Editor’s Choice Articles

We provide an extensive and systematic investigation of exciton dynamics in droplet epitaxial quantum dots comparing the cases of (311)A, (001), and (111)A surfaces. Despite a similar s-shell exciton structure common to the three cases, the absence of a wetting layer for (311)A and (111)A samples leads to a larger carrier confinement compared to (001), where a wetting layer is present. This leads to a more pronounced dependence of the binding energies of s-shell excitons on the quantum dot size and to the strong anti-binding character of the positive-charged exciton for smaller quantum dots. In-plane geometrical anisotropies of (311)A and (001) quantum dots lead to a large electron-hole fine interaction (fine structure splitting (FSS) ∼100 μeV), whereas for the three-fold symmetric (111)A counterpart, this figure of merit is reduced by about one order of magnitude. In all these cases, we do not observe any size dependence of the fine structure splitting. Heavy-hole/light-hole mixing is present in all the studied cases, leading to a broad spread of linear polarization anisotropy (from 0 up to about 50%) irrespective of surface orientation (symmetry of the confinement), fine structure splitting, and nanostructure size. These results are important for the further development of ideal single and entangled photon sources based on semiconductor quantum dots. Full article

Achieving nanostructures with high surface area is one of the most challenging tasks as this metric usually plays a key role in technological applications, such as energy storage, gas sensing or photocatalysis, fields in which NiO is gaining increasing attention recently. Furthermore, the advent of modern NiO-based devices can take advantage of a deeper knowledge of the doping process in NiO, and the fabrication of p-n heterojunctions. By controlling experimental conditions such as dopant concentration, reaction time, temperature or pH, NiO morphology and doping mechanisms can be modulated. In this work, undoped and Sn doped nanoparticles and NiO/SnO₂ nanostructures with high surface areas were obtained as a result of Sn incorporation. We demonstrate that Sn incorporation leads to the formation of nanosticks morphology, not previously observed for undoped NiO, promoting p-n heterostructures. Consequently, a surface area value around 340 m²/g was obtained for NiO nanoparticles with 4.7 at.% of Sn, which is nearly nine times higher than that of undoped NiO. The presence of Sn with different oxidation states and variable Ni³⁺/Ni²⁺ ratio as a function of the Sn content were also verified by XPS, suggesting a combination of two charge compensation mechanisms (electronic and ionic) for the substitution of Ni²⁺ by Sn⁴⁺. These results make Sn doped NiO nanostructures a potential candidate for a high number of technological applications, in which implementations can be achieved in the form of NiO–SnO₂ p-n heterostructures. Full article

The ideal gas model is an important and useful model in classical thermodynamics. This remains so for small systems. Molecules in a gas can be adsorbed on the surface of a sphere. Both the free gas molecules and the adsorbed molecules may be modeled as ideal for low densities. The adsorption energy, $U^s$, plays an important role in the analysis. For small adsorbents this energy depends on the curvature of the adsorbent. We model the adsorbent as a sphere with surface area $\Omega =4\pi R^2$, where R is the radius of the sphere. We calculate the partition function for a grand canonical ensemble of two-dimensional adsorbed phases. When connected with the nanothermodynamic framework this gives us the relevant thermodynamic variables for the adsorbed phase controlled by the temperature T, surface area $\Omega$, and chemical potential $\mu$. The dependence of intensive variables on size may then be systematically investigated starting from the simplest model, namely the ideal adsorbed phase. This dependence is a characteristic feature of small systems which is naturally expressed by the subdivision potential of nanothermodynamics. For surface problems, the nanothermodynamic approach is different, but equivalent to Gibbs’ surface thermodynamics. It is however a general approach to the thermodynamics of small systems, and may therefore be applied to systems that do not have well defined surfaces. It is therefore desirable and useful to improve our basic understanding of nanothermodynamics. Full article

Square-shaped or rectangular nanoparticles (NPs) of lanthanum oxide (LaO_x) were synthesized and layered by convective self-assembly to demonstrate an analog memristive device in this study. Along with non-volatile analog memory effect, selection diode property could be co-existent without any implementation of heterogeneous multiple stacks with ~1 μm thick LaO_x NPs layer. Current–voltage (I–V) behavior of the LaO_x NPs resistive switching (RS) device has shown an evolved current level with memristive behavior and additional rectification functionality with threshold voltage. The concurrent memristor and diode type selector characteristics were examined with electrical stimuli or spikes for the duration of 10–50 ms pulse biases. The pulsed spike increased current levels at a read voltage of +0.2 V sequentially along with ±7 V biases, which have emulated neuromorphic operation of long-term potentiation (LTP). This study can open a new application of rare-earth LaO_x NPs as a component of neuromorphic synaptic device. Full article

In this work, the ternary titanium, copper, and silver (Ti-Cu-Ag) system is investigated as a potential candidate for the production of mechanically robust biomedical thin films. The coatings are produced by physical vapor deposition—magnetron sputtering (MS-PVD). The composite thin films are deposited on a silicon (100) substrate. The ratio between Ti and Cu was approximately kept one, with the variation of the Ag content between 10 and 35 at.%, while the power on the targets is changed during each deposition to get the desired Ag content. Thin film characterization is performed by X-ray diffraction (XRD), nanoindentation (modulus and hardness), to quantitatively evaluate the scratch adhesion, and atomic force microscopy to determine the surface topography. The residual stresses are measured by focused ion beam and digital image correlation method (FIB-DIC). The produced Ti-Cu-Ag thin films appear to be smooth, uniformly thick, and exhibit amorphous structure for the Ag contents lower than 25 at.%, with a transition to partially crystalline structure for higher Ag concentrations. The Ti-Cu control film shows higher values of 124.5 GPa and 7.85 GPa for modulus and hardness, respectively. There is a clear trend of continuous decrease in the modulus and hardness with the increase of Ag content, as lowest value of 105.5 GPa and 6 GPa for 35 at.% Ag containing thin films. In particular, a transition from the compressive (−36.5 MPa) to tensile residual stresses between 229 MPa and 288 MPa are observed with an increasing Ag content. The obtained results suggest that the Ag concentration should not exceed 25 at.%, in order to avoid an excessive reduction of the modulus and hardness with maintaining (at the same time) the potential for an increase of the antibacterial properties. In summary, Ti-Cu-Ag thin films shows characteristic mechanical properties that can be used to improve the properties of biomedical implants such as Ti-alloys and stainless steel. Full article

Cellulose nanofibril (CNF)-added polyvinylpyrrolidone (PVP) hydrogels were prepared using different types of CNFs and their properties were investigated. CNFs with different morphology and surface charge properties were prepared through quaternization and carboxymethylation pretreatments. The quaternized CNF exhibited the narrow and uniform width, and higher viscoelastic property compared to untreated and carboxymethylated CNF. When CNF was incorporated to PVP hydrogel, gel contents of all hydrogels were similar, irrespective of CNF addition quantity or CNF type. However, the absorptivity of the hydrogels in a swelling medium increased by adding CNF. In particular, the quaternized CNF-added PVP hydrogel exhibited the highest swelling ability. Unlike that of hydrogels with untreated and carboxymethylated CNFs, the storage modulus of PVP hydrogels after swelling significantly increased with an increase in the content of the quaternized CNF. These indicate that a PVP hydrogel with a high absorptivity and storage modulus can be prepared by incorporating the proper type of CNF. Full article

