Nanomaterials

The therapeutic inhibition of immune checkpoints, including cytotoxic T lymphocyte-associated protein (CTLA)-4 and programmed cell death 1 (PD-1), through the use of function blocking antibodies can confer improved clinical outcomes by invigorating CD8⁺ T cell-mediated anticancer immunity. However, low rates of patient responses and the high rate of immune-related adverse events remain significant challenges to broadening the benefit of this therapeutic class, termed immune checkpoint blockade (ICB). To overcome these significant limitations, controlled delivery and release strategies offer unique advantages relevant to this therapeutic class, which is typically administered systemically (e.g., intravenously), but more recently, has been shown to be highly efficacious using locoregional routes of administration. As such, in this paper, we describe an in situ crosslinked hydrogel for the sustained release of antibodies blocking CTLA-4 and PD-1 signaling from a locoregional injection proximal to the tumor site. This formulation results in efficient and durable anticancer effects with a reduced systemic toxicity compared to the bolus delivery of free antibody using an equivalent injection route. This formulation and strategy thus represent an approach for achieving the efficient and safe delivery of antibodies for ICB cancer immunotherapy. Full article

Nanoparticles (NPs) show various properties depending on their composition, size, and surface coating, which shape their interactions with biological systems. In particular, NPs have been shown to interact with immune cells, that represent a sensitive surveillance system of external and internal stimuli. In this light, in vitro models represent useful tools for investigating nano-bio-interactions in immune cells of different organisms, including invertebrates. In this work, the effects of selected types of NPs with different core composition, size and functionalization (custom-made PVP-AuNP and commercial nanopolystyrenes PS-NH₂ and PS-COOH) were investigated in the hemocytes of the marine bivalve Mytilus galloprovincialis. The role of exposure medium was evaluated using either artificial seawater (ASW) or hemolymph serum (HS). Hemocyte morphology was investigated by scanning electron microscopy (SEM) and different functional parameters (lysosomal membrane stability, phagocytosis, and lysozyme release) were evaluated. The results show distinct morphological and functional changes induced in mussel hemocytes depending on the NP type and exposure medium. Mussel hemocytes may represent a powerful alternative in vitro model for a rapid pre-screening strategy for NPs, whose utilization will contribute to the understanding of the possible impact of environmental exposure to NPs in marine invertebrates. Full article

Herein, it has been shown that betulin can be transformed into its biologically active oxo-derivatives (betulone, betulinic and betulonic aldehydes) by liquid-phase oxidation over supported silver catalysts under mild conditions. In order to identify the main factors determining the catalytic behavior of nanosilver catalysts in betulin oxidation, silver was deposited on various alumina supports (γ-alumina and boehmite) using deposition–precipitation with NaOH and incipient wetness impregnation methods, followed by treatment in H₂ or O₂. Silver catalysts and the corresponding supports were characterized by X-ray diffraction, nitrogen physisorption, inductively coupled plasma optical emission spectroscopy, photoelectron spectroscopy and transmission electron microscopy. It was found that the support nature, preparation and treatment methods predetermine not only the average Ag nanoparticles size and their distribution, but also the selectivity of betulin oxidation, and thereby, the catalytic behavior of Ag catalysts. In fact, the support nature had the most considerable effect. Betulin conversion, depending on the support, increased in the following order: Ag/boehmite < Ag/boehmite (calcined) < Ag/γ-alumina. However, in the same order, the share of side reactions catalyzed by strong Lewis acid centers of the support also increased. Poisoning of the latter by NaOH during catalysts preparation can reduce side reactions. Additionally, it was revealed that the betulin oxidation catalyzed by nanosilver catalysts is a structure-sensitive reaction. Full article

