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
Fabrication and Characterization of Hybrid Films Based on NiFe2O4 Nanoparticles in a Polymeric Matrix for Applications in Organic Electronics
Nanomaterials 2023, 13(9), 1525; https://doi.org/10.3390/nano13091525 - 30 Apr 2023
Viewed by 779
Abstract
Hybrid films for applications in organic electronics from NiFe2O4 nanoparticles (NPs) in poly(3,4 ethylene dioxythiophene), poly(4-styrenesulfonate) (PEDOT:PSS), and poly(methyl methacrylate) (PMMA) were fabricated by the spin-coating technique. The films were characterized by infrared spectroscopy, atomic force microscopy, scanning electron microscopy, [...] Read more.
Hybrid films for applications in organic electronics from NiFe2O4 nanoparticles (NPs) in poly(3,4 ethylene dioxythiophene), poly(4-styrenesulfonate) (PEDOT:PSS), and poly(methyl methacrylate) (PMMA) were fabricated by the spin-coating technique. The films were characterized by infrared spectroscopy, atomic force microscopy, scanning electron microscopy, and energy-dispersive spectroscopy to subsequently determine their optical parameters. The electronic transport of the hybrid films was determined in bulk heterojunction devices. The presence of NiFe2O4 NPs reinforces mechanical properties and increases transmittance in the hybrid films; the PEDOT:PSS-NiFe2O4 NPs film is the one that has a maximum stress of 28 MPa and a Knoop hardness of 0.103, while the PMMA-NiFe2O4 NPs film has the highest transmittance of (87%). The Tauc band gap is in the range of 3.78–3.9 eV, and the Urbach energy is in the range of 0.24–0.33 eV. Regarding electrical behavior, the main effect is exerted by the matrix, although the current carried is of the same order of magnitude for the two devices: glass/ITO/polymer-NiFe2O4 NPs/Ag. NiFe2O4 NPs enhance the mechanical, optical, and electrical behavior of the hybrid films and can be used as semi-transparent anodes and as active layers. Full article
(This article belongs to the Special Issue Functional Nanomaterials for Flexible Electronics)
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Article
The Influence of the Size of BN NSs on Silkworm Development and Tissue Microstructure
Nanomaterials 2023, 13(9), 1502; https://doi.org/10.3390/nano13091502 - 27 Apr 2023
Viewed by 548
Abstract
Boron nitride nanosheets (BN NSs) have emerged as promising materials in a wide range of biomedical applications. Despite the extensive studies on these bio-nano interfacial systems, one critical concern is their toxicity, which is affected by a variety of factors, including size. This [...] Read more.
Boron nitride nanosheets (BN NSs) have emerged as promising materials in a wide range of biomedical applications. Despite the extensive studies on these bio-nano interfacial systems, one critical concern is their toxicity, which is affected by a variety of factors, including size. This study aimed at assessing the relationship between BN NSs size and toxicity. Two silkworm strains (qiufeng × baiyu and Nistari 7019) were used as model organisms to investigate the effect of different sizes of BN NSs (BN NSs-1, thickness of 41.5 nm and diameter of 270.7 nm; BN NSs-2, thickness of 48.2 nm and diameter of 562.2 nm) on silkworm mortality, growth, cocoon weight, and tissue microstructure. The findings show that exposure to BN NSs in this work has no lethal adverse effects on silkworm growth or tissue microstructure. BN NSs have a higher effect on the growth rate of qiufeng × baiyu compared to Nistari 7019, demonstrating that the same treatment does not favorably affect the Nistari 7019 strain, as there is no significant increase in cocoon weight. Overall, the study suggests that the sizes of BN NSs employed in this study are relatively safe and have less negative impact on silkworms. This offers significant insights into the effect of BN NSs size, a crucial factor to consider for their safe use in biomedical applications. Full article
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Article
Ultra-Sensitive and Fast Humidity Sensors Based on Direct Laser-Scribed Graphene Oxide/Carbon Nanotubes Composites
Nanomaterials 2023, 13(9), 1473; https://doi.org/10.3390/nano13091473 - 26 Apr 2023
Cited by 1 | Viewed by 612
Abstract
In this paper, the relative humidity sensor properties of graphene oxide (GO) and graphene oxide/multiwalled nanotubes (GO/MWNTs) composites have been investigated. Composite sensors were fabricated by direct laser scribing and characterized using UV-vis-NIR, Raman, Fourier transform infrared, and X-ray photoemission spectroscopies, electron scanning [...] Read more.
In this paper, the relative humidity sensor properties of graphene oxide (GO) and graphene oxide/multiwalled nanotubes (GO/MWNTs) composites have been investigated. Composite sensors were fabricated by direct laser scribing and characterized using UV-vis-NIR, Raman, Fourier transform infrared, and X-ray photoemission spectroscopies, electron scanning microscopy coupled with energy-dispersive X-ray analysis, and impedance spectroscopy (IS). These methods confirm the composite homogeneity and laser reduction of GO/MWNT with dominant GO characteristics, while ISresults analysis reveals the circuit model for rGO-GO-rGO structure and the effect of MWNT on the sensor properties. Although direct laser scribing of GO-based humidity sensor shows an outstanding response (|ΔZ|/|Z| up to 638,800%), a lack of stability and repeatability has been observed. GO/MWNT-based humidity sensors are more conductive than GO sensors and relatively less sensitive (|ΔZ|/|Z| = 163,000%). However, they are more stable in harsh humid conditions, repeatable, and reproducible even after several years of shelf-life. In addition, they have fast response/recovery times of 10.7 s and 9.3 s and an ultra-fast response time of 61 ms when abrupt humidification/dehumidification is applied by respiration. All carbon-based sensors’ overall properties confirm the advantage of introducing the GO/MWNT hybrid and laser direct writing to produce stable structures and sensors. Full article
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Article
The Mechanism of Manganese Ferrite Nanomaterials Promoting Drought Resistance in Rice
Nanomaterials 2023, 13(9), 1484; https://doi.org/10.3390/nano13091484 - 26 Apr 2023
Viewed by 518
Abstract
Strategies to reduce the risk of drought damage are urgently needed as intensified climate change threatens agricultural production. One potential strategy was using nanomaterials (NMs) to enhance plant resistance by regulating various physiological and biochemical processes. In the present study, 10 mg kg [...] Read more.
Strategies to reduce the risk of drought damage are urgently needed as intensified climate change threatens agricultural production. One potential strategy was using nanomaterials (NMs) to enhance plant resistance by regulating various physiological and biochemical processes. In the present study, 10 mg kg−1 manganese ferrite (MnFe2O4) NMs had the optimal enhancement to elevate the levels of biomass, photosynthesis, nutrient elements, and polysaccharide in rice by 10.9–525.0%, respectively, under drought stress. The MnFe2O4 NMs were internalized by rice plants, which provided the possibility for rice to better cope with drought. Furthermore, as compared with drought control and equivalent ion control, the introduction of MnFe2O4 NMs into the roots significantly upregulated the drought-sensing gene CLE25 (29.4%) and the receptor gene NCED3 (59.9%). This activation stimulated downstream abscisic acid, proline, malondialdehyde, and wax biosynthesis by 23.3%, 38.9%, 7.2%, and 26.2%, respectively. In addition, 10 mg·kg−1 MnFe2O4 NMs significantly upregulated the relative expressions of OR1, AUX2, AUX3, PIN1a, and PIN2, and increased IAA content significantly, resulting in an enlarged root angle and a deeper and denser root to help the plant withstand drought stresses. The nutritional quality of rice grains was also improved. Our study provides crucial insight for developing nano-enabled strategies to improve crop productivity and resilience to climate change. Full article
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Article
Chitin-Derived Nitrogen-Doped Carbon Nanopaper with Subwavelength Nanoporous Structures for Solar Thermal Heating
Nanomaterials 2023, 13(9), 1480; https://doi.org/10.3390/nano13091480 - 26 Apr 2023
Viewed by 554
Abstract
Sustainable biomass-derived carbons have attracted research interest because of their ability to effectively absorb and convert solar light to thermal energy, a phenomenon known as solar thermal heating. Although their carbon-based molecular and nanoporous structures should be customized to achieve enhanced solar thermal [...] Read more.
Sustainable biomass-derived carbons have attracted research interest because of their ability to effectively absorb and convert solar light to thermal energy, a phenomenon known as solar thermal heating. Although their carbon-based molecular and nanoporous structures should be customized to achieve enhanced solar thermal heating performance, such customization has insufficiently progressed. In this study, we transformed a chitin nanofiber/water dispersion into paper, referred to as chitin nanopaper, with subwavelength nanoporous structures by spatially controlled drying, followed by temperature-controlled carbonization without any pretreatment to customize the carbon-based molecular structures. The optimal carbonization temperature for enhancing the solar absorption and solar thermal heating performance of the chitin nanopaper was determined to be 400 °C. Furthermore, we observed that the nitrogen component, which afforded nitrogen-doped carbon structures, and the high morphological stability of chitin nanofibers against carbonization, which maintained subwavelength nanoporous structures even after carbonization, contributed to the improved solar absorption of the carbonized chitin nanopaper. The carbonized chitin nanopaper exhibited a higher solar thermal heating performance than the carbonized cellulose nanopaper and commercial nanocarbon materials, thus demonstrating significant potential as an excellent solar thermal material. Full article
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Article
Targeting of Tomato Bushy Stunt Virus with a Genetically Fused C-End Rule Peptide
Nanomaterials 2023, 13(8), 1428; https://doi.org/10.3390/nano13081428 - 21 Apr 2023
Viewed by 650
Abstract
Homing peptides are widely used to improve the delivery of drugs, imaging agents, and nanoparticles (NPs) to their target sites. Plant virus-based particles represent an emerging class of structurally diverse nanocarriers that are biocompatible, biodegradable, safe, and cost-effective. Similar to synthetic NPs, these [...] Read more.
