Editor’s Choice Articles

SiO_x thin films were prepared using magnetron sputtering with different O₂ flow rates on a silicon substrate. The samples were characterized using Fourier transform infrared spectroscopy in transmission and reflection, covering a spectral range of 5 to 25 μm. By employing a multilayer model, the values of the complex refractive index that best fit the experimental transmission and reflection results were optimized using the Brendel–Bormann oscillator model. The results demonstrate the significance of selecting an appropriate range of O₂ flow rates to modify the SiO_x stoichiometry, as well as how the refractive index values can be altered between those of Si and SiO₂ in the mid-infrared range. Full article

The strength of metals and alloys at elevated temperatures typically decreases due to the recovery, recrystallization, grain growth, and growth of second-phase particles. We report here a cold-worked Cu-Al₂O₃ composite did not recrystallize up to a temperature of 0.83T_m of Cu. The composite was manufactured through the internal oxidation process of dilute Cu-0.15 wt.% Al alloy and was characterized by transmission electron microscopy to study the nature of oxide precipitates. As a result of internal oxidation, a small volume fraction (1%) of Al₂O₃ particles forms. In addition, a high density of extremely fine (2–5 nm) Cu₂O particles has been observed to form epitaxially within the elongated Cu grains. These finely dispersed second-phase Cu₂O particles enhance the Zener drag significantly by three orders of magnitude as compared to Al₂O₃ particles and retain their original size and spacing at elevated temperatures. This limits the grain boundary migration and the nucleation of defect-free regions of different orientations and inhibits the recrystallization process at elevated temperatures. In addition, due to the limited grain boundary migration, a bundle of stacking faults appears instead of annealing twins. This investigation has led to a better understanding of how to prevent the recrystallization process of heavily deformed metallic material containing oxide particles. Full article

Radiotherapy (RT) involves delivering X-ray beams to the tumor site to trigger DNA damage. In this approach, it is fundamental to preserve healthy cells and to confine the X-ray beam only to the malignant cells. The integration of gold nanoparticles (AuNPs) in the X-ray methodology could be considered a powerful tool to improve the efficacy of RT. Indeed, AuNPs have proven to be excellent allies in contrasting tumor pathology upon RT due to their high photoelectric absorption coefficient and unique physiochemical properties. However, an analysis of their physical and morphological reaction to X-ray exposure is necessary to fully understand the AuNPs’ behavior upon irradiation before treating the cells, since there are currently no studies on the evaluation of potential NP morphological changes upon specific irradiations. In this work, we synthesized two differently shaped AuNPs adopting two different techniques to achieve either spherical or star-shaped AuNPs. The spherical AuNPs were obtained with the Turkevich–Frens method, while the star-shaped AuNPs (AuNSs) involved a seed-mediated approach. We then characterized all AuNPs with Transmission Electron Microscopy (TEM), Uv-Vis spectroscopy, Dynamic Light Scattering (DLS), zeta potential and Fourier Transform Infrared (FTIR) spectroscopy. The next step involved the treatment of AuNPs with two different doses of X-radiation commonly used in RT, namely 1.8 Gy and 2 Gy, respectively. Following the X-rays’ exposure, the AuNPs were further characterized to investigate their possible physicochemical and morphological alterations induced with the X-rays. We found that AuNPs do not undergo any alteration, concluding that they can be safely used in RT treatments. Lastly, the actin rearrangements of THP-1 monocytes treated with AuNPs were also assessed in terms of coherency. This is a key proof to evaluate the possible activation of an immune response, which still represents a big limitation for the clinical translation of NPs. Full article

Polymer-based dielectric composites are of great importance in advanced electronic industries and energy storage because of their high dielectric constant, good processability, low weight, and low dielectric loss. FDM (Fused Deposition Modeling) is a greatly accessible additive manufacturing technology, which has a number of applications in the fabrication of RF components, but the unavoidable porosity in FDM 3D-printed materials, which affects the dielectric properties of the materials, and the difficulty of large-scale fabrication of composites by FDM limit its application scope. This study’s main focus is on how the matrix, filler, interface, and FDM 3D printing parameters influence the electrical properties of FDM-printed polymer-based dielectric composites. This review article starts with the fundamental theory of dielectrics. It is followed by a summary of the factors influencing dielectric properties in recent research developments, as well as a projection for the future development of FDM-prepared polymer-based dielectric composites. Finally, improving the comprehensive performance of dielectric composites is an important direction for future development. Full article

We demonstrate a simple, low-energy method whereby tomato mosaic virus (ToMV) particles can be used to template the production of nanowires and particles consisting of alloys of gold (Au), platinum (Pt) and palladium (Pd) in various combinations. Selective nanowire growth within the inner channel of the particles was achieved using the polymeric capping agent polyvinylpyrrolidone (PVP_K30) and the reducing agent ascorbic acid. The reaction conditions also resulted in the deposition of alloy nanoparticles on the external surface of the rods in addition to the nanowire structures within the internal cavity. The resulting materials were characterized using a variety of electron microscopic and spectroscopic techniques, which revealed both the structural and chemical composition of the alloys within the nanomaterials. Full article

The short- and long-term impacts of nanoparticles (NPs) in consumer products are not fully understood. Current European Union (EU) regulations enforce transparency on products containing NPs in cosmetic formulations; however, those set by the U.S. Food and Drug Administration are lacking. This study demonstrates the potential of single-particle inductively coupled plasma tandem mass spectrometry (spICP-MS/MS) as a screening method for NPs present in powder-based facial cosmetics (herein referred to as FCs). A proposed spICP-MS/MS method is presented along with recommended criteria to confirm particle presence and particle detection thresholds in seven FCs. FC products of varying colors, market values, and applications were analyzed for the presence of Bi, Cr, Mg, Mn, Pb, Sn, Ag, Al, and Zn NPs based on their ingredient lists as well as those commonly used in cosmetic formulations. The presence of NPs smaller than 100 nm was observed in all FC samples, and no correlations with their presence and market value were observed. Here, we report qualitative and semi-quantitative results for seven FC samples ranging in color, brand, and shimmer. Full article

TiB₂ is a promising material for several fields including impact-resistant armor, wear-resistant coatings, cutting tools and crucibles given its physical, mechanical and chemical properties, especially due to the combination of high hardness and exceptional wear resistance. It is however very difficult to sinter below 2000 °C, even under mechanical pressure; moreover, the low fracture toughness limits the applicability of the ceramic material. By using sintering additives, it is possible to improve the sintering process and increase the mechanical properties since the additives react with oxidized layers and form secondary phases. In this study, different preparation methods and various combinations of additives (B₄C, Si₃N₄ and MoSi₂) via hot pressing sintering have been explored. Through the synergy between optimized process and tailored composition, an almost fully dense material was obtained at 1700 °C with hardness of 24.4 ± 0.2 GPa and fracture toughness of 5.4 ± 0.2 MPa m^1/2. However, the highest hardness (24.5 ± 0.2 GPa) and density values were obtained for only the high-energy-milled sample with WC-Co media, featuring a core–shell grain structure. Finally, optical properties for selected samples were measured, identifying the high-energy-milled TiB₂ as the sample with the highest spectral selectivity α/ε and solar absorptance. Full article

