skin sensitization by nanomaterials, the results of this study showed that silica nanoparticles did not induce skin sensitization. Full article
(This article belongs to the Special Issue Biological and Toxicological Studies of Nanoparticles)
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Article
Chlorosulfonic Acid Stretched Carbon Nanotube Sheet for Flexible and Low-Voltage Heating Applications
Nanomaterials 2021, 11(8), 2132; https://doi.org/10.3390/nano11082132 - 21 Aug 2021
Cited by 1
Abstract
The carbon nanotube (CNT) is celebrated for its electrothermal property, which indicates the capability of a material to transform electrical energy into heat due to the Joule effect. The CNT nanostructure itself, as a one-dimensional material, limits the electron conduction path, thereby creating [...] Read more.
The carbon nanotube (CNT) is celebrated for its electrothermal property, which indicates the capability of a material to transform electrical energy into heat due to the Joule effect. The CNT nanostructure itself, as a one-dimensional material, limits the electron conduction path, thereby creating a unique heating phenomenon. In this work, we explore the possible correlation between CNT alignment in sheets and heating performance. The alignment of carbon nanotubes is induced by immersion and stretching in chlorosulfonic acid (CSA) solution. The developed CSA-stretched CNT sheet demonstrated excellent heating performance with a fast response rate of 6.5 °C/s and reached 180 °C in less than 30 s under a low voltage of 2.5 V. The heating profile of the stretched CNT sheet remained stable after bending and twisting movements, making it a suitable heating material for wearable devices, heatable smart windows, and in de-icing or defogging applications. The specific strength and specific conductance of the CSA-stretched CNT sheet also increased five- and two-fold, respectively, in comparison to the pristine CNT sheet. Full article
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Article
Characteristic Variabilities of Subnanometer EOT La2O3 Gate Dielectric Film of Nano CMOS Devices
Nanomaterials 2021, 11(8), 2118; https://doi.org/10.3390/nano11082118 - 20 Aug 2021
Abstract
As CMOS devices are scaled down to a nanoscale range, characteristic variability has become a critical issue for yield and performance control of gigascale integrated circuit manufacturing. Nanoscale in size, few monolayers thick, and less thermally stable high-k interfaces all together cause more [...] Read more.
As CMOS devices are scaled down to a nanoscale range, characteristic variability has become a critical issue for yield and performance control of gigascale integrated circuit manufacturing. Nanoscale in size, few monolayers thick, and less thermally stable high-k interfaces all together cause more significant surface roughness-induced local electric field fluctuation and thus leads to a large device characteristic variability. This paper presents a comprehensive study and detailed discussion on the gate leakage variabilities of nanoscale devices corresponding to the surface roughness effects. By taking the W/La2O3/Si structure as an example, capacitance and leakage current variabilities were found to increase pronouncedly for samples even with a very low-temperature thermal annealing at 300 °C. These results can be explained consistently with the increase in surface roughness as a result of local oxidation at the La2O3/Si interface and the interface reactions at the W/La2O3 interface. The surface roughness effects are expected to be severe in future generations’ devices with even thinner gate dielectric film and smaller size of the devices. Full article
(This article belongs to the Special Issue Abridging the CMOS Technology)
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