Homing peptides are widely used to improve the delivery of drugs, imaging agents, and nanoparticles (NPs) to their target sites. Plant virus-based particles represent an emerging class of structurally diverse nanocarriers that are biocompatible, biodegradable, safe, and cost-effective. Similar to synthetic NPs, these particles can be loaded with imaging agents and/or drugs and functionalized with affinity ligands for targeted delivery. Here we report the development of a peptide-guided Tomato Bushy Stunt Virus (TBSV)-based nanocarrier platform for affinity targeting with the C-terminal C-end rule (CendR) peptide, RPARPAR (RPAR). Flow cytometry and confocal microscopy demonstrated that the TBSV-RPAR NPs bind specifically to and internalize in cells positive for the peptide receptor neuropilin-1 (NRP-1). TBSV-RPAR particles loaded with a widely used anticancer anthracycline, doxorubicin, showed selective cytotoxicity on NRP-1-expressing cells. Following systemic administration in mice, RPAR functionalization conferred TBSV particles the ability to accumulate in the lung tissue. Collectively, these studies show the feasibility of the CendR-targeted TBSV platform for the precision delivery of payloads. Full article
(This article belongs to the Special Issue Advances in Nanoscale Materials in Biomedicine)
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Review
A Review on the Applications of Natural Biodegradable Nano Polymers in Cardiac Tissue Engineering
Nanomaterials 2023, 13(8), 1374; https://doi.org/10.3390/nano13081374 - 15 Apr 2023
Viewed by 651
Abstract
As cardiac diseases, which mostly result in heart failure, are increasing rapidly worldwide, heart transplantation seems the only solution for saving lives. However, this practice is not always possible due to several reasons, such as scarcity of donors, rejection of organs from recipient [...] Read more.
As cardiac diseases, which mostly result in heart failure, are increasing rapidly worldwide, heart transplantation seems the only solution for saving lives. However, this practice is not always possible due to several reasons, such as scarcity of donors, rejection of organs from recipient bodies, or costly medical procedures. In the framework of nanotechnology, nanomaterials greatly contribute to the development of these cardiovascular scaffolds as they provide an easy regeneration of the tissues. Currently, functional nanofibers can be used in the production of stem cells and in the regeneration of cells and tissues. The small size of nanomaterials, however, leads to changes in their chemical and physical characteristics that could alter their interaction and exposure to stem cells with cells and tissues. This article aims to review the naturally occurring biodegradable nanomaterials that are used in cardiovascular tissue engineering for the development of cardiac patches, vessels, and tissues. Moreover, this article also provides an overview of cell sources used for cardiac tissue engineering, explains the anatomy and physiology of the human heart, and explores the regeneration of cardiac cells and the nanofabrication approaches used in cardiac tissue engineering as well as scaffolds. Full article
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Review
Iron Oxide@Mesoporous Silica Core-Shell Nanoparticles as Multimodal Platforms for Magnetic Resonance Imaging, Magnetic Hyperthermia, Near-Infrared Light Photothermia, and Drug Delivery
Nanomaterials 2023, 13(8), 1342; https://doi.org/10.3390/nano13081342 - 12 Apr 2023
Cited by 1 | Viewed by 1052
Abstract
The design of core-shell nanocomposites composed of an iron oxide core and a silica shell offers promising applications in the nanomedicine field, especially for developing efficient theranostic systems which may be useful for cancer treatments. This review article addresses the different ways to [...] Read more.
The design of core-shell nanocomposites composed of an iron oxide core and a silica shell offers promising applications in the nanomedicine field, especially for developing efficient theranostic systems which may be useful for cancer treatments. This review article addresses the different ways to build iron oxide@silica core-shell nanoparticles and it reviews their properties and developments for hyperthermia therapies (magnetically or light-induced), combined with drug delivery and MRI imaging. It also highlights the various challenges encountered, such as the issues associated with in vivo injection in terms of NP–cell interactions or the control of the heat dissipation from the core of the NP to the external environment at the macro or nanoscale. Full article
(This article belongs to the Special Issue Plasmonic and Magnetic Nanoparticles for Localized-Hyperthermia)
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Article
First-Principles Calculation of MoO2 and MoO3 Electronic and Optical Properties Compared with Experimental Data
Nanomaterials 2023, 13(8), 1319; https://doi.org/10.3390/nano13081319 - 09 Apr 2023
Viewed by 608
Abstract
MoO3 and MoO2 systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO3 adopts a thermodynamically stable orthorhombic phase (α-MoO3) belonging to the space group [...] Read more.
MoO3 and MoO2 systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO3 adopts a thermodynamically stable orthorhombic phase (α-MoO3) belonging to the space group Pbmn, while MoO2 assumes a monoclinic arrangement characterized by space group P21/c. In the present paper, we investigated the electronic and optical properties of both MoO3 and MoO2 by using Density Functional Theory calculations, in particular, the Meta Generalized Gradient Approximation (MGGA) SCAN functional together with the PseudoDojo pseudopotential, which were used for the first time to obtain a deeper insight into the nature of different Mo–O bonds in these materials. The calculated density of states, the band gap, and the band structure were confirmed and validated by comparison with already available experimental results, while the optical properties were validated by recording optical spectra. Furthermore, the calculated band-gap energy value for the orthorhombic MoO3 showed the best match to the experimental value reported in the literature. All these findings suggest that the newly proposed theoretical techniques reproduce the experimental evidence of both MoO2 and MoO3 systems with high accuracy. Full article
(This article belongs to the Special Issue First-Principle Calculation Study of Nanomaterials)
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Article
DNA-Templated Silver Nanoclusters as Dual-Mode Sensitive Probes for Self-Powered Biosensor Fueled by Glucose
Nanomaterials 2023, 13(8), 1299; https://doi.org/10.3390/nano13081299 - 07 Apr 2023
Viewed by 664
Abstract
Nanomaterials have been extensively explored in developing sensors due to their unique properties, contributing to the development of reliable sensor designs with improved sensitivity and specificity. Herein, we propose the construction of a fluorescent/electrochemical dual-mode self-powered biosensor for advanced biosensing using DNA-templated silver [...] Read more.
Nanomaterials have been extensively explored in developing sensors due to their unique properties, contributing to the development of reliable sensor designs with improved sensitivity and specificity. Herein, we propose the construction of a fluorescent/electrochemical dual-mode self-powered biosensor for advanced biosensing using DNA-templated silver nanoclusters (AgNCs@DNA). AgNC@DNA, due to its small size, exhibits advantageous characteristics as an optical probe. We investigated the sensing efficacy of AgNCs@DNA as a fluorescent probe for glucose detection. Fluorescence emitted by AgNCs@DNA served as the readout signal as a response to more H2O2 being generated by glucose oxidase for increasing glucose levels. The second readout signal of this dual-mode biosensor was utilized via the electrochemical route, where AgNCs served as charge mediators between the glucose oxidase (GOx) enzyme and carbon working electrode during the oxidation process of glucose catalyzed by GOx. The developed biosensor features low-level limits of detection (LODs), ~23 μM for optical and ~29 μM for electrochemical readout, which are much lower than the typical glucose concentrations found in body fluids, including blood, urine, tears, and sweat. The low LODs, simultaneous utilization of different readout strategies, and self-powered design demonstrated in this study open new prospects for developing next-generation biosensor devices. Full article
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Article
Beyond Conventional Sensing: Hybrid Plasmonic Metasurfaces and Bound States in the Continuum
Nanomaterials 2023, 13(7), 1261; https://doi.org/10.3390/nano13071261 - 03 Apr 2023
Cited by 1 | Viewed by 920
Abstract
Fano resonances result from the strong coupling and interference between a broad background state and a narrow, almost discrete state, leading to the emergence of asymmetric scattering spectral profiles. Under certain conditions, Fano resonances can experience a collapse of their width due to [...] Read more.
Fano resonances result from the strong coupling and interference between a broad background state and a narrow, almost discrete state, leading to the emergence of asymmetric scattering spectral profiles. Under certain conditions, Fano resonances can experience a collapse of their width due to the destructive interference of strongly coupled modes, resulting in the formation of bound states in the continuum (BIC). In such cases, the modes are simultaneously localized in the nanostructure and coexist with radiating waves, leading to an increase in the quality factor, which is virtually unlimited. In this work, we report on the design of a layered hybrid plasmonic-dielectric metasurface that facilitates strong mode coupling and the formation of BIC, resulting in resonances with a high quality factor. We demonstrate the possibility of controlling Fano resonances and tuning Rabi splitting using the nanoantenna dimensions. We also experimentally demonstrate the generalized Kerker effect in a binary arrangement of silicon nanodisks, which allows for the tuning of the collective modes and creates new photonic functionalities and improved sensing capabilities. Our findings have promising implications for developing plasmonic sensors that leverage strong light-matter interactions in hybrid metasurfaces. Full article
(This article belongs to the Special Issue Nanostructure-Based Plasmonic Sensing and Devices)
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Review
Recent Progress of 2D Layered Materials in Water-in-Salt/Deep Eutectic Solvent-Based Liquid Electrolytes for Supercapacitors
Nanomaterials 2023, 13(7), 1257; https://doi.org/10.3390/nano13071257 - 02 Apr 2023
Viewed by 965
Abstract
Supercapacitors are candidates with the greatest potential for use in sustainable energy resources. Extensive research is being carried out to improve the performances of state-of-art supercapacitors to meet our increased energy demands because of huge technological innovations in various fields. The development of [...] Read more.