The exceptional property of plasmonic materials to localize light into sub-wavelength regimes has significant importance in various applications, especially in photovoltaics. In this study, we report the localized surface plasmon-enhanced perovskite solar cell (PSC) performance of plasmonic gold nanoparticles (AuNPs) embedded into a titanium oxide (TiO₂) microdot array (MDA), which was deposited using the inkjet printing technique. The X-ray (XRD) analysis of MAPI (methyl ammonium lead iodide) perovskite films deposited on glass substrates with and without MDA revealed no destructive effect of MDA on the perovskite structure. Moreover, a 12% increase in the crystallite size of perovskite with MDA was registered. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) techniques revealed the morphology of the TiO₂_MDA and TiO₂-AuNPs_MDA. The finite-difference time-domain (FDTD) simulation was employed to evaluate the absorption cross-sections and local field enhancement of AuNPs in the TiO₂ and TiO₂/MAPI surrounding media. Reflectance UV-Vis spectra of the samples comprising glass/TiO₂ ETL/TiO₂_MDA (ETL—an electron transport layer) with and without AuNPs in TiO₂_MDA were studied, and the band gap (E_g) values of MAPI have been calculated using the Kubelka–Munk equation. The MDA introduction did not influence the band gap value, which remained at ~1.6 eV for all the samples. The photovoltaic performance of the fabricated PSC with and without MDA and the corresponding key parameters of the solar cells have also been studied and discussed in detail. The findings indicated a significant power conversion efficiency improvement of over 47% in the PSCs with the introduction of the TiO₂-AuNPs_MDA on the ETL/MAPI interface compared to the reference device. Our study demonstrates the significant enhancement achieved in halide PSC by utilizing AuNPs within a TiO₂_MDA. This approach holds great promise for advancing the efficiency and performance of photovoltaic devices. Full article

Among semiconductor metal oxides, that are an important class of sensing materials, titanium dioxide (TiO₂) thin films are widely employed as sensors because of their high chemical and mechanical stability in harsh environments, non-toxicity, eco-compatibility, and photocatalytic properties. TiO₂-based chemical oxygen demand (COD) sensors exploit the photocatalytic properties of TiO₂ in inducing the oxidation of organic compounds to CO₂. In this work, we discuss nanostructured TiO₂ thin films grown via low-pressure metal organic chemical vapor deposition (MOCVD) on metallic AISI 316 mesh. To increase the surface sensing area, different inorganic acid-based chemical etching protocols have been developed, determining the optimal experimental conditions for adequate substrate roughness. Both chemically etched pristine meshes and the MOCVD-coated ones have been studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) microanalysis, and X-ray photoelectron spectroscopy (XPS). We demonstrate that etching by HCl/H₂SO₄ at 55 °C provides the most suitable surface morphology. To investigate the behavior of the developed high surface area TiO₂ thin films as COD sensors, photocatalytic degradation of functional model pollutants based on ISO 10678:2010 has been tested, showing for the best performing acid-etched mesh coated with polycrystalline TiO₂ an increase of 60% in activity, and degrading 66 µmol of MB per square meter per hour. Full article

Two-dimensional multiferroic (2D) materials have garnered significant attention due to their potential in high-density, low-power multistate storage and spintronics applications. MXenes, a class of 2D transition metal carbides and nitrides, were first discovered in 2011, and have become the focus of research in various disciplines. Our study, utilizing first-principles calculations, examines the lattice structures, and electronic and magnetic properties of nitride MXenes with intrinsic band gaps, including V₂NF₂, V₂NO₂, Cr₂NF₂, Mo₂NO₂, Mo₂NF₂, and Mn₂NO₂. These nitride MXenes exhibit orbital ordering, and in some cases the orbital ordering induces magnetoelastic coupling or magnetoelectric coupling. Most notably, Cr₂NF₂ is a ferroelastic material with a spiral magnetic ordered phase, and the spiral magnetization propagation vector is coupled with the direction of ferroelastic strain. The ferroelectric phase can exist as an excited state in V₂NO₂, Cr₂NF₂, and Mo₂NF₂, with their magnetic order being coupled with polar displacements through orbital ordering. Our results also suggest that similar magnetoelectric coupling effects persist in the Janus MXenes V₈N₄O₇F, Cr₈N₄F₇O, and Mo₈N₄F₇O. Remarkably, different phases of Mo₈N₄F₇O, characterized by orbital ordering rearrangements, can be switched by applying external strain or an external electric field. Overall, our theoretical findings suggest that nitride MXenes hold promise as 2D multiferroic materials. Full article

In this study, Pt nanoparticles-loaded nitrogen-doped mesoporous carbon nanotube (Pt/NMCT) was successfully synthesized through a polydopamine-mediated “one-pot” co-deposition strategy. The Pt source was introduced during the co-deposition of polydopamine and silica on the surface of SiO₂ nanowire (SiO₂ NW), and Pt atoms were fixed in the skeleton by the chelation of polydopamine. Thus, in the subsequent calcination process in nitrogen atmosphere, the growth and agglomeration of Pt nanoparticles were effectively restricted, achieving the in situ loading of uniformly dispersed, ultra-small (~2 nm) Pt nanoparticles. The method is mild, convenient, and does not require additional surfactants, reducing agents, or stabilizers. At the same time, the use of the dual silica templates (SiO₂ NW and the co-deposited silica nanoclusters) brought about a hierarchical pore structure with a high specific surface area (620 m² g⁻¹) and a large pore volume (1.46 cm³ g⁻¹). The loading process of Pt was studied by analyzing the electron microscope and X-ray photoelectron spectroscopy of the intermediate products. The catalytic performance of Pt/NMCT was investigated in the reduction of 4-nitrophenol. The Pt/NMCT with a hierarchical pore structure had an apparent reaction rate constant of 0.184 min⁻¹, significantly higher than that of the sample, without the removal of the silica templates to generate the hierarchical porosity (0.017 min⁻¹). This work provides an outstanding contribution to the design of supported noble metal catalysts and also highlights the importance of the hierarchical pore structure for catalytic activity. Full article

The complete removal of low concentration organic pollutants from wastewater to obtain clean water has always been a highly desired but challenging issue. In response to this, we proposed a new strategy to fabricate a carbon-in-silicate nanohybrid composite by recycling dye-loaded layered clay adsorbent and converting them to new heterogeneous carbon-in-silicate nanocomposite through an associated calcination-hydrothermal activation process. It has been confirmed that most of the dye molecules were present in waste rectorite adsorbent using an intercalation mode, which can be in situ converted to carbon in the confined interlayer spacing of rectorite. The further hydrothermal activation process may further improve the pore structure and increase surface active sites. As expected, the optimal composite shows extremely high removal rates of 99.6% and 99.5% for Methylene blue (MB) and Basic Red 14 (BR) at low concentrations (25 mg/L), respectively. In addition, the composite adsorbent also shows high removal capacity for single-component and two-component dyes in deionized water and actual water (i.e., Yellow River water, Yangtze River water, and seawater) with a removal rate higher than 99%. The adsorbent has good reusability, and the adsorption efficiency is still above 93% after five regeneration cycles. The waste clay adsorbent-derived composite adsorbent can be used as an inexpensive material for the decontamination of dyed wastewater. Full article

The visible-light-driven photocatalytic degradation of pharmaceutical pollutants in aquatic environments is a promising strategy for addressing water pollution problems. This work highlights the use of bromine-ion-doped layered Aurivillius oxide, Bi₂WO₆, to synergistically optimize the morphology and increase the formation of active sites on the photocatalyst’s surface. The layered Bi₂WO₆ nanoplates were synthesized by a facile hydrothermal reaction in which bromine (Br⁻) ions were introduced by adding cetyltrimethylammonium bromide (CTAB)/tetrabutylammonium bromide (TBAB)/potassium bromide (KBr). The as-synthesized Bi₂WO₆ nanoplates displayed higher photocatalytic tetracycline degradation activity (~83.5%) than the Bi₂WO₆ microspheres (~48.2%), which were obtained without the addition of Br precursors in the reaction medium. The presence of Br⁻ was verified experimentally, and the newly formed Bi₂WO₆ developed as nanoplates where the adsorbed Br⁻ ions restricted the multilayer stacking. Considering the significant morphology change, increased specific surface area, and enhanced photocatalytic performance, using a synthesis approach mediated by Br⁻ ions to design layered photocatalysts is expected to be a promising system for advancing water remediation. Full article