Microbubbles have already reached clinical practice as ultrasound contrast agents for angiography. However, modification of the bubbles’ shell is needed to produce probes for ultrasound and multimodal (fluorescence/photoacoustic) imaging methods in combination with theranostics (diagnostics and therapeutics). In the present work, hybrid structures based on microbubbles with an air core and a shell composed of bovine serum albumin, albumin-coated gold nanoparticles, and clinically available photodynamic dyes (zinc phthalocyanine, indocyanine green) were shown to achieve multimodal imaging for potential applications in photodynamic therapy. Microbubbles with an average size of 1.5 ± 0.3 μm and concentration up to 1.2 × 10⁹ microbubbles/mL were obtained and characterized. The introduction of the dye into the system reduced the solution’s surface tension, leading to an increase in the concentration and stability of bubbles. The combination of gold nanoparticles and photodynamic dyes’ influence on the fluorescent signal and probes’ stability is described. The potential use of the obtained probes in biomedical applications was evaluated using fluorescence tomography, raster-scanning optoacoustic microscopy and ultrasound response measurements using a medical ultrasound device at the frequency of 33 MHz. The results demonstrate the impact of microbubbles’ stabilization using gold nanoparticle/photodynamic dye hybrid structures to achieve probe applications in theranostics. Full article

Cellulose nanofiber (CNF) and hybrid zeolite imidazole framework (HZ) are an emerging biomaterial and a porous carbonous material, respectively. The composite of these two materials could have versatile physiochemical characteristics. A cellulose nanofiber and cobalt-containing zeolite framework-based composite was prepared using an in-situ and eco-friendly chemical method followed by pyrolysis. The composite was comprised of cobalt nanoparticles decorated on highly graphitized N-doped nanoporous carbons (NPC) wrapped with carbon nanotubes (CNTs) produced from the direct carbonization of HZ. By varying the ratio of CNF in the composite, we determined the optimal concentration and characterized the derived samples using sophisticated techniques. Scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS) confirmed the functionalization of CNF in the metallic cobalt-covered N-doped NPC wrapped with CNTs. The CNF–HZNPC composite electrodes show superior electrochemical performance, which is suitable for supercapacitor applications; its specific capacitance is 146 F/g at 1 A/g. Furthermore, the composite electrodes retain a cycling stability of about 90% over 2000 charge–discharge cycles at 10 A/g. The superior electrochemical properties of the cellulose make it a promising candidate for developing electrodes for energy storage applications. Full article

Graphene is promising for next-generation devices. However, one of the primary challenges in realizing these devices is the scalable growth of high-quality few-layer graphene (FLG) on device-type wafers; it is difficult to do so while balancing both quality and affordability. High-quality graphene is grown on expensive SiC bulk crystals, while graphene on SiC thin films grown on Si substrates (GOS) exhibits low quality but affordable cost. We propose a new method for the growth of high-quality FLG on a new template named “hybrid SiC”. The hybrid SiC is produced by bonding a SiC bulk crystal with an affordable device-type wafer and subsequently peeling off the SiC bulk crystal to obtain a single-crystalline SiC thin film on the wafer. The quality of FLG on this hybrid SiC is comparable to that of FLG on SiC bulk crystals and much higher than of GOS. FLG on the hybrid SiC exhibited high carrier mobilities, comparable to those on SiC bulk crystals, as anticipated from the linear band dispersions. Transistors using FLG on the hybrid SiC showed the potential to operate in terahertz frequencies. The proposed method is suited for growing high-quality FLG on desired substrates with the aim of realizing graphene-based high-speed devices. Full article

Design and development of novel inorganic nanocarriers for encapsulation of natural antimicrobial substances for food packaging applications have received great interest during the last years. Natural nanoclays are the most investigated nanocarriers and recently interest has also grown in the synthetically produced porous silica particles. However, these different carrier matrices have not been compared in terms of their loading capability and subsequent release. In this study, the feasibility of porous silica particles (with different pore structures and/or surface functionalities) and commercially available nanoclays were evaluated as encapsulation matrices. Two well-studied antimicrobial substances, thymol and curcumin, were chosen as volatile and non-volatile model compounds, respectively. The encapsulation efficiency, and the subsequent dispersibility and release, of these substances differed significantly among the nanocarriers. Encapsulation of the volatile compound highly depends on the inner surface area, i.e., the protective pore environment, and an optimal nanocarrier can protect the encapsulated thymol from volatilization. For the non-volatile compound, only the release rate and dispersibility are affected by the pore structure. Further, water-activated release of the volatile compound was demonstrated and exhibited good antimicrobial efficacy in the vapor phase against Staphylococcus aureus. This comparative study can provide a base for selecting the right nanocarrier aimed at a specific food packaging application. No nanocarrier can be considered as a universally applicable one. Full article

We analyze how the changes in the dimension of carbon nanomaterial (CNM) affect their catalytic conversion of secondary aliphatic alcohols. Carbon nanotubes (CNTs) consolidated by spark plasma sintering (SPS) were inactive in the conversion of secondary C₃-C₄ aliphatic alcohols because of the «healing» of defects in carbon structure during SPS. Gas-phase treatment of consolidated CNTs with HNO₃ vapors led to their surface oxidation without destruction of the bulk structure of pellets. The oxygen content in consolidated CNTs determined by X-ray photoelectron spectroscopy increased from 11.3 to 14.9 at. % with increasing the oxidation time from 3 to 6 h. Despite the decrease in the specific surface area, the oxidized samples showed enhanced catalytic activity in alcohol conversion because of the increased number of oxygen radicals with unpaired electrons, which was established by electron paramagnetic resonance spectroscopy. We conclude that the structure of CNM determines the content and/or ratio of sp² and sp³-hybridized carbon atoms in the material. The experimental and literature data demonstrated that sp³-hybridized carbon atoms on the surface are probably the preferable site for catalytic conversion of alcohols. Full article

To obtain selective hydrogenation catalysts with low noble metal content, two carbon-supported Mo-Pt bimetallic catalysts have been synthesized from two different molybdenum precursors, i.e., Na₂MoO₄ and (NH₄)₆Mo₇O₂₄. The results obtained by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) combined with the presence and strength of acid sites clarified the different catalytic behavior toward cinnamaldehyde hydrogenation. After impregnating the carbon support with Mo precursors, each sample was used either as is or treated at 400 °C in N₂ flow, as support for Pt nanoparticles (NPs). The heating treatment before Pt deposition had a positive effect on the catalytic performance. Indeed, TEM analyses showed very homogeneously dispersed Pt NPs only when they were deposited on the heat-treated Mo/C supports, and XPS analyses revealed an increase in both the exposure and reduction of Pt, which was probably tuned by different MoO₃/MoO₂ ratios. Moreover, the different acid properties of the catalysts resulted in different selectivity. Full article

