Nanomaterials

Nanoparticles can play valuable roles in delivering nucleic acids, including microRNAs (miRNA), which are small, non-coding RNA segments. In this way, nanoparticles may exert post-transcriptional regulatory influences on various inflammatory conditions and bone disorders. This study used biocompatible, core–cone-structured, mesoporous silica nanoparticles (MSN-CC) to deliver miRNA-26a to macrophages in order to influence osteogenesis in vitro. The loaded nanoparticles (MSN-CC-miRNA-26) showed low-level toxicity towards macrophages (RAW 264.7 cells) and were internalized efficiently, causing the reduced expression of pro-inflammatory cytokines, as seen via real-time PCR and cytokine immunoassays. The conditioned macrophages created a favorable osteoimmune environment for MC3T3-E1 preosteoblasts, driving osteogenic differentiation with enhanced osteogenic marker expression, alkaline phosphatase (ALP) production, extracellular matrix formation, and calcium deposition. An indirect co-culture system revealed that direct osteogenic induction and immunomodulation by MSN-CC-miRNA-26a synergistically increased bone production due to the crosstalk between MSN-CC-miRNA-26a-conditioned macrophages and MSN-CC-miRNA-26a-treated preosteoblasts. These findings demonstrate the value of nanoparticle delivery of miR-NA-26a using MSN-CC for suppressing the production of pro-inflammatory cytokines with macrophages and for driving osteogenic differentiation in preosteoblasts via osteoimmune modulation. Full article

The application of metal nanoparticles in industry and medicine results in their release into the environment, which can have a negative impact on human health. The effects of gold (AuNPs) and copper (CuNPs) nanoparticles at the concentration range of 1–200 mg/L on parsley (Petroselinum crispum) under conditions of root exposure and their translocation in roots and leaves were investigated in a 10-day experiment. The content of copper and gold in soil and plant segments was determined using ICP-OES and ICP-MS techniques, while the morphology of nanoparticles was analyzed using transmission electron microscopy. Differences in the nanoparticle uptake and translocation were observed: CuNPs mainly accumulated in soil (4.4–465 mg/kg), while accumulation in the leaves were at the control level. AuNPs mainly accumulated in soil (0.04–108 mg/kg), followed by roots (0.05–45 mg/kg) and leaves (0.16–53 mg/kg). The influence of AuNPs and CuNPs on the biochemical parameters of parsley was on the content of carotenoids, the levels of chlorophyll, and antioxidant activity. Application of CuNPs even at the lowest concentration led to a significant reduction in carotenoids and total chlorophyll content. AuNPs at low concentrations promoted an increase in the content of carotenoids; however, they also significantly reduced it at concentrations higher than 10 mg/L. To our knowledge, this is the first study of the effect of metal nanoparticles on parsley. Full article

The carbon dioxide reduction reaction (CO2RR) is a promising method to both reduce greenhouse gas carbon dioxide (CO₂) concentrations and provide an alternative to fossil fuel by converting water and CO₂ into high-energy-density chemicals. Nevertheless, the CO2RR suffers from high chemical reaction barriers and low selectivity. Here we demonstrate that 4 nm gap plasmonic nano-finger arrays provide a reliable and repeatable plasmon-resonant photocatalyst for multiple-electrons reactions: the CO2RR to generate higher-order hydrocarbons. Electromagnetics simulation shows that hot spots with 10,000 light intensity enhancement can be achieved using nano-gap fingers under a resonant wavelength of 638 nm. From cryogenic ¹H-NMR spectra, formic acid and acetic acid productions are observed with a nano-fingers array sample. After 1 h laser irradiation, we only observe the generation of formic acid in the liquid solution. While increasing the laser irradiation period, we observe both formic and acetic acid in the liquid solution. We also observe that laser irradiation at different wavelengths significantly affected the generation of formic acid and acetic acid. The ratio, 2.29, of the product concentration generated at the resonant wavelength 638 nm and the non-resonant wavelength 405 nm is close to the ratio, 4.93, of the generated hot electrons inside the TiO₂ layer at different wavelengths from the electromagnetics simulation. This shows that product generation is related to the strength of localized electric fields. Full article