To evaluate lung toxicity due to inhalation of multi-walled carbon nanotubes (MWCNTs) in rats, we developed a unique MWCNT aerosol generator based on dry aerosolization using the aerodynamic cyclone principle. Rats were exposed to MWNT-7 (also known as Mutsui-7 and MWCNT-7) aerosolized using this device. We report here an analysis of previously published data and additional unpublished data obtained in 1-day, 2-week, 13-week, and 2-year inhalation exposure studies. In one-day studies, it was found that approximately 50% of the deposited MWNT-7 fibers were cleared the day after the end of exposure, but that clearance of the remaining fibers was markedly reduced. This is in agreement with the premise that the rapidly cleared fibers were deposited in the ciliated airways while the slowly cleared fibers were deposited beyond the ciliated airways in the respiratory zone. Macrophage clearance of MWNT-7 fibers from the alveoli was limited. Instead of macrophage clearance from the alveoli, containment of MWNT-7 fibers within induced granulomatous lesions was observed. The earliest changes indicative of pulmonary toxicity were seen in the bronchoalveolar lavage fluid. Macrophage-associated inflammation persisted from the one-day exposure to MWNT-7 to the end of the two-year exposure period. Correlation of lung tumor development with MWNT-7 lung burden required incorporating the concept of area under the curve for the duration of the study; the development of lung tumors induced by MWNT-7 correlated with lung burden and the duration of MWNT-7 residence in the lung. Full article

Hydrogen is a promising green fuel carrier that can replace fossil fuels; however, its storage is still a challenge. Carbon-based materials with metal catalysts have recently been the focus of research for solid-state hydrogen storage due to their efficacy and low cost. Here, we report on the exfoliation of expanded graphite (EG) through high shear mixing and probe tip sonication methods to form graphene-based nanomaterial ShEG and sEG, respectively. The exfoliation processes were optimized based on electrochemical capacitance measurements. The exfoliated EG was further functionalized with palladium nanoparticles (Pd-NP) for solid-state hydrogen storage. The prepared graphene-based nanomaterials (ShEG and sEG) and the nanocomposites (Pd-ShEG and Pd-sEG) were characterized with various traditional techniques (e.g., SEM, TEM, EDX, XPS, Raman, XRD) and the advanced high-resolution pair distribution function (HRPDF) analysis. Electrochemical hydrogen uptake and release (Q_H) were measured, showing that the sEG decorated with Pd-NP (Pd-sEG, 31.05 mC cm⁻²) and ShEG with Pd-NP (Pd-ShEG, 24.54 mC cm⁻²) had a notable improvement over Pd-NP (9.87 mC cm⁻²) and the composite of Pd-EG (14.7 mC cm⁻²). Q_H showed a strong linear relationship with an effective surface area to volume ratio, indicating nanoparticle size as a determining factor for hydrogen uptake and release. This work is a promising step toward the design of the high-performance solid-state hydrogen storage devices through mechanical exfoliation of the substrate EG to control nanoparticle size and dispersion. Full article

Lubricant (or oil)-impregnated porous surface has been considered as a promising surface treatment to realize multifunctionality. In this study, silicone oil was impregnated into a hard porous oxide layer created by the plasma electrolytic oxidation (PEO) of aluminum (Al) alloys. The monolayer of polydimethylsiloxane (PDMS) from silicone oil is formed on a porous oxide layer; thus, a water-repellent slippery oil-impregnated surface is realized on Al alloy, showing a low contact angle hysteresis of less than 5°. This water repellency significantly enhanced the corrosion resistance by more than four orders of magnitude compared to that of the PEO-treated Al alloy without silicone oil impregnation. The silicone oil within the porous oxide layer also provides a lubricating effect to improve wear resistance by reducing friction coefficients from ~0.6 to ~0.1. In addition, because the PDMS monolayer can be restored by frictional heat, the water-repellent surface is tolerant to physical damage to the oxide surface. Hence, the results of this fundamental study provide a new approach for the post-treatment of PEO for Al alloys. Full article

Magnetism plays a pivotal role in many biological systems. However, the intensity of the magnetic forces exerted between magnetic bodies is usually low, which demands the development of ultra-sensitivity tools for proper sensing. In this framework, magnetic force microscopy (MFM) offers excellent lateral resolution and the possibility of conducting single-molecule studies like other single-probe microscopy (SPM) techniques. This comprehensive review attempts to describe the paramount importance of magnetic forces for biological applications by highlighting MFM’s main advantages but also intrinsic limitations. While the working principles are described in depth, the article also focuses on novel micro- and nanofabrication procedures for MFM tips, which enhance the magnetic response signal of tested biomaterials compared to commercial nanoprobes. This work also depicts some relevant examples where MFM can quantitatively assess the magnetic performance of nanomaterials involved in biological systems, including magnetotactic bacteria, cryptochrome flavoproteins, and magnetic nanoparticles that can interact with animal tissues. Additionally, the most promising perspectives in this field are highlighted to make the reader aware of upcoming challenges when aiming toward quantum technologies. Full article

We investigated solution-grown single crystals of multidimensional 2D–3D hybrid lead bromide perovskites using spatially resolved photocurrent and photoluminescence. Scanning photocurrent microscopy (SPCM) measurements where the electrodes consisted of a dip probe contact and a back contact. The crystals revealed significant differences between 3D and multidimensional 2D–3D perovskites under biased detection, not only in terms of photocarrier decay length values but also in the spatial dynamics across the crystal. In general, the photocurrent maps indicate that the closer the border proximity, the shorter the effective decay length, thus suggesting a determinant role of the border recombination centers in monocrystalline samples. In this case, multidimensional 2D–3D perovskites exhibited a simple fitting model consisting of a single exponential, while 3D perovskites demonstrated two distinct charge carrier migration dynamics within the crystal: fast and slow. Although the first one matches that of the 2D–3D perovskite, the long decay of the 3D sample exhibits a value two orders of magnitude larger. This difference could be attributed to the presence of interlayer screening and a larger exciton binding energy of the multidimensional 2D–3D perovskites with respect to their 3D counterparts. Full article

In a contemporary sustainable economy, innovation is a prerequisite to recycling waste into new efficient materials designed to minimize pollution and conserve non-renewable natural resources. Using an innovative approach to remediating metal-polluted water, in this study, eggshell waste was used to prepare two new low-cost nanoadsorbents for the retrieval of nickel from aqueous solutions. Scanning electron microscopy (SEM) results show that in the first eggshell–zeolite (EZ) adsorbent, the zeolite nanoparticles were loaded in the eggshell pores. The preparation for the second (iron(III) oxide-hydroxide)–eggshell–zeolite (FEZ) nanoadsorbent led to double functionalization of the eggshell base with the zeolite nanoparticles, upon simultaneous loading of the pores of the eggshell and zeolite surface with FeOOH particles. Structural modification of the eggshell led to a significant increase in the specific surface, as confirmed using BET analysis. These features enabled the composite EZ and FEZ to remove nickel from aqueous solutions with high performance and adsorption capacities of 321.1 mg/g and 287.9 mg/g, respectively. The results indicate that nickel adsorption on EZ and FEZ is a multimolecular layer, spontaneous, and endothermic process. Concomitantly, the desorption results reflect the high reusability of these two nanomaterials, collectively suggesting the use of waste in the design of new, low-cost, and highly efficient composite nanoadsorbents for environmental bioremediation. Full article