Supercapacitors are candidates with the greatest potential for use in sustainable energy resources. Extensive research is being carried out to improve the performances of state-of-art supercapacitors to meet our increased energy demands because of huge technological innovations in various fields. The development of high-performing materials for supercapacitor components such as electrodes, electrolytes, current collectors, and separators is inevitable. To boost research in materials design and production toward supercapacitors, the up-to-date collection of recent advancements is necessary for the benefit of active researchers. This review summarizes the most recent developments of water-in-salt (WIS) and deep eutectic solvents (DES), which are considered significant electrolyte systems to advance the energy density of supercapacitors, with a focus on two-dimensional layered nanomaterials. It provides a comprehensive survey of 2D materials (graphene, MXenes, and transition-metal oxides/dichalcogenides/sulfides) employed in supercapacitors using WIS/DES electrolytes. The synthesis and characterization of various 2D materials along with their electrochemical performances in WIS and DES electrolyte systems are described. In addition, the challenges and opportunities for the next-generation supercapacitor devices are summarily discussed. Full article
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Article
Effect of Nanographene Coating on the Seebeck Coefficient of Mesoporous Silicon
Nanomaterials 2023, 13(7), 1254; https://doi.org/10.3390/nano13071254 - 01 Apr 2023
Viewed by 989
Abstract
Nanographene–mesoporous silicon (G-PSi) composites have recently emerged as a promising class of nanomaterials with tuneable physical properties. In this study, we investigated the impact of nanographene coating on the Seebeck coefficient of mesoporous silicon (PSi) obtained by varying two parameters: porosity and thickness. [...] Read more.
Nanographene–mesoporous silicon (G-PSi) composites have recently emerged as a promising class of nanomaterials with tuneable physical properties. In this study, we investigated the impact of nanographene coating on the Seebeck coefficient of mesoporous silicon (PSi) obtained by varying two parameters: porosity and thickness. To achieve this, an electrochemical etching process on p + doped Si is presented for the control of the parameters (thicknesses varying from 20 to 160 µm, and a porosity close to 50%), and for nanographene incorporation through chemical vapor deposition. Raman and XPS spectroscopies confirmed the presence of nanographene on PSi. Using a homemade ZT meter, the Seebeck coefficient of the p + doped Si matrix was evaluated at close to 100 ± 15 µV/K and confirmed by UPS spectroscopy analysis. Our findings suggest that the Seebeck coefficient of the porous Si can be measured independently from that of the substrate by fitting measurements on samples with a different thickness of the porous layer. The value of the Seebeck coefficient for the porous Si is of the order of 750 ± 40 µV/K. Furthermore, the incorporation of nanographene induced a drastic decrease to approximately 120 ± 15 µV/K, a value similar to that of its silicon substrate. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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Article
Monitoring the Surface Energy Change of Nanoparticles in Functionalization Reactions with the NanoTraPPED Method
Nanomaterials 2023, 13(7), 1246; https://doi.org/10.3390/nano13071246 - 31 Mar 2023
Viewed by 544
Abstract
Performing chemical functionalization on the surface of nanoparticles underlies their use in applications. Probing that a physicochemical transformation has indeed occurred on a nanoparticles’ surface is rather difficult. For this reason, we propose that a macroscopic parameter, namely the surface energy γ, can [...] Read more.
Performing chemical functionalization on the surface of nanoparticles underlies their use in applications. Probing that a physicochemical transformation has indeed occurred on a nanoparticles’ surface is rather difficult. For this reason, we propose that a macroscopic parameter, namely the surface energy γ, can monitor the physicochemical transformations taking place at the surface of nanoparticles. Determining the surface energy of macroscopic surfaces is trivial, but it is very challenging for nanoparticles. In this work we demonstrate that the Nanoparticles Trapped on Polymerized Pickering Emulsion Droplet (NanoTraPPED) method can be successfully deployed to monitor the evolution of surface energies γ, with its γp polar and γd dispersive components of the silica nanoparticles at each stage of two surface reactions: (i) amination by siloxane chemistry, coupling reaction of a 2,4-dihydroxy benzaldehyde and formation of a Schiff base ligand, followed by coordination of metal ions and (ii) epoxide ring opening and formation of azide. The change in surface energy and its components are discussed and analyzed for each step of the two reactions. It is observed that large variations in surface energy are observed with the complexity of the molecular structure attaching to nanoparticle surface, while functional group replacement leads to only small changes in the surface energies. Full article
(This article belongs to the Special Issue Morphological Design and Synthesis of Nanoparticles)
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Article
Nitrogen-Doped Graphene Oxide as Efficient Metal-Free Electrocatalyst in PEM Fuel Cells
Nanomaterials 2023, 13(7), 1233; https://doi.org/10.3390/nano13071233 - 30 Mar 2023
Viewed by 751
Abstract
Nitrogen-doped graphene is currently recognized as one of the most promising catalysts for the oxygen reduction reaction (ORR). It has been demonstrated to act as a metal-free electrode with good electrocatalytic activity and long-term operation stability, excellent for the ORR in proton exchange [...] Read more.
Nitrogen-doped graphene is currently recognized as one of the most promising catalysts for the oxygen reduction reaction (ORR). It has been demonstrated to act as a metal-free electrode with good electrocatalytic activity and long-term operation stability, excellent for the ORR in proton exchange membrane fuel cells (PEMFCs). As a consequence, intensive research has been dedicated to the investigation of this catalyst through varying the methodologies for the synthesis, characterization, and technologies improvement. A simple, scalable, single-step synthesis method for nitrogen-doped graphene oxide preparation was adopted in this paper. The physical and chemical properties of various materials obtained from different precursors have been evaluated and compared, leading to the conclusion that ammonia allows for a higher resulting nitrogen concentration, due to its high vapor pressure, which facilitates the functionalization reaction of graphene oxide. Electrochemical measurements indicated that the presence of nitrogen-doped oxide can effectively enhance the electrocatalytic activity and stability for ORR, making it a viable candidate for practical application as a PEMFC cathode electrode. Full article
(This article belongs to the Special Issue Nanomaterials for Chemical Engineering (Volume II))
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Article
A Novel Drastic Peptide Genetically Adapted to Biomimetic Scaffolds “Delivers” Osteogenic Signals to Human Mesenchymal Stem Cells
Nanomaterials 2023, 13(7), 1236; https://doi.org/10.3390/nano13071236 - 30 Mar 2023
Viewed by 851
Abstract
This work describes the design, preparation, and deep investigation of “intelligent nanobiomaterials” that fulfill the safety rules and aim to serve as “signal deliverers” for osteogenesis, harboring a specific peptide that promotes and enhances osteogenesis at the end of their hydrogel fibers. The [...] Read more.
This work describes the design, preparation, and deep investigation of “intelligent nanobiomaterials” that fulfill the safety rules and aim to serve as “signal deliverers” for osteogenesis, harboring a specific peptide that promotes and enhances osteogenesis at the end of their hydrogel fibers. The de novo synthesized protein fibers, besides their mechanical properties owed to their protein constituents from elastin, silk fibroin and mussel-foot adhesive protein-1 as well as to cell-attachment peptides from extracellular matrix glycoproteins, incorporate the Bone Morphogenetic Protein-2 (BMP2) peptide (AISMLYLDEN) that, according to our studies, serves as “signal deliverer” for osteogenesis. The osteogenetic capacity of the biomaterial has been evidenced by investigating the osteogenic marker genes ALP, RUNX2, Osteocalcin, COL1A1, BMPR1A, and BMPR2, which were increased drastically in cells cultured on scaffold-BMP2 for 21 days, even in the absence of osteogenesis medium. In addition, the induction of phosphorylation of intracellular Smad-1/5 and Erk-1/2 proteins clearly supported the osteogenetic capacity of the biomaterial. Full article
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Article
Plasma Nitridation Effect on β-Ga2O3 Semiconductors
Nanomaterials 2023, 13(7), 1199; https://doi.org/10.3390/nano13071199 - 28 Mar 2023
Viewed by 650
Abstract
The electrical and optoelectronic performance of semiconductor devices are mainly affected by the presence of defects or crystal imperfections in the semiconductor. Oxygen vacancies are one of the most common defects and are known to serve as electron trap sites whose energy levels [...] Read more.