In this study, we experimentally demonstrated the control of light transmission through a slab of plasmonic liquid metacrystal by an external electric field. By applying the external static field, we were able to induce macroscopic anisotropy, which caused the polarization-dependent suppression of transmission at resonant frequencies. Such behavior indicates the selective plasmon excitation governed by the orientation of the meta-atoms with respect to the polarization of the electromagnetic wave. The problem of light transmission through a plasmonic liquid metacrystal was analyzed theoretically from first principles, and the obtained results were compared with the experimental data. Full article

Highly luminescent europium complexes modified mesoporous silica particles (MSP) were synthesized as an imaging probes for both in-vitro diagnostic and in-vivo cellular tracking agents. Europium β-diketone chelates (4,4,4-trifluoro-l-(2-thienyl)-l,3-butanedione) trioctylphosphine europium (III) (Eu(TTA)₃(P(Oct)₃)₃) were incorporated inside the nanocavities that existed in hierarchical MSP (Eu@MSP). The MSP and Eu@MSP on mouse bone marrow-derived macrophages (BMDMs) did not show any toxic effect. The MSP and Eu@MSP in the BMDMs were found at cytoplasm without any degradation and immunogenicity. However, both pro- and anti-inflammatory cytokines of macrophages were significantly increased when lipopolysaccharide and a high concentration (100 μg/mL) of MSP and Eu@MSP were treated simultaneously. Full article

An experimental nano-filled coating, based on a fluorine resin containing SiO₂ nano-particles, was applied on calcareous stones, representative of materials used in buildings and monuments of the Mediterranean basin; for comparison purposes, two commercial products were applied on the same substrates. The efficacy of the protective treatments was assessed by analyzing different characteristics of the three experimental/commercial products, i.e., color changes and permeability to water vapor to evaluate the treatments’ harmlessness; capillary water absorption and water stone contact angle to evaluate the protection against water ingress; oleophobicity of the treated surfaces and the behavior under staining by acrylic blue-colored spray paint and felt-tip marker to verify the anti-graffiti action. Finally, the properties of the treated stone surfaces were analyzed also after the application of pancreatin, used to simulate bird excreta (guano). The protective coatings were found to promote graffiti removal, reducing also the detrimental effects due to simulated guano. The experimental nano-filled product, in addition, was able to provide outstanding performance but using smaller amounts of product in comparison to commercial systems. Full article

Silicon is a promising material for high-energy anode materials for the next generation of lithium-ion batteries. The gain in specific capacity depends highly on the quality of the Si dispersion and on the size and shape of the nano-silicon. The aim of this study is to investigate the impact of the size/shape of Si on the electrochemical performance of conventional Li-ion batteries. The scalable synthesis processes of both nanoparticles and nanowires in the 10–100 nm size range are discussed. In cycling lithium batteries, the initial specific capacity is significantly higher for nanoparticles than for nanowires. We demonstrate a linear correlation of the first Coulombic efficiency with the specific area of the Si materials. In long-term cycling tests, the electrochemical performance of the nanoparticles fades faster due to an increased internal resistance, whereas the smallest nanowires show an impressive cycling stability. Finally, the reversibility of the electrochemical processes is found to be highly dependent on the size/shape of the Si particles and its impact on lithiation depth, formation of crystalline Li₁₅Si₄ in cycling, and Li transport pathways. Full article

We present an innovative implementation of the solid-state-biased coherent detection (SSBCD) technique, which we have recently introduced for the reconstruction of both amplitude and phase of ultra-broadband terahertz pulses. In our previous works, the SSBCD method has been operated via a heterodyne scheme, which involves demanding square-wave voltage amplifiers, phase-locked to the THz pulse train, as well as an electronic circuit for the demodulation of the readout signal. Here, we demonstrate that the SSBCD technique can be operated via a very simple homodyne scheme, exploiting plain static bias voltages. We show that the homodyne SSBCD signal turns into a bipolar transient when the static field overcomes the THz field strength, without the requirement of an additional demodulating circuit. Moreover, we introduce a differential configuration, which extends the applicability of the homodyne scheme to higher THz field strengths, also leading a two-fold improvement of the dynamic range compared to the heterodyne counterpart. Finally, we demonstrate that, by reversing the sign of the static voltage, it is possible to directly retrieve the absolute THz pulse polarity. The homodyne configuration makes the SSBCD technique of much easier access, leading to a vast range of field-resolved applications. Full article

We report the results of experimental and theoretical studies of phonon modes in GaN/AlN superlattices (SLs) with a period of several atomic layers, grown by submonolayer digital plasma-assisted molecular-beam epitaxy, which have a great potential for use in quantum and stress engineering. Using detailed group-theoretical analysis, the genesis of the SL vibrational modes from the modes of bulk AlN and GaN crystals is established. Ab initio calculations in the framework of the density functional theory, aimed at studying the phonon states, are performed for SLs with both equal and unequal layer thicknesses. The frequencies of the vibrational modes are calculated, and atomic displacement patterns are obtained. Raman spectra are calculated and compared with the experimental ones. The results of the ab initio calculations are in good agreement with the experimental Raman spectra and the results of the group-theoretical analysis. As a result of comprehensive studies, the correlations between the parameters of acoustic and optical phonons and the structure of SLs are obtained. This opens up new possibilities for the analysis of the structural characteristics of short-period GaN/AlN SLs using Raman spectroscopy. The results obtained can be used to optimize the growth technologies aimed to form structurally perfect short-period GaN/AlN SLs. Full article

The exploitation of self-assembled coatings comprising graphite oxide (GO) nanoplates has been recently demonstrated as a promising route to improve the fire safety of flexible polyurethane (PU) foams. However, limited knowledge has been gathered on the correlations between the physical and chemical properties of different GO grades and the performance obtained in this application. This work addresses the effects of the nanoparticle dimensions on the layer-by-layer (LbL) assembly and flame-retardant properties of GO-based coatings deposited on PU foams. To this aim, three GO bearing different lateral sizes and thicknesses were selected and LbL-assembled with chitosan (CHIT). Coating growth and morphology were evaluated by FTIR and FESEM, respectively. The resulting CHIT/GO assemblies were demonstrated to be capable of slowing down the combustion of the PU both in flammability and forced combustion tests. In addition, compressive stress/strain tests pointed out that the LbL-coated foams (22–24 kg/m³) could easily replace denser commercial PU foam (40–50 kg/m³) with weight reduction potentials in the transport field. These results are correlated with the properties of the employed GO. The production of assemblies characterized by a high density of CHIT/GO interfaces is identified as the main parameter controlling the FR efficiency and the mechanical properties of the coatings. Full article