Exposure to nanoparticles is inevitable as they become widely used in industry, cosmetics, and foods. However, knowledge of their (patho)physiological effects on biological entry routes of the human body and their underlying molecular mechanisms is still fragmented. Here, we examined the molecular effects of amorphous silica nanoparticles (aSiNPs) on cell lines mimicking the alveolar-capillary barrier of the lung. After state-of-the-art characterization of the used aSiNPs and the cell model, we performed cell viability-based assays and a protein analysis to determine the aSiNP-induced cell toxicity and underlying signaling mechanisms. We revealed that aSiNPs induce apoptosis in a dose-, time-, and size-dependent manner. aSiNP-induced toxicity involves the inhibition of pro-survival pathways, such as PI3K/AKT and ERK signaling, correlating with reduced expression of the anti-apoptotic protein Survivin on the protein and transcriptional levels. Furthermore, induced Survivin overexpression mediated resistance against aSiNP-toxicity. Thus, we present the first experimental evidence suggesting Survivin as a critical cytoprotective resistor against silica-based nanotoxicity, which may also play a role in responses to other NPs. Although Survivin’s relevance as a biomarker for nanotoxicity needs to be demonstrated in vivo, our data give general impetus to investigate the pharmacological modulation of Survivin`s functions to attenuate the harmful effects of acute or chronic inhalative NP exposure. Full article

Lactoferrin (Lf) is a globular glycoprotein found mainly in milk. It has a very high affinity for iron(III) ions, and its fully saturated form is called holoLf. The antimicrobial, antiviral, anticancer, and immunomodulatory properties of Lf have been studied extensively for the past two decades. However, to demonstrate therapeutic benefits, Lf has to be efficiently delivered to the intestinal tract in its structurally intact form. This work aimed to optimize the encapsulation of holoLf in a system based on the versatile Eudragit^® RS polymer to protect Lf against the proteolytic environment of the stomach. Microparticles (MPs) with entrapped holoLf were obtained with satisfactory entrapment efficiency (90–95%), high loading capacity (9.7%), and suitable morphology (spherical without cracks or pores). Detailed studies of the Lf release from the MPs under conditions that included simulated gastric or intestinal fluids, prepared according to the 10th edition of the European Pharmacopeia, showed that MPs partially protected holoLf against enzymatic digestion and ionic iron release. The preincubation of MPs loaded with holoLf under conditions simulating the stomach environment resulted in the release of 40% of Lf from the MPs. The protein released was saturated with iron ions at 33%, was structurally intact, and its iron scavenging properties were preserved. Full article

The synergistic combination of hybrid perovskites with graphene-related materials is leading to optoelectronic devices with enhanced performance and stability. Still, taking advantage of the solution processing of perovskite onto graphene is especially challenging. Here, MAPbBr₃ perovskite is grown on single-layer graphene/graphene oxide (Gr/GO) patterns with 120 µm periodicity using a solution-processed method. MAPbBr₃ rounded crystals are formed with sizes ranging from nanometers to microns, either forming continuous films or dispersed particles. A detailed morphological and structural study reveals a fully oriented perovskite and very different growth habits on the Gr/GO micro-patterns, which we relate to the substrate characteristics and the nucleation rate. A simple method for controlling the nucleation rate is proposed based on the concentration of the precursor solution and the number of deposited perovskite layers. The photoluminescence is analyzed in terms of the crystal size, strain, and structural changes observed. Notably, the growth on top of Gr/GO leads to a huge photostability of the MAPbBr₃ compared with that on glass. Especially outstanding is that of the microcrystals, which endure light densities as high as 130 kW/cm². These results allow for anticipating the design of integrated nanostructures and nanoengineered devices by growing high-stability perovskite directly on Gr/GO substrates. Full article

Due to environmental concerns regarding single-use plastic materials, major efforts are being made to develop new material concepts based on biodegradable and renewable resources, e.g., wood pulp. In this study, we assessed two types of wood pulp fibres, i.e., thermomechanical pulp (TMP) and Kraft pulp fibres, and tested the performance of the fibres in wet-moulding and thermopressing trials. Kraft pulp fibres appeared to retain more water than TMP, increasing the dewatering time during wet-moulding and apparently increasing the compression resistance of the pulp during thermoforming. Additionally, cellulose nanofibres (CNF) were added to the pulps, which improved the mechanical properties of the final thermopressed specimens. However, the addition of CNF to the pulps (from 2 to 6%) had a further decrease in the dewatering efficiency in the wet-moulding process, and this effect was more pronounced in the Kraft pulp specimens. The mechanical performance of the thermoformed specimens was in the same range as the plastic materials that are conventionally used in food packaging, i.e., modulus 0.6–1.2 GPa, strength 49 MPa and elongation 6–9%. Finally, this study demonstrates the potential of wood pulps to form three-dimensional thermoformed products. Full article

The increasing use of graphene oxide (GO) will result in its release into the environment; therefore, it is essential to determine its final fate and possible metabolism by organisms. The objective of this study was to assess the possible role of the aryl hydrocarbon receptor (AhR)-dependent cytochrome P4501A (Cyp1A) detoxification activities on the catabolism of GO. Our hypothesis is that GO cannot initially interact with the AhR, but that after an initial degradation caused by other mechanisms, small fractions of GO could activate the AhR, inducing Cyp1A. The environmental pollutant benzo(k)fluoranthene (BkF) was used for the initial activation of the AhR in the rainbow trout (Oncorhynchus mykiss) cell line RTL-W1. Pre-, co-, and post-exposure experiments with GO were performed and Cyp1A induction was monitored. The strong stimulation of Cyp1A observed in cells after exposure to GO, when BkF levels were not detected in the system, suggests a direct action of GO. The role of the AhR was confirmed by a blockage of the observed effects in co-treatment experiments with αNF (an AhR antagonist). These results suggest a possible role for the AhR and Cyp1A system in the cellular metabolism of GO and that GO could modulate the toxicity of environmental pollutants. Full article

Herein, we present a new heterogeneous catalyst active toward glucose to formic acid methyl ester oxidation. The catalyst was fabricated via electrostatic immobilization of the inorganic polyoxometalate HPA-5 catalyst H₈[PMo₇V₅O₄₀] onto the pore surface of amphiphilic block copolymer membranes prepared via non-solvent-induced phase separation (NIPS). The catalyst immobilization was achieved via wet impregnation due to strong coulombic interactions between protonated tertiary amino groups of the polar poly(2-(dimethylamino)ethyl methacrylate) block and the anionic catalyst. Overall, three sets of five consecutive catalytic cycles were performed in an autoclave under 90 °С and 11.5 bar air pressure in methanol, and the corresponding yields of formic acid methyl ester were quantified via head-space gas chromatography. The obtained results demonstrate that the membrane maintains its catalytic activity over multiple cycles, resulting in high to moderate yields in comparison to a homogeneous catalytic system. Nevertheless, presumably due to leaching, the catalytic activity declines over five catalytic cycles. The morphological and chemical changes of the membrane during the prolonged catalysis under harsh conditions were examined in detail using different analytic tools, and it seems that the underlying block copolymer is not affected by the catalytic process. Full article

Exposure to metal nanoparticles is potentially harmful, particularly when occurring during embryogenesis. In this study, we tested the effects of commercial AuNPs and AgNPs, widely used in many fields for their features, on the early development of Xenopus laevis, an anuran amphibian key model species in toxicity testing. Through the Frog Embryo Teratogenesis Assay—Xenopus test (FETAX), we ascertained that both nanoparticles did not influence the survival rate but induced morphological anomalies like modifications of head and branchial arch cartilages, depigmentation of the dorsal area, damage to the intestinal brush border, and heart rate alteration. The expression of genes involved in the early pathways of embryo development was also modified. This study suggests that both types of nanoparticles are toxic though nonlethal, thus indicating that their use requires attention and further study to better clarify their activity in animals and, more importantly, in humans. Full article