Hospitals and nursing home wards are areas prone to the propagation of infections and are of particular concern regarding the spreading of dangerous viruses and multidrug-resistant bacteria (MDRB). MDRB infections comprise approximately 20% of cases in hospitals and nursing homes. Healthcare textiles, such as blankets, are ubiquitous in hospitals and nursing home wards and may be easily shared between patients/users without an adequate pre-cleaning process. Therefore, functionalizing these textiles with antimicrobial properties may considerably reduce the microbial load and prevent the propagation of infections, including MDRB. Blankets are mainly comprised of knitted cotton (CO), polyester (PES), and cotton-polyester (CO–PES). These fabrics were functionalized with novel gold-hydroxyapatite nanoparticles (AuNPs-HAp) that possess antimicrobial properties, due to the presence of the AuNPs’ amine and carboxyl groups, and low propensity to display toxicity. For optimal functionalization of the knitted fabrics, two pre-treatments, four different surfactants, and two incorporation processes were evaluated. Furthermore, exhaustion parameters (time and temperature) were subjected to a design of experiments (DoE) optimization. The concentration of AuNPs-HAp in the fabrics and their washing fastness were critical factors assessed through color difference (ΔE). The best performing knitted fabric was half bleached CO, functionalized using a surfactant combination of Imerol^® Jet-B (surfactant A) and Luprintol^® Emulsifier PE New (surfactant D) through exhaustion at 70 °C for 10 min. This knitted CO displayed antibacterial properties even after 20 washing cycles, showing its potential to be used in comfort textiles within healthcare environments. Full article

Photovoltaics are being transformed by perovskite solar cells. The power conversion efficiency of these solar cells has increased significantly, and even higher efficiencies are possible. The scientific community has gained much attention due to perovskites’ potential. Herein, the electron-only devices were prepared by spin-coating and introducing the organic molecule dibenzo-18-crown-6 (DC) to CsPbI₂Br perovskite precursor solution. The current-voltage (I-V) and J-V curves were measured. The morphologies and elemental composition information of the samples were obtained by SEM, XRD, XPS, Raman, and photoluminescence (PL) spectroscopies. The distinct impact of organic DC molecules on the phase, morphology, and optical properties of perovskite films are examined and interpreted with experimental results. The efficiency of the photovoltaic device in the control group is 9.76%, and the device efficiency gradually increases with the increase of DC concentration. When the concentration is 0.3%, the device efficiency is the best, reaching 11.57%, short-circuit current is 14.01 mA/cm², the open circuit voltage is 1.19 V, and the fill factor is 0.7. The presence of DC molecules effectively controlled the perovskite crystallization process by inhibiting the in-situ generations of impurity phases and minimizing the defect density of the film. Full article

Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure–property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure–property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure–property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm² V⁻¹ s⁻¹, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure–property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices. Full article

Flexible electronics have enormous potential for applications that are not achievable in standard electronics. In particular, important technological advances have been made in terms of their performance characteristics and potential range of applications, ranging from medical care, packaging, lighting and signage, consumer electronics, and alternative energy. In this study, we develop a novel method for fabricating flexible conductive carbon nanotube (CNT) films on various substrates. The fabricated conductive CNT films exhibited satisfactory conductivity, flexibility, and durability. The conductivity of the conductive CNT film was maintained at the same level of sheet resistance after bending cycles. The fabrication process is dry, solution-free, and convenient for mass production. Scanning electron microscopy revealed that CNTs were uniformly dispersed over the substrate. The prepared conductive CNT film was applied to collect an electrocardiogram (ECG) signal, which showed good performance compared to traditional electrodes. The conductive CNT film determined the long-term stability of the electrodes under bending or other mechanical stresses. The well-demonstrated fabrication process for flexible conductive CNT films has great potential in the field of bioelectronics. Full article

