Editor’s Choice Articles

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

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Article

12 pages, 7938 KiB  
Article
Resist-Free Directed Self-Assembly Chemo-Epitaxy Approach for Line/Space Patterning
by Tommaso Jacopo Giammaria, Ahmed Gharbi, Anne Paquet, Paul Nealey and Raluca Tiron
Nanomaterials 2020, 10(12), 2443; https://doi.org/10.3390/nano10122443 - 7 Dec 2020
Cited by 2 | Viewed by 2617
Abstract
This work reports a novel, simple, and resist-free chemo-epitaxy process permitting the directed self-assembly (DSA) of lamella polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) on a 300 mm wafer. 193i lithography is used to manufacture topographical guiding silicon oxide line/space patterns. The critical [...] Read more.
This work reports a novel, simple, and resist-free chemo-epitaxy process permitting the directed self-assembly (DSA) of lamella polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) on a 300 mm wafer. 193i lithography is used to manufacture topographical guiding silicon oxide line/space patterns. The critical dimension (CD) of the silicon oxide line obtained can be easily trimmed by means of wet or dry etching: it allows a good control of the CD that permits finely tuning the guideline and the background dimensions. The chemical pattern that permits the DSA of the BCP is formed by a polystyrene (PS) guide and brush layers obtained with the grafting of the neutral layer polystyrene-random-polymethylmethacrylate (PS-r-PMMA). Moreover, data regarding the line edge roughness (LER) and line width roughness (LWR) are discussed with reference to the literature and to the stringent requirements of semiconductor technology. Full article
(This article belongs to the Special Issue Nanoscale Self-Assembly: Nanopatterning and Metrology)
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25 pages, 3181 KiB  
Article
Three-Year Study of Markers of Oxidative Stress in Exhaled Breath Condensate in Workers Producing Nanocomposites, Extended by Plasma and Urine Analysis in Last Two Years
by Daniela Pelclova, Vladimir Zdimal, Martin Komarc, Jaroslav Schwarz, Jakub Ondracek, Lucie Ondrackova, Martin Kostejn, Stepanka Vlckova, Zdenka Fenclova, Stepanka Dvorackova, Lucie Lischkova, Pavlina Klusackova, Viktoriia Kolesnikova, Andrea Rossnerova and Tomas Navratil
Nanomaterials 2020, 10(12), 2440; https://doi.org/10.3390/nano10122440 - 6 Dec 2020
Cited by 18 | Viewed by 2397
Abstract
Human data concerning exposure to nanoparticles are very limited, and biomarkers for monitoring exposure are urgently needed. In a follow-up of a 2016 study in a nanocomposites plant, in which only exhaled breath condensate (EBC) was examined, eight markers of oxidative stress were [...] Read more.
Human data concerning exposure to nanoparticles are very limited, and biomarkers for monitoring exposure are urgently needed. In a follow-up of a 2016 study in a nanocomposites plant, in which only exhaled breath condensate (EBC) was examined, eight markers of oxidative stress were analyzed in three bodily fluids, i.e., EBC, plasma and urine, in both pre-shift and post-shift samples in 2017 and 2018. Aerosol exposures were monitored. Mass concentration in 2017 was 0.351 mg/m3 during machining, and 0.179 and 0.217 mg/m3 during machining and welding, respectively, in 2018. In number concentrations, nanoparticles formed 96%, 90% and 59%, respectively. In both years, pre-shift elevations of 50.0% in EBC, 37.5% in plasma and 6.25% in urine biomarkers were observed. Post-shift elevation reached 62.5% in EBC, 68.8% in plasma and 18.8% in urine samples. The same trend was observed in all biological fluids. Individual factors were responsible for the elevation of control subjects’ afternoon vs. morning markers in 2018; all were significantly lower compared to those of workers. Malondialdehyde levels were always acutely shifted, and 8-hydroxy-2-deoxyguanosine levels best showed chronic exposure effect. EBC and plasma analysis appear to be the ideal fluids for bio-monitoring of oxidative stress arising from engineered nanomaterials. Potential late effects need to be targeted and prevented, as there is a similarity of EBC findings in patients with silicosis and asbestosis. Full article
(This article belongs to the Special Issue Frontiers in Nanotoxicology)
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23 pages, 5938 KiB  
Article
Photosensitive Thin Films Based on Drop Cast and Langmuir-Blodgett Hydrophilic and Hydrophobic CdS Nanoparticles
by Momoka Nagamine, Magdalena Osial, Justyna Widera-Kalinowska, Krystyna Jackowska and Paweł Krysiński
Nanomaterials 2020, 10(12), 2437; https://doi.org/10.3390/nano10122437 - 5 Dec 2020
Cited by 7 | Viewed by 2368
Abstract
Comparative photoelectrochemical studies of cadmium sulfide (CdS) nanoparticles with either hydrophilic or hydrophobic surface properties are presented. Oleylamine organic shells provided CdS nanoparticles with hydrophobic behavior, affecting the photoelectrochemical properties of such nanostructured semiconductor. Hydrophilic CdS nanoparticles were drop-cast on the electrode, whereas [...] Read more.
Comparative photoelectrochemical studies of cadmium sulfide (CdS) nanoparticles with either hydrophilic or hydrophobic surface properties are presented. Oleylamine organic shells provided CdS nanoparticles with hydrophobic behavior, affecting the photoelectrochemical properties of such nanostructured semiconductor. Hydrophilic CdS nanoparticles were drop-cast on the electrode, whereas the hydrophobic ones were transferred in a controlled manner with Langmuir-Blodgett technique. The substantial hindrance of photopotential and photocurrent was observed for L-B CdS films as compared to the hydrophilic, uncoated nanoparticles that were drop-cast directly on the electrode surface. The electron lifetime in both hydrophilic and hydrophobic nanocrystalline CdS was determined, revealing longer carrier lifetime for oleylamine coated CdS nanoparticles, ascribed to the trapping of charge at the interface of the organic shell/CdS nanoparticle and to the dominant influence of the resistance of the organic shell against the flux of charges. The “on” transients of the photocurrent responses, observed only for the oleylamine-coated nanoparticles, were resolved, yielding the potential-dependent rate constants of the redox processes occurring at the interface. Full article
(This article belongs to the Special Issue Synthesis and Functionalization of Colloidal Nanoparticles)
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12 pages, 3382 KiB  
Article
Electrical Conduction Behavior of High-Performance Microcellular Nanocomposites Made of Graphene Nanoplatelet-Filled Polysulfone
by Hooman Abbasi, Marcelo Antunes and José Ignacio Velasco
Nanomaterials 2020, 10(12), 2425; https://doi.org/10.3390/nano10122425 - 4 Dec 2020
Cited by 3 | Viewed by 1660
Abstract
Graphene nanoplatelet (GnP)-filled polysulfone (PSU) cellular nanocomposites, prepared by two different methods—namely, water vapor-induced phase separation (WVIPS) and supercritical CO2 dissolution (scCO2) foaming—were produced with a range of densities from 0.4 to 0.6 g/cm3 and characterized in terms of [...] Read more.
Graphene nanoplatelet (GnP)-filled polysulfone (PSU) cellular nanocomposites, prepared by two different methods—namely, water vapor-induced phase separation (WVIPS) and supercritical CO2 dissolution (scCO2) foaming—were produced with a range of densities from 0.4 to 0.6 g/cm3 and characterized in terms of their structure and electrical conduction behavior. The GnP content was varied from 0 to 10 wt%. The electrical conductivity values were increased with the amount of GnP for the three different studied foam series. The highest values were found for the microcellular nanocomposites prepared by the WVIPS method, reaching as high as 8.17 × 10−2 S/m for 10 wt% GnP. The variation trend of the electrical conductivity for each series was analyzed by applying both the percolation and the tunneling models. Comparatively, the tunneling model showed a better fitting in the prediction of the electrical conductivity. The preparation technique of the cellular nanocomposite affected the resultant cellular structure of the nanocomposite and, as a result, the porosity or gas volume fraction (Vg). A higher porosity resulted in a higher electrical conductivity, with the lightest foams being prepared by the WVIPS method, showing electrical conductivities two orders of magnitude higher than the equivalent foams prepared by the scCO2 dissolution technique. Full article
(This article belongs to the Special Issue Multifunctional Polymer-Based Nanocomposite Materials)
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18 pages, 3322 KiB  
Article
Electrostatic Design of Polar Metal–Organic Framework Thin Films
by Giulia Nascimbeni, Christof Wöll and Egbert Zojer
Nanomaterials 2020, 10(12), 2420; https://doi.org/10.3390/nano10122420 - 3 Dec 2020
Cited by 6 | Viewed by 2953
Abstract
In recent years, optical and electronic properties of metal–organic frameworks (MOFs) have increasingly shifted into the focus of interest of the scientific community. Here, we discuss a strategy for conveniently tuning these properties through electrostatic design. More specifically, based on quantum-mechanical simulations, we [...] Read more.
In recent years, optical and electronic properties of metal–organic frameworks (MOFs) have increasingly shifted into the focus of interest of the scientific community. Here, we discuss a strategy for conveniently tuning these properties through electrostatic design. More specifically, based on quantum-mechanical simulations, we suggest an approach for creating a gradient of the electrostatic potential within a MOF thin film, exploiting collective electrostatic effects. With a suitable orientation of polar apical linkers, the resulting non-centrosymmetric packing results in an energy staircase of the frontier electronic states reminiscent of the situation in a pin-photodiode. The observed one dimensional gradient of the electrostatic potential causes a closure of the global energy gap and also shifts core-level energies by an amount equaling the size of the original band gap. The realization of such assemblies could be based on so-called pillared layer MOFs fabricated in an oriented fashion on a solid substrate employing layer by layer growth techniques. In this context, the simulations provide guidelines regarding the design of the polar apical linker molecules that would allow the realization of MOF thin films with the (vast majority of the) molecular dipole moments pointing in the same direction. Full article
(This article belongs to the Section Inorganic Materials and Metal-Organic Frameworks)
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21 pages, 30592 KiB  
Article
Creation of Gold Nanoparticles in ZnO by Ion Implantation–DFT and Experimental Studies
by Jakub Cajzl, Karla Jeníčková, Pavla Nekvindová, Alena Michalcová, Martin Veselý, Anna Macková, Petr Malinský, Adéla Jágerová, Romana Mikšová and Shavkat Akhmadaliev
Nanomaterials 2020, 10(12), 2392; https://doi.org/10.3390/nano10122392 - 30 Nov 2020
Cited by 10 | Viewed by 2667
Abstract
Three different crystallographic orientations of the wurtzite ZnO structure (labeled as c-plane, a-plane and m-plane) were implanted with Au+ ions using various energies and fluences to form gold nanoparticles (GNPs). The ion implantation process was followed by annealing at [...] Read more.