By taking advantage of the outstanding intrinsic optoelectronic properties of perovskite-based photovoltaic materials, together with the strong near-infrared (NIR) absorption and electronic confinement in PbS quantum dots (QDs), sub-bandgap photocurrent generation is possible, opening the way for solar cell efficiencies surpassing the classical limits. The present study shows an effective methodology for the inclusion of high densities of colloidal PbS QDs in a MAPbI₃ (methylammonium lead iodide) perovskite matrix as a means to enhance the spectral window of photon absorption of the perovskite host film and allow photocurrent production below its bandgap. The QDs were introduced in the perovskite matrix in different sizes and concentrations to study the formation of quantum-confined levels within the host bandgap and the potential formation of a delocalized intermediate mini-band (IB). Pronounced sub-bandgap (in NIR) absorption was optically confirmed with the introduction of QDs in the perovskite. The consequent photocurrent generation was demonstrated via photoconductivity measurements, which indicated IB establishment in the films. Despite verifying the reduced crystallinity of the MAPbI₃ matrix with a higher concentration and size of the embedded QDs, the nanostructured films showed pronounced enhancement (above 10-fold) in NIR absorption and consequent photocurrent generation at photon energies below the perovskite bandgap. Full article

The cold sintering process (CSP) for synthesizing oxide-based electrolytes, which uses water transient solvents and uniaxial pressure, is a promising alternative to the conventional high temperature sintering process due to its low temperature (<200 °C) and short processing time (<2 h). However, the formation of amorphous secondary phases in the intergranular regions, which results in poor ionic conductivity (σ), remains a challenge. In this study, we introduced high-boiling solvents of dimethylformamide (DMF, b.p.: 153 °C) and dimethyl sulfoxide (DMSO, b.p.: 189 °C) as transient solvents to develop composite electrolytes of Li₁.₅Al₀.₅Ge₁.₅(PO₄)₃ (LAGP) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Our results show that composite electrolytes processed with the DMF/water mixture (CSP LAGP-LiTFSI DMF/H₂O) yield a high σ of 10⁻⁴ S cm⁻¹ at room temperature and high relative densities of >87%. Furthermore, the composite electrolytes exhibit good thermal stability; the σ maintains its initial value after heat treatment. In contrast, the composite electrolytes processed with the DMSO/water mixture and water alone show thermal degradation. The CSP LAGP-LiTFSI DMF/H₂O composite electrolytes exhibit long-term stability, showing no signs of short circuiting after 350 h at 0.1 mAh cm⁻² in Li symmetric cells. Our work highlights the importance of selecting appropriate transient solvents for producing efficient and stable composite electrolytes using CSP. Full article

Yttrium oxide (Y₂O₃) resistive random-access memory (RRAM) devices were fabricated using the sol–gel process on indium tin oxide/glass substrates. These devices exhibited conventional bipolar RRAM characteristics without requiring a high-voltage forming process. The effect of current compliance on the Y₂O₃ RRAM devices was investigated, and the results revealed that the resistance values gradually decreased with increasing set current compliance values. By regulating these values, the formation of pure Ag conductive filament could be restricted. The dominant oxygen ion diffusion and migration within Y₂O₃ leads to the formation of oxygen vacancies and Ag metal-mixed conductive filaments between the two electrodes. The filament composition changes from pure Ag metal to Ag metal mixed with oxygen vacancies, which is crucial for realizing multilevel cell (MLC) switching. Consequently, intermediate resistance values were obtained, which were suitable for MLC switching. The fabricated Y₂O₃ RRAM devices could function as a MLC with a capacity of two bits in one cell, utilizing three low-resistance states and one common high-resistance state. The potential of the Y₂O₃ RRAM devices for neural networks was further explored through numerical simulations. Hardware neural networks based on the Y₂O₃ RRAM devices demonstrated effective digit image classification with a high accuracy rate of approximately 88%, comparable to the ideal software-based classification (~92%). This indicates that the proposed RRAM can be utilized as a memory component in practical neuromorphic systems. Full article

Cleaning represents an important and challenging operation in the conservation of cultural heritage, and at present, a key issue consists in the development of more sustainable, “green” materials and methods to perform it. In the present work, a novel xylene-in-water microemulsion based on nonionic surfactants with low toxicity was obtained, designed as low-impact cleaning agent for metallic historic objects. Phase diagram of the mixtures containing polyoxyethylene-polyoxypropilene triblock copolymer Pluronic P84 and D-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS) as surfactants, water, ethanol and xylene was studied, and a microemulsion with low surfactant content was selected as suitable cleaning nanosystem. Essential oils (EOs) from thyme and cinnamon leaf were added to the selected microemulsion in order to include other beneficial properties such as anticorrosive and antifungal protection. The microemulsions with or without EOs were characterized by size, size distribution and zeta potential. The cleaning efficacy of the tested microemulsions was assessed based on their ability to remove two types of artificial dirt by using X-ray energy dispersion spectrometry (EDX), scanning electron microscopy (SEM), contact angle measurements and color analysis. Microemulsions exhibit high capacity to remove artificial dirt from model copper coupons in spite of very low content of the organic solvent. Both thyme and cinnamon oil loading microemulsions prove to significantly reduce the corrosion rate of treated metallic plates compared to those of bare copper. The antifungal activity of the novel type of microemulsion was evaluated against Aspergillus niger, reported as main treat in biocorrosion of historic copper artifacts. Application of microemulsion with small amounts of EOs on Cu plates inhibits the growth of fungi, providing a good fungicidal effect. Full article

The development of functional catalysts for the photogeneration of hydrogen (H₂) via water-splitting is crucial in the pursuit of sustainable energy solutions. To that end, metal-sulfide semiconductors, such as CdS and ZnS, can play a significant role in the process due to their interesting optoelectronic and catalytic properties. However, inefficient charge-carrier dissociation and poor photochemical stability remain significant limitations to photocatalytic efficiency. Herein, dual-semiconductor nanocomposites of ZnS/CdS nanocrystal assemblies (NCAs) are developed as efficient visible light photocatalysts for H₂ generation. The resultant materials, synthesized via a polymer-templated self-polymerization method, comprise a unique combination of ~5–7 nm-sized metal-sulfide nanoparticles that are interlinked to form a 3D open-pore structure with large internal surface area (up to 285 m² g⁻¹) and uniform pores (circa 6–7 nm). By adjusting the ratio of constituent nanoparticles, the optimized ZnS/CdS catalyst with 50 wt.% ZnS content demonstrates a remarkable stability and visible light H₂-evolution activity (~29 mmol g⁻¹ h⁻¹ mass activity) with an apparent quantum yield (AQY) of 60% at 420 nm. Photocatalytic evaluation experiments combined with electrochemical and spectroscopic studies suggest that the superior photocatalytic performance of these materials stems from the accessible 3D open-pore structure and the efficient defect-mediated charge transfer mechanism at the ZnS/CdS nanointerfaces. Overall, this work provides a new perspective for designing functional and stable photocatalytic materials for sustainable H₂ production. Full article