A cost-effective, scalable and versatile method of preparing nano-ink without hazardous chemical precursors is a prerequisite for widespread adoption of printed electronics. Precursor-free synthesis by spark discharge is promising for this purpose. The synthesis of platinum nanoparticles (PtNPs) using a spark discharge under Ar, N₂, and air has been investigated to prepare highly conductive nano-ink. The size, chemical composition, and mass production rate of PtNPs significantly depended on the carrier gas. Pure metallic PtNPs with sizes of 5.5 ± 1.8 and 7.1 ± 2.4 nm were formed under Ar and N₂, respectively. PtNPs with sizes of 18.2 ± 9.0 nm produced using air consisted of amorphous oxide PtO and metallic Pt. The mass production rates of PtNPs were 53 ± 6, 366 ± 59, and 490 ± 36 mg/h using a spark discharge under Ar, N₂, and air, respectively. It was found that the energy dissipated in the spark gap is not a significant parameter that determines the mass production rate. Stable Pt nano-ink (25 wt.%) was prepared only on the basis of PtNPs synthesized under air. Narrow (about 30 μm) and conductive Pt lines were formed by the aerosol jet printing with prepared nano-ink. The resistivity of the Pt lines sintered at 750 °C was (1.2 ± 0.1)·10⁻⁷ Ω·m, which is about 1.1 times higher than that of bulk Pt. Full article

Gold nanoparticles depending on their shape and mixtures of multiple shapes can exhibit peculiar optical properties, including the dichroic effect typical of the Lycurgus cup, which has puzzled scientists for a long time. Such optical properties have been recently exploited in several fields such as paint technology, sensors, dichroic polarizers, display (LCD) devices, laser applications, solar cells and photothermal therapy among others. In this article, we have demonstrated a simple room temperature one-pot synthesis of gold sol displaying a dichroic effect using a slow reduction protocol involving only trisodium citrate as a reducing agent. We found that the dichroic gold sol can be easily formed at room temperature by reducing gold salt by trisodium citrate below a certain critical concentration. The sol displayed an orangish-brown color in scattered/reflected light and violet/blue/indigo/purple/red/pink in transmitted light, depending on the experimental conditions. With minor changes such as the introduction of a third molecule or replacing a small amount of water in the reaction mixture with ethanol, the color of the gold sol under transmitted light changed and a variety of shades of red, pink, cobalt blue, violet, magenta and purple were obtained. The main advantage of the proposed method lies in its simplicity, which involves the identification of the right ratio of the reactants, and simple mixing of reactants at room temperature with no other requirements. TEM micrographs displayed the formation of two main types of particles viz. single crystal gold nanoplates and polycrystalline faceted polyhedron nanoparticles. The mechanism of growth of the nanoplates and faceted polyhedron particles have been described by an enhanced diffusion limited aggregation numerical scheme, where it was assumed that both trisodium citrate and the gold ions in solution undergo a stochastic Brownian motion, and that the evolution of the entire system is regulated by a principle of energy minimization. The predictions of the model matched with the experiments with a good accuracy, indicating that the initial hypothesis is correct. Full article

This article, a part of the larger research project of Surface-Enhanced Raman Scattering (SERS), describes an advanced study focusing on the shapes and materials of Tip-Enhanced Raman Scattering (TERS) designated to serve as part of a novel imager device. The initial aim was to define the optimal shape of the “probe”: tip or cavity, round or sharp. The investigations focused on the effect of shape (hemi-sphere, hemispheroid, ellipsoidal cavity, ellipsoidal rod, nano-cone), and the effect of material (Ag, Au, Al) on enhancement, as well as the effect of excitation wavelengths on the electric field. Complementary results were collected: numerical simulations consolidated with analytical models, based on solid assumptions. Preliminary experimental results of fabrication and structural characterization are also presented. Thorough analyses were performed around critical parameters, such as the plasmonic metal—Silver, Aluminium or Gold—using Rakic model, the tip geometry—sphere, spheroid, ellipsoid, nano-cone, nano-shell, rod, cavity—and the geometry of the plasmonic array: cross-talk in multiple nanostructures. These combined outcomes result in an optimized TERS design for a large number of applications. Full article

Electrochemical deposition of interconnected nanowires and nanotubes made of ferromagnetic metals into track-etched polycarbonate templates with crossed nanochannels has been revealed suitable for the fabrication of mechanically stable three-dimensional magnetic nanostructures with large surface area. These 3D networks embedded into flexible polymer membranes are also planar and lightweight. This fabrication technique allows for the control of the geometric characteristics and material composition of interconnected magnetic nanowire or nanotube networks, which can be used to fine-tune their magnetic and magneto-transport properties. The magnetostatic contribution to the magnetic anisotropy of crossed nanowire networks can be easily controlled using the diameter, packing density, or angle distribution characteristics. Furthermore, the fabrication of Co and Co-rich NiCo alloy crossed nanowires with textured hcp phases leads to an additional significant magnetocrystalline contribution to the magnetic anisotropy that can either compete or add to the magnetostatic contribution. The fabrication of an interconnected nanotube network has also been demonstrated, where the hollow core and the control over the tube wall thickness add another degree of freedom to control the magnetic properties and magnetization reversal mechanisms. Finally, three-dimensional networks made of interconnected multilayered nanowire with a succession of ferromagnetic and non-magnetic layers have been successfully fabricated, leading to giant magnetoresistance responses measured in the current-perpendicular-to-plane configuration. These interconnected nanowire networks have high potential as integrated, reliable, and stable magnetic field sensors; magnetic devices for memory and logic operations; or neuromorphic computing. Full article

In this paper, characterisation of exciton generation is carried out in three bulk-heterojunction organic solar cells (BHJ OSCs)—OSC1: an inverted non-fullerene (NF) BHJ OSC; OSC2: a conventional NF BHJ OSC; and OSC3: a conventional fullerene BHJ OSC. It is found that the overlap of the regions of strong constructive interference of incident and reflected electric fields of electromagnetic waves and those of high photon absorption within the active layer depends on the active layer thickness. An optimal thickness of the active layer can thus be obtained at which this overlap is maximum. We have simulated the rates of total exciton generation and position dependent exciton generation within the active layer as a function of the thicknesses of all the layers in all three OSCs and optimised their structures. Based on our simulated results, the inverted NF BHJ OSC1 is found to have better short circuit current density which may lead to better photovoltaic performance than the other two. It is expected that the results of this paper may provide guidance in fabricating highly efficient and cost effective BHJ OSCs. Full article