Three different crystallographic orientations of the wurtzite ZnO structure (labeled as c-plane, a-plane and m-plane) were implanted with Au+ ions using various energies and fluences to form gold nanoparticles (GNPs). The ion implantation process was followed by annealing at 600 °C in an oxygen atmosphere to decrease the number of unwanted defects and improve luminescence properties. With regard to our previous publications, the paper provides a summary of theoretical and experimental results, i.e., both DFT and FLUX simulations, as well as experimental results from TEM, HRTEM, RBS, RBS/C, Raman spectroscopy and photoluminescence. From the results, it follows that in the ZnO structure, implanted gold atoms are located in random interstitial positions —experimentally, the amount of interstitial gold atoms increased with increasing ion implantation fluence. During ion implantation and subsequent annealing, the metal clusters and nanoparticles with sizes from 2 to 20 nm were formed. The crystal structure of the resulting gold was not cubic (confirmed by diffraction patterns), but it had a hexagonal close-packed (hcp) arrangement. The ion implantation of gold leads to the creation of Zn and O interstitial defects and extended defects with distinct character in various crystallographic cuts of ZnO, where significant O-sublattice disordering occurred in m-plane ZnO. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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17 pages, 5301 KiB  
Article
Sulfate-Containing Composite Based on Ni-Rich Layered Oxide LiNi0.8Mn0.1Co0.1O2 as High-Performance Cathode Material for Li-ion Batteries
by Aleksandra A. Savina, Elena D. Orlova, Anatolii V. Morozov, Sergey Yu. Luchkin and Artem M. Abakumov
Nanomaterials 2020, 10(12), 2381; https://doi.org/10.3390/nano10122381 - 29 Nov 2020
Cited by 13 | Viewed by 4260
Abstract
Composite positive electrode materials (1−x) LiNi0.8Mn0.1Co0.1O2xLi2SO4 (x = 0.002–0.005) for Li-ion batteries have been synthesized via conventional hydroxide or carbonate coprecipitation routes with subsequent high-temperature lithiation in [...] Read more.
Composite positive electrode materials (1−x) LiNi0.8Mn0.1Co0.1O2xLi2SO4 (x = 0.002–0.005) for Li-ion batteries have been synthesized via conventional hydroxide or carbonate coprecipitation routes with subsequent high-temperature lithiation in either air or oxygen atmosphere. A comparative study of the materials prepared from transition metal sulfates (i.e., containing sulfur) and acetates (i.e., sulfur-free) with powder X-ray diffraction, electron diffraction, high angle annular dark field transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy revealed that the sulfur-containing species occur as amorphous Li2SO4 at the grain boundaries and intergranular contacts of the primary NMC811 crystallites. This results in a noticeable enhancement of rate capability and capacity retention over prolonged charge/discharge cycling compared to their sulfur-free analogs. The improvement is attributed to suppressing the high voltage phase transition and the associated accumulation of anti-site disorder upon cycling and improving the secondary agglomerates’ mechanical integrity by increasing interfacial fracture toughness through linking primary NMC811 particles with soft Li2SO4 binder, as demonstrated with nanoindentation experiments. As the synthesis of the (1−x) LiNi0.8Mn0.1Co0.1O2xLi2SO4 composites do not require additional operational steps to introduce sulfur, these electrode materials might demonstrate high potential for commercialization. Full article
(This article belongs to the Section Energy and Catalysis)
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10 pages, 1615 KiB  
Article
Band Gap Measurements of Nano-Meter Sized Rutile Thin Films
by Nikolaos C. Diamantopoulos, Alexandros Barnasas, Christos. S. Garoufalis, Dimitrios I. Anyfantis, Nikolaos Bouropoulos, Panagiotis Poulopoulos and Sotirios Baskoutas
Nanomaterials 2020, 10(12), 2379; https://doi.org/10.3390/nano10122379 - 29 Nov 2020
Cited by 16 | Viewed by 2432
Abstract
Thin Titanium films were fabricated on quartz substrates by radio frequency magnetron sputtering under high vacuum. Subsequent annealing at temperatures of 600 C in air resulted in single-phase TiO2 with the structure of rutile, as X-ray diffraction experiment demonstrates. [...] Read more.
Thin Titanium films were fabricated on quartz substrates by radio frequency magnetron sputtering under high vacuum. Subsequent annealing at temperatures of 600 C in air resulted in single-phase TiO2 with the structure of rutile, as X-ray diffraction experiment demonstrates. Atomic-force microscopy images verify the high crystalline quality and allow us to determine the grain size even for ultrathin TiO2 films. Rutile has a direct energy band gap at about 3.0–3.2 eV; however, the transitions between the valence and conduction band are dipole forbidden. Just a few meV above that, there is an indirect band gap. The first intense absorption peak appears at about 4 eV. Tauc plots for the position of the indirect band gap show a “blue shift” with decreasing film thickness. Moreover, we find a similar shift for the position of the first absorbance peak studied by the derivative method. The results indicate the presence of quantum confinement effects. This conclusion is supported by theoretical calculations based on a combination of the effective mass theory and the Hartree Fock approximation. Full article
(This article belongs to the Section Nanocomposite Materials)
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11 pages, 3014 KiB  
Article
Silicon-Carbide (SiC) Nanocrystal Technology and Characterization and Its Applications in Memory Structures
by Andrzej Mazurak, Robert Mroczyński, David Beke and Adam Gali
Nanomaterials 2020, 10(12), 2387; https://doi.org/10.3390/nano10122387 - 29 Nov 2020
Cited by 8 | Viewed by 2928
Abstract
Colloidal cubic silicon-carbide nanocrystals have been fabricated, characterized, and introduced into metal–insulator–semiconductor and metal–insulator–metal structures based on hafnium oxide layers. The fabricated structures were characterized through the stress-and-sense measurements in terms of device capacitance, flat-band voltage shift, switching characteristics, and retention time. The [...] Read more.
Colloidal cubic silicon-carbide nanocrystals have been fabricated, characterized, and introduced into metal–insulator–semiconductor and metal–insulator–metal structures based on hafnium oxide layers. The fabricated structures were characterized through the stress-and-sense measurements in terms of device capacitance, flat-band voltage shift, switching characteristics, and retention time. The examined electrical performance of the sample structures has demonstrated the feasibility of the application of both types of structures based on SiC nanoparticles in memory devices. Full article
(This article belongs to the Special Issue Nanomaterials Based on IV-Group Semiconductors)
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25 pages, 3697 KiB  
Article
Parametric Optimization of an Air–Liquid Interface System for Flow-Through Inhalation Exposure to Nanoparticles: Assessing Dosimetry and Intracellular Uptake of CeO2 Nanoparticles
by Lars B. Leibrock, Harald Jungnickel, Jutta Tentschert, Aaron Katz, Blaza Toman, Elijah J. Petersen, Frank S. Bierkandt, Ajay Vikram Singh, Peter Laux and Andreas Luch
Nanomaterials 2020, 10(12), 2369; https://doi.org/10.3390/nano10122369 - 28 Nov 2020
Cited by 26 | Viewed by 4113
Abstract
Air–liquid interface (ALI) systems have been widely used in recent years to investigate the inhalation toxicity of many gaseous compounds, chemicals, and nanomaterials and represent an emerging and promising in vitro method to supplement in vivo studies. ALI exposure reflects the physiological conditions [...] Read more.
Air–liquid interface (ALI) systems have been widely used in recent years to investigate the inhalation toxicity of many gaseous compounds, chemicals, and nanomaterials and represent an emerging and promising in vitro method to supplement in vivo studies. ALI exposure reflects the physiological conditions of the deep lung more closely to subacute in vivo inhalation scenarios compared to submerged exposure. The comparability of the toxicological results obtained from in vivo and in vitro inhalation data is still challenging. The robustness of ALI exposure scenarios is not yet well understood, but critical for the potential standardization of these methods. We report a cause-and-effect (C&E) analysis of a flow through ALI exposure system. The influence of five different instrumental and physiological parameters affecting cell viability and exposure parameters of a human lung cell line in vitro (exposure duration, relative humidity, temperature, CO2 concentration and flow rate) was investigated. After exposing lung epithelia cells to a CeO2 nanoparticle (NP) aerosol, intracellular CeO2 concentrations reached values similar to those found in a recent subacute rat inhalation study in vivo. This is the first study showing that the NP concentration reached in vitro using a flow through ALI system were the same as those in an in vivo study. Full article
(This article belongs to the Special Issue Design, Development, and Production of Nanocarriers and Nanovehicles)
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22 pages, 4336 KiB  
Article
Strategies for Controlling Through-Space Charge Transport in Metal-Organic Frameworks via Structural Modifications
by Christian Winkler and Egbert Zojer
Nanomaterials 2020, 10(12), 2372; https://doi.org/10.3390/nano10122372 - 28 Nov 2020
Cited by 5 | Viewed by 3372
Abstract
In recent years, charge transport in metal-organic frameworks (MOFs) has shifted into the focus of scientific research. In this context, systems with efficient through-space charge transport pathways resulting from π-stacked conjugated linkers are of particular interest. In the current manuscript, we use [...] Read more.
In recent years, charge transport in metal-organic frameworks (MOFs) has shifted into the focus of scientific research. In this context, systems with efficient through-space charge transport pathways resulting from π-stacked conjugated linkers are of particular interest. In the current manuscript, we use density functional theory-based simulations to provide a detailed understanding of such MOFs, which, in the present case, are derived from the prototypical Zn2(TTFTB) system (with TTFTB4− corresponding to tetrathiafulvalene tetrabenzoate). In particular, we show that factors such as the relative arrangement of neighboring linkers and the details of the structural conformations of the individual building blocks have a profound impact on bandwidths and charge transfer. Considering the helical stacking of individual tetrathiafulvalene (TTF) molecules around a screw axis as the dominant symmetry element in Zn2(TTFTB)-derived materials, the focus, here, is primarily on the impact of the relative rotation of neighboring molecules. Not unexpectedly, changing the stacking distance in the helix also plays a distinct role, especially for structures which display large electronic couplings to start with. The presented results provide guidelines for achieving structures with improved electronic couplings. It is, however, also shown that structural defects (especially missing linkers) provide major obstacles to charge transport in the studied, essentially one-dimensional systems. This suggests that especially the sample quality is a decisive factor for ensuring efficient through-space charge transport in MOFs comprising stacked π-systems. Full article
(This article belongs to the Section Inorganic Materials and Metal-Organic Frameworks)
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24 pages, 2329 KiB  
Article
Development of Active Barrier Multilayer Films Based on Electrospun Antimicrobial Hot-Tack Food Waste Derived Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Cellulose Nanocrystal Interlayers
by Kelly J. Figueroa-Lopez, Sergio Torres-Giner, Inmaculada Angulo, Maria Pardo-Figuerez, Jose Manuel Escuin, Ana Isabel Bourbon, Luis Cabedo, Yuval Nevo, Miguel A. Cerqueira and Jose M. Lagaron
Nanomaterials 2020, 10(12), 2356; https://doi.org/10.3390/nano10122356 - 27 Nov 2020
Cited by 28 | Viewed by 9668
Abstract
Active multilayer films based on polyhydroxyalkanoates (PHAs) with and without high barrier coatings of cellulose nanocrystals (CNCs) were herein successfully developed. To this end, an electrospun antimicrobial hot-tack layer made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from cheese whey, a by-product from the [...] Read more.
Active multilayer films based on polyhydroxyalkanoates (PHAs) with and without high barrier coatings of cellulose nanocrystals (CNCs) were herein successfully developed. To this end, an electrospun antimicrobial hot-tack layer made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from cheese whey, a by-product from the dairy industry, was deposited on a previously manufactured blown film of commercial food contact PHA-based resin. A hybrid combination of oregano essential oil (OEO) and zinc oxide nanoparticles (ZnONPs) were incorporated during the electrospinning process into the PHBV nanofibers at 2.5 and 2.25 wt%, respectively, in order to provide antimicrobial properties. A barrier CNC coating was also applied by casting from an aqueous solution of nanocellulose at 2 wt% using a rod at 1m/min. The whole multilayer structure was thereafter assembled in a pilot roll-to-roll laminating system, where the blown PHA-based film was located as the outer layers while the electrospun antimicrobial hot-tack PHBV layer and the barrier CNC coating were placed as interlayers. The resultant multilayer films, having a final thickness in the 130–150 µm range, were characterized to ascertain their potential in biodegradable food packaging. The multilayers showed contact transparency, interlayer adhesion, improved barrier to water and limonene vapors, and intermediate mechanical performance. Moreover, the films presented high antimicrobial and antioxidant activities in both open and closed systems for up to 15 days. Finally, the food safety of the multilayers was assessed by migration and cytotoxicity tests, demonstrating that the films are safe to use in both alcoholic and acid food simulants and they are also not cytotoxic for Caco-2 cells. Full article
(This article belongs to the Special Issue Advances in Food Nanotechnology)
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11 pages, 514 KiB  
Article
A Legendre–Fenchel Transform for Molecular Stretching Energies
by Eivind Bering, Dick Bedeaux, Signe Kjelstrup, Astrid S. de Wijn, Ivan Latella and J. Miguel Rubi
Nanomaterials 2020, 10(12), 2355; https://doi.org/10.3390/nano10122355 - 27 Nov 2020
Cited by 6 | Viewed by 1853
Abstract
Single-molecular polymers can be used to analyze to what extent thermodynamics applies when the size of the system is drastically reduced. We have recently verified using molecular-dynamics simulations that isometric and isotensional stretching of a small polymer result in Helmholtz and Gibbs stretching [...] Read more.