Carbon-doped boron nitride (denoted by BN/C) was prepared through the pyrolysis at 1100 °C of a nanostructured mixture of an alkyl amine borane adduct and ammonia borane. The alkyl amine borane adduct acts as a soft template to obtain nanospheres. This bottom-up approach for the synthesis of nanostructured BN/C is relatively simple and compelling. It allows the structure obtained during the emulsion process to be kept. The final BN/C materials are microporous, with interconnected pores in the nanometer range (0.8 nm), a large specific surface area of up to 767 m²·g⁻¹ and a pore volume of 0.32 cm³·g⁻¹. The gas sorption studied with CO₂ demonstrated an appealing uptake of 3.43 mmol·g⁻¹ at 0 °C, a high CO₂/N₂ selectivity (21) and 99% recyclability after up to five adsorption–desorption cycles. Full article

For a very long period, tin was considered one of the most important metals for humans due to its easy access in nature and abundance of sources. In the past, tin was mainly used to make various utensils and weapons. Today, nanostructured tin and especially its oxide materials have been found to possess many characteristic physical and chemical properties that allow their use as functional materials in various fields such as energy storage, photocatalytic process, gas sensors, and solar cells. This review discusses current methods for the synthesis of Sn/SnO₂ composite materials in form of powder or thin film, as well as the application of the most advanced characterization tools based on large-scale synchrotron radiation facilities to study their chemical composition and electronic features. In addition, the applications of Sn/SnO₂ composites in various fields are presented in detail. Full article

We study the low-temperature (T = 4.7 K) emission dynamics of a thin film of methylammonium lead bromide (MAPbBr${}_3$), prepared via the anti-solvent method. Using intensity-dependent (over 5 decades) hyperspectral microscopy under quasi-resonant (532 nm) continuous wave excitation, we revealed spatial inhomogeneities in the thin film emission. This was drastically different at the band-edge (∼550 nm, sharp peaks) than in the emission tail (∼568 nm, continuum of emission). We are able to observe regions of the film at the micrometer scale where emission is dominated by excitons, in between regions of trap emission. Varying the density of absorbed photons by the MAPbBr${}_3$ thin films, two-color fluorescence lifetime imaging microscopy unraveled the emission dynamics: a fast, resolution-limited (∼200 ps) monoexponential tangled with a stretched exponential decay. We associate the first to the relaxation of excitons and the latter to trap emission dynamics. The obtained stretching exponents can be interpreted as the result of a two-dimensional electron diffusion process: Förster resonant transfer mechanism. Furthermore, the non-vanishing fast monoexponential component even in the tail of the MAPbBr${}_3$ emission indicates the subsistence of localized excitons. Finally, we estimate the density of traps in MAPbBr${}_3$ thin films prepared using the anti-solvent method at n∼10${}^{17}$ cm${}^{-3}$. Full article

Electrochemical and optical platforms are commonly employed in designing biosensors. However, one signal readout can easily lead to inaccuracies due to the effect of nonstandard test procedures, different operators, and experimental environments. We have developed a dual-signal protocol that combined two transducer principles in one aptamer-based biosensor by simultaneously performing electrochemical- and extraordinary optical transmission (EOT)-based plasmonic detection using gold nanopit arrays (AuNpA). Compared with full hole structures, we found that nanopits, that did not fully penetrate the gold film, not only exhibited a better plasmonic bandwidth and refractive index sensitivity both in the finite-difference time-domain simulation and in experiments by shielding the gold/quartz mode but also enlarged the electrochemical active surface area. Therefore, the periodic non-fully penetrating AuNpA were modified with ferrocene-labeled human serum albumin aptamer receptors. The formation of the receptor layer and human serum albumin binding complex induced a conformational change, which resulted in variation in the electron transfer between the electro-active ferrocene units and the AuNpA surface. Simultaneously, the binding event caused a surface plasmon polaritons wavelength shift corresponding to a change in the surface refractive index. Interestingly, although both transducers recorded the same binding process, they led to different limits of detection, dynamic ranges, and sensitivities. The electrochemical transducer showed a dynamic detection range from 1 nM to 600 $\mathsf{\mu }$M, while the optical transducer covered high concentrations from 100 $\mathsf{\mu }$M to 600 $\mathsf{\mu }$M. This study not only provides new insights into the design of plasmonic nanostructures but also potentially opens an exciting avenue for dual-signal disease diagnosis and point-of-care testing applications. Full article

We report the electroluminescence (EL) characteristics of blue ultra-thin emissive layer (U-EML) phosphorescent (PH) organic light-emitting diodes (OLED) and thermally activated delayed fluorescence (TADF) OLED. A variety of transport layer (TL) materials were used in the fabricated OLEDs. The well-known FIrpic and DMAC-DPS were used with a thickness of 0.3 nm, which is relatively thicker than the optimal thickness (0.15 nm) of the blue phosphorescent ultra-thin emissive layer to ensure sufficient energy transfer. While FIrpic showed overall high efficiency in various TLs, DMAC-DPS exhibited three times lower efficiency in limited TLs. To clarify/identify low efficiency and to improve the EL, the thickness of DMAC-DPS was varied. A significantly higher and comparable efficiency was observed with a thickness of 4.5 nm, which is 15 times thicker. This thickness was oriented from the TADF itself, which reduces quenching in a triplet–triplet annihilation compared to the PH process. The thinner optimal thickness compared with ~30 nm of fluorescent OLEDs suggests that there still is quenching taking place. We expect that the efficiency of TADF U-EML OLEDs can be enhanced through further research on controlling the exciton quenching using multiple U-EMLs with spacers and a novel material with a high energy transfer rate (ΔE_S-T). Full article

Biosensors based on graphene field-effect transistors (G-FET) for detecting COVID-19 spike S protein and its receptor ACE2 were reported. The graphene, directly synthesized on SiO₂/Si substrate by microwave plasma-enhanced chemical vapor deposition (MW-PECVD), was used for FET biosensor fabrication. The commercial graphene, CVD-grown on a copper substrate and subsequently transferred onto a glass substrate, was applied for comparison purposes. The graphene structure and surface morphology were studied by Raman scattering spectroscopy and atomic force microscope. Graphene surfaces were functionalized by an aromatic molecule PBASE (1-pyrenebutanoic acid succinimidyl ester), and subsequent immobilization of the receptor angiotensin-converting enzyme 2 (ACE2) was performed. A microfluidic system was developed, and transfer curves of liquid-gated FET were measured after each graphene surface modification procedure to investigate ACE2 immobilization by varying its concentration and subsequent spike S protein detection. The directly synthesized graphene FET sensitivity to the receptor ACE2, evaluated in terms of the Dirac voltage shift, exceeded the sensitivity of the transferred commercial graphene-based FET. The concentration of the spike S protein was detected in the range of 10 ag/mL up to 10 μg/mL by using a developed microfluidic system and measuring the transfer characteristics of the liquid-gated G-FETs. It was found that the shift of the Dirac voltage depends on the spike S concentration and was 27 mV with saturation at 10 pg/mL for directly synthesized G-FET biosensor, while for transferred G-FET, the maximal shift of 70 mV was obtained at 10 μg/mL with a tendency of saturation at 10 ng/mL. The detection limit as low as 10 ag/mL was achieved for both G-FETs. The sensitivity of the biosensors at spike S concentration of 10 pg/mL measured as relative current change at a constant gate voltage corresponding to the highest transconductance of the G-FETs was found at 5.6% and 8.8% for directly synthesized and transferred graphene biosensors, respectively. Thus, MW-PECVD-synthesized graphene-based biosensor demonstrating high sensitivity and low detection limit has excellent potential for applications in COVID-19 diagnostics. Full article