To enhance the bioactivity of poly(lactic acid) (PLA), a potential bone repair material, without the lowering of mechanical strength, hydroxyapatite (HA) was introduced in the form of nanofibers as the filler for application in spinal implant materials. HA nanofibers (HANF) with aspect ratio as high as ~100 were synthesized by controlling the starting pH of the reaction. While the tensile and flexural strength of PLA/HANF composites were enhanced compared with those of PLA resin, and were higher for the composites with HANF of higher aspect ratio. To further strengthen the composites, HANF was grafted with PLA chain to form HANF-g-PLA, which could improve the interface between the HANF and matrix PLA. PLA/HANF-g-PLA composites showed even higher tensile and flexural strength than PLA/HANF composites, apparently due to the better dispersion and interfacial adhesion. The composite containing 10 wt% HANF-g-PLA showed the flexural strength of 124 MPa, which was 25% higher than that of PLA resin. In the bioactivity test using a simulated body fluid solution, the rate and uniformity of the apatite growth were observed to be higher for the composites with HANF, and were even higher for those with HANF-g-PLA. This study suggested the possibility of using the PLA/HANF-g-PLA composite in the field of spinal implant materials. Full article

In this work, the antibacterial activity of silver nanoparticles (AgNPs) synthesized using Areca catechu extracts against three species of antibiotic-susceptible and three species of resistant bacteria was investigated. The effects of this plant were more promising when compared with other medicinal plants tested. The hydrothermal extract of Areca catechu was mixed with silver nitrate to synthesize AgNPs. The synthesized particle characteristics were analyzed by UV–Vis spectrophotometry, scanning electron microscopy (SEM), dynamic light scattering (DLS), and Fourier-transform infrared spectroscopy (FT-IR). Minimum inhibitory concentration and minimum bactericidal concentration tests were conducted to confirm antibacterial activity and the results showed that AgNPs synthesized using Areca catechu extracts effectively inhibited the growth of bacterial species. Moreover, the SEM images of the bacterial species treated with AgNPs synthesized with Areca catechu extracts showed that clusters of AgNPs were attached to the surface of the bacterial cell wall, which could induce destruction of the cell membranes. The results suggest that AgNPs synthesized with Areca catechu extracts have the potential to treat antibiotic-resistant bacteria known as the major cause of nosocomial infections. Full article

Oxide inverse opals (IOs) with their high surface area and open porosity are promising candidates for catalyst support applications. Supports with confined mesoporous domains are of added value to heterogeneous catalysis. However, the fabrication of IOs with mesoporous or sub-macroporous voids (<100 nm) continues to be a challenge, and the diffusion of tracers in quasi-mesoporous IOs is yet to be adequately studied. In order to address these two problems, we synthesized ZnO IOs films with tunable pore sizes using chemical bath deposition and template-based approach. By decreasing the size of polystyrene (PS) template particles towards the mesoporous range, ZnO IOs with 50 nm-sized pores and open porosity were synthesized. The effect of the template-removal method on the pore geometry (spherical vs. gyroidal) was studied. The infiltration depth in the template was determined, and the factors influencing infiltration were assessed. The crystallinity and photonic stop-band of the IOs were studied using X-Ray diffraction and UV-Vis, respectively. The infiltration of tracer molecules (Alexa Fluor 488) in multilayered quasi-mesoporous ZnO IOs was confirmed via confocal laser scanning microscopy, while fluorescence correlation spectroscopy analysis revealed two distinct diffusion times in IOs assigned to diffusion through the pores (fast) and adsorption on the pore walls (slow). Full article

The nanowire platform offers great opportunities for improving the quality and range of applications of semiconductor quantum wells and dots. Here, we present the self-catalyzed growth of InAs/InSb/InAs axial heterostructured nanowires with a single defect-free InSb quantum dot, on Si substrates, by chemical beam epitaxy. A systematic variation of the growth parameters for the InAs top segment has been investigated and the resulting nanowire morphology analyzed. We found that the growth temperature strongly influences the axial and radial growth rates of the top InAs segment. As a consequence, we can reduce the InAs shell thickness around the InSb quantum dot by increasing the InAs growth temperature. Moreover, we observed that both axial and radial growth rates are enhanced by the As line pressure as long as the In droplet on the top of the nanowire is preserved. Finally, the time evolution of the diameter along the entire length of the nanowires allowed us to understand that there are two In diffusion paths contributing to the radial InAs growth and that the interplay of these two mechanisms together with the total length of the nanowires determine the final shape of the nanowires. This study provides insights in understanding the growth mechanisms of self-catalyzed InSb/InAs quantum dot nanowires, and our results can be extended also to the growth of other self-catalyzed heterostructured nanowires, providing useful guidelines for the realization of quantum structures with the desired morphology and properties. Full article

With the growth of nanotechnologies, concerns raised regarding the potential adverse effects of nanoparticles (NPs), especially on the respiratory tract. Adverse outcome pathways (AOP) have become recently the subject of intensive studies in order to get a better understanding of the mechanisms of NP toxicity, and hence hopefully predict the health risks associated with NP exposure. Herein, we propose a putative AOP for the lung toxicity of NPs using emerging nanomaterials called carbon dots (CDs), and in vivo and in vitro experimental approaches. We first investigated the effect of a single administration of CDs on mouse airways. We showed that CDs induce an acute lung inflammation and identified airway macrophages as target cells of CDs. Then, we studied the cellular responses induced by CDs in an in vitro model of macrophages. We observed that CDs are internalized by these cells (molecular initial event) and induce a series of key events, including loss of lysosomal integrity and mitochondrial disruption (organelle responses), as well as oxidative stress, inflammasome activation, inflammatory cytokine upregulation and macrophage death (cellular responses). All these effects triggering lung inflammation as tissular response may lead to acute lung injury. Full article

The object of this study is a comparison between solid lipid nanoparticles and ethosomes for caffeic acid delivery through the skin. Caffeic acid is a potent antioxidant molecule whose cutaneous administration is hampered by its low solubility and scarce stability. In order to improve its therapeutic potential, caffeic acid has been encapsulated within solid lipid nanoparticles and ethosomes. The effect of lipid matrix has been evaluated on the morphology and size distribution of solid lipid nanoparticles and ethosomes loaded with caffeic acid. Particularly, morphology has been investigated by cryogenic transmission electron microscopy and small angle X-ray scattering, while mean diameters have been evaluated by photon correlation spectroscopy. The antioxidant power has been evaluated by the 2,2-diphenyl-1-picrylhydrazyl methodology. The influence of the type of nanoparticulate system on caffeic acid diffusion has been evaluated by Franz cells associated to the nylon membrane, while to evaluate caffeic acid permeation through the skin, an amperometric study has been conducted, which was based on a porcine skin-covered oxygen electrode. This apparatus allows measuring the O₂ concentration changes in the membrane induced by polyphenols and H₂O₂ reaction in the skin. The antioxidative reactions in the skin induced by caffeic acid administered by solid lipid nanoparticles or ethosomes have been evaluated. Franz cell results indicated that caffeic acid diffusion from ethosomes was 18-fold slower with respect to solid lipid nanoparticles. The amperometric method evidenced the transdermal delivery effect of ethosome, indicating an intense antioxidant activity of caffeic acid and a very low response in the case of SLN. Finally, an irritation patch test conducted on 20 human volunteers demonstrated that both ethosomes and solid lipid nanoparticles can be safely applied on the skin. Full article