Single-molecular polymers can be used to analyze to what extent thermodynamics applies when the size of the system is drastically reduced. We have recently verified using molecular-dynamics simulations that isometric and isotensional stretching of a small polymer result in Helmholtz and Gibbs stretching energies, which are not related to a Legendre transform, as they are for sufficiently long polymers. This disparity has also been observed experimentally. Using molecular dynamics simulations of polyethylene-oxide, we document for the first time that the Helmholtz and Gibbs stretching energies can be related by a Legendre–Fenchel transform. This opens up a possibility to apply this transform to other systems which are small in Hill’s sense. Full article
(This article belongs to the Special Issue Nanoscale Thermodynamics)
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14 pages, 3596 KiB  
Article
Enhancing and Tuning the Nonlinear Optical Response and Wavelength-Agile Strong Optical Limiting Action of N-octylamine Modified Fluorographenes
by Aristeidis Stathis, Michalis Stavrou, Ioannis Papadakis, Ievgen Obratzov and Stelios Couris
Nanomaterials 2020, 10(11), 2319; https://doi.org/10.3390/nano10112319 - 23 Nov 2020
Cited by 8 | Viewed by 2560
Abstract
Fluorographene has been recently shown to be a suitable platform for synthesizing numerous graphene derivatives with desired properties. In that respect, N-octylamine-modified fluorographenes with variable degrees of functionalization are studied and their nonlinear optical properties are assessed using 4 ns pulses. A [...] Read more.
Fluorographene has been recently shown to be a suitable platform for synthesizing numerous graphene derivatives with desired properties. In that respect, N-octylamine-modified fluorographenes with variable degrees of functionalization are studied and their nonlinear optical properties are assessed using 4 ns pulses. A very strong enhancement of the nonlinear optical response and a very efficient optical limiting action are observed, being strongly dependent on the degree of functionalization of fluorographene. The observed enhanced response is attributed to the increasing number of defects because of the incorporation of N-heteroatoms in the graphitic network upon functionalization with N-octylamine. The present work paves the way for the controlled covalent functionalization of graphene enabling a scalable access to a wide portfolio of graphene derivatives with custom-tailored properties. Full article
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13 pages, 4210 KiB  
Article
CO2 Adsorption in Metal-Organic Framework Mg-MOF-74: Effects of Inter-Crystalline Space
by Siddharth Gautam and David Cole
Nanomaterials 2020, 10(11), 2274; https://doi.org/10.3390/nano10112274 - 17 Nov 2020
Cited by 18 | Viewed by 7870
Abstract
Metal-Organic Frameworks (MOF) have been identified as highly efficient nanoporous adsorbents for CO2 storage. In particular, Mg-MOF-74 has been shown to promise exceptionally high CO2 sorption. Although several studies have reported adsorption isotherms of CO2 in Mg-MOF-74, the effect of [...] Read more.
Metal-Organic Frameworks (MOF) have been identified as highly efficient nanoporous adsorbents for CO2 storage. In particular, Mg-MOF-74 has been shown to promise exceptionally high CO2 sorption. Although several studies have reported adsorption isotherms of CO2 in Mg-MOF-74, the effect of inter-crystalline spacing in Mg-MOF-74 on the sorption of CO2 has not been addressed. These effects have been shown to be profound for a quadrupolar molecule like CO2 in the case of silicalite (Phys. Chem. Chem. Phys. 22 (2020) 13951). Here, we report the effects of inter-crystalline spacing on the adsorption of CO2 in Mg-MOF-74, studied using grand canonical Monte Carlo (GCMC) simulations. The inter-crystalline spacing is found to enhance adsorption at the crystallite surfaces. Larger inter-crystalline spacing up to twice the kinetic diameter of CO2 results in higher adsorption and larger crystallite sizes suppress adsorption. Magnitudes of the inter-crystalline space relative to the kinetic diameter of the adsorbed fluid and the surface to volume ratio of the adsorbent crystallites are found to be important factors determining the adsorption amounts. The results of this study suggest that the ideal Mg-MOF-74 sample for CO2 storage applications should have smaller crystallites separated from each other with an inter-crystalline space of approximately twice the kinetic diameter of CO2. Full article
(This article belongs to the Section Inorganic Materials and Metal-Organic Frameworks)
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13 pages, 4519 KiB  
Article
Synthesis, Structure and Electrical Resistivity of Carbon Nanotubes Synthesized over Group VIII Metallocenes
by Aida R. Karaeva, Sergey A. Urvanov, Nikita V. Kazennov, Eduard B. Mitberg and Vladimir Z. Mordkovich
Nanomaterials 2020, 10(11), 2279; https://doi.org/10.3390/nano10112279 - 17 Nov 2020
Cited by 15 | Viewed by 2790
Abstract
The paper reports the synthesis of carbon nanotubes from ethanol over group VIII (Fe, Co, Ni) catalysts derived from corresponding metallocenes. Several unexpected cooperative effects are reported, which are never observed in the case of individual metallocenes such as the commonly used ferrocene [...] Read more.
The paper reports the synthesis of carbon nanotubes from ethanol over group VIII (Fe, Co, Ni) catalysts derived from corresponding metallocenes. Several unexpected cooperative effects are reported, which are never observed in the case of individual metallocenes such as the commonly used ferrocene catalyst Fe(C5H5)2. The formation of very long (up to several µm) straight monocrystal metal kernels inside the carbon nanotubes was the most interesting effect. The use of trimetal catalysts (Fe1-x-yCoxNiy)(C5H5)2 resulted in the sharp increase in the yield of carbon nanotubes. The electrical conductivity of the produced nanotubes is determined by the nature of the catalyst. The variation of individual metals in the Ni-Co-Fe leads to a drop of the electrical resistivity of nanotube samples by the order of magnitude, i.e., from 1.0 × 10−3 to 1.1 × 10−5 Ω∙m. A controlled change in the electrophysical properties of the nanotubes can make it possible to expand their use as fillers in composites, photothermal and tunable magnetic nanomaterials with pre-designed electrical conductivity and other electromagnetic properties. Full article
(This article belongs to the Special Issue Mechanical and Electrical Properties of Novel Nanocomposites)
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12 pages, 3421 KiB  
Article
Effects of Mg and Sb Substitution on the Magnetic Properties of Magnetic Field Annealed MnBi Alloys
by Hui-Dong Qian, Yang Yang, Jung Tae Lim, Jong-Woo Kim, Chul-Jin Choi and Jihoon Park
Nanomaterials 2020, 10(11), 2265; https://doi.org/10.3390/nano10112265 - 16 Nov 2020
Cited by 6 | Viewed by 2477
Abstract
Rare-earth-free permanent magnets have attracted considerable attention due to their favorable properties and applicability for cost-effective, high-efficiency, and sustainable energy devices. However, the magnetic field annealing process, which enhances the performance of permanent magnets, needs to be optimized for different magnetic fields and [...] Read more.
Rare-earth-free permanent magnets have attracted considerable attention due to their favorable properties and applicability for cost-effective, high-efficiency, and sustainable energy devices. However, the magnetic field annealing process, which enhances the performance of permanent magnets, needs to be optimized for different magnetic fields and phases. Therefore, we investigated the effect of composition on the crystallization of amorphous MnBi to the ferromagnetic low-temperature phase (LTP). The optimal compositions and conditions were applied to magnetic field annealing under 2.5 T for elemental Mg- and Sb/Mg pair-substituted MnBi. The optimum MnBi composition for the highest purity LTP was determined to be Mn56Bi44, and its maximum energy product, (BH)max, was 5.62 MGOe. The Mg-substituted MnBi exhibited enhanced squareness (Mr/Ms), coercivity (Hc), and (BH)max values up to 0.8, 9659 Oe, and 5.64 MGOe, respectively, whereas the same values for the Sb/Mg pair-substituted MnBi were 0.76, 7038 Oe, and 5.60 MGOe, respectively. The substitution effects were also investigated using first-principles calculations. The density of states and total magnetic moments of Mn16Bi15Mg and Mn16Bi15Sb were similar to those of pure Mn16Bi16. Conversely, the Sb-substituted MnBi resulted in a dramatic enhancement in the anisotropy constant (K) from a small negative value (−0.85 MJ/m3) to a large positive value (6.042 MJ/m3). Full article
(This article belongs to the Special Issue Synthesis and Properties of Nanocrystalline Magnetic Materials)
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8 pages, 3931 KiB  
Article
Effect of ZnO and SnO2 Nanolayers at Grain Boundaries on Thermoelectric Properties of Polycrystalline Skutterudites
by Sang-il Kim, Jiwoo An, Woo-Jae Lee, Se Hun Kwon, Woo Hyun Nam, Nguyen Van Du, Jong-Min Oh, Sang-Mo Koo, Jung Young Cho and Weon Ho Shin
Nanomaterials 2020, 10(11), 2270; https://doi.org/10.3390/nano10112270 - 16 Nov 2020
Cited by 6 | Viewed by 2273
Abstract
Nanostructuring is considered one of the key approaches to achieve highly efficient thermoelectric alloys by reducing thermal conductivity. In this study, we investigated the effect of oxide (ZnO and SnO2) nanolayers at the grain boundaries of polycrystalline In0.2Yb0.1 [...] Read more.
Nanostructuring is considered one of the key approaches to achieve highly efficient thermoelectric alloys by reducing thermal conductivity. In this study, we investigated the effect of oxide (ZnO and SnO2) nanolayers at the grain boundaries of polycrystalline In0.2Yb0.1Co4Sb12 skutterudites on their electrical and thermal transport properties. Skutterudite powders with oxide nanolayers were prepared by atomic layer deposition method, and the number of deposition cycles was varied to control the coating thickness. The coated powders were consolidated by spark plasma sintering. With increasing number of deposition cycle, the electrical conductivity gradually decreased, while the Seebeck coefficient changed insignificantly; this indicates that the carrier mobility decreased due to the oxide nanolayers. In contrast, the lattice thermal conductivity increased with an increase in the number of deposition cycles, demonstrating the reduction in phonon scattering by grain boundaries owing to the oxide nanolayers. Thus, we could easily control the thermoelectric properties of skutterudite materials through adjusting the oxide nanolayer by atomic layer deposition method. Full article
(This article belongs to the Special Issue Nanotechnology for Green Chemical Engineering)
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16 pages, 4741 KiB  
Article
Langmuir Films of Perfluorinated Fatty Alcohols: Evidence of Spontaneous Formation of Solid Aggregates at Zero Surface Pressure and Very Low Surface Density
by Pedro Silva, Duarte Nova, Miguel Teixeira, Vitória Cardoso, Pedro Morgado, Bruno Nunes, Rogério Colaço, Marie-Claude Fauré, Philippe Fontaine, Michel Goldmann and Eduardo J. M. Filipe
Nanomaterials 2020, 10(11), 2257; https://doi.org/10.3390/nano10112257 - 14 Nov 2020
Cited by 6 | Viewed by 2773
Abstract
In this work, Langmuir films of two highly fluorinated fatty alcohols, CF3(CF2)12CH2OH (F14OH) and CF3(CF2)16CH2OH (F18OH), were studied. Atomic Force Microscopy (AFM) images of the films transferred [...] Read more.