The electrical and optoelectronic performance of semiconductor devices are mainly affected by the presence of defects or crystal imperfections in the semiconductor. Oxygen vacancies are one of the most common defects and are known to serve as electron trap sites whose energy levels are below the conduction band (CB) edge for metal oxide semiconductors, including β-Ga2O3. In this study, the effects of plasma nitridation (PN) on polycrystalline β-Ga2O3 thin films are discussed. In detail, the electrical and optical properties of polycrystalline β-Ga2O3 thin films are compared at different PN treatment times. The results show that PN treatment on polycrystalline β-Ga2O3 thin films effectively diminish the electron trap sites. This PN treatment technology could improve the device performance of both electronics and optoelectronics. Full article
(This article belongs to the Special Issue Ga2O3-Based Nanomaterials)
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Article
Optoelectrical Properties of Transparent Conductive Films Fabricated with Ag Nanoparticle-Suspended Emulsion under Various Formulations and Coating Conditions
Nanomaterials 2023, 13(7), 1191; https://doi.org/10.3390/nano13071191 - 27 Mar 2023
Viewed by 524
Abstract
Transparent conductive films (TCFs) were fabricated through bar-coating with a water-in-toluene emulsion containing Ag nanoparticles (AgNPs). Morphological changes in the self-assembled TCF networks under different emulsion formulations and coating conditions and the corresponding optoelectrical properties were investigated. In preparing various emulsions, the concentration [...] Read more.
Transparent conductive films (TCFs) were fabricated through bar-coating with a water-in-toluene emulsion containing Ag nanoparticles (AgNPs). Morphological changes in the self-assembled TCF networks under different emulsion formulations and coating conditions and the corresponding optoelectrical properties were investigated. In preparing various emulsions, the concentration of AgNPs and the water weight fraction were important factors for determining the size of the water droplets, which plays a decisive role in controlling the optoelectrical properties of the TCFs affected by open cells and conductive lines. An increased concentration of AgNPs and decreased water weight fraction resulted in a decreased droplet size, thus altering the optoelectrical properties. The coating conditions, such as coating thickness and drying temperature, changed the degree of water droplet coalescence due to different emulsion drying rates, which also affected the final self-assembled network structure and optoelectrical properties of the TCFs. Systematically controlling various material and process conditions, we explored a coating strategy to enhance the optoelectrical properties of TCFs, resulting in an achieved transmittance of 86 ± 0.2%, a haze of 4 ± 0.2%, and a sheet resistance of 35 ± 2.8 Ω/□. TCFs with such optimal properties can be applied to touch screen fields. Full article
(This article belongs to the Special Issue Self-Assembly Phenomenon in Nanoscale Systems)
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Review
The Potential of ICP-MS as a Complementary Tool in Nanoparticle–Protein Corona Analysis
Nanomaterials 2023, 13(6), 1132; https://doi.org/10.3390/nano13061132 - 22 Mar 2023
Viewed by 774
Abstract
The prolific applicability of nanomaterials has made them a common citizen in biological systems, where they interact with proteins forming a biological corona complex. These complexes drive the interaction of nanomaterials with and within the cells, bringing forward numerous potential applications in nanobiomedicine, [...] Read more.
The prolific applicability of nanomaterials has made them a common citizen in biological systems, where they interact with proteins forming a biological corona complex. These complexes drive the interaction of nanomaterials with and within the cells, bringing forward numerous potential applications in nanobiomedicine, but also arising toxicological issues and concerns. Proper characterization of the protein corona complex is a great challenge typically handled with the combination of several techniques. Surprisingly, despite inductively coupled plasma mass spectrometry (ICP-MS) being a powerful quantitative technique whose application in nanomaterials characterization and quantification has been consolidated in the last decade, its application to nanoparticle–protein corona studies is scarce. Furthermore, in the last decades, ICP-MS has experienced a turning point in its capabilities for protein quantification through sulfur detection, hence becoming a generic quantitative detector. In this regard, we would like to introduce the potential of ICP-MS in the nanoparticle protein corona complex characterization and quantification complementary to current methods and protocols. Full article
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Article
A DFT Study of Ruthenium fcc Nano-Dots: Size-Dependent Induced Magnetic Moments
Nanomaterials 2023, 13(6), 1118; https://doi.org/10.3390/nano13061118 - 21 Mar 2023
Viewed by 728
Abstract
Many areas of electronics, engineering and manufacturing rely on ferromagnetic materials, including iron, nickel and cobalt. Very few other materials have an innate magnetic moment rather than induced magnetic properties, which are more common. However, in a previous study of ruthenium nanoparticles, the [...] Read more.
Many areas of electronics, engineering and manufacturing rely on ferromagnetic materials, including iron, nickel and cobalt. Very few other materials have an innate magnetic moment rather than induced magnetic properties, which are more common. However, in a previous study of ruthenium nanoparticles, the smallest nano-dots showed significant magnetic moments. Furthermore, ruthenium nanoparticles with a face-centred cubic (fcc) packing structure exhibit high catalytic activity towards several reactions and such catalysts are of special interest for the electrocatalytic production of hydrogen. Previous calculations have shown that the energy per atom resembles that of the bulk energy per atom when the surface-to-bulk ratio < 1, but in its smallest form, nano-dots exhibit a range of other properties. Therefore, in this study, we have carried out calculations based on the density functional theory (DFT) with long-range dispersion corrections DFT-D3 and DFT-D3-(BJ) to systematically investigate the magnetic moments of two different morphologies and various sizes of Ru nano-dots in the fcc phase. To confirm the results obtained by the plane-wave DFT methodologies, additional atom-centred DFT calculations were carried out on the smallest nano-dots to establish accurate spin-splitting energetics. Surprisingly, we found that in most cases, the high spin electronic structures had the most favourable energies and were hence the most stable. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
The Application of Nanofibrous Resonant Membranes for Room Acoustics
Nanomaterials 2023, 13(6), 1115; https://doi.org/10.3390/nano13061115 - 21 Mar 2023
Viewed by 515
Abstract
Solitary sound absorbing elements exist; however, their construction is massive and heavy, which largely limits their use. These elements are generally made of porous materials that serve to reduce the amplitude of the reflected sound waves. Materials based on the resonance principle (oscillating [...] Read more.
Solitary sound absorbing elements exist; however, their construction is massive and heavy, which largely limits their use. These elements are generally made of porous materials that serve to reduce the amplitude of the reflected sound waves. Materials based on the resonance principle (oscillating membranes, plates, and Helmholtz’s resonators) can also be used for sound absorption. A limitation of these elements is the absorption of a very narrow sound band to which these elements are “tuned”. For other frequencies, the absorption is very low. The aim of the solution is to achieve a high sound absorption efficiency at a very low weight. A nanofibrous membrane was used to create high sound absorption in synergy with special grids working as a cavity resonator. Prototypes of the nanofibrous resonant membrane on a grid with a thickness of 2 mm and an air gap of 50 mm already showed a high level of sound absorption (0.6–0.8) at a frequency of 300 Hz, which is a very unique result. Since acoustic elements, i.e., lighting, tiles, and ceilings, are designed for interiors, an essential part of the research is also the achievement of the lighting function and the emphasis on aesthetic design. Full article
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Article
Fine Structure Splitting of Phonon-Assisted Excitonic Transition in (PEA)2PbI4 Two-Dimensional Perovskites
Nanomaterials 2023, 13(6), 1119; https://doi.org/10.3390/nano13061119 - 21 Mar 2023
Viewed by 943
Abstract
Two-dimensional van der Waals materials exhibit particularly strong excitonic effects, which causes them to be an exceptionally interesting platform for the investigation of exciton physics. A notable example is the two-dimensional Ruddlesden–Popper perovskites, where quantum and dielectric confinement together with soft, polar, and [...] Read more.
Two-dimensional van der Waals materials exhibit particularly strong excitonic effects, which causes them to be an exceptionally interesting platform for the investigation of exciton physics. A notable example is the two-dimensional Ruddlesden–Popper perovskites, where quantum and dielectric confinement together with soft, polar, and low symmetry lattice create a unique background for electron and hole interaction. Here, with the use of polarization-resolved optical spectroscopy, we have demonstrated that the simultaneous presence of tightly bound excitons, together with strong exciton–phonon coupling, allows for observing the exciton fine structure splitting of the phonon-assisted transitions of two-dimensional perovskite (PEA)2PbI4, where PEA stands for phenylethylammonium. We demonstrate that the phonon-assisted sidebands characteristic for (PEA)2PbI4 are split and linearly polarized, mimicking the characteristics of the corresponding zero-phonon lines. Interestingly, the splitting of differently polarized phonon-assisted transitions can be different from that of the zero-phonon lines. We attribute this effect to the selective coupling of linearly polarized exciton states to non-degenerate phonon modes of different symmetries resulting from the low symmetry of (PEA)2PbI4 lattice. Full article
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Article
Enhanced Electroluminescence from a Silicon Nanocrystal/Silicon Carbide Multilayer Light-Emitting Diode
Nanomaterials 2023, 13(6), 1109; https://doi.org/10.3390/nano13061109 - 20 Mar 2023
Viewed by 717
Abstract
Developing high-performance Si-based light-emitting devices is the key step to realizing all-Si-based optical telecommunication. Usually, silica (SiO2) as the host matrix is used to passivate silicon nanocrystals, and a strong quantum confinement effect can be observed due to the large band [...] Read more.