The temperature dependent density of Al and Ga droplets deposited on AlGaAs with molecular beam epitaxy is studied theoretically. Such droplets are important for applications in quantum information technology and can be functionalized e.g., by droplet epitaxy or droplet etching for the self-assembled generation of quantum emitters. After an estimation based on a scaling analysis, the droplet densities are simulated using first a mean-field rate model and second a kinetic Monte Carlo (KMC) simulation basing on an atomistic representation of the mobile adatoms. The modeling of droplet nucleation with a very high surface activity of the adatoms and ultra-low droplet densities down to 5 × 10${}^6$ cm${}^{-2}$ is highly demanding in particular for the KMC simulation. Both models consider two material related model parameters, the energy barrier $E_S$ for surface diffusion of free adatoms and the energy barrier $E_E$ for escape of atoms from droplets. The rate model quantitatively reproduces the droplet densities with $E_S$ = 0.19 eV, $E_E$ = 1.71 eV for Al droplets and $E_S$ = 0.115 eV for Ga droplets. For Ga, the values of $E_E$ are temperature dependent indicating the relevance of additional processes. Interestingly, the critical nucleus size depends on deposition time, which conflicts with the assumptions of the scaling model. Using a multiscale KMC algorithm to substantially shorten the computation times, Al droplets up to 460 ℃ on a 7500 × 7500 simulation field and Ga droplets up to 550 ℃ are simulated. The results show a very good agreement with the experiments using $E_S$ = 0.19 eV, $E_E$ = 1.44 eV for Al, and $E_S$ = 0.115 eV, $E_E$ = 1.24 eV ($T\le$ 300 ℃) or $E_E$ = 1.24 + 0.06 (T[℃]-300)/100 eV ($T>300$ ℃) for Ga. The deviating $E_E$ is attributed to a re-nucleation effect that is not considered in the mean-field assumption of the rate model. Full article

Nanobridge Josephson junctions and nanometer-scale superconducting quantum interference devices (nanoSQUIDs) based on titanium nitride (TiN) thin films are described. The TiN films have a room temperature resistivity of ~15 µΩ·cm, a superconducting transition temperature T_c of up to 5.3 K and a coherence length ξ(4.2 K) of ~105 nm. They were deposited using pulsed DC magnetron sputtering from a stoichiometric TiN target onto Si (100) substrates that were heated to 800 °C. Electron beam lithography and highly selective reactive ion etching were used to fabricate nanoSQUIDs with 20-nm-wide nanobridge Josephson junctions of variable thickness. X-ray and high-resolution electron microscopy studies were performed. Non-hysteretic I(V) characteristics of the nanobridges and nanoSQUIDs, as well as peak-to-peak modulations of up to 17 µV in the V(B) characteristics of the nanoSQUIDs, were measured at 4.2 K. The technology offers prospects for superconducting electronics based on nanobridge Josephson junctions operating within the framework of the Ginzburg–Landau theory at 4.2 K. Full article

Hybrid organic-inorganic perovskites are very promising semiconductors for many optoelectronic applications, although their extensive use is limited by their poor stability under environmental conditions. In this work, we synthesize two-dimensional perovskite single crystals and investigate their optical and structural evolution under continuous light irradiation. We found that the hydrophobic nature of the fluorinated component, together with the absence of grain boundary defects, lead to improved material stability thanks to the creation of a robust barrier that preserve the crystalline structure, hindering photo-degradation processes usually promoted by oxygen and moisture. Full article

The hydroxyapatite nanopowders of the Eu³⁺-doped, Cu²⁺-doped, and Eu³⁺/Cu²⁺-co-doped Ca₁₀(PO₄)₆(OH)₂ were prepared by a microwave-assisted hydrothermal method. The structural and morphological properties of the products were investigated by X-ray powder diffraction (XRD), transmission electron microscopy techniques (TEM), and infrared spectroscopy (FT-IR). The average crystal size and the unit cell parameters were calculated by a Rietveld refinement tool. The absorption, emission excitation, emission, and luminescence decay time were recorded and studied in detail. The ⁵D₀ → ⁷F₂ transition is the most intense transition. The Eu³⁺ ions occupied two independent crystallographic sites in these materials exhibited in emission spectra: one Ca(1) site with C₃ symmetry and one Ca(2) sites with C_s symmetry. The Eu³⁺ emission is strongly quenched by Cu²⁺ ions, and the luminescence decay time is much shorter in the case of Eu³⁺/Cu²⁺ co-doped materials than in Eu³⁺-doped materials. The luminescence quenching mechanism as well as the schematic energy level diagram showing the Eu³⁺ emission quenching mechanism using Cu²⁺ ions are proposed. The electron paramagnetic resonance (EPR) technique revealed the existence of at least two different coordination environments for copper(II) ion. Full article