In this work, Langmuir films of two highly fluorinated fatty alcohols, CF3(CF2)12CH2OH (F14OH) and CF3(CF2)16CH2OH (F18OH), were studied. Atomic Force Microscopy (AFM) images of the films transferred at zero surface pressure and low surface density onto the surface of silicon wafers by the Langmuir-Blodgett technique revealed, for the first time, the existence of solid-like domains with well-defined mostly hexagonal (starry) shapes in the case of F18OH, and with an entangled structure of threads in the case of F14OH. A (20:80) molar mixture of the two alcohols displayed a surprising combination of the two patterns: hexagonal domains surrounded by zigzagging threads, clearly demonstrating that the two alcohols segregate during the 2D crystallization process. Grazing Incidence X-ray Diffraction (GIXD) measurements confirmed that the molecules of both alcohols organize in 2D hexagonal lattices. Atomistic Molecular Dynamics (MD) simulations provide a visualization of the structure of the domains and allow a molecular-level interpretation of the experimental observations. The simulation results clearly showed that perfluorinated alcohols have an intrinsic tendency to aggregate, even at very low surface density. The formed domains are highly organized compared to those of hydrogenated alcohols with similar chain length. Very probably, this tendency is a consequence of the characteristic stiffness of the perfluorinated chains. The diffraction spectrum calculated from the simulation trajectories compares favorably with the experimental spectra, fully validating the simulations and the proposed interpretation. The present results highlight for the first time an inherent tendency of perfluorinated chains to aggregate, even at very low surface density, forming highly organized 2D structures. We believe these findings are important to fully understand related phenomena, such as the formation of hemi-micelles of semifluorinated alkanes at the surface of water and the 2D segregation in mixed Langmuir films of hydrogenated and fluorinated fatty acids. Full article
(This article belongs to the Special Issue Nanoscale 2D Structure and Self-Assembled Properties)
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21 pages, 6102 KiB  
Article
Improved Hardness and Thermal Stability of Nanocrystalline Nickel Electrodeposited with the Addition of Cysteine
by Tamás Kolonits, Zsolt Czigány, László Péter, Imre Bakonyi and Jenő Gubicza
Nanomaterials 2020, 10(11), 2254; https://doi.org/10.3390/nano10112254 - 13 Nov 2020
Cited by 4 | Viewed by 2075
Abstract
Experiments were conducted for the study of the effect of cysteine addition on the microstructure of nanocrystalline Ni films electrodeposited from a nickel sulfate-based bath. Furthermore, the thermal stability of the nanostructure of Ni layers processed with cysteine addition was also investigated. It [...] Read more.
Experiments were conducted for the study of the effect of cysteine addition on the microstructure of nanocrystalline Ni films electrodeposited from a nickel sulfate-based bath. Furthermore, the thermal stability of the nanostructure of Ni layers processed with cysteine addition was also investigated. It was found that with increasing cysteine content in the bath, the grain size decreased, while the dislocation density and the twin fault probability increased. Simultaneously, the hardness increased due to cysteine addition through various effects. Saturation in the microstructure and hardness was achieved at cysteine contents of 0.3–0.4 g/L. Moreover, the texture changed from (220) to (200) with increasing the concentration of cysteine. The hardness of the Ni films processed with the addition of 0.4 g/L cysteine (∼6800 MPa) was higher than the values obtained for other additives in the literature (<6000 MPa). This hardness was further enhanced to ∼8400 MPa when the Ni film was heated up to 500 K. It was revealed that the hardness remained as high as 6000 MPa even after heating up to 750 K, while for other additives, the hardness decreased below 3000 MPa at the same temperature. Full article
(This article belongs to the Special Issue Advances in Micro- and Nanomechanics)
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11 pages, 4575 KiB  
Article
Synthesis of Core–Double Shell Nylon-ZnO/Polypyrrole Electrospun Nanofibers
by Mihaela Beregoi, Nicoleta Preda, Andreea Costas, Monica Enculescu, Raluca Florentina Negrea, Horia Iovu and Ionut Enculescu
Nanomaterials 2020, 10(11), 2241; https://doi.org/10.3390/nano10112241 - 12 Nov 2020
Cited by 8 | Viewed by 2458
Abstract
Core–double shell nylon-ZnO/polypyrrole electrospun nanofibers were fabricated by combining three straightforward methods (electrospinning, sol–gel synthesis and electrodeposition). The hybrid fibrous organic–inorganic nanocomposite was obtained starting from freestanding nylon 6/6 nanofibers obtained through electrospinning. Nylon meshes were functionalized with a very thin, continuous ZnO [...] Read more.
Core–double shell nylon-ZnO/polypyrrole electrospun nanofibers were fabricated by combining three straightforward methods (electrospinning, sol–gel synthesis and electrodeposition). The hybrid fibrous organic–inorganic nanocomposite was obtained starting from freestanding nylon 6/6 nanofibers obtained through electrospinning. Nylon meshes were functionalized with a very thin, continuous ZnO film by a sol–gel process and thermally treated in order to increase its crystallinity. Further, the ZnO coated networks were used as a working electrode for the electrochemical deposition of a very thin, homogenous polypyrrole layer. X-ray diffraction measurements were employed for characterizing the ZnO structures while spectroscopic techniques such as FTIR and Raman were employed for describing the polypyrrole layer. An elemental analysis was performed through X-ray microanalysis, confirming the expected double shell structure. A detailed micromorphological characterization through FESEM and TEM assays evidenced the deposition of both organic and inorganic layers. Highly transparent, flexible due to the presence of the polymer core and embedding a semiconducting heterojunction, such materials can be easily tailored and integrated in functional platforms with a wide range of applications. Full article
(This article belongs to the Special Issue Thin Films Based on Nanocomposites)
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26 pages, 7052 KiB  
Article
Thermodynamic Behaviors of Adsorbed Methane Storage Systems Based on Nanoporous Carbon Adsorbents Prepared from Coconut Shells
by Ilya E. Men’shchikov, Andrey V. Shkolin, Evgeny M. Strizhenov, Elena V. Khozina, Sergey S. Chugaev, Andrey A. Shiryaev, Anatoly A. Fomkin and Anatoly A. Zherdev
Nanomaterials 2020, 10(11), 2243; https://doi.org/10.3390/nano10112243 - 12 Nov 2020
Cited by 22 | Viewed by 2759
Abstract
The present work focused on the experimental study of the performance of a scaled system of adsorbed natural gas (ANG) storage and transportation based on carbon adsorbents. For this purpose, three different samples of activated carbons (AC) were prepared by varying the size [...] Read more.
The present work focused on the experimental study of the performance of a scaled system of adsorbed natural gas (ANG) storage and transportation based on carbon adsorbents. For this purpose, three different samples of activated carbons (AC) were prepared by varying the size of coconut shell char granules and steam activation conditions. The parameters of their porous structure, morphology, and chemical composition were determined from the nitrogen adsorption at 77 K, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and scanning electron microscopy (SEM) measurements. The methane adsorption data measured within the temperature range from 178 to 360 K and at pressures up to 25 MPa enabled us to identify the most efficient adsorbent among the studied materials: AC-90S. The differential heats of methane adsorption on AC-90S were determined in order to simulate the gas charge/discharge processes in the ANG system using a mathematical model with consideration for thermal effects. The results of simulating the charge/discharge processes under two different conditions of heat exchange are consistent with the experimentally determined temperature distribution over a scaled ANG storage tank filled with the compacted AC-90S adsorbent and equipped with temperature sensors and heat-exchanger devices. The amounts of methane delivered from the ANG storage system employing AC-90S as an adsorbent differ from the model predictions by 4–6%. Both the experiments and mathematical modeling showed that the thermal regulation of the ANG storage tank ensured the higher rates of charge/discharge processes compared to the thermal insulation. Full article
(This article belongs to the Special Issue Nanostructured Carbons for Environmental and Energy Technologies)
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16 pages, 8106 KiB  
Article
Reduced Graphene Oxide Sheets as Inhibitors of the Photochemical Reactions of α-Lipoic Acid in the Presence of Ag and Au Nanoparticles
by N’ghaya Toulbe, Malvina S. Stroe, Monica Daescu, Radu Cercel, Alin Mogos, Daniela Dragoman, Marcela Socol, Ionel Mercioniu and Mihaela Baibarac
Nanomaterials 2020, 10(11), 2238; https://doi.org/10.3390/nano10112238 - 11 Nov 2020
Cited by 5 | Viewed by 2766
Abstract
The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of α-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in [...] Read more.
The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of α-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines’ position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets. Full article
(This article belongs to the Special Issue Properties and Applications of Graphene and Its Derivatives)
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15 pages, 3089 KiB  
Article
Femtosecond Double-Pulse Laser Ablation and Deposition of Co-Doped ZnS Thin Films
by Ignacio Lopez-Quintas, Esther Rebollar, David Ávila-Brande, Jesús G. Izquierdo, Luis Bañares, Carlos Díaz-Guerra, Ana Urbieta, Marta Castillejo, Rebeca de Nalda and Margarita Martín
Nanomaterials 2020, 10(11), 2229; https://doi.org/10.3390/nano10112229 - 10 Nov 2020
Cited by 11 | Viewed by 2557
Abstract
Nanostructured thin films of Co-doped zinc sulfide were synthesized through femtosecond pulsed laser deposition. The scheme involved ablation of physically mixed Co and ZnS with pairs of ultrashort pulses separated in time in the 0–300 ps range. In situ monitorization of the deposition [...] Read more.
Nanostructured thin films of Co-doped zinc sulfide were synthesized through femtosecond pulsed laser deposition. The scheme involved ablation of physically mixed Co and ZnS with pairs of ultrashort pulses separated in time in the 0–300 ps range. In situ monitorization of the deposition process was carried out through a simultaneous reflectivity measurement. The crystallinity of generated nanoparticles and the inclusion of Co in the ZnS lattice is demonstrated by transmission electron microscopy and energy dispersive X-ray microanalysis (TEM-EDX) characterization. Surface morphology, Raman response, and photoluminescence of the films have also been assessed. The role of interpulse temporal separation is most visible in the thickness of the films obtained at the same total fluence, with much thicker films deposited with short delays than with individual uncoupled pulses. The proportion of Co in the synthesized doped ZnS nanoparticles is found to be substantially lower than the original proportion, and practically independent on interpulse delay. Full article
(This article belongs to the Special Issue Laser Synthesis and Modification of Materials at the Nanoscale)
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10 pages, 3798 KiB  
Article
Highly Conductive PEDOT:PSS Thin Films with Two-Dimensional Lamellar Stacked Multi-Layers
by Youngno Kim, Yunryeol Kim and Jung Hyun Kim
Nanomaterials 2020, 10(11), 2211; https://doi.org/10.3390/nano10112211 - 6 Nov 2020
Cited by 28 | Viewed by 5429
Abstract
Conjugated polymers are desired as organic electrode materials because of their functional properties such as solution process, low cost, and transparency. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), in particular, shows the highest applicability, but its heterogeneous structure presents limitations in terms of electrical conductivity. In this study, [...] Read more.