Developing high-performance Si-based light-emitting devices is the key step to realizing all-Si-based optical telecommunication. Usually, silica (SiO2) as the host matrix is used to passivate silicon nanocrystals, and a strong quantum confinement effect can be observed due to the large band offset between Si and SiO2 (~8.9 eV). Here, for further development of device properties, we fabricate Si nanocrystals (NCs)/SiC multilayers and study the changes in photoelectric properties of the LEDs induced by P dopants. PL peaks centered at 500 nm, 650 nm and 800 nm can be detected, which are attributed to surface states between SiC and Si NCs, amorphous SiC and Si NCs, respectively. PL intensities are first enhanced and then decreased after introducing P dopants. It is believed that the enhancement is due to passivation of the Si dangling bonds at the surface of Si NCs, while the suppression is ascribed to enhanced Auger recombination and new defects induced by excessive P dopants. Un-doped and P-doped LEDs based on Si NCs/SiC multilayers are fabricated and the performance is enhanced greatly after doping. As fitted, emission peaks near 500 nm and 750 nm can be detected. The current density-voltage properties indicate that the carrier transport process is dominated by FN tunneling mechanisms, while the linear relationship between the integrated EL intensity and injection current illustrates that the EL mechanism is attributed to recombination of electron–hole pairs at Si NCs induced by bipolar injection. After doping, the integrated EL intensities are enhanced by about an order of magnitude, indicating that EQE is greatly improved. Full article
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Review
Graphene-Related Nanomaterials for Biomedical Applications
Nanomaterials 2023, 13(6), 1092; https://doi.org/10.3390/nano13061092 - 17 Mar 2023
Viewed by 1375
Abstract
This paper builds on the context and recent progress on the control, reproducibility, and limitations of using graphene and graphene-related materials (GRMs) in biomedical applications. The review describes the human hazard assessment of GRMs in in vitro and in vivo studies, highlights the [...] Read more.
This paper builds on the context and recent progress on the control, reproducibility, and limitations of using graphene and graphene-related materials (GRMs) in biomedical applications. The review describes the human hazard assessment of GRMs in in vitro and in vivo studies, highlights the composition–structure–activity relationships that cause toxicity for these substances, and identifies the key parameters that determine the activation of their biological effects. GRMs are designed to offer the advantage of facilitating unique biomedical applications that impact different techniques in medicine, especially in neuroscience. Due to the increasing utilization of GRMs, there is a need to comprehensively assess the potential impact of these materials on human health. Various outcomes associated with GRMs, including biocompatibility, biodegradability, beneficial effects on cell proliferation, differentiation rates, apoptosis, necrosis, autophagy, oxidative stress, physical destruction, DNA damage, and inflammatory responses, have led to an increasing interest in these regenerative nanostructured materials. Considering the existence of graphene-related nanomaterials with different physicochemical properties, the materials are expected to exhibit unique modes of interactions with biomolecules, cells, and tissues depending on their size, chemical composition, and hydrophil-to-hydrophobe ratio. Understanding such interactions is crucial from two perspectives, namely, from the perspectives of their toxicity and biological uses. The main aim of this study is to assess and tune the diverse properties that must be considered when planning biomedical applications. These properties include flexibility, transparency, surface chemistry (hydrophil–hydrophobe ratio), thermoelectrical conductibility, loading and release capacity, and biocompatibility. Full article
(This article belongs to the Special Issue Next-Generation Nanomaterials: Preparation and Applications)
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Review
Innovative Approaches to Semi-Transparent Perovskite Solar Cells
Nanomaterials 2023, 13(6), 1084; https://doi.org/10.3390/nano13061084 - 16 Mar 2023
Viewed by 1623
Abstract
Perovskite solar cells (PSCs) are advancing rapidly and have reached a performance comparable to that of silicon solar cells. Recently, they have been expanding into a variety of applications based on the excellent photoelectric properties of perovskite. Semi-transparent PSCs (ST-PSCs) are one promising [...] Read more.
Perovskite solar cells (PSCs) are advancing rapidly and have reached a performance comparable to that of silicon solar cells. Recently, they have been expanding into a variety of applications based on the excellent photoelectric properties of perovskite. Semi-transparent PSCs (ST-PSCs) are one promising application that utilizes the tunable transmittance of perovskite photoactive layers, which can be used in tandem solar cells (TSC) and building-integrated photovoltaics (BIPV). However, the inverse relationship between light transmittance and efficiency is a challenge in the development of ST-PSCs. To overcome these challenges, numerous studies are underway, including those on band-gap tuning, high-performance charge transport layers and electrodes, and creating island-shaped microstructures. This review provides a general and concise summary of the innovative approaches in ST-PSCs, including advances in the perovskite photoactive layer, transparent electrodes, device structures and their applications in TSC and BIPV. Furthermore, the essential requirements and challenges to be addressed to realize ST-PSCs are discussed, and the prospects of ST-PSCs are presented. Full article
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Article
WO3 Nanorods Decorated with Very Small Amount of Pt for Effective Hydrogen Evolution Reaction
Nanomaterials 2023, 13(6), 1071; https://doi.org/10.3390/nano13061071 - 16 Mar 2023
Viewed by 652
Abstract
The electrochemical hydrogen evolution reaction (HER) is one of the most promising green methods for the efficient production of renewable and sustainable H2, for which platinum possesses the highest catalytic activity. Cost-effective alternatives can be obtained by reducing the Pt amount [...] Read more.
The electrochemical hydrogen evolution reaction (HER) is one of the most promising green methods for the efficient production of renewable and sustainable H2, for which platinum possesses the highest catalytic activity. Cost-effective alternatives can be obtained by reducing the Pt amount and still preserving its activity. The Pt nanoparticle decoration of suitable current collectors can be effectively realized by using transition metal oxide (TMO) nanostructures. Among them, WO3 nanorods are the most eligible option, thanks to their high stability in acidic environments, and large availability. Herein, a simple and affordable hydrothermal route is used for the synthesis of hexagonal WO3 nanorods (average length and diameter of 400 and 50 nm, respectively), whose crystal structure is modified after annealing at 400 °C for 60 min, to obtain a mixed hexagonal/monoclinic crystal structure. These nanostructures were investigated as support for the ultra-low-Pt nanoparticles (0.2–1.13 μg/cm2): decoration occurs by drop casting some drops of a Pt nanoparticle aqueous solution and the electrodes were tested for the HER in acidic environment. Pt-decorated WO3 nanorods were characterized by performing scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Rutherford backscattering spectrometry (RBS), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and chronopotentiometry. HER catalytic activity is studied as a function of the total Pt nanoparticle loading, thus obtaining an outstanding overpotential of 32 mV at 10 mA/cm2, a Tafel slope of 31 mV/dec, a turn-over frequency of 5 Hz at −15 mV, and a mass activity of 9 A/mg at 10 mA/cm2 for the sample decorated with the highest Pt amount (1.13 μg/cm2). These data show that WO3 nanorods act as excellent supports for the development of an ultra-low-Pt-amount-based cathode for efficient and low-cost electrochemical HER. Full article
(This article belongs to the Topic Hydrogen Production Processes)
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Article
Additive Manufacturing and Combustion Characteristics of Polyethylene Oxide/Aluminum/Copper Oxide-Based Energetic Nanocomposites for Enhancing the Propulsion of Small Projectiles
Nanomaterials 2023, 13(6), 1052; https://doi.org/10.3390/nano13061052 - 15 Mar 2023
Viewed by 707
Abstract
The application of nanoscale energetic materials (nEMs) composed of metal and oxidizer nanoparticles (NPs) in thermal engineering systems is limited by their relatively high sensitivity and complex three-dimensional (3D) formability. Polymers can be added to nEMs to lower the sensitivity and improve the [...] Read more.
The application of nanoscale energetic materials (nEMs) composed of metal and oxidizer nanoparticles (NPs) in thermal engineering systems is limited by their relatively high sensitivity and complex three-dimensional (3D) formability. Polymers can be added to nEMs to lower the sensitivity and improve the formability of 3D structures. In this study, the effect of the addition of polyethylene oxide (PEO; polymer) on the combustion characteristics of aluminum (Al; fuel)/copper oxide (CuO; oxidizer)-based nEMs is investigated. With an increase in the PEO content, the resulting PEO/nEM composites are desensitized to relatively high electrical spark discharges. However, the maximum explosion-induced pressure decreases significantly, and the combustion flame fails to propagate when the PEO content exceeds 15 wt.%. Therefore, the optimal PEO content in a nEM matrix must be accurately determined to achieve a compromise between sensitivity and reactivity. To demonstrate their potential application as composite solid propellants (CSPs), 3D-printed disks composed of PEO/nEM composites were assembled using additive manufacturing. They were cross-stacked with conventional potassium nitrate (KNO3)/sucrose (C12H22O11)-based disk-shaped CSPs in a combustion chamber of small rocket motors. Propulsion tests indicated that the specific impulse of KNSU/PEO/nEM (nEMs: 3.4 wt.%)-based CSPs was at a maximum value, which is approximately three times higher than that of KNSU CSPs without nEMs. This suggests that the addition of an optimized amount of polymer to nEMs is beneficial for various CSPs with compromised sensitivity and reactivity and excellent 3D formability, which can significantly enhance the propulsion of small projectiles. Full article
(This article belongs to the Section Nanocomposite Materials)
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Article
Single-Walled vs. Multi-Walled Carbon Nanotubes: Influence of Physico-Chemical Properties on Toxicogenomics Responses in Mouse Lungs
Nanomaterials 2023, 13(6), 1059; https://doi.org/10.3390/nano13061059 - 15 Mar 2023
Cited by 1 | Viewed by 940
Abstract
Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) are nanomaterials with one or multiple layers of carbon sheets. While it is suggested that various properties influence their toxicity, the specific mechanisms are not completely known. This study was aimed to determine if [...] Read more.
Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) are nanomaterials with one or multiple layers of carbon sheets. While it is suggested that various properties influence their toxicity, the specific mechanisms are not completely known. This study was aimed to determine if single or multi-walled structures and surface functionalization influence pulmonary toxicity and to identify the underlying mechanisms of toxicity. Female C57BL/6J BomTac mice were exposed to a single dose of 6, 18, or 54 μg/mouse of twelve SWCNTs or MWCNTs of different properties. Neutrophil influx and DNA damage were assessed on days 1 and 28 post-exposure. Genome microarrays and various bioinformatics and statistical methods were used to identify the biological processes, pathways and functions altered post-exposure to CNTs. All CNTs were ranked for their potency to induce transcriptional perturbation using benchmark dose modelling. All CNTs induced tissue inflammation. MWCNTs were more genotoxic than SWCNTs. Transcriptomics analysis showed similar responses across CNTs at the pathway level at the high dose, which included the perturbation of inflammatory, cellular stress, metabolism, and DNA damage responses. Of all CNTs, one pristine SWCNT was found to be the most potent and potentially fibrogenic, so it should be prioritized for further toxicity testing. Full article
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Article
Exploring the Role of Miniemulsion Nanodroplet Confinement on the Crystallization of MoO3: Morphology Control and Insight on Crystal Formation by In Situ Time-Resolved SAXS/WAXS
Nanomaterials 2023, 13(6), 1046; https://doi.org/10.3390/nano13061046 - 14 Mar 2023
Viewed by 526
Abstract
Enclosed nanoscale volumes, i.e., confined spaces, represent a fascinating playground for the controlled synthesis of inorganic materials, albeit their role in determining the synthetic outcome is currently not fully understood. Herein, we address the synthesis of MoO3 nano- and microrods with hexagonal [...] Read more.
Enclosed nanoscale volumes, i.e., confined spaces, represent a fascinating playground for the controlled synthesis of inorganic materials, albeit their role in determining the synthetic outcome is currently not fully understood. Herein, we address the synthesis of MoO3 nano- and microrods with hexagonal section in inverse miniemulsion droplets and batch conditions, evaluating the effects of spatial confinement offered by miniemulsion droplets on their crystallization. Several synthetic parameters were systematically screened and their effect on the crystal structure of h-MoO3, as well as on its size, size distribution and morphology, were investigated. Moreover, a direct insight on the crystallization pathway of MoO3 in both synthetic conditions and as a function of synthetic parameters was provided by an in situ time-resolved SAXS/WAXS study, that confirmed the role of miniemulsion confined space in altering the stepwise process of the formation of h-MoO3. Full article
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Review
Recent Advances in Metal-Based NanoEnhancers for Particle Therapy
Nanomaterials 2023, 13(6), 1011; https://doi.org/10.3390/nano13061011 - 10 Mar 2023
Viewed by 799
Abstract
Radiotherapy is one of the most common therapeutic regimens for cancer treatment. Over the past decade, proton therapy (PT) has emerged as an advanced type of radiotherapy (RT) that uses proton beams instead of conventional photon RT. Both PT and carbon-ion beam therapy [...] Read more.
Radiotherapy is one of the most common therapeutic regimens for cancer treatment. Over the past decade, proton therapy (PT) has emerged as an advanced type of radiotherapy (RT) that uses proton beams instead of conventional photon RT. Both PT and carbon-ion beam therapy (CIBT) exhibit excellent therapeutic results because of the physical characteristics of the resulting Bragg peaks, which has been exploited for cancer treatment in medical centers worldwide. Although particle therapies show significant advantages to photon RT by minimizing the radiation damage to normal tissue after the tumors, they still cause damage to normal tissue before the tumor. Since the physical mechanisms are different from particle therapy and photon RT, efforts have been made to ameliorate these effects by combining nanomaterials and particle therapies to improve tumor targeting by concentrating the radiation effects. Metallic nanoparticles (MNPs) exhibit many unique properties, such as strong X-ray absorption cross-sections and catalytic activity, and they are considered nano-radioenhancers (NREs) for RT. In this review, we systematically summarize the putative mechanisms involved in NRE-induced radioenhancement in particle therapy and the experimental results in in vitro and in vivo models. We also discuss the potential of translating preclinical metal-based NP-enhanced particle therapy studies into clinical practice using examples of several metal-based NREs, such as SPION, Abraxane, AGuIX, and NBTXR3. Furthermore, the future challenges and development of NREs for PT are presented for clinical translation. Finally, we propose a roadmap to pursue future studies to strengthen the interplay of particle therapy and nanomedicine. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Biophotonics: Prognosis and Therapeutics)
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Review
Investigation of Soft Matter Nanomechanics by Atomic Force Microscopy and Optical Tweezers: A Comprehensive Review
Nanomaterials 2023, 13(6), 963; https://doi.org/10.3390/nano13060963 - 07 Mar 2023
Cited by 7 | Viewed by 1618
Abstract
Soft matter exhibits a multitude of intrinsic physico-chemical attributes. Their mechanical properties are crucial characteristics to define their performance. In this context, the rigidity of these systems under exerted load forces is covered by the field of biomechanics. Moreover, cellular transduction processes which [...] Read more.
Soft matter exhibits a multitude of intrinsic physico-chemical attributes. Their mechanical properties are crucial characteristics to define their performance. In this context, the rigidity of these systems under exerted load forces is covered by the field of biomechanics. Moreover, cellular transduction processes which are involved in health and disease conditions are significantly affected by exogenous biomechanical actions. In this framework, atomic force microscopy (AFM) and optical tweezers (OT) can play an important role to determine the biomechanical parameters of the investigated systems at the single-molecule level. This review aims to fully comprehend the interplay between mechanical forces and soft matter systems. In particular, we outline the capabilities of AFM and OT compared to other classical bulk techniques to determine nanomechanical parameters such as Young’s modulus. We also provide some recent examples of nanomechanical measurements performed using AFM and OT in hydrogels, biopolymers and cellular systems, among others. We expect the present manuscript will aid potential readers and stakeholders to fully understand the potential applications of AFM and OT to soft matter systems. Full article
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Article
Clot Imaging Using Photostable Nanodiamond
Nanomaterials 2023, 13(6), 961; https://doi.org/10.3390/nano13060961 - 07 Mar 2023
Viewed by 722
Abstract
While thrombosis is the leading cause of morbidity and mortality in the United States, an understanding of its triggers, progression, and response to anticoagulant therapy is lacking. Intravital fluorescence microscopy has advanced the study of thrombus formation by providing targeted, multi-color contrast. However, [...] Read more.
While thrombosis is the leading cause of morbidity and mortality in the United States, an understanding of its triggers, progression, and response to anticoagulant therapy is lacking. Intravital fluorescence microscopy has advanced the study of thrombus formation by providing targeted, multi-color contrast. However, photodegradation of fluorophores limits the application in longitudinal studies (e.g., clot progression and/or dissolution). Fluorescent nanodiamond (FND) is a fluorophore which utilizes intrinsic fluorescence of chromogenic centers within and protected by the diamond crystalline lattice. Recent developments in diamond processing have allowed for the controlled production of nanodiamonds emitting in green or red. Here, the use of FND to label blood clots and/or clot lysis is demonstrated and compared to commonly used organic fluorophores. Model ex vivo clots were formed with incorporated labeled fibrinogen to allow imaging. FND was shown to match the morphology of organic fluorophore labels absent of photobleaching over time. The addition of tissue plasminogen activator (tPa) allowed visualization of the clot lysis stage, which is vital to studies of both DVT and pulmonary embolism resolution. Full article
(This article belongs to the Special Issue Nanodiamond Applications: From Biomedicine to Quantum Optics)
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Article
Novel Rare Earth (RE)-Free Nanocomposite Magnets Derived from L10-Phase Systems
Nanomaterials 2023, 13(5), 912; https://doi.org/10.3390/nano13050912 - 01 Mar 2023
Viewed by 744
Abstract
In the quest for novel rare earth (RE)-free magnetic materials, which also exhibit other additional properties such as good corrosion resistance and potential to operate at higher temperatures, an alloy deriving from the binary FePt system, with Mo and B addition, has been [...] Read more.