CsPbBr${}_3$ has attracted great attention due to unique optical properties. The understanding of the multiexciton process is crucial for improving the performance of the photoelectric devices based on CsPbBr${}_3$ nanocrystals. In this paper, the ultrafast dynamics of CsPbBr${}_3$ nanocrystals is investigated by using femtosecond transient absorption spectroscopy. It is found that Auger recombination lifetime increases with the decrease of the excitation intensity, while the trend is opposite for the hot-exciton cooling time. The time of the hot-carriers cooling to the band edge is increased when the excitation energy is increased from 2.82 eV (440 nm) to 3.82 eV (325 nm). The lifetime of the Auger recombination reaches the value of 126 ps with the excitation wavelength of 440 nm. The recombination lifetime of the single exciton is about 7 ns in CsPbBr${}_3$ nanocrystals determined by nanosecond time-resolved photoluminescence spectroscopy. The exciton binding energy is 44 meV for CsPbBr${}_3$ nanocrystals measured by the temperature-dependent steady-state photoluminescence spectroscopy. These findings provide a favorable insight into applications such as solar cells and light-emitting devices based on CsPbBr${}_3$ nanocrystals. Full article

Nanotechnology-based drug delivery provides a promising area for improving the efficacy of cancer treatments. Therefore, we investigate the potential of using quantum dots (QDs) as drug carriers for antitumor unsymmetrical bisacridine derivatives (UAs) to cancer cells. We examine the influence of QD–UA hybrids on the cellular uptake, internalization (Confocal Laser Scanning Microscope), and the biological response (flow cytometry and light microscopy) in lung H460 and colon HCT116 cancer cells. We show the time-dependent cellular uptake of QD–UA hybrids, which were more efficiently retained inside the cells compared to UAs alone, especially in H460 cells, which could be due to multiple endocytosis pathways. In contrast, in HCT116 cells, the hybrids were taken up only by one endocytosis mechanism. Both UAs and their hybrids induced apoptosis in H460 and HCT116 cells (to a greater extent in H460). Cells which did not die underwent senescence more efficiently following QDs–UAs treatment, compared to UAs alone. Cellular senescence was not observed in HCT116 cells following treatment with both UAs and their hybrids. Importantly, QD_green/red themselves did not provoke toxic responses in cancer or normal cells. In conclusion, QDs are good candidates for targeted UA delivery carriers to cancer cells while protecting normal cells from toxic drug activities. Full article

Recently, different kinds of energy band structures have been utilized to improve the photoelectric properties of zinc oxide (ZnO). In this work, ZnO nanorods were prepared by the hydrothermal method and then decorated with silver sulfide (Ag₂S)/zinc sulfide (ZnS) via two-step successive ionic layer adsorption and reaction method. The photoelectric properties of nanocomposites are investigated. The results show that ZnO decorated with Ag₂S/ZnS can improve the photocurrent of photodetectors from 0.34 to 0.56 A at bias of 9 V. With the immersion time increasing from 15 to 60 minutes, the photocurrent of photodetectors increases by 0.22 A. The holes in the valence band of ZnO can be transferred to the valence band of ZnS and Ag₂S, which promotes the separation and suppresses the recombination of hole-electron pairs generated in ZnO. Moreover, electrons excited by ultraviolet (UV) light in Ag₂S can also be injected into the conduction band of ZnO, which causes the photocurrent to increase more than the ZnO photodetector. Full article

In the past few decades, curcumin, a natural polyphenolic phytochemical, has been studied for treating a wide variety of diseases. It has shown promising results as a potential curative agent for a variety of diseases. However, its inherent limitations, such as poor aqueous solubility, poor absorbability, fast metabolic rate, and quick elimination from the body, have limited its application beyond preclinical studies. A huge number of studies have been made to address the issues of curcumin and to maximally utilize its potentials. Many review articles have tried to assess and summarize different nanocarriers, especially organic nanocarriers, for nanoformulations with curcumin. Nevertheless, few exclusive reviews on the progress in nanoformulation of curcumin with inorganic nanomaterials have been made. In this review, we present an exclusive summary of the progress in nanoformulation of curcumin with metal oxide nanoparticles. The beneficial feature of the metal oxide nanoparticles used in the curcumin nanoformulation, the different approaches followed in formulating curcumin with the metal oxides, and the corresponding results, protective effect of curcumin from different metal oxide caused toxicities, and concluding remarks are presented in the review. Full article