Conjugated polymers are desired as organic electrode materials because of their functional properties such as solution process, low cost, and transparency. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), in particular, shows the highest applicability, but its heterogeneous structure presents limitations in terms of electrical conductivity. In this study, a facile method to fabricate multi-layered thin films with higher ordered structures was developed. Through the etching process with H2SO4 and dimethyl sulfoxide(DMSO), the insulated rich-PSS was removed from the upper layer to improve its electrical properties and rearrange the PEDOT molecular structures. The thickness of PEDOT:PSS thin films was experimentally optimized to maximize the enhancement of carrier mobility via a layer-by-layer (LBL) process. The combined method, consisted of etching and the LBL process, showed the improvement of the charge carrier mobility from 0.62 to 2.80 cm2 V−1 s−1. The morphology and crystallinity of the ordered PEDOT:PSS structure were investigated by X-ray photoemission spectroscopy (XPS), Raman, and X-ray diffraction (XRD). As a result, two-dimensional lamellar-stacked PEDOT:PSS thin films were fabricated through the repetitive etching and LBL process. The optimized PEDOT:PSS thin film showed an excellent electrical conductivity of 3026 S cm−1, which is 3.8 times higher than that of the pristine film (801 S cm−1). Full article
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16 pages, 28691 KiB  
Article
On the Formation of Black Silicon Features by Plasma-Less Etching of Silicon in Molecular Fluorine Gas
by Bishal Kafle, Ahmed Ismail Ridoy, Eleni Miethig, Laurent Clochard, Edward Duffy, Marc Hofmann and Jochen Rentsch
Nanomaterials 2020, 10(11), 2214; https://doi.org/10.3390/nano10112214 - 6 Nov 2020
Cited by 10 | Viewed by 2712
Abstract
In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F2/N2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a [...] Read more.
In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F2/N2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a high volume manufacturing etching platform such as silicon photovoltaics. Specifically, the current study focuses on developing an effective front-side texturing process on Si(100) wafers. Statistical variation of the tool parameters is performed to achieve high etching rates and low surface reflection of the textured silicon surface. It is observed that the rate and anisotropy of the etching process are strongly defined by the interaction effects between process parameters such as substrate temperature, F2 concentration, and process duration. The etching forms features of sub-micron dimensions on c-Si surface. By maintaining the anisotropic nature of etching, weighted surface reflection (Rw) as low as Rw < 2% in Si(100) is achievable. The lowering of Rw is mainly due to the formation of deep, density grade nanostructures, so-called black silicon, with lateral dimensions that are smaller to the major wavelength ranges of interest in silicon photovoltaics. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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18 pages, 10404 KiB  
Article
Molecular Dynamics Studies of Poly(Lactic Acid) Nanoparticles and Their Interactions with Vitamin E and TLR Agonists Pam1CSK4 and Pam3CSK4
by Simon Megy, Stephanie Aguero, David Da Costa, Myriam Lamrayah, Morgane Berthet, Charlotte Primard, Bernard Verrier and Raphael Terreux
Nanomaterials 2020, 10(11), 2209; https://doi.org/10.3390/nano10112209 - 5 Nov 2020
Cited by 9 | Viewed by 3457
Abstract
Poly(lactic acid) (PLA) nanoparticles (NPs) are widely investigated due to their bioresorbable, biocompatible and low immunogen properties. Interestingly, many recent studies show that they can be efficiently used as drug delivery systems or as adjuvants to enhance vaccine efficacy. Our work focuses on [...] Read more.
Poly(lactic acid) (PLA) nanoparticles (NPs) are widely investigated due to their bioresorbable, biocompatible and low immunogen properties. Interestingly, many recent studies show that they can be efficiently used as drug delivery systems or as adjuvants to enhance vaccine efficacy. Our work focuses on the molecular mechanisms involved during the nanoprecipitation of PLA NPs from concentrated solutions of lactic acid polymeric chains, and their specific interactions with biologically relevant molecules. In this study, we evaluated the ability of a PLA-based nanoparticle drug carrier to vectorize either vitamin E or the Toll-like receptor (TLR) agonists Pam1CSK4 and Pam3CSK4, which are potent activators of the proinflammatory transcription factor NF-κB. We used dissipative particle dynamics (DPD) to simulate large systems mimicking the nanoprecipitation process for a complete NP. Our results evidenced that after the NP formation, Pam1CSK4 and Pam3CSK4 molecules end up located on the surface of the particle, interacting with the PLA chains via their fatty acid chains, whereas vitamin E molecules are buried deeper in the core of the particle. Our results allow for a better understanding of the molecular mechanisms responsible for the formation of the PLA NPs and their interactions with biological molecules located either on their surfaces or encapsulated within them. This work should allow for a rapid development of better biodegradable and safe vectorization systems with new drugs in the near future. Full article
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20 pages, 3990 KiB  
Article
Structural Study of (Hydroxypropyl)Methyl Cellulose Microemulsion-Based Gels Used for Biocompatible Encapsulations
by Evdokia Vassiliadi, Evgenia Mitsou, Spyridon Avramiotis, Christos L. Chochos, Franz Pirolt, Martin Medebach, Otto Glatter, Aristotelis Xenakis and Maria Zoumpanioti
Nanomaterials 2020, 10(11), 2204; https://doi.org/10.3390/nano10112204 - 5 Nov 2020
Cited by 4 | Viewed by 2265
Abstract
(Hydroxypropyl)methyl cellulose (HPMC) can be used to form gels integrating a w/o microemulsion. The formulation in which a microemulsion is mixed with a hydrated HPMC matrix has been successfully used as a carrier of biocompatible ingredients. However, little is known about the structure [...] Read more.
(Hydroxypropyl)methyl cellulose (HPMC) can be used to form gels integrating a w/o microemulsion. The formulation in which a microemulsion is mixed with a hydrated HPMC matrix has been successfully used as a carrier of biocompatible ingredients. However, little is known about the structure of these systems. To elucidate this, scanning electron microscopy was used to examine the morphology and the bulk of the microemulsion-based gels (MBGs) and small-angle X-ray scattering to clarify the structure and detect any residual reverse micelles after microemulsion incorporation in the gel. Electron paramagnetic resonance spectroscopy was applied using spin probes to investigate the polar and non-polar areas of the gel. Furthermore, the enzyme-labelling technique was followed to investigate the location of an enzyme in the matrix. A structural model for HPMC matrix is proposed according to which, although a w/o microemulsion is essential to form the final gel, no microemulsion droplets can be detected after incorporation in the gel. Channels are formed by the organic solvent (oil), which are coated by surfactant molecules and a water layer in which the enzyme can be hosted. Full article
(This article belongs to the Section Biology and Medicines)
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16 pages, 5798 KiB  
Article
Effect of DNA Origami Nanostructures on hIAPP Aggregation
by Marcel Hanke, Alejandro Gonzalez Orive, Guido Grundmeier and Adrian Keller
Nanomaterials 2020, 10(11), 2200; https://doi.org/10.3390/nano10112200 - 4 Nov 2020
Cited by 8 | Viewed by 3773
Abstract
The aggregation of human islet amyloid polypeptide (hIAPP) plays a major role in the pathogenesis of type 2 diabetes mellitus (T2DM), and numerous strategies for controlling hIAPP aggregation have been investigated so far. In particular, several organic and inorganic nanoparticles (NPs) have shown [...] Read more.
The aggregation of human islet amyloid polypeptide (hIAPP) plays a major role in the pathogenesis of type 2 diabetes mellitus (T2DM), and numerous strategies for controlling hIAPP aggregation have been investigated so far. In particular, several organic and inorganic nanoparticles (NPs) have shown the potential to influence the aggregation of hIAPP and other amyloidogenic proteins and peptides. In addition to conventional NPs, DNA nanostructures are receiving more and more attention from the biomedical field. Therefore, in this work, we investigated the effects of two different DNA origami nanostructures on hIAPP aggregation. To this end, we employed in situ turbidity measurements and ex situ atomic force microscopy (AFM). The turbidity measurements revealed a retarding effect of the DNA nanostructures on hIAPP aggregation, while the AFM results showed the co-aggregation of hIAPP with the DNA origami nanostructures into hybrid peptide–DNA aggregates. We assume that this was caused by strong electrostatic interactions between the negatively charged DNA origami nanostructures and the positively charged peptide. Most intriguingly, the influence of the DNA origami nanostructures on hIAPP aggregation differed from that of genomic double-stranded DNA (dsDNA) and appeared to depend on DNA origami superstructure. DNA origami nanostructures may thus represent a novel route for modulating amyloid aggregation in vivo. Full article
(This article belongs to the Special Issue The Application of DNA Nanotechnology)
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16 pages, 2633 KiB  
Article
Empirical Modelling of Hydrodynamic Effects on Starch Nanoparticles Precipitation in a Spinning Disc Reactor
by Sahr Sana, Vladimir Zivkovic and Kamelia Boodhoo
Nanomaterials 2020, 10(11), 2202; https://doi.org/10.3390/nano10112202 - 4 Nov 2020
Cited by 6 | Viewed by 3016
Abstract
Empirical correlations have been developed to relate experimentally determined starch nanoparticle size obtained in a solvent–antisolvent precipitation process with key hydrodynamic parameters of a spinning disc reactor (SDR). Three different combinations of dimensionless groups including a conventional Reynolds number (Re), rotational [...] Read more.
Empirical correlations have been developed to relate experimentally determined starch nanoparticle size obtained in a solvent–antisolvent precipitation process with key hydrodynamic parameters of a spinning disc reactor (SDR). Three different combinations of dimensionless groups including a conventional Reynolds number (Re), rotational Reynolds number (Reω) and Rossby number (Ro) have been applied in individual models for two disc surfaces (smooth and grooved) to represent operating variables affecting film flow such as liquid flowrate and disc rotational speed, whilst initial supersaturation (S) has been included to represent varying antisolvent concentrations. Model 1 featuring a combination of Re, Reω and S shows good agreement with the experimental data for both the grooved and smooth discs. For the grooved disc, Re has a greater impact on particle size, whereas Reω is more influential on the smooth disc surface, the difference likely being due to the passive mixing induced by the grooves irrespective of the magnitude of the disc speed. Supersaturation has little impact on particle size within the limited initial supersaturation range studied. Model 2 which characterises both flow rate and disc rotational speed through Ro alone and combined with Re was less accurate in predicting particle size due to several inherent limitations. Full article
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13 pages, 1447 KiB  
Article
Surface Enhanced Raman Scattering on Regular Arrays of Gold Nanostructures: Impact of Long-Range Interactions and the Surrounding Medium
by Iman Ragheb, Macilia Braïk, Stéphanie Lau-Truong, Abderrahmane Belkhir, Anna Rumyantseva, Sergei Kostcheev, Pierre-Michel Adam, Alexandre Chevillot-Biraud, Georges Lévi, Jean Aubard, Leïla Boubekeur-Lecaque and Nordin Félidj
Nanomaterials 2020, 10(11), 2201; https://doi.org/10.3390/nano10112201 - 4 Nov 2020
Cited by 9 | Viewed by 2448
Abstract
Long-range interaction in regular metallic nanostructure arrays can provide the possibility to manipulate their optical properties, governed by the excitation of localized surface plasmon (LSP) resonances. When assembling the nanoparticles in an array, interactions between nanoparticles can result in a strong electromagnetic coupling [...] Read more.