Fluorescent hydrogels are promising candidate materials for portable biosensors to be used in point-of-care diagnosis because (1) they have a greater capacity for binding organic molecules than immunochromatographic test systems, determined by the immobilization of affinity labels within the three-dimensional hydrogel structure; (2) fluorescent detection is more sensitive than the colorimetric detection of gold nanoparticles or stained latex microparticles; (3) the properties of the gel matrix can be finely tuned for better compatibility and detection of different analytes; and (4) hydrogel biosensors can be made to be reusable and suitable for studying dynamic processes in real time. Water-soluble fluorescent nanocrystals are widely used for in vitro and in vivo biological imaging due to their unique optical properties, and hydrogels based on these allow the preservation of these properties in bulk composite macrostructures. Here we review the techniques for obtaining analyte-sensitive fluorescent hydrogels based on nanocrystals, the main methods used for detecting the fluorescent signal changes, and the approaches to the formation of inorganic fluorescent hydrogels via sol–gel phase transition using surface ligands of the nanocrystals. Full article

Eliminating hazardous contaminants is a necessity for maintaining a healthy environment on Earth. This work used a sustainable method to create Iron–Zinc nanocomposites with polyvinyl alcohol assistance. Mentha Piperita (mint leaf) extract was used as a reductant in the green synthesis of bimetallic nanocomposites. Doping with Poly Vinyl Alcohol (PVA) caused a reduction in crystallite size and greater lattice parameters. XRD, FTIR, EDS, and SEM techniques were used to establish their surface morphology and structural characterization. The high-performance nanocomposites were used to remove malachite green (MG) dye using the ultrasonic adsorption technique. Adsorption experiments were designed by central composite design and optimized by response surface methodology. According to this study, 77.87% of the dye was removed at the optimum optimized parameters (10.0 mg L⁻¹ was the concentration of MG dye at a time of 8.0 min, pH 9.0, and 0.02 g of adsorbent amount) with adsorption capacity up to 92.59 mg·g⁻¹. The dye adsorption followed Freundlich’s isotherm model and the pseudo-second-order kinetic model. Thermodynamic analysis affirmed the spontaneous nature of adsorption due to negative ΔG^o values. As a result, the suggested approach offers a framework for creating an effective and affordable technique to remove the dye from a simulated wastewater system for environmental conservation. Full article

Adsorption of toxic compounds from water using zeolites and magnetite was developed due to the various advantages of their applicability. In the last twenty years, the use of zeolite-based compositions in the form of zeolite/inorganic or zeolite/polymer and magnetite has been accelerated for the adsorption of emergent compounds from water sources. The main adsorption mechanisms using zeolite and magnetite nanomaterials are high surface adsorption, ion exchange capacity and electrostatic interaction. This paper shows the capacity of Fe₃O₄ and ZSM-5 nanomaterials of adsorbing the emerging pollutant acetaminophen (paracetamol) during the treatment of wastewater. The efficiencies of the Fe₃O₄ and ZSM-5 in the wastewater process were systematically investigated using adsorption kinetics. During the study, the concentration of acetaminophen in the wastewater was varied from 50 to 280 mg/L, and the maximum Fe₃O₄ adsorption capacity increased from 25.3 to 68.9 mg/g. The adsorption capacity of each studied material was performed for three pH values (4, 6, 8) of the wastewater. Langmuir and Freundlich isotherm models were used to characterize acetaminophen adsorption on Fe₃O₄ and ZSM-5 materials. The highest efficiencies in the treatment of wastewater were obtained at a pH value of 6. Fe₃O₄ nanomaterial presented a higher removal efficiency (84.6%) compared to ZSM-5 nanomaterial (75.4%). The results of the experiments show that both materials have a potential to be used as an effective adsorbents for the removal of acetaminophen from wastewater. Full article

Porous carbon materials have demonstrated exceptional performance in various energy and environment-related applications. Recently, research on supercapacitors has been steadily increasing, and porous carbon materials have emerged as the most significant electrode material for supercapacitors. Nonetheless, the high cost and potential for environmental pollution associated with the preparation process of porous carbon materials remain significant issues. This paper presents an overview of common methods for preparing porous carbon materials, including the carbon-activation method, hard-templating method, soft-templating method, sacrificial-templating method, and self-templating method. Additionally, we also review several emerging methods for the preparation of porous carbon materials, such as copolymer pyrolysis, carbohydrate self-activation, and laser scribing. We then categorise porous carbons based on their pore sizes and the presence or absence of heteroatom doping. Finally, we provide an overview of recent applications of porous carbon materials as electrodes for supercapacitors. Full article