The photovoltaic effect in the anodic formation of silicon dioxide (SiO₂) on porous silicon (PS) surfaces was investigated toward developing a potential passivation technique to achieve high efficiency nanostructured Si solar cells. The PS layers were prepared by electrochemical anodization in hydrofluoric acid (HF) containing electrolyte. An anodic SiO₂ layer was formed on the PS surface via a bottom-up anodization mechanism in HCl/H₂O solution at room temperature. The thickness of the oxide layer for surface passivation was precisely controlled by adjusting the anodizing current density and the passivation time, for optimal oxidation on the PS layer while maintaining its original nanostructure. HRTEM characterization of the microstructure of the PS layer confirms an atomic lattice matching at the PS/Si interface. The dependence of photovoltaic performance, series resistance, and shunt resistance on passivation time was examined. Due to sufficient passivation on the PS surface, a sample with anodization duration of 30 s achieved the best conversion efficiency of 10.7%. The external quantum efficiency (EQE) and internal quantum efficiency (IQE) indicate a significant decrease in reflectivity due to the PS anti-reflection property and indicate superior performance due to SiO₂ surface passivation. In conclusion, the surface of PS solar cells could be successfully passivated by electrochemical anodization. Full article

In this work, hybrid zinc oxide–iron oxide (ZnOFe) magnetic nanoparticles were synthesized employing Olea europaea leaf aqueous extract as a reducing/chelating and capping medium. The resulting magnetic nanoparticles were characterized by basic spectroscopic and microscopic techniques, namely, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fourier-transform infrared (FTIR) and atomic force microscopy (AFM), exhibiting a spherical shape, average size of 15–17 nm, and a functionalized surface. Lipase from Thermomyces lanuginosus (TLL) was efficiently immobilized on the surface of ZnOFe nanoparticles through physical absorption. The activity of immobilized lipase was found to directly depend on the enzyme to support the mass ratio, and also demonstrated improved pH and temperature activity range compared to free lipase. Furthermore, the novel magnetic nanobiocatalyst (ZnOFe-TLL) was applied to the preparation of hydroxytyrosyl fatty acid esters, including derivatives with omega-3 fatty acids, in non-aqueous media. Conversion yields up to 90% were observed in non-polar solvents, including hydrophobic ionic liquids. Different factors affecting the biocatalyst performance were studied. ZnOFe-TLL was reutilized for eight subsequent cycles, exhibiting 90% remaining esterification activity (720 h of total operation at 50 °C). The green synthesized magnetic nanoparticles, reported here for the first time, are excellent candidates as nanosupports for the immobilization of enzymes with industrial interest, giving rise to nanobiocatalysts with elevated features. Full article

Chronic wounds affect millions of patients worldwide, and it is estimated that this number will increase steadily in the future due to population ageing. The research of new therapeutic approaches to wound healing includes the development of nanofibrous meshes and the use of platelet lysate (PL) to stimulate skin regeneration. This study considers a combination of a degradable electrospun nanofibrous blend of poly(L-lactide-co-ε-caprolactone) and poly(ε-caprolactone) (PLCL/PCL) membranes (NF) and fibrin loaded with various concentrations of PL aimed at the development of bioactive skin wound healing dressings. The cytocompatibility of the NF membranes, as well as the effect of PL, was evaluated in both monocultures and co-cultures of human keratinocytes and human endothelial cells. We determined that the keratinocytes were able to adhere on all the membranes, and their increased proliferation and differentiation was observed on the membranes that contained fibrin with at least 50% of PL (Fbg + PL) after 14 days. With respect to the co-culture experiments, the membranes with fibrin with 20% of PL were observed to enhance the metabolic activity of endothelial cells and their migration, and the proliferation and differentiation of keratinocytes. The results suggest that the newly developed NF combined with fibrin and PL, described in the study, provides a promising dressing for chronic wound healing purposes. Full article