Long-range interaction in regular metallic nanostructure arrays can provide the possibility to manipulate their optical properties, governed by the excitation of localized surface plasmon (LSP) resonances. When assembling the nanoparticles in an array, interactions between nanoparticles can result in a strong electromagnetic coupling for specific grating constants. Such a grating effect leads to narrow LSP peaks due to the emergence of new radiative orders in the plane of the substrate, and thus, an important improvement of the intensity of the local electric field. In this work, we report on the optical study of LSP modes supported by square arrays of gold nanodiscs deposited on an indium tin oxyde (ITO) coated glass substrate, and its impact on the surface enhanced Raman scattering (SERS) of a molecular adsorbate, the mercapto benzoic acid (4-MBA). We estimated the Raman gain of these molecules, by varying the grating constant and the refractive index of the surrounding medium of the superstrate, from an asymmetric medium (air) to a symmetric one (oil). We show that the Raman gain can be improved with one order of magnitude in a symmetric medium compared to SERS experiments in air, by considering the appropriate grating constant. Our experimental results are supported by FDTD calculations, and confirm the importance of the grating effect in the design of SERS substrates. Full article
(This article belongs to the Special Issue Application of Novel Plasmonic Nanomaterials on SERS)
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16 pages, 4204 KiB  
Article
Capsules Rheology in Carreau–Yasuda Fluids
by Alessandro Coclite, Giuseppe Maria Coclite and Domenico De Tommasi
Nanomaterials 2020, 10(11), 2190; https://doi.org/10.3390/nano10112190 - 3 Nov 2020
Cited by 6 | Viewed by 2511
Abstract
In this paper, a Multi Relaxation Time Lattice Boltzmann scheme is used to describe the evolution of a non-Newtonian fluid. Such method is coupled with an Immersed-Boundary technique for the transport of arbitrarily shaped objects navigating the flow. The no-slip boundary conditions on [...] Read more.
In this paper, a Multi Relaxation Time Lattice Boltzmann scheme is used to describe the evolution of a non-Newtonian fluid. Such method is coupled with an Immersed-Boundary technique for the transport of arbitrarily shaped objects navigating the flow. The no-slip boundary conditions on immersed bodies are imposed through a convenient forcing term accounting for the hydrodynamic force generated by the presence of immersed geometries added to momentum equation. Moreover, such forcing term accounts also for the force induced by the shear-dependent viscosity model characterizing the non-Newtonian behavior of the considered fluid. Firstly, the present model is validated against well-known benchmarks, namely the parabolic velocity profile obtained for the flow within two infinite laminae for five values of the viscosity model exponent, n = 0.25, 0.50, 0.75, 1.0, and 1.5. Then, the flow within a squared lid-driven cavity for Re = 1000 and 5000 (being Re the Reynolds number) is computed as a function of n for a shear-thinning (n < 1) fluid. Indeed, the local decrements in the viscosity field achieved in high-shear zones implies the increment in the local Reynolds number, thus moving the position of near-walls minima towards lateral walls. Moreover, the revolution under shear of neutrally buoyant plain elliptical capsules with different Aspect Ratio (AR = 2 and 3) is analyzed for shear-thinning (n < 1), Newtonian (n = 1), and shear-thickening (n > 1) surrounding fluids. Interestingly, the power law by Huang et al. describing the revolution period of such capsules as a function of the Reynolds number and the existence of a critical value, Rec, after which the tumbling is inhibited in confirmed also for non-Newtonian fluids. Analogously, the equilibrium lateral position yeq of such neutrally buoyant capsules when transported in a plane-Couette flow is studied detailing the variation of yeq as a function of the Reynolds number as well as of the exponent n. Full article
(This article belongs to the Special Issue Multiscale Innovative Materials and Structures)
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14 pages, 41918 KiB  
Article
Influence of Nanotopography on Early Bone Healing during Controlled Implant Loading
by Renan de Barros e Lima Bueno, Katia J. Ponce, Ana Paula Dias, Dainelys Guadarrama Bello, John B. Brunski and Antonio Nanci
Nanomaterials 2020, 10(11), 2191; https://doi.org/10.3390/nano10112191 - 3 Nov 2020
Cited by 7 | Viewed by 2043
Abstract
Nanoscale surface modifications influence peri-implant cell fate decisions and implant loading generates local tissue deformation, both of which will invariably impact bone healing. The objective of this study is to determine how loading affects healing around implants with nanotopography. Implants with a nanoporous [...] Read more.
Nanoscale surface modifications influence peri-implant cell fate decisions and implant loading generates local tissue deformation, both of which will invariably impact bone healing. The objective of this study is to determine how loading affects healing around implants with nanotopography. Implants with a nanoporous surface were placed in over-sized osteotomies in rat tibiae and held stable by a system that permits controlled loading. Three regimens were applied: (a) no loading, (b) one daily loading session with a force of 1.5N, and (c) two such daily sessions. At 7 days post implantation, animals were sacrificed for histomorphometric and DNA microarray analyses. Implants subjected to no loading or only one daily loading session achieved high bone-implant contact (BIC), bone-implant distance (BID) and bone formation area near the implant (BFAt) values, while those subjected to two daily loading sessions showed less BFAt and BIC and more BID. Gene expression profiles differed between all groups mainly in unidentified genes, and no modulation of genes associated with inflammatory pathways was detected. These results indicate that implants with nanotopography can achieve a high level of bone formation even under micromotion and limit the inflammatory response to the implant surface. Full article
(This article belongs to the Special Issue Nanostructured Materials for Biomedicine and Bioengineering)
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27 pages, 6075 KiB  
Article
Magnetotransport Properties of Ferromagnetic Nanoparticles in a Semiconductor Matrix Studied by Precise Size-Selective Cluster Ion Beam Deposition
by Nicolas Gack, Gleb Iankevich, Cahit Benel, Robert Kruk, Di Wang, Horst Hahn and Thomas Reisinger
Nanomaterials 2020, 10(11), 2192; https://doi.org/10.3390/nano10112192 - 3 Nov 2020
Cited by 7 | Viewed by 2226
Abstract
The combination of magnetic and semiconducting properties in one material system has great potential for integration of emerging spintronics with conventional semiconductor technology. One standard route for the synthesis of magnetic semiconductors is doping of semiconductors with magnetic atoms. In many semiconductor–magnetic–dopant systems, [...] Read more.
The combination of magnetic and semiconducting properties in one material system has great potential for integration of emerging spintronics with conventional semiconductor technology. One standard route for the synthesis of magnetic semiconductors is doping of semiconductors with magnetic atoms. In many semiconductor–magnetic–dopant systems, the magnetic atoms form precipitates within the semiconducting matrix. An alternative and controlled way to realize such nanocomposite materials is the assembly by co-deposition of size-selected cluster ions and a semiconductor. Here we follow the latter approach to demonstrate that this fabrication route can be used to independently study the influence of cluster concentration and cluster size on magneto-transport properties. In this case we study Fe clusters composed of approximately 500 or 1000 atoms soft-landed into a thermally evaporated amorphous Ge matrix. The analysis of field and temperature dependent transport shows that tunneling processes affected by Coulomb blockade dominate at low temperatures. The nanocomposites show saturating tunneling magnetoresistance, additionally superimposed by at least one other effect not saturating upon the maximum applied field of 6 T. The nanocomposites’ resistivity and the observed tunneling magnetoresistance depend exponentially on the average distance between cluster surfaces. On the contrary, there is no notable influence of the cluster size on the tunneling magnetoresistance. Full article
(This article belongs to the Section Nanocomposite Materials)
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16 pages, 5799 KiB  
Article
Structure-Property Relationships of 2D Ga/In Chalcogenides
by Pingping Jiang, Pascal Boulet and Marie-Christine Record
Nanomaterials 2020, 10(11), 2188; https://doi.org/10.3390/nano10112188 - 2 Nov 2020
Cited by 2 | Viewed by 1960
Abstract
Two-dimensional MX (M = Ga, In; X = S, Se, Te) homo- and heterostructures are of interest in electronics and optoelectronics. Structural, electronic and optical properties of bulk and layered MX and GaX/InX heterostructures have been investigated comprehensively using density functional theory (DFT) [...] Read more.
Two-dimensional MX (M = Ga, In; X = S, Se, Te) homo- and heterostructures are of interest in electronics and optoelectronics. Structural, electronic and optical properties of bulk and layered MX and GaX/InX heterostructures have been investigated comprehensively using density functional theory (DFT) calculations. Based on the quantum theory of atoms in molecules, topological analyses of bond degree (BD), bond length (BL) and bond angle (BA) have been detailed for interpreting interatomic interactions, hence the structure–property relationship. The X–X BD correlates linearly with the ratio of local potential and kinetic energy, and decreases as X goes from S to Te. For van der Waals (vdW) homo- and heterostructures of GaX and InX, a cubic relationship between microscopic interatomic interaction and macroscopic electromagnetic behavior has been established firstly relating to weighted absolute BD summation and static dielectric constant. A decisive role of vdW interaction in layer-dependent properties has been identified. The GaX/InX heterostructures have bandgaps in the range 0.23–1.49 eV, absorption coefficients over 10−5 cm−1 and maximum conversion efficiency over 27%. Under strain, discordant BD evolutions are responsible for the exclusively distributed electrons and holes in sublayers of GaX/InX. Meanwhile, the interlayer BA adjustment with lattice mismatch explains the constraint-free lattice of the vdW heterostructure. Full article
(This article belongs to the Special Issue 2D Materials and Their Heterostructures and Superlattices)
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27 pages, 19340 KiB  
Article
Investigation of the Ionic Liquid Graphene Electric Double Layer in Supercapacitors Using Constant Potential Simulations
by Baris Demir and Debra J. Searles
Nanomaterials 2020, 10(11), 2181; https://doi.org/10.3390/nano10112181 - 1 Nov 2020
Cited by 24 | Viewed by 3826
Abstract
In this work, we investigate the effect of the cation structure on the structure and dynamics of the electrode–electrolyte interface using molecular dynamics simulations. A constant potential method is used to capture the behaviour of 1-ethyl-3-methylimidazolium bis (trifluoromethane)sulfonimide ([C2mim][NTf2]) [...] Read more.
In this work, we investigate the effect of the cation structure on the structure and dynamics of the electrode–electrolyte interface using molecular dynamics simulations. A constant potential method is used to capture the behaviour of 1-ethyl-3-methylimidazolium bis (trifluoromethane)sulfonimide ([C2mim][NTf2]) and butyltrimethylammonium bis(trifluoromethane) sulfonimide ([N4,1,1,1][NTf2]) ionic liquids at varying potential differences applied across the supercapacitor. We find that the details of the structure in the electric double layer and the dynamics differ significantly, yet the charge profile and capacitance do not vary greatly. For the systems considered, charging results in the rearrangement and reorientation of ions within ∼1 nm of the electrode rather than the diffusion of ions to/from the bulk region. This occurs on timescales of O(10 ns) for the ionic liquids considered, and depends on the viscosity of the fluid. Full article
(This article belongs to the Special Issue Ionic Interfaces in Smart Polymer Materials)
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18 pages, 8651 KiB  
Article
The Role of the Laser-Induced Oxide Layer in the Formation of Laser-Induced Periodic Surface Structures
by Camilo Florian, Jean-Luc Déziel, Sabrina V. Kirner, Jan Siegel and Jörn Bonse
Nanomaterials 2020, 10(1), 147; https://doi.org/10.3390/nano10010147 - 14 Jan 2020
Cited by 35 | Viewed by 4658
Abstract
Laser-induced periodic surface structures (LIPSS) are often present when processing solid targets with linearly polarized ultrashort laser pulses. The different irradiation parameters to produce them on metals, semiconductors and dielectrics have been studied extensively, identifying suitable regimes to tailor its properties for applications [...] Read more.