In the quest for novel rare earth (RE)-free magnetic materials, which also exhibit other additional properties such as good corrosion resistance and potential to operate at higher temperatures, an alloy deriving from the binary FePt system, with Mo and B addition, has been synthesized for the first time, using the out-of-equilibrium method of rapid solidification form the melt. The alloy with the composition Fe49Pt26Mo2B23 has been subjected to thermal analysis through differential scanning calorimetry in order to detect the structural disorder – order phase transformation as well as to study the crystallization processes. For the stabilization of the formed hard magnetic phase, the sample has been annealed at 600 °C and further structurally and magnetically characterized by means of X-ray diffraction, transmission electron microscopy, 57Fe Mössbauer spectrometry as well as magnetometry experiments. It has been proven that after annealing at 600 °C the tetragonal hard magnetic L10 phase emerges via crystallization from a disordered cubic precursor and becomes the predominant phase in terms of relative abundance. Moreover, it has been revealed by quantitative analysis via Mössbauer spectroscopy that the annealed sample exhibits a complex phase structure, where the L10 hard magnetic phase is accompanied by few other soft magnetic phases, in minority abundance: the cubic A1, orthorhombic Fe2B and residual intergranular region. The magnetic parameters have been derived from 300 K hysteresis loops. It was shown that, contrary to the as-cast sample which behaves as a typical soft magnet, the annealed sample presents strong coercivity and high remanent magnetization, accompanied by a large saturation magnetization. These findings offers good insight into the potential developing of novel class of RE-free permanent magnets, based on Fe-Pt-Mo-B, where the magnetic performance emerges from the co-existence of hard and soft magnetic phases in controlled and tunable proportions, capable of finding good applicability in fields requiring good catalytic properties and strong corrosion resistance. Full article
(This article belongs to the Special Issue Novel RE-free Nanocomposite Magnets)
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Article
Templated Synthesis of Diamond Nanopillar Arrays Using Porous Anodic Aluminium Oxide (AAO) Membranes
Nanomaterials 2023, 13(5), 888; https://doi.org/10.3390/nano13050888 - 27 Feb 2023
Viewed by 1026
Abstract
Diamond nanostructures are mostly produced from bulk diamond (single- or polycrystalline) by using time-consuming and/or costly subtractive manufacturing methods. In this study, we report the bottom-up synthesis of ordered diamond nanopillar arrays by using porous anodic aluminium oxide (AAO). Commercial ultrathin AAO membranes [...] Read more.
Diamond nanostructures are mostly produced from bulk diamond (single- or polycrystalline) by using time-consuming and/or costly subtractive manufacturing methods. In this study, we report the bottom-up synthesis of ordered diamond nanopillar arrays by using porous anodic aluminium oxide (AAO). Commercial ultrathin AAO membranes were adopted as the growth template in a straightforward, three-step fabrication process involving chemical vapor deposition (CVD) and the transfer and removal of the alumina foils. Two types of AAO membranes with distinct nominal pore size were employed and transferred onto the nucleation side of CVD diamond sheets. Subsequently, diamond nanopillars were grown directly on these sheets. After removal of the AAO template by chemical etching, ordered arrays of submicron and nanoscale diamond pillars with ~325 nm and ~85 nm diameters were successfully released. Full article
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Review
In Vitro Models of Bacterial Biofilms: Innovative Tools to Improve Understanding and Treatment of Infections
Nanomaterials 2023, 13(5), 904; https://doi.org/10.3390/nano13050904 - 27 Feb 2023
Viewed by 1176
Abstract
Bacterial infections are a growing concern to the health care systems. Bacteria in the human body are often found embedded in a dense 3D structure, the biofilm, which makes their eradication even more challenging. Indeed, bacteria in biofilm are protected from external hazards [...] Read more.
Bacterial infections are a growing concern to the health care systems. Bacteria in the human body are often found embedded in a dense 3D structure, the biofilm, which makes their eradication even more challenging. Indeed, bacteria in biofilm are protected from external hazards and are more prone to develop antibiotic resistance. Moreover, biofilms are highly heterogeneous, with properties dependent on the bacteria species, the anatomic localization, and the nutrient/flow conditions. Therefore, antibiotic screening and testing would strongly benefit from reliable in vitro models of bacterial biofilms. This review article summarizes the main features of biofilms, with particular focus on parameters affecting biofilm composition and mechanical properties. Moreover, a thorough overview of the in vitro biofilm models recently developed is presented, focusing on both traditional and advanced approaches. Static, dynamic, and microcosm models are described, and their main features, advantages, and disadvantages are compared and discussed. Full article
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Review
Adaptive 2D and Pseudo-2D Systems: Molecular, Polymeric, and Colloidal Building Blocks for Tailored Complexity
Nanomaterials 2023, 13(5), 855; https://doi.org/10.3390/nano13050855 - 25 Feb 2023
Viewed by 1665
Abstract
Two-dimensional and pseudo-2D systems come in various forms. Membranes separating protocells from the environment were necessary for life to occur. Later, compartmentalization allowed for the development of more complex cellular structures. Nowadays, 2D materials (e.g., graphene, molybdenum disulfide) are revolutionizing the smart materials [...] Read more.
Two-dimensional and pseudo-2D systems come in various forms. Membranes separating protocells from the environment were necessary for life to occur. Later, compartmentalization allowed for the development of more complex cellular structures. Nowadays, 2D materials (e.g., graphene, molybdenum disulfide) are revolutionizing the smart materials industry. Surface engineering allows for novel functionalities, as only a limited number of bulk materials have the desired surface properties. This is realized via physical treatment (e.g., plasma treatment, rubbing), chemical modifications, thin film deposition (using both chemical and physical methods), doping and formulation of composites, or coating. However, artificial systems are usually static. Nature creates dynamic and responsive structures, which facilitates the formation of complex systems. The challenge of nanotechnology, physical chemistry, and materials science is to develop artificial adaptive systems. Dynamic 2D and pseudo-2D designs are needed for future developments of life-like materials and networked chemical systems in which the sequences of the stimuli would control the consecutive stages of the given process. This is crucial to achieving versatility, improved performance, energy efficiency, and sustainability. Here, we review the advancements in studies on adaptive, responsive, dynamic, and out-of-equilibrium 2D and pseudo-2D systems composed of molecules, polymers, and nano/microparticles. Full article
(This article belongs to the Special Issue Recent Advances in Surfaces and Interfaces of Nanofilms)
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Article
Block Copolymer Adsorption on the Surface of Multi-Walled Carbon Nanotubes for Dispersion in N,N Dimethyl Formamide
Nanomaterials 2023, 13(5), 838; https://doi.org/10.3390/nano13050838 - 23 Feb 2023
Viewed by 801
Abstract
This research aims to characterize the adsorption morphology of block copolymer dispersants of the styrene-block-4-vinylpyridine family (S4VP) on the surface of multi-walled carbon nanotubes (MWCNT) in a polar organic solvent, N,N-dimethyl formamide (DMF). Good, unagglomerated dispersion is important in several [...] Read more.
This research aims to characterize the adsorption morphology of block copolymer dispersants of the styrene-block-4-vinylpyridine family (S4VP) on the surface of multi-walled carbon nanotubes (MWCNT) in a polar organic solvent, N,N-dimethyl formamide (DMF). Good, unagglomerated dispersion is important in several applications such as fabricating CNT nanocomposites in a polymer film for electronic or optical devices. Small-angle neutron scattering (SANS) measurements, using the contrast variation (CV) method, are used to evaluate the density and extension of the polymer chains adsorbed on the nanotube surface, which can yield insight into the means of successful dispersion. The results show that the block copolymers adsorb onto the MWCNT surface as a continuous coverage of low polymer concentration. Poly(styrene) (PS) blocks adsorb more tightly, forming a 20 Å layer containing about 6 wt.% PS, whereas poly(4-vinylpyridine) (P4VP) blocks emanate into the solvent, forming a thicker shell (totaling 110 Å in radius) but of very dilute (<1 wt.%) polymer concentration. This indicates strong chain extension. Increasing the PS molecular weight increases the thickness of the adsorbed layer but decreases the overall polymer concentration within it. These results are relevant for the ability of dispersed CNTs to form a strong interface with matrix polymers in composites, due to the extension of the 4VP chains allowing for entanglement with matrix chains. The sparse polymer coverage of the CNT surface may provide sufficient space to form CNT-CNT contacts in processed films and composites, which are important for electrical or thermal conductivity. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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Article
Proton Therapy, Magnetic Nanoparticles and Hyperthermia as Combined Treatment for Pancreatic BxPC3 Tumor Cells
Nanomaterials 2023, 13(5), 791; https://doi.org/10.3390/nano13050791 - 21 Feb 2023
Viewed by 793
Abstract
We present an investigation of the effects on BxPC3 pancreatic cancer cells of proton therapy combined with hyperthermia, assisted by magnetic fluid hyperthermia performed with the use of magnetic nanoparticles. The cells’ response to the combined treatment has been evaluated by means of [...] Read more.
We present an investigation of the effects on BxPC3 pancreatic cancer cells of proton therapy combined with hyperthermia, assisted by magnetic fluid hyperthermia performed with the use of magnetic nanoparticles. The cells’ response to the combined treatment has been evaluated by means of the clonogenic survival assay and the estimation of DNA Double Strand Breaks (DSBs). The Reactive Oxygen Species (ROS) production, the tumor cell invasion and the cell cycle variations have also been studied. The experimental results have shown that the combination of proton therapy, MNPs administration and hyperthermia gives a clonogenic survival that is much smaller than the single irradiation treatment at all doses, thus suggesting a new effective combined therapy for the pancreatic tumor. Importantly, the effect of the therapies used here is synergistic. Moreover, after proton irradiation, the hyperthermia treatment was able to increase the number of DSBs, even though just at 6 h after the treatment. Noticeably, the magnetic nanoparticles’ presence induces radiosensitization effects, and hyperthermia increases the production of ROS, which contributes to cytotoxic cellular effects and to a wide variety of lesions including DNA damage. The present study indicates a new way for clinical translation of combined therapies, also in the vision of an increasing number of hospitals that will use the proton therapy technique in the near future for different kinds of radio-resistant cancers. Full article
(This article belongs to the Special Issue Functionalized Magnetic Nanomaterials)
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Article
In Situ Observations Reveal the Five-fold Twin-Involved Growth of Gold Nanorods by Particle Attachment
Nanomaterials 2023, 13(5), 796; https://doi.org/10.3390/nano13050796 - 21 Feb 2023
Viewed by 846
Abstract
Crystallization plays a critical role in determining crystal size, purity and morphology. Therefore, uncovering the growth dynamics of nanoparticles (NPs) atomically is important for the controllable fabrication of nanocrystals with desired geometry and properties. Herein, we conducted in situ atomic-scale observations on the [...] Read more.