Beeswax is a bio-sourced, renewable, and even edible material that stands as a convincing option to provide paper-based food packaging with moisture resistance. Nonetheless, the difficulty of dispersing it in water limits its applicability. This work uses oxidized, negatively charged cellulose nanofibers along with glycerol to stabilize beeswax-in-water emulsions above the melting point of the wax. The synergistic effects of nanocellulose and glycerol granted the stability of the dispersion even when it cooled down, but only if the concentration of nanofibers was high enough. This required concentration (0.6–0.9 wt%) depended on the degree of oxidation of the cellulose nanofibers. Rheological hindrance was essential to prevent the buoyancy of beeswax particles, while the presence of glycerol prevented excessive aggregation. The mixtures had yield stress and showed pseudoplastic behavior at a high enough shear rate, with their apparent viscosity being positively influenced by the surface charge density of the nanofibers. When applied to packaging paper, the nanocellulose-stabilized beeswax suspensions not only enhanced its barrier properties towards liquid water (reaching a contact angle of 96°) and water vapor (<100 g m⁻² d⁻¹), but also to grease (Kit rating: 5) and airflow (>1400 Gurley s). While falling short of polyethylene-coated paper, this overall improvement, attained using only one layer of a biobased coating suspension, should be understood as a step towards replacing synthetic waxes and plastic laminates. Full article

The characteristics of water vapor adsorption depend on the structure, porosity, and functional groups of the material. Metal–organic framework (MOF)-derived carbon (MDC) is a novel material that exhibits a high specific area and tunable pore sizes by exploiting the stable structure and porosity of pure MOF materials. Herein, two types of aluminum-based MOFs were used as precursors to synthesize hydrophobic microporous C-MDC and micro-mesoporous A-MDC via carbonization and activation depending on the type of ligands in the precursors. C-MDC and A-MDC have different pore characteristics and exhibit distinct water adsorption properties. C-MDC with hydrophobic properties and micropores exhibited negligible water adsorption (108.54 mgg⁻¹) at relatively low pressures (P/P₀~0.3) but showed a rapid increase in water adsorption ability (475.7 mgg⁻¹) at relative pressures of about 0.6. A comparison with the isotherm model indicated that the results were consistent with the theories, which include site filling at low relative pressure and pore filling at high relative pressure. In particular, the Do–Do model specialized for type 5 showed excellent agreement. Full article

Microemulsions are nanocolloidal systems composed of water, an oil, and a surfactant, sometimes with an additional co-surfactant, which have found a wide range of practical applications, including the extractive removal of contaminants from polluted water. In this study, microemulsion systems, including a nonionic surfactant (Brij 30), water, and esters selected from two homologous series of C₁–C₆ alkyl acetates and ethyl C₁–C₄ carboxylates, respectively, were prepared by the surfactant titration method. Phase transitions leading to the formation of Winsor II and Winsor IV microemulsions were observed and phase diagrams were constructed. The dependences of phase transitions on the salinity and pH and the addition of isopropanol as a co-surfactant were also investigated. Some physical properties, namely density, refractive index, electrical conductivity, dynamic viscosity, and particle size, were measured for a selection of Winsor IV microemulsions, providing further insight into some other phase transitions occurring in the monophasic domains of phase diagrams. Finally, Winsor II microemulsions were tested as extraction solvents for the removal of four tricyclic antidepressant drugs from aqueous media. Propyl acetate/Brij 30/H₂O microemulsions provided the best extraction yields (>90%), the highest Nernst distribution coefficients (~40–88), and a large volumetric ratio of almost 3 between the recovered purified water and the resulting microemulsion extract. Increasing the ionic strength (salinity) or the pH of the aqueous antidepressant solutions led to an improvement in extraction efficiencies, approaching 100%. These results could be extrapolated to other classes of pharmaceutical contaminants and suggest ester- and nonionic surfactant-based microemulsions are a promising tool for environmental remediation. Full article

The eggshell is a biomineral consisting of CaCO₃ in the form of calcite phase and a pervading organic matrix (1–3.5 wt.%). Transforming eggshell calcite particles into calcium phosphate (apatite) micro-nanoparticles opens the door to repurposing the eggshell waste as materials with potential biomedical applications, fulfilling the principles of the circular economy. Previous methods to obtain these particles consisted mainly of two steps, the first one involving the calcination of the eggshell. In this research, direct transformation by a one-pot hydrothermal method ranging from 100–200 °C was studied, using suspensions with a stoichiometric P/CaCO₃ ratio, K₂HPO₄ as P reagent, and eggshells particles (Ø < 50 μm) both untreated and treated with NaClO to remove surface organic matter. In the untreated group, the complete conversion was achieved at 160 °C, and most particles displayed a hexagonal plate morphology, eventually with a central hole. In the treated group, this replacement occurred at 180 °C, yielding granular (spherulitic) apatite nanoparticles. The eggshell particles and apatite micro-nanoparticles were cytocompatible when incubated with MG-63 human osteosarcoma cells and m17.ASC murine mesenchymal stem cells and promoted the osteogenic differentiation of m17.ASC cells. The study results are useful for designing and fabricating biocompatible microstructured materials with osteoinductive properties for applications in bone tissue engineering and dentistry. Full article

Silicon nitride films are widely used as the charge storage layer of charge trap flash (CTF) devices due to their high charge trap densities. The nature of the charge trapping sites in these materials responsible for the memory effect in CTF devices is still unclear. Most prominently, the Si dangling bond or K-center has been identified as an amphoteric trap center. Nevertheless, experiments have shown that these dangling bonds only make up a small portion of the total density of electrical active defects, motivating the search for other charge trapping sites. Here, we use a machine-learned force field to create model structures of amorphous Si${}_3$N${}_4$ by simulating a melt-and-quench procedure with a molecular dynamics algorithm. Subsequently, we employ density functional theory in conjunction with a hybrid functional to investigate the structural properties and electronic states of our model structures. We show that electrons and holes can localize near over- and under-coordinated atoms, thereby introducing defect states in the band gap after structural relaxation. We analyze these trapping sites within a nonradiative multi-phonon model by calculating relaxation energies and thermodynamic charge transition levels. The resulting defect parameters are used to model the potential energy curves of the defect systems in different charge states and to extract the classical energy barrier for charge transfer. The high energy barriers for charge emission compared to the vanishing barriers for charge capture at the defect sites show that intrinsic electron traps can contribute to the memory effect in charge trap flash devices. Full article

Bioactive glasses (BGs) are especially useful materials in soft and bone tissue engineering and even in dentistry. They can be the solution to many medical problems, and they have a huge role in the healing processes of bone fractures. Interestingly, they can also promote skin regeneration and wound healing. Bioactive glasses are able to attach to the bone tissues and form an apatite layer which further initiates the biomineralization process. The formed intermediate apatite layer makes a connection between the hard tissue and the bioactive glass material which results in faster healing without any complications or side effects. This review paper summarizes the most recent advancement in the preparation of diverse types of BGs, such as silicate-, borate- and phosphate-based bioactive glasses. We discuss their physical, chemical, and mechanical properties detailing how they affect their biological performances. In order to get a deeper insight into the state-of-the-art in this area, we also consider their medical applications, such as bone regeneration, wound care, and dental/bone implant coatings. Full article

Cordyceps extract and withaferin A (Wi-A) are natural compounds that have therapeutic effects on non-alcoholic fatty liver disease (NAFLD). However, their efficacy is limited and a long treatment duration is usually required. To enhance their efficiency, the synergistic effects of nanobubble water (NBW) derived from nitrogen, hydrogen, and oxygen gases were investigated. Results showed that the physical properties of all three NBWs, including nanobubble density (10⁸ particles/mL) and zeta potential (below −22 mV), were stable during 48 h of storage. Hydrogen and nitrogen NBWs did not reduce, but instead promoted, free fatty acid-induced lipid accumulation in HepG2 cells. In contrast, oxygen NBW synergistically enhanced the effects of cordyceps extract and Wi-A. The lipid content decreased by 29% and 33% in the oxygen NBW + cordyceps extract and oxygen NBW + Wi-A groups, respectively, compared to reductions of 22% and 16% by aqueous extracts without NB. This study found that NBW may enhance the lipid-reducing effects of natural compounds, such as cordyceps extract and withaferin A, in hepatic cells. Further studies in animal experiments are needed to determine whether NBW has a potential application in NAFLD. Full article