Laser-induced periodic surface structures (LIPSS) are often present when processing solid targets with linearly polarized ultrashort laser pulses. The different irradiation parameters to produce them on metals, semiconductors and dielectrics have been studied extensively, identifying suitable regimes to tailor its properties for applications in the fields of optics, medicine, fluidics and tribology, to name a few. One important parameter widely present when exposing the samples to the high intensities provided by these laser pulses in air environment, that generally is not considered, is the formation of a superficial laser-induced oxide layer. In this paper, we fabricate LIPSS on a layer of the oxidation prone hard-coating material chromium nitride in order to investigate the impact of the laser-induced oxide layer on its formation. A variety of complementary surface analytic techniques were employed, revealing morphological, chemical and structural characteristics of well-known high-spatial frequency LIPSS (HSFL) together with a new type of low-spatial frequency LIPSS (LSFL) with an anomalous orientation parallel to the laser polarization. Based on this input, we performed finite-difference time-domain calculations considering a layered system resembling the geometry of the HSFL along with the presence of a laser-induced oxide layer. The simulations support a scenario that the new type of LSFL is formed at the interface between the laser-induced oxide layer and the non-altered material underneath. These findings suggest that LSFL structures parallel to the polarization can be easily induced in materials that are prone to oxidation. Full article
(This article belongs to the Special Issue Laser-Generated Periodic Nanostructures)
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35 pages, 1386 KiB  
Review
Engineered and Mimicked Extracellular Nanovesicles for Therapeutic Delivery
by Verena Poinsot, Nathalie Pizzinat and Varravaddheay Ong-Meang
Nanomaterials 2024, 14(7), 639; https://doi.org/10.3390/nano14070639 - 6 Apr 2024
Viewed by 800
Abstract
Exosomes are spherical extracellular nanovesicles with an endosomal origin and unilamellar lipid-bilayer structure with sizes ranging from 30 to 100 nm. They contain a large range of proteins, lipids, and nucleic acid species, depending on the state and origin of the extracellular vesicle [...] Read more.
Exosomes are spherical extracellular nanovesicles with an endosomal origin and unilamellar lipid-bilayer structure with sizes ranging from 30 to 100 nm. They contain a large range of proteins, lipids, and nucleic acid species, depending on the state and origin of the extracellular vesicle (EV)-secreting cell. EVs’ function is to encapsulate part of the EV-producing cell content, to transport it through biological fluids to a targeted recipient, and to deliver their cargos specifically within the aimed recipient cells. Therefore, exosomes are considered to be potential biological drug-delivery systems that can stably deliver their cargo into targeted cells. Various cell-derived exosomes are produced for medical issues, but their use for therapeutic purposes still faces several problems. Some of these difficulties can be avoided by resorting to hemisynthetic approaches. We highlight here the uses of alternative exosome-mimes involving cell-membrane coatings on artificial nanocarriers or the hybridization between exosomes and liposomes. We also detail the drug-loading strategies deployed to make them drug-carrier systems and summarize the ongoing clinical trials involving exosomes or exosome-like structures. Finally, we summarize the open questions before considering exosome-like disposals for confident therapeutic delivery. Full article
(This article belongs to the Special Issue Advances in Pharmaceutical Applications of Lipid-Based Nanoparticles)
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24 pages, 8974 KiB  
Review
Autonomous Nanorobots as Miniaturized Surgeons for Intracellular Applications
by Daitian Tang, Xiqi Peng, Song Wu and Songsong Tang
Nanomaterials 2024, 14(7), 595; https://doi.org/10.3390/nano14070595 - 28 Mar 2024
Viewed by 1036
Abstract
Artificial nanorobots have emerged as promising tools for a wide range of biomedical applications, including biosensing, detoxification, and drug delivery. Their unique ability to navigate confined spaces with precise control extends their operational scope to the cellular or subcellular level. By combining tailored [...] Read more.
Artificial nanorobots have emerged as promising tools for a wide range of biomedical applications, including biosensing, detoxification, and drug delivery. Their unique ability to navigate confined spaces with precise control extends their operational scope to the cellular or subcellular level. By combining tailored surface functionality and propulsion mechanisms, nanorobots demonstrate rapid penetration of cell membranes and efficient internalization, enhancing intracellular delivery capabilities. Moreover, their robust motion within cells enables targeted interactions with intracellular components, such as proteins, molecules, and organelles, leading to superior performance in intracellular biosensing and organelle-targeted cargo delivery. Consequently, nanorobots hold significant potential as miniaturized surgeons capable of directly modulating cellular dynamics and combating metastasis, thereby maximizing therapeutic outcomes for precision therapy. In this review, we provide an overview of the propulsion modes of nanorobots and discuss essential factors to harness propulsive energy from the local environment or external power sources, including structure, material, and engine selection. We then discuss key advancements in nanorobot technology for various intracellular applications. Finally, we address important considerations for future nanorobot design to facilitate their translation into clinical practice and unlock their full potential in biomedical research and healthcare. Full article
(This article belongs to the Special Issue Innovation in Nanoparticles for Biomedical Applications)
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33 pages, 9959 KiB  
Review
Resistive Switching Devices for Neuromorphic Computing: From Foundations to Chip Level Innovations
by Kannan Udaya Mohanan
Nanomaterials 2024, 14(6), 527; https://doi.org/10.3390/nano14060527 - 15 Mar 2024
Viewed by 1380
Abstract
Neuromorphic computing has emerged as an alternative computing paradigm to address the increasing computing needs for data-intensive applications. In this context, resistive random access memory (RRAM) devices have garnered immense interest among the neuromorphic research community due to their capability to emulate intricate [...] Read more.
Neuromorphic computing has emerged as an alternative computing paradigm to address the increasing computing needs for data-intensive applications. In this context, resistive random access memory (RRAM) devices have garnered immense interest among the neuromorphic research community due to their capability to emulate intricate neuronal behaviors. RRAM devices excel in terms of their compact size, fast switching capabilities, high ON/OFF ratio, and low energy consumption, among other advantages. This review focuses on the multifaceted aspects of RRAM devices and their application to brain-inspired computing. The review begins with a brief overview of the essential biological concepts that inspire the development of bio-mimetic computing architectures. It then discusses the various types of resistive switching behaviors observed in RRAM devices and the detailed physical mechanisms underlying their operation. Next, a comprehensive discussion on the diverse material choices adapted in recent literature has been carried out, with special emphasis on the benchmark results from recent research literature. Further, the review provides a holistic analysis of the emerging trends in neuromorphic applications, highlighting the state-of-the-art results utilizing RRAM devices. Commercial chip-level applications are given special emphasis in identifying some of the salient research results. Finally, the current challenges and future outlook of RRAM-based devices for neuromorphic research have been summarized. Thus, this review provides valuable understanding along with critical insights and up-to-date information on the latest findings from the field of resistive switching devices towards brain-inspired computing. Full article
(This article belongs to the Special Issue Neuromorphic Devices: Materials, Structures and Bionic Applications)
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24 pages, 2443 KiB  
Review
An Updated Overview of Silica Aerogel-Based Nanomaterials
by Adelina-Gabriela Niculescu, Dana-Ionela Tudorache, Maria Bocioagă, Dan Eduard Mihaiescu, Tony Hadibarata and Alexandru Mihai Grumezescu
Nanomaterials 2024, 14(5), 469; https://doi.org/10.3390/nano14050469 - 4 Mar 2024
Cited by 2 | Viewed by 2428
Abstract
Silica aerogels have gained much interest due to their unique properties, such as being the lightest solid material, having small pore sizes, high porosity, and ultralow thermal conductivity. Also, the advancements in synthesis methods have enabled the creation of silica aerogel-based composites in [...] Read more.
Silica aerogels have gained much interest due to their unique properties, such as being the lightest solid material, having small pore sizes, high porosity, and ultralow thermal conductivity. Also, the advancements in synthesis methods have enabled the creation of silica aerogel-based composites in combination with different materials, for example, polymers, metals, and carbon-based structures. These new silica-based materials combine the properties of silica with the other materials to create a new and reinforced architecture with significantly valuable uses in different fields. Therefore, the importance of silica aerogels has been emphasized by presenting their properties, synthesis process, composites, and numerous applications, offering an updated background for further research in this interdisciplinary domain. Full article
(This article belongs to the Collection Metallic and Metal Oxide Nanohybrids and Their Applications)
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30 pages, 4620 KiB  
Review
Recent Advances in Tactile Sensory Systems: Mechanisms, Fabrication, and Applications
by Jianguo Xi, Huaiwen Yang, Xinyu Li, Ruilai Wei, Taiping Zhang, Lin Dong, Zhenjun Yang, Zuqing Yuan, Junlu Sun and Qilin Hua
Nanomaterials 2024, 14(5), 465; https://doi.org/10.3390/nano14050465 - 4 Mar 2024
Viewed by 2106
Abstract
Flexible electronics is a cutting-edge field that has paved the way for artificial tactile systems that mimic biological functions of sensing mechanical stimuli. These systems have an immense potential to enhance human–machine interactions (HMIs). However, tactile sensing still faces formidable challenges in delivering [...] Read more.
Flexible electronics is a cutting-edge field that has paved the way for artificial tactile systems that mimic biological functions of sensing mechanical stimuli. These systems have an immense potential to enhance human–machine interactions (HMIs). However, tactile sensing still faces formidable challenges in delivering precise and nuanced feedback, such as achieving a high sensitivity to emulate human touch, coping with environmental variability, and devising algorithms that can effectively interpret tactile data for meaningful interactions in diverse contexts. In this review, we summarize the recent advances of tactile sensory systems, such as piezoresistive, capacitive, piezoelectric, and triboelectric tactile sensors. We also review the state-of-the-art fabrication techniques for artificial tactile sensors. Next, we focus on the potential applications of HMIs, such as intelligent robotics, wearable devices, prosthetics, and medical healthcare. Finally, we conclude with the challenges and future development trends of tactile sensors. Full article
(This article belongs to the Special Issue Advances in Flexible Nanoelectronics)
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23 pages, 4263 KiB  
Review
Zein-Based Nanoparticles as Active Platforms for Sustainable Applications: Recent Advances and Perspectives
by Emilia Oleandro, Mariamelia Stanzione, Giovanna Giuliana Buonocore and Marino Lavorgna
Nanomaterials 2024, 14(5), 414; https://doi.org/10.3390/nano14050414 - 23 Feb 2024
Cited by 2 | Viewed by 1213
Abstract
Nanomaterials, due to their unique structural and functional features, are widely investigated for potential applications in a wide range of industrial sectors. In this context, protein-based nanoparticles, given proteins’ abundance, non-toxicity, and stability, offer a promising and sustainable methodology for encapsulation and protection, [...] Read more.
Nanomaterials, due to their unique structural and functional features, are widely investigated for potential applications in a wide range of industrial sectors. In this context, protein-based nanoparticles, given proteins’ abundance, non-toxicity, and stability, offer a promising and sustainable methodology for encapsulation and protection, and can be used in engineered nanocarriers that are capable of releasing active compounds on demand. Zein is a plant-based protein extracted from corn, and it is biocompatible, biodegradable, and amphiphilic. Several approaches and technologies are currently involved in zein-based nanoparticle preparation, such as antisolvent precipitation, spray drying, supercritical processes, coacervation, and emulsion procedures. Thanks to their peculiar characteristics, zein-based nanoparticles are widely used as nanocarriers of active compounds in targeted application fields such as drug delivery, bioimaging, or soft tissue engineering, as reported by others. The main goal of this review is to investigate the use of zein-based nanocarriers for different advanced applications including food/food packaging, cosmetics, and agriculture, which are attracting researchers’ efforts, and to exploit the future potential development of zein NPs in the field of cultural heritage, which is still relatively unexplored. Moreover, the presented overview focuses on several preparation methods (i.e., antisolvent processes, spry drying), correlating the different analyzed methodologies to NPs’ structural and functional properties and their capability to act as carriers of bioactive compounds, both to preserve their activity and to tune their release in specific working conditions. Full article
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22 pages, 2713 KiB  
Review
Titanium Dioxide Nanoparticles Doped with Iron for Water Treatment via Photocatalysis: A Review
by Domenico Rosa, Nigar Abbasova and Luca Di Palma
Nanomaterials 2024, 14(3), 293; https://doi.org/10.3390/nano14030293 - 31 Jan 2024
Cited by 1 | Viewed by 1198
Abstract
Iron-doped titanium dioxide nanoparticles are widely employed for photocatalytic applications under visible light due to their promising performance. Nevertheless, the manufacturing process, the role of Fe3+ ions within the crystal lattice of titanium dioxide, and their impact on operational parameters are still [...] Read more.