We have described for the first time the thermodynamic state of a highly confined single-phase and single-component fluid in a slit pore using Hill’s thermodynamics of small systems. Hill’s theory has been named nanothermodynamics. We started by constructing an ensemble of slit pores for controlled temperature, volume, surface area, and chemical potential. We have presented the integral and differential properties according to Hill, and used them to define the disjoining pressure on the new basis. We identified all thermodynamic pressures by their mechanical counterparts in a consistent manner, and have given evidence that the identification holds true using molecular simulations. We computed the entropy and energy densities, and found in agreement with the literature, that the structures at the wall are of an energetic, not entropic nature. We have shown that the subdivision potential is unequal to zero for small wall surface areas. We have showed how Hill’s method can be used to find new Maxwell relations of a confined fluid, in addition to a scaling relation, which applies when the walls are far enough apart. By this expansion of nanothermodynamics, we have set the stage for further developments of the thermodynamics of confined fluids, a field that is central in nanotechnology. Full article

Nano-scaled thermoelectric materials attract significant interest due to their improved physical properties as compared to bulk materials. Well-shaped nanoparticles such as nano-bars and nano-cubes were observed in the known thermoelectric material PbTe. Their extended two-dimensional nano-layer arrangements form directly in situ through electron-beam treatment in the transmission electron microscope. The experiments show the atomistic depletion mechanism of the initial crystal and the recrystallization of PbTe nanoparticles out of the microparticles due to the local atomic-scale transport via the gas phase beyond a threshold current density of the beam. Full article

Magnetic hyperthermia on core-shell nanoparticles bears promising achievements, especially in biomedical applications. Here, thanks to magnetic hyperthermia, γ-Fe₂O₃ cores are able to release a DNA target mimicking the liver specific oncotarget miRNA-122. Our silica coated magnetic nanoparticles not only allow the grafting at their surface of a significant number of oligonucleotides but are also shown to be as efficient, by local heating, as 95 °C global heating when submitted to an alternative magnetic field, while keeping the solution at 28 °C, crucial for biological media and energy efficiency. Moreover, a slight modification of the silica coating process revealed an increased heating power, well adapted for the release of small oligonucleotides such as microRNA. Full article

Structure of model bimetallic PdAu nanoparticles is analyzed aiming to find Pd:Au ratios optimal for existence of Pd1 single-atom surface sites inside outer Au atomic shell. The analysis is performed using density-functional theory (DFT) calculations and topological approach based on DFT-parameterized topological energy expression. The number of the surface Pd1 sites in the absence of adsorbates is calculated as a function of Pd concentration inside the particles. At low Pd contents none of the Pd atoms emerge on the surface in the lowest-energy chemical orderings. However, surface Pd1 sites become stable, when Pd content inside a Pd-Au particle reaches ca. 60%. Further Pd content increase up to almost pure Pd core is accompanied by increased concentration of surface Pd atoms, mostly as Pd1 sites, although larger Pd ensembles as dimers and linear trimers are formed as well. Analysis of the chemical orderings inside PdAu nanoparticles at different Pd contents revealed that enrichment of the subsurface shell by Pd with predominant occupation of its edge positions precedes emergence of Pd surface species. Full article

Strontium bismuth tantalate (SBT) ferroelectric-gate field-effect transistors (FeFETs) with channel lengths of 85 nm were fabricated by a replacement-gate process. They had metal/ferroelectric/insulator/semiconductor stacked-gate structures of Ir/SBT/HfO₂/Si. In the fabrication process, we prepared dummy-gate transistor patterns and then replaced the dummy substances with an SBT precursor. After forming Ir gate electrodes on the SBT, the whole gate stacks were annealed for SBT crystallization. Nonvolatility was confirmed by long stable data retention measured for 10⁵ s. High erase-and-program endurance of the FeFETs was demonstrated for up to 10⁹ cycles. By the new process proposed in this work, SBT-FeFETs acquire good channel-area scalability in geometry along with lithography ability. Full article

Based on a thermodynamic model, we quantify the impact of adding silicon atoms to a catalyst droplet on the nucleation and growth of ternary III–V nanowires grown via the self-catalyzed vapor–liquid–solid process. Three technologically relevant ternaries are studied: InGaAs, AlGaAs and InGaN. For As-based alloys, it is shown that adding silicon atoms to the droplet increases the nanowire nucleation probability, which can increase by several orders magnitude depending on the initial chemical composition of the catalyst. Conversely, silicon atoms are found to suppress the nucleation rate of InGaN nanowires of different compositions. These results can be useful for understanding and controlling the vapor–liquid–solid growth of ternary III–V nanowires on silicon substrates as well as their intentional doping with Si. Full article

One-dimensional nanowires based on Group III-nitride materials are emerging as one of the most promising structures for applications of light-emitting diodes (LEDs), laser diodes (LDs), solar cells, and photocatalysts. However, leading to the so-called “green gap” in photonics, the fabrication of high concentration indium gallium nitride (InGaN) and long-InGaN structures remains still challenging. In this study, we performed simulations for structural modeling of uniform temperature distribution in a nanowire epitaxy, and have successfully developed high-concentration InGaN and long-InGaN nanowire heterostructures on silicon (Si) substrate using molecular beam epitaxy (MBE) system. From scanning electron microscope (SEM) and transmission electron microscope (TEM) results, it was confirmed that the various doped-InGaN nanowire structures show much higher crystal quality compared to conventional nanowire structures. By introducing a new three-step modulated growth technique, the n-/p-InGaN active regions were greatly increased and the optical properties were also dramatically improved due to reduced phase separation. In addition, a multi-band p-InGaN/GaN heterostructure was successfully fabricated with the core–shell nanowire structures, which enable the emission of light in the entire visible spectral range, and protect the InGaN surface from surface recombination. This paper offers important insight into the design and epitaxial growth of InGaN nanowire heterostructures. Full article

Recently, two-dimensional gallium and aluminum nitrides have triggered a vast interest in their tunable optical and electronic properties. Continuation of this research requires a detailed understanding of their atomic structure. Here, by using first-principles calculations we reported a systematic study of phase stability of 2D-GaN and 2D-AlN. We showed that the films undergo a phase transition from a graphene-like to a wurtzite structure with a thickness increase, whereas the early reported body-centered-tetragonal phase requires specific conditions for stabilization. Additionally, we studied how the functionalization of the surface can modify the film structure as exemplified by hydrogenation. Full article