Crystallization plays a critical role in determining crystal size, purity and morphology. Therefore, uncovering the growth dynamics of nanoparticles (NPs) atomically is important for the controllable fabrication of nanocrystals with desired geometry and properties. Herein, we conducted in situ atomic-scale observations on the growth of Au nanorods (NRs) by particle attachment within an aberration-corrected transmission electron microscope (AC-TEM). The results show that the attachment of spherical colloidal Au NPs with a size of about 10 nm involves the formation and growth of neck-like (NL) structures, followed by five-fold twin intermediate states and total atomic rearrangement. The statistical analyses show that the length and diameter of Au NRs can be well regulated by the number of tip-to-tip Au NPs and the size of colloidal Au NPs, respectively. The results highlight five-fold twin-involved particle attachment in spherical Au NPs with a size of 3–14 nm, and provide insights into the fabrication of Au NRs using irradiation chemistry. Full article
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Article
Bioactive Composite Methacrylated Gellan Gum for 3D-Printed Bone Tissue-Engineered Scaffolds
Nanomaterials 2023, 13(4), 772; https://doi.org/10.3390/nano13040772 - 19 Feb 2023
Cited by 1 | Viewed by 850
Abstract
Gellan gum (GG) was chemically modified with methacrylic moieties to produce a photocrosslinkable biomaterial ink, hereinafter called methacrylated GG (GGMA), with improved physico-chemical properties, mechanical behavior and stability under physiological conditions. Afterwards, GGMA was functionalized by incorporating two different bioactive compounds, a naturally [...] Read more.
Gellan gum (GG) was chemically modified with methacrylic moieties to produce a photocrosslinkable biomaterial ink, hereinafter called methacrylated GG (GGMA), with improved physico-chemical properties, mechanical behavior and stability under physiological conditions. Afterwards, GGMA was functionalized by incorporating two different bioactive compounds, a naturally derived eumelanin extracted from the black soldier fly (BSF-Eumel), or hydroxyapatite nanoparticles (HAp), synthesized by the sol–gel method. Different ink formulations based on GGMA (2 and 4% (w/v)), BSF-Eumel, at a selected concentration (0.3125 mg/mL), or HAp (10 and 30% wHAp/wGGMA) were developed and processed by three-dimensional (3D) printing. All the functionalized GGMA-based ink formulations allowed obtaining 3D-printed GGMA-based scaffolds with a well-organized structure. For both bioactive signals, the scaffolds with the highest GGMA concentration (4% (w/v)) and the highest percentage of infill (45%) showed the best performances in terms of morphological and mechanical properties. Indeed, these scaffolds showed a good structural integrity over 28 days. Given the presence of negatively charged groups along the eumelanin backbone, scaffolds consisting of GGMA/BSF-Eumel demonstrated a higher stability. From a mechanical point of view, GGMA/BSF-Eumel scaffolds exhibited values of storage modulus similar to those of GGMA ones, while the inclusion of HAp at 30% (wHAp/wGGMA) led to a storage modulus of 32.5 kPa, 3.5-fold greater than neat GGMA. In vitro studies proved the capability of the bioactivated 3D-printed scaffolds to support 7F2 osteoblast cell growth and differentiation. BSF-Eumel and HAp triggered a different time-dependent physiological response in the osteoblasts. Specifically, while the ink with BSF-Eumel acted as a stimulus towards cell proliferation, reaching the highest value at 14 days, a higher expression of alkaline phosphatase activity was detected for scaffolds consisting of GGMA and HAp. The overall findings demonstrated the possible use of these biomaterial inks for 3D-printed bone tissue-engineered scaffolds. Full article
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Article
Enhanced Magnetism and Anomalous Hall Transport through Two-Dimensional Tungsten Disulfide Interfaces
Nanomaterials 2023, 13(4), 771; https://doi.org/10.3390/nano13040771 - 18 Feb 2023
Cited by 2 | Viewed by 980
Abstract
The magnetic proximity effect (MPE) has recently been explored to manipulate interfacial properties of two-dimensional (2D) transition metal dichalcogenide (TMD)/ferromagnet heterostructures for use in spintronics and valleytronics. However, a full understanding of the MPE and its temperature and magnetic field evolution in these [...] Read more.
The magnetic proximity effect (MPE) has recently been explored to manipulate interfacial properties of two-dimensional (2D) transition metal dichalcogenide (TMD)/ferromagnet heterostructures for use in spintronics and valleytronics. However, a full understanding of the MPE and its temperature and magnetic field evolution in these systems is lacking. In this study, the MPE has been probed in Pt/WS2/BPIO (biphase iron oxide, Fe3O4 and α-Fe2O3) heterostructures through a comprehensive investigation of their magnetic and transport properties using magnetometry, four-probe resistivity, and anomalous Hall effect (AHE) measurements. Density functional theory (DFT) calculations are performed to complement the experimental findings. We found that the presence of monolayer WS2 flakes reduces the magnetization of BPIO and hence the total magnetization of Pt/WS2/BPIO at T > ~120 K—the Verwey transition temperature of Fe3O4 (TV). However, an enhanced magnetization is achieved at T < TV. In the latter case, a comparative analysis of the transport properties of Pt/WS2/BPIO and Pt/BPIO from AHE measurements reveals ferromagnetic coupling at the WS2/BPIO interface. Our study forms the foundation for understanding MPE-mediated interfacial properties and paves a new pathway for designing 2D TMD/magnet heterostructures for applications in spintronics, opto-spincaloritronics, and valleytronics. Full article
(This article belongs to the Special Issue Nano-Structured Thin Films: Growth, Characteristics, and Application)
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Article
Environmentally Friendly Improvement of Plasmonic Nanostructure Functionality towards Magnetic Resonance Applications
Nanomaterials 2023, 13(4), 764; https://doi.org/10.3390/nano13040764 - 17 Feb 2023
Viewed by 892
Abstract
Plasmonic nanostructures have attracted a broad research interest due to their application perspectives in various fields such as biosensing, catalysis, photovoltaics, and biomedicine. Their synthesis by pulsed laser ablation in pure water enables eliminating various side effects originating from chemical contamination. Another advantage [...] Read more.
Plasmonic nanostructures have attracted a broad research interest due to their application perspectives in various fields such as biosensing, catalysis, photovoltaics, and biomedicine. Their synthesis by pulsed laser ablation in pure water enables eliminating various side effects originating from chemical contamination. Another advantage of pulsed laser ablation in liquids (PLAL) is the possibility to controllably produce plasmonic nanoparticles (NPs) in combination with other plasmonic or magnetic materials, thus enhancing their functionality. However, the PLAL technique is still challenging in respect of merging metallic and semiconductor specific features in nanosized objects that could significantly broaden application areas of plasmonic nanostructures. In this work, we performed synthesis of hybrid AuSi NPs with novel modalities by ultrashort laser ablation of bulk gold in water containing silicon NPs. The Au/Si atomic ratio in the nanohybrids was finely varied from 0.5 to 3.5 when changing the initial Si NPs concentration in water from 70 µg/mL to 10 µg/mL, respectively, without requiring any complex chemical procedures. It has been found that the laser-fluence-insensitive silicon content depends on the mass of nanohybrids. A high concentration of paramagnetic defects (2.2·× 1018 spin/g) in polycrystalline plasmonic NPs has been achieved. Our findings can open further prospects for plasmonic nanostructures as contrast agents in optical and magnetic resonance imaging techniques, biosensing, and cancer theranostics. Full article
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Article
Selected Area Deposition of High Purity Gold for Functional 3D Architectures
Nanomaterials 2023, 13(4), 757; https://doi.org/10.3390/nano13040757 - 17 Feb 2023
Viewed by 984
Abstract
Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings [...] Read more.
Selected area deposition of high purity gold films onto nanoscale 3D architectures is highly desirable as gold is conductive, inert, plasmonically active, and can be functionalized with thiol chemistries, which are useful in many biological applications. Here, we show that high-purity gold coatings can be selectively grown with the Me2Au (acac) precursor onto nanoscale 3D architectures via a pulsed laser pyrolytic chemical vapor deposition process. The selected area of deposition is achieved due to the high thermal resistance of the nanoscale geometries. Focused electron beam induced deposits (FEBID) and carbon nanofibers are functionalized with gold coatings, and we demonstrate the effects that laser irradiance, pulse width, and precursor pressure have on the growth rate. Furthermore, we demonstrate selected area deposition with a feature-targeting resolutions of ~100 and 5 µm, using diode lasers coupled to a multimode (915 nm) and single mode (785 nm) fiber optic, respectively. The experimental results are rationalized via finite element thermal modeling. Full article
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