In this work, a facile synthesis method was adopted to synthesize MOF-14 with mesoporous structure. The physical properties of the samples were characterized by PXRD, FESEM, TEM and FT-IR spectrometry. By coating the mesoporous-structure MOF-14 on the surface of a quartz crystal microbalance (QCM), the fabricated gravimetric sensor exhibits high sensitivity to p-toluene vapor even at trace levels. Additionally, the limit of detection (LOD) of the sensor obtained experimentally is lower than 100 ppb, and the theoretical detection limit is 57 ppb. Furthermore, good gas selectivity and fast response (15 s) and recovery (20 s) abilities are also illustrated along with high sensitivity. These sensing data indicate the excellent performance of the fabricated mesoporous-structure MOF-14-based p-xylene QCM sensor. On the basis of temperature-varying experiments, an adsorption enthalpy of −59.88 kJ/mol was obtained, implying the existence of moderate and reversible chemisorption between MOF-14 and p-xylene molecules. This is the crucial factor that endows MOF-14 with exceptional p-xylene-sensing abilities. This work has proved that MOF materials such as MOF-14 are promising in gravimetric-type gas-sensing applications and worthy of future study. Full article

Metal–organic frameworks (MOFs), composed of metal nodes and inorganic linkers, are promising for a wide range of applications due to their unique periodic frameworks. Understanding structure–activity relationships can facilitate the development of new MOFs. Transmission electron microscopy (TEM) is a powerful technique to characterize the microstructures of MOFs at the atomic scale. In addition, it is possible to directly visualize the microstructural evolution of MOFs in real time under working conditions via in situ TEM setups. Although MOFs are sensitive to high-energy electron beams, much progress has been made due to the development of advanced TEM. In this review, we first introduce the main damage mechanisms for MOFs under electron-beam irradiation and two strategies to minimize these damages: low-dose TEM and cryo-TEM. Then we discuss three typical techniques to analyze the microstructure of MOFs, including three-dimensional electron diffraction, imaging using direct-detection electron-counting cameras, and iDPC-STEM. Groundbreaking milestones and research advances of MOFs structures obtained with these techniques are highlighted. In situ TEM studies are reviewed to provide insights into the dynamics of MOFs induced by various stimuli. Additionally, perspectives are analyzed for promising TEM techniques in the research of MOFs’ structures. Full article

Two-dimensional (2D) MXenes sheet-like micro-structures have attracted attention as an effective electrochemical energy storage material due to their efficient electrolyte/cation interfacial charge transports inside the 2D sheets which results in ultrahigh rate capability and high volumetric capacitance. In this article, Ti₃C₂T_x MXene is prepared by a combination of ball milling and chemical etching from Ti₃AlC₂ powder. The effects of ball milling and etching duration on the physiochemical properties are also explored, as well as the electrochemical performance of as-prepared Ti₃C₂ MXene. The electrochemical performances of 6 h mechanochemically treated and 12 h chemically etched MXene (BM-12H) exhibit an electric double layer capacitance behavior with an enhanced specific capacitance of 146.3 F g⁻¹ compared to 24 and 48 h treated samples. Moreover, 5000-cycle stability tested sample’s (BM-12H) charge/discharge show increased specific capacitance due to the termination of the -OH group, intercalation of K⁺ ion and transformation to TiO₂/Ti₃C₂ hybrid structure in a 3 M KOH electrolyte. Interestingly, a symmetric supercapacitor (SSC) device fabricated in a 1 M LiPF₆ electrolyte in order to extend the voltage window up to 3 V shows a pseudocapacitance behavior due to Li on interaction/de-intercalation. In addition, the SSC shows an excellent energy and power density of 138.33 W h kg⁻¹ and 1500 W kg⁻¹, respectively. The ball milling pre-treated MXene exhibited an excellent performance and stability due to the increased interlayer distance between the MXene sheets and intercalation and deintercalation of Li⁺ ions. Full article

In this paper, the effect of atomic layer deposition (ALD)-derived Al₂O₃ passivation layers and annealing temperatures on the interfacial chemistry and transport properties of sputtering-deposited Er₂O₃ high-k gate dielectrics on Si substrate has been investigated. X-ray photoelectron spectroscopy (XPS) analyses have showed that the ALD-derived Al₂O₃ passivation layer remarkably prevents the formation of