The generation of high order harmonics from femtosecond mid-IR laser pulses in ZnO has shown great potential to reveal new insight into the ultrafast electron dynamics on a few femtosecond timescale. In this work we report on the experimental investigation of photoluminescence and high-order harmonic generation (HHG) in a ZnO single crystal and polycrystalline thin film irradiated with intense femtosecond mid-IR laser pulses. The ellipticity dependence of the HHG process is experimentally studied up to the 17th harmonic order for various driving laser wavelengths in the spectral range 3–4 µm. Interband Zener tunneling is found to exhibit a significant excitation efficiency drop for circularly polarized strong-field pump pulses. For higher harmonics with energies larger than the bandgap, the measured ellipticity dependence can be quantitatively described by numerical simulations based on the density matrix equations. The ellipticity dependence of the below and above ZnO band gap harmonics as a function of the laser wavelength provides an efficient method for distinguishing the dominant HHG mechanism for different harmonic orders. Full article

Recently, a new family of the Janus NbSeTe monolayer has exciting development prospects for two-dimensional (2D) asymmetric layered materials that demonstrate outstanding properties for high-performance nanoelectronics and optoelectronics applications. Motivated by the fascinating properties of the Janus monolayer, we have studied the gas sensing properties of the Janus NbSeTe monolayer for CO, CO${}_2$, NO, NO${}_2$, H${}_2$S, and SO${}_2$ gas molecules using first-principles calculations that will have eminent application in the field of personal security, protection of the environment, and various other industries. We have calculated the adsorption energies and sensing height from the Janus NbSeTe monolayer surface to the gas molecules to detect the binding strength for these considered toxic gases. In addition, considerable charge transfer between Janus monolayer and gas molecules were calculated to confirm the detection of toxic gases. Due to the presence of asymmetric structures of the Janus NbSeTe monolayer, the projected density of states, charge transfer, binding strength, and transport properties displayed distinct behavior when these toxic gases absorbed at Se- and Te-sites of the Janus monolayer. Based on the ultra-low recovery time in the order of $\mu s$ for NO and NO${}_2$ and $ps$ for CO, CO${}_2$, H${}_2$S, and SO${}_2$ gas molecules in the visible region at room temperature suggest that the Janus monolayer as a better candidate for reusable sensors for gas sensing materials. From the transport properties, it can be observed that there is a significant variation of $I-V$ characteristics and sensitivity of the Janus NbSeTe monolayer before and after adsorbing gas molecules demonstrates the feasibility of NbSeTe material that makes it an ideal material for a high-sensitivity gas sensor. Full article

Due to their outstanding physicochemical properties, the next generation of the graphene family—graphene quantum dots (GQDs)—are at the cutting edge of nanotechnology development. GQDs generally possess many hydrophilic functionalities which allow their dispersibility in water but, on the other hand, could interfere with reactions that are mainly performed in organic solvents, as for cycloaddition reactions. We investigated the 1,3-dipolar cycloaddition (1,3-DCA) reactions of the C-ethoxycarbonyl N-methyl nitrone 1a and the newly synthesized C-diethoxyphosphorylpropilidene N-benzyl nitrone 1b with the surface of GQDs, affording the isoxazolidine cycloadducts isox-GQDs 2a and isox-GQDs 2b. Reactions were performed in mild and eco-friendly conditions, through the use of a natural deep eutectic solvent (NADES), free of chloride or any metal ions in its composition, and formed by the zwitterionic trimethylglycine as the -bond acceptor, and glycolic acid as the hydrogen-bond donor. The results reported in this study have for the first time proved the possibility of performing cycloaddition reactions directly to the p-cloud of the GQDs surface. The use of DES for the cycloaddition reactions on GQDs, other than to improve the solubility of reactants, has been shown to bring additional advantages because of the great affinity of these green solvents with aromatic systems. Full article

Graphene oxide (GO) can be defined as a single monolayer of graphite with oxygen-containing functionalities such as epoxides, alcohols, and carboxylic acids. It is an interesting alternative to graphene for many applications due to its exceptional properties and feasibility of functionalization. In this study, electrochemically exfoliated graphene oxides (EGOs) with different amounts of surface groups, hence level of oxidation, were prepared by an electrochemical two-stage approach using graphite as raw material. A complete characterization of the EGOs was carried out in order to correlate their surface topography, interlayer spacing, defect content, and specific surface area (SSA) with their electrical, thermal, and mechanical properties. It has been found that the SSA has a direct relationship with the d-spacing. The EGOs electrical resistance decreases with increasing SSA while rises with increasing the D/G band intensity ratio in the Raman spectra, hence the defect content. Their thermal stability under both nitrogen and dry air atmospheres depends on both their oxidation level and defect content. Their macroscopic mechanical properties, namely the Young’s modulus and tensile strength, are influenced by the defect content, while no correlation was found with their SSA or interlayer spacing. Young moduli values as high as 54 GPa have been measured, which corroborates that the developed method preserves the integrity of the graphene flakes. Understanding the structure-property relationships in these materials is useful for the design of modified GOs with controllable morphologies and properties for a wide range of applications in electrical/electronic devices. Full article

Goethite is a naturally anisotropic, antiferromagnetic iron oxide. Following its atomic structure, crystals grow into a fine needle shape that has interesting properties in a magnetic field. The needles align parallel to weak magnetic fields and perpendicular when subjected to high fields. We synthesized goethite nanorods with lengths between 200 nm and 650 nm in a two-step process. In a first step we synthesized precursor particles made of akaganeite (β-FeOOH) rods from iron(III)chloride. The precursors were then treated in a hydrothermal reactor under alkaline conditions with NaOH and polyvinylpyrrolidone (PVP) to form goethite needles. The aspect ratio was tunable between 8 and 15, based on the conditions during hydrothermal treatment. The orientation of these particles in a magnetic field was investigated by small angle X-ray scattering (SAXS). We observed that the field strength required to trigger a reorientation is dependent on the length and aspect ratio of the particles and could be shifted from 85 mT for the small particles to about 147 mT for the large particles. These particles could provide highly interesting magnetic properties to nanocomposites, that could then be used for sensing applications or membranes. Full article

We have previously demonstrated that we can grow p-type GaAs nanowires using Zn doping during gold catalyzed growth with aerotaxy. In this investigation, we show how to calculate the hole concentrations in such nanowires. We base the calculations on the Zhang–Northrup defect formation energy. Using density functional theory, we calculate the energy of the defect, a Zn atom on a Ga site, using a supercell approach. The chemical potentials of Zn and Ga in the liquid catalyst particle are calculated from a thermodynamically assessed database including Au, Zn, Ga, and As. These quantities together with the chemical potential of the carriers enable us to calculate the hole concentration in the nanowires self-consistently. We validate our theoretical results against aerotaxy grown GaAs nanowires where we have varied the hole concentration by varying the Zn/Ga ratio in the aerotaxy growth. Full article