The understanding of interactions between nanomaterials and biological molecules is of primary importance for biomedical applications of nanomaterials, as well as for the evaluation of their possible toxic effects. Here, we carried out extensive molecular dynamics simulations of the adsorption properties of about 30 small molecules representing biomolecular fragments at ZnS surfaces in aqueous media. We computed adsorption free energies and potentials of mean force of amino acid side chain analogs, lipids, and sugar fragments to ZnS (110) crystal surface and to a spherical ZnS nanoparticle. Furthermore, we investigated the effect of poly-methylmethacrylate (PMMA) coating on the adsorption preferences of biomolecules to ZnS. We found that only a few anionic molecules: aspartic and glutamic acids side chains, as well as the anionic form of cysteine show significant binding to pristine ZnS surface, while other molecules show weak or no binding. Spherical ZnS nanoparticles show stronger binding of these molecules due to binding at the edges between different surface facets. Coating of ZnS by PMMA changes binding preferences drastically: the molecules that adsorb to a pristine ZnS surface do not adsorb on PMMA-coated surfaces, while some others, particularly hydrophobic or aromatic amino-acids, show high binding affinity due to binding to the coating. We investigate further the hydration properties of the ZnS surface and relate them to the binding preferences of biomolecules. Full article

This paper describes a novel nanoformulation for dual MRI/US in vivo monitoring of drug delivery/release. The nanosystem was made of a perfluoropentane core coated with phospholipids stabilized by glycol chitosan crosslinked with triphosphate ions, and it was co-loaded with the prodrug prednisolone phosphate (PLP) and the structurally similar MRI agent Gd-DTPAMA-CHOL. Importantly, the in vitro release of PLP and Gd-DTPAMA-CHOL from the nanocarrier showed similar profiles, validating the potential impact of the MRI agent as an imaging reporter for the drug release. On the other hand, the nanobubbles were also detectable by US imaging both in vitro and in vivo. Therefore, the temporal evolution of both MRI and US contrast after the administration of the proposed nanosystem could report on the delivery and the release kinetics of the transported drug in a given lesion. Full article

Both biomedical applications and safety assessments of manufactured nanomaterials require a thorough understanding of the interaction between nanomaterials and cells, including how nanomaterials enter cells, transport within cells, and leave cells. However, compared to the extensively studied uptake and trafficking of nanoparticles (NPs) in cells, less attention has been paid to the exocytosis of NPs. Yet exocytosis is an indispensable process of regulating the content of NPs in cells, which in turn influences, even decides, the toxicity of NPs to cells. A comprehensive understanding of the mechanisms and influencing factors of the exocytosis of NPs is not only essential for the safety assessment of NPs but also helpful for guiding the design of safe and highly effective NP-based materials for various purposes. Herein, we review the current status and progress of studies on the exocytosis of NPs. Firstly, we introduce experimental procedures and considerations. Then, exocytosis mechanisms/pathways are summarized with a detailed introduction of the main pathways (lysosomal and endoplasmic reticulum/Golgi pathway) and the role of microtubules; the patterns of exocytosis kinetics are presented and discussed. Subsequently, the influencing factors (initial content and location of intracellular NPs, physiochemical properties of NPs, cell type, and extracellular conditions) are fully discussed. Although there are inconsistent results, some rules are obtained, like smaller and charged NPs are more easily excreted. Finally, the challenges and future directions in the field have been discussed. Full article

The fabrication of trilayer superconductor-insulator-superconductor (SIS) Josephson junctions with high-temperature superconductor (HTS) electrodes requires atomically perfect interfaces. Therefore, despite great interest and efforts, this remained a challenge for over three decades. Here, we report the discovery of a new family of metastable materials, La_2−xSr_xZnO₄ (LSZO), synthesized by atomic-layer-by-layer molecular beam epitaxy (ALL-MBE). We show that LSZO is insulating and epitaxially compatible with an HTS compound, La_2−xSr_xCuO₄ (LSCO). Since the “parent” compound La₂ZnO₄ (LZO) is easier to grow, here we focus on this material as our insulating layer. Growing LZO at very low temperatures to reduce cation interdiffusion makes LSCO/LZO interfaces atomically sharp. We show that in LSCO/LZO/LSCO trilayers, the superconducting properties of the LSCO electrodes remain undiminished, unlike in previous attempts with insulator barriers made of other materials. This opens prospects to produce high-quality HTS tunnel junctions. Full article

Although chitosan-stabilized selenium nanoparticles (Ch-SeNPs) have emerged as a promising chemical form of selenium for anticancer purposes, gathering more profound knowledge related to molecular dysfunctions contributes significantly to the promotion of their evolution as a chemotherapeutic drug. In this sense, metabolites are the end products in the flow of gene expression and, thus, the most sensitive to changes in the physiological state of a biological system. Therefore, metabolomics provides a functional readout of the biochemical activity and cell state. In the present study, we evaluated alterations in the metabolomes of HepG2 cells after the exposure to Ch-SeNPs to elucidate the biomolecular mechanisms involved in their therapeutic effect. A targeted metabolomic approach was conducted to evaluate the levels of four of the main energy-related metabolites (adenosine triphosphate (ATP); adenosine diphosphate (ADP); nicotinamide adenine dinucleotide (NAD⁺); and 1,4-dihydronicotinamide adenine dinucleotide (NADH)), revealing alterations as a result of exposure to Ch-SeNPs related to a shortage in the energy supply system in the cell. In addition, an untargeted metabolomic experiment was performed, which allowed for the study of alterations in the global metabolic profile as a consequence of Ch-SeNP exposure. The results indicate that the TCA cycle and glycolytic pathways were impaired, while alternative pathways such as glutaminolysis and cysteine metabolism were upregulated. Additionally, increased fructose levels suggested the induction of hypoxia-like conditions. These findings highlight the potential of Ch-SeNPs to disrupt cancer cell metabolism and provide insights into the mechanisms underlying their antitumor effects. Full article

Silicon-based photodetectors are attractive as low-cost and environmentally friendly optical sensors. Also, their compatibility with complementary metal-oxide-semiconductor (CMOS) technology is advantageous for the development of silicon photonics systems. However, extending optical responsivity of silicon-based photodetectors to the mid-infrared (mid-IR) wavelength range remains challenging. In developing mid-IR infrared Schottky detectors, nanoscale metals are critical. Nonetheless, one key factor is the Fermi-level pinning effect at the metal/silicon interface and the presence of metal-induced gap states (MIGS). Here, we demonstrate the utilization of the passivated surface layer on semiconductor materials as an insulating material in metal-insulator-semiconductor (MIS) contacts to mitigate the Fermi-level pinning effect. The removal of Fermi-level pinning effectively reduces the Schottky barrier height by 12.5% to 16%. The demonstrated devices exhibit a high responsivity of up to 234 μA/W at a wavelength of 2 μm, 48.2 μA/W at 3 μm, and 1.75 μA/W at 6 μm. The corresponding detectivities at 2 and 3 μm are 1.17 × 10⁸ cm Hz^1/2 W⁻¹ and 2.41 × 10⁷ cm Hz^1/2 W⁻¹, respectively. The expanded sensing wavelength range contributes to the application development of future silicon photonics integration platforms. Full article