Iron-doped titanium dioxide nanoparticles are widely employed for photocatalytic applications under visible light due to their promising performance. Nevertheless, the manufacturing process, the role of Fe3+ ions within the crystal lattice of titanium dioxide, and their impact on operational parameters are still a subject of controversy. Based on these assumptions, the primary objective of this review is to delineate the role of iron, ascertain the optimal quantity, and elucidate its influence on the main photocatalysis parameters, including nanoparticle size, band gap, surface area, anatase–rutile transition, and point of zero charge. Moreover, an optimized synthesis method based on comprehensive data and insights from the existing literature is proposed, focusing exclusively on iron-doped titanium oxide while excluding other dopant variants. Full article
(This article belongs to the Section Environmental Nanoscience and Nanotechnology)
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19 pages, 5934 KiB  
Review
Tissue Nanotransfection Silicon Chip and Related Electroporation-Based Technologies for In Vivo Tissue Reprogramming
by Yi Xuan, Cong Wang, Subhadip Ghatak and Chandan K. Sen
Nanomaterials 2024, 14(2), 217; https://doi.org/10.3390/nano14020217 - 19 Jan 2024
Viewed by 2017
Abstract
Tissue nanotransfection (TNT), a cutting-edge technique of in vivo gene therapy, has gained substantial attention in various applications ranging from in vivo tissue reprogramming in regenerative medicine, and wound healing to cancer treatment. This technique harnesses the advancements in the semiconductor processes, facilitating [...] Read more.
Tissue nanotransfection (TNT), a cutting-edge technique of in vivo gene therapy, has gained substantial attention in various applications ranging from in vivo tissue reprogramming in regenerative medicine, and wound healing to cancer treatment. This technique harnesses the advancements in the semiconductor processes, facilitating the integration of conventional transdermal gene delivery methods—nanoelectroporation and microneedle technologies. TNT silicon chips have demonstrated considerable promise in reprogramming fibroblast cells of skin in vivo into vascular or neural cells in preclinical studies to assist in the recovery of injured limbs and damaged brain tissue. More recently, the application of TNT chips has been extended to the area of exosomes, which are vital for intracellular communication to track their functionality during the wound healing process. In this review, we provide an in-depth examination of the design, fabrication, and applications of TNT silicon chips, alongside a critical analysis of the electroporation-based gene transfer mechanisms. Additionally, the review discussed the existing limitations and challenges in the current technique, which may project future trajectories in the landscape of gene therapy. Through this exploration, the review aims to shed light on the prospects of TNT in the broader context of gene therapy and tissue regeneration. Full article
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24 pages, 6825 KiB  
Review
Progress of One-Dimensional SiC Nanomaterials: Design, Fabrication and Sensing Applications
by Haiyan Liu, Xiaoshan Zhang, Nana Xu, Cheng Han, Nan Wu, Bing Wang and Yingde Wang
Nanomaterials 2024, 14(2), 187; https://doi.org/10.3390/nano14020187 - 13 Jan 2024
Viewed by 1112
Abstract
One-dimensional silicon carbide (SiC) nanomaterials hold great promise for a series of applications, such as nanoelectronic devices, sensors, supercapacitors, and catalyst carriers, attributed to their unique electrical, mechanical, and physicochemical properties. Recent progress in their design and fabrication has led to a deep [...] Read more.
One-dimensional silicon carbide (SiC) nanomaterials hold great promise for a series of applications, such as nanoelectronic devices, sensors, supercapacitors, and catalyst carriers, attributed to their unique electrical, mechanical, and physicochemical properties. Recent progress in their design and fabrication has led to a deep understanding of the structural evolution and structure–property correlation. Several unique attributes, such as high electron mobility, offer SiC nanomaterials an opportunity in the design of SiC-based sensors with high sensitivity. In this review, a brief introduction to the structure and properties of SiC is first presented, and the latest progress in design and fabrication of one-dimensional SiC nanomaterials is summarized. Then, the sensing applications of one-dimensional SiC nanomaterials are reviewed. Finally, our perspectives on the important research direction and future opportunities of one-dimensional SiC nanomaterial for sensors are proposed. Full article
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22 pages, 12294 KiB  
Review
Field Manipulations in On-Chip Micro/Nanoscale Lasers Based on Colloid Nanocrystals
by Yazhou Gu, Zhengmei Yang and Zhitong Li
Nanomaterials 2023, 13(23), 3069; https://doi.org/10.3390/nano13233069 - 3 Dec 2023
Cited by 1 | Viewed by 977
Abstract
Owning to merits such as bandgap tunability, solution processability, large absorption coefficients, and high photoluminescence quantum yields, colloidal quantum dots (CQDs) emerged as a promising gain material to make on-chip micro/nanoscale lasers with high silicon compatibility. In this paper, we review the recent [...] Read more.
Owning to merits such as bandgap tunability, solution processability, large absorption coefficients, and high photoluminescence quantum yields, colloidal quantum dots (CQDs) emerged as a promising gain material to make on-chip micro/nanoscale lasers with high silicon compatibility. In this paper, we review the recent progress in CQD on-chip micro/nanoscale lasers, with a special focus on the physical properties achieved through field manipulation schemes in different types of cavities. Key aspects include manipulating and engineering wavelength, polarization, and direction as well as coupling and light extraction. Finally, we give our prospects for future research directions toward the integration of robust CQD nano/microscale lasers with photonic integrated circuits. Full article
(This article belongs to the Special Issue Recent Development of Semiconductor Nanocrystals)
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15 pages, 968 KiB  
Review
Application of Zeolites and Zeolitic Imidazolate Frameworks in Dentistry—A Narrative Review
by Laura Jiaxuan Li, Chun-Hung Chu and Ollie Yiru Yu
Nanomaterials 2023, 13(22), 2973; https://doi.org/10.3390/nano13222973 - 18 Nov 2023
Cited by 1 | Viewed by 1873
Abstract
Zeolites and zeolitic imidazolate frameworks (ZIFs) are crystalline aluminosilicates with porous structure, which are closely linked with nanomaterials. They are characterized by enhanced ion exchange capacity, physical–chemical stability, thermal stability and biocompatibility, making them a promising material for dental applications. This review aimed [...] Read more.
Zeolites and zeolitic imidazolate frameworks (ZIFs) are crystalline aluminosilicates with porous structure, which are closely linked with nanomaterials. They are characterized by enhanced ion exchange capacity, physical–chemical stability, thermal stability and biocompatibility, making them a promising material for dental applications. This review aimed to provide an overview of the application of zeolites and ZIFs in dentistry. The common zeolite compounds for dental application include silver zeolite, zinc zeolite, calcium zeolite and strontium zeolite. The common ZIFs for dental application include ZIF-8 and ZIF-67. Zeolites and ZIFs have been employed in various areas of dentistry, such as restorative dentistry, endodontics, prosthodontics, implantology, periodontics, orthodontics and oral surgery. In restorative dentistry, zeolites and ZIFs are used as antimicrobial additives in dental adhesives and restorative materials. In endodontics, zeolites are used in root-end fillings, root canal irritants, root canal sealers and bone matrix scaffolds for peri-apical diseases. In prosthodontics, zeolites can be incorporated into denture bases, tissue conditioners, soft denture liners and dental prostheses. In implantology, zeolites and ZIFs are applied in dental implants, bone graft materials, bone adhesive hydrogels, drug delivery systems and electrospinning. In periodontics, zeolites can be applied as antibacterial agents for deep periodontal pockets, while ZIFs can be embedded in guided tissue regeneration membranes and guided bone regeneration membranes. In orthodontics, zeolites can be applied in orthodontic appliances. Additionally, for oral surgery, zeolites can be used in oral cancer diagnostic marker membranes, maxillofacial prosthesis silicone elastomer and tooth extraction medicines, while ZIFs can be incorporated to osteogenic glue or used as a carrier for antitumour drugs. In summary, zeolites have a broad application in dentistry and are receiving more attention from clinicians and researchers. Full article
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26 pages, 3595 KiB  
Review
A Comprehensive Review on Electrocatalytic Applications of 2D Metallenes
by Mohamed A. Basyooni-M. Kabatas
Nanomaterials 2023, 13(22), 2966; https://doi.org/10.3390/nano13222966 - 17 Nov 2023
Cited by 1 | Viewed by 1203
Abstract
This review introduces metallenes, a cutting-edge form of atomically thin two-dimensional (2D) metals, gaining attention in energy and catalysis. Their unique physicochemical and electronic properties make them promising for applications like catalysis. Metallenes stand out due to their abundance of under-coordinated metal atoms, [...] Read more.
This review introduces metallenes, a cutting-edge form of atomically thin two-dimensional (2D) metals, gaining attention in energy and catalysis. Their unique physicochemical and electronic properties make them promising for applications like catalysis. Metallenes stand out due to their abundance of under-coordinated metal atoms, enhancing the catalytic potential by improving atomic utilization and intrinsic activity. This review explores the utility of 2D metals as electrocatalysts in sustainable energy conversion, focusing on the Oxygen Evolution Reaction, Oxygen Reduction Reaction, Fuel Oxidation Reaction, and Carbon Dioxide Reduction Reaction. Aimed at researchers in nanomaterials and energy, the review is a comprehensive resource for unlocking the potential of 2D metals in creating a sustainable energy landscape. Full article
(This article belongs to the Special Issue 2D and Carbon Nanomaterials for Energy Conversion and Storage)
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34 pages, 4141 KiB  
Review
Development of Processes and Catalysts for Biomass to Hydrocarbons at Moderate Conditions: A Comprehensive Review
by Reem Shomal and Ying Zheng
Nanomaterials 2023, 13(21), 2845; https://doi.org/10.3390/nano13212845 - 27 Oct 2023
Viewed by 1249
Abstract
This comprehensive review explores recent catalyst advancements for the hydrodeoxygenation (HDO) of aromatic oxygenates derived from lignin, with a specific focus on the selective production of valuable aromatics under moderate reaction conditions. It addresses critical challenges in bio-crude oil upgrading, encompassing issues related [...] Read more.
This comprehensive review explores recent catalyst advancements for the hydrodeoxygenation (HDO) of aromatic oxygenates derived from lignin, with a specific focus on the selective production of valuable aromatics under moderate reaction conditions. It addresses critical challenges in bio-crude oil upgrading, encompassing issues related to catalyst deactivation from coking, methods to mitigate deactivation, and techniques for catalyst regeneration. The study investigates various oxygenates found in bio-crude oil, such as phenol, guaiacol, anisole, and catechol, elucidating their conversion pathways during HDO. The review emphasizes the paramount importance of selectively generating arenes by directly cleaving C–O bonds while avoiding unwanted ring hydrogenation pathways. A comparative analysis of different bio-crude oil upgrading processes underscores the need to enhance biofuel quality for practical applications. Additionally, the review focuses on catalyst design for HDO. It compares six major catalyst categories, including metal sulfides, transition metals, metal phosphides, nitrides, carbides, and oxides, to provide insights for efficient bio-crude oil upgrading toward sustainable and eco-friendly energy alternatives. Full article
(This article belongs to the Special Issue From Biomass to Nanomaterials)
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