Synthetic organic 2D materials are attracting careful attention of researchers due to their excellent functionality in various applications, including storage batteries, catalysis, thermoelectricity, advanced electronics, superconductors, optoelectronics, etc. In this work, thiacalix[4]arene derivatives functionalized by geranyl fragments at the lower rim in cone and 1,3-alternate conformations, that are capable of controlled self-assembly in a 2D nanostructures were synthesized. X-ray diffraction analysis showed the formation of 2D monomolecular-layer nanosheets from synthesized thiacalix[4]arenes, the distance between which depends on the stereoisomer used. It was established by DSC, FSC, and PXRD methods that the obtained macrocycles are capable of forming different crystalline polymorphs, moreover dimethyl sulphoxide (DMSO) is contributing to the formation of a more stable polymorph for cone stereoisomer. The obtained crystalline 2D materials based on synthesized thiacalix[4]arenes can find application in material science and medicine for the development of modern pharmaceuticals and new generation materials. Full article

Diamond nanoparticles have been synthesized using various methods. Nanodiamonds generated in the gas phase were captured on the membrane of a transmission electron microscope grid during a hot filament chemical vapor deposition (HFCVD) diamond process. In total, ~600 nanoparticles, which were captured for 10 s in six conditions of the capture temperatures of 900 °C, 600 °C and 300 °C and the gas mixtures of 1% CH₄-99% H₂ and 3% CH₄-97% H₂, were analyzed for phase identification using high-resolution transmission electron microscopy and fast Fourier transformation. Hexagonal diamond, i-carbon, n-diamond, and cubic diamond were identified. The observation of two or more carbon allotropes captured on the same membrane suggested their coexistence in the gas phase during HFCVD. The crystal structure of carbon allotropes was related to the size of the nanodiamond. The crystal structure of the nanoparticles affected the crystal structure of diamond deposited for 8 h. Confirmation of various carbon allotropes provides new insight into the nanodiamond synthesis in the gas phase and the growth mechanism of HFCVD diamond. Full article

In the present work, the porous metal-organic framework (MOF) Basolite^®F300 (Fe-BTC) was tested as a potential drug-releasing depot to enhance the solubility of the anticancer drug paclitaxel (PTX) and to prepare controlled release formulations after its encapsulation in amphiphilic methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles. Investigation revealed that drug adsorption in Fe-BTC reached approximately 40%, a relatively high level, and also led to an overall drug amorphization as confirmed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The dissolution rate of PTX-loaded MOF was substantially enhanced achieving a complete (100%) release within four days, while the neat drug only reached a 13% maximum rate (3–4 days). This PTX-Fe-BTC nanocomposite was further encapsulated into a mPEG-PCL matrix, a typical aliphatic amphiphilic copolyester synthesized in our lab, whose biocompatibility was validated by in vitro cytotoxicity tests toward human umbilical vein endothelial cells (HUVEC). Encapsulation was performed according to the solid-in-oil-in-water emulsion/solvent evaporation technique, resulting in nanoparticles of about 143 nm, slightly larger of those prepared without the pre-adsorption of PTX on Fe-BTC (138 nm, respectively). Transmission electron microscopy (TEM) imaging revealed that spherical nanoparticles with embedded PTX-loaded Fe-BTC nanoparticles were indeed fabricated, with sizes ranging from 80 to 150 nm. Regions of the composite Fe-BTC-PTX system in the infrared (IR) spectrum are identified as signatures of the drug-MOF interaction. The dissolution profiles of all nanoparticles showed an initial burst release, attributed to the drug amount located at the nanoparticles surface or close to it, followed by a steadily and controlled release. This is corroborated by computational analysis that reveals that PTX attaches effectively to Fe-BTC building blocks, but its relatively large size limits diffusion through crystalline regions of Fe-BTC. The dissolution behaviour can be described through a bimodal diffusivity model. The nanoparticles studied could serve as potential chemotherapeutic candidates for PTX delivery. Full article

Encapsulated magnetic nanoparticles are of increasing interest for biomedical applications. However, up to now, it is still not possible to characterize their localized magnetic properties within the capsules. Magnetic Force Microscopy (MFM) has proved to be a suitable technique to image magnetic nanoparticles at ambient conditions revealing information about the spatial distribution and the magnetic properties of the nanoparticles simultaneously. However, MFM measurements on magnetic nanoparticles lead to falsifications of the magnetic MFM signal due to the topographic crosstalk. The origin of the topographic crosstalk in MFM has been proven to be capacitive coupling effects due to distance change between the substrate and tip measuring above the nanoparticle. In this paper, we present data fusion of the topography measurements of Atomic Force Microscopy (AFM) and the phase image of MFM measurements in combination with the theory of capacitive coupling in order to eliminate the topographic crosstalk in the phase image. This method offers a novel approach for the magnetic visualization of encapsulated magnetic nanoparticles. Full article

This paper presents an experimental study about the preparation, by electrospinning, of uranium carbide fibers with nanometric grain size. Viscous solutions of cellulose acetate and uranyl salts (acetate, acetylacetonate, and formate) on acetic acid and 2,4-pentanedione, adjusted to three different polymer concentrations, 10, 12.5, and 15 weight %, were used for electrospinning. Good quality precursor fibers were obtained from solutions with a 15% cellulose acetate concentration, the best ones being produced from the uranyl acetate solution. As-spun precursor fibers were then decomposed by slow heating until 823 K under argon, resulting in a mixture of nano-grained UO₂ and C fibers. A last carboreduction was then carried out under vacuum at 2073 K for 2 h. The final material displayed UC_2−y as the major phase, with grain sizes in the 4 nm–10 nm range. UO_2+x was still present in moderate concentrations (~30 vol.%). This is due to uncomplete carboreduction that can be explained by the fiber morphology, limiting the effective contact between C and UO₂ grains. Full article

Electrolyte composition is a crucial factor determining the capacitive properties of a supercapacitor device. However, its complex influence on the energy storage mechanisms has not yet been fully elucidated. For this purpose, in this study, the role of three different types of electrolytes based on a propylene carbonate (PC) solution containing tetrabutylammonium perchlorate (TBAClO₄), lithium perchlorate (LiClO₄) and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide (N₁₁₁₄TFSI) ionic liquid on vertically-oriented graphene nanosheet electrodes has been investigated. Herein, in situ electrochemical quartz crystal microbalance (EQCM) and its coupling with electrochemical impedance spectroscopy (EIS), known as ac-electrogravimetry, have allowed the dynamic aspects of the (co)electroadsorption processes at the electrode-electrolyte interface to be examined. A major contribution of ClO₄⁻ anions (TBAClO₄) was evidenced, whereas in the PC/N₁₁₁₄TFSI mixture (50:50 wt%) both anions (TFSI⁻) and cations (N₁₁₁₄⁺) were symmetrically exchanged during cycling. In the particular case of LiClO₄, solvation of Li⁺ cations in PC was involved, affecting the kinetics of electroadsorption. These results demonstrate the suitability of dynamic electrogravimetric methods to unveil the interfacial exchange properties of mobile species for the conception of new high performance energy storage devices. Full article