Gas sensitive structures made of nanowires exhibit extremally large specific surface area, and a great number of chemically active centres that can react with the ambient atmosphere. This makes the use of nanomaterials promising for super sensitive gas sensor applications. Monoclinic β-Ga₂O₃ nanowires (NWs) were synthesized from metallic gallium at atmospheric pressure in the presence of nitrogen and water vapor. The nanowires were grown directly on interdigitated gold electrodes screen printed on Al₂O₃ substrates, which constituted the gas sensor structure. The observations made with transmission electron microscope (TEM) have shown that the nanowires are monocrystalline and their diameters vary from 80 to 300 nm with the average value of approximately 170 nm. Au droplets were found to be anchored at the tips of the nanowires which may indicate that the nanowires followed the Vapor–Liquid–Solid (VLS) mechanism of growth. The conductivity of β-Ga₂O₃ NWs increases in the presence of volatile organic compounds (VOC) even in the temperature below 600 °C. The gas sensor based on the synthesized β-Ga₂O₃ NWs shows peak sensitivity to 100 ppm of ethanol of 75.1 at 760 °C, while peak sensitivity to 100 ppm of acetone is 27.5 at 690 °C. Full article

Silver oxide nanoparticles with controlled particle size were successfully obtained utilizing citrate-intercalated layered double hydroxide (LDH) as a substrate and Ag⁺ as a precursor. The lattice of LDH was partially dissolved during the reaction by Ag⁺. The released hydroxyl and citrate acted as a reactant in crystal growth and a size controlling capping agent, respectively. X-ray diffraction, X-ray photoelectron spectroscopy, and microscopic measurements clearly showed the development of nano-sized silver oxide particles on the LDH surface. The particle size, homogeneity and purity of silver oxide were influenced by the stoichiometric ratio of Ag/Al. At the lowest silver ratio, the particle size was the smallest, while the chemical purity was the highest. X-ray photoelectron spectroscopy and UV-vis spectroscopy results suggested that the high Ag/Al ratio tended to produce silver oxide with a complex silver environment. The small particle size and homogeneous distribution of silver oxide showed advantages in antibacterial efficacy compared with bulk silver oxide. LDH with an appropriate ratio could be utilized as a substrate to grow silver oxide nanoparticles with controlled size with effective antibacterial performance. Full article

In this study, bitumen modified by fumed silica nanoparticles was characterized through dynamic shear rheometer tests, scanning electron microscopy, and Fourier transform infrared spectroscopy. The fumed silica nanoparticles were used in three different ratios, i.e., 0.1, 0.2 and 0.3 wt.-% of bitumen. Specifically, the modified bitumen characteristics were studied after laboratory aging by analyzing the chemical composition and rheological properties. From the determination of oxidation degree and carbonyl index it was found that the resistance of the modified bitumen to ultraviolet aging was improved with the increasing nanoparticle content. In bitumen modified by fumed silica nanoparticles, the nanoparticles were well dispersed. Moreover, the results illustrated that the bitumen properties were improved, and the improvement effect of 0.1 wt.-% fumed silica nanoparticles was more distinct than the higher concentrations. Full article

Efficient application of carbon nanotubes (CNTs) in nano-devices and nano-materials requires comprehensive understanding of their mechanical properties. As observations suggest size dependent behaviour, non-classical theories preserving the memory of body’s internal structure via additional material parameters offer great potential when a continuum modelling is to be preferred. In the present study, micropolar theory of elasticity is adopted due to its peculiar character allowing for incorporation of scale effects through additional kinematic descriptors and work-conjugated stress measures. An optimisation approach is presented to provide unified material parameters for two specific class of single-walled carbon nanotubes (e.g., armchair and zigzag) by minimizing the difference between the apparent shear modulus obtained from molecular dynamics (MD) simulation and micropolar beam model considering both solid and tubular cross-sections. The results clearly reveal that micropolar theory is more suitable compared to internally constraint couple stress theory, due to the essentiality of having skew-symmetric stress and strain measures, as well as to the classical local theory (Cauchy of Grade 1), which cannot accounts for scale effects. To the best of authors’ knowledge, this is the first time that unified material parameters of CNTs are derived through a combined MD-micropolar continuum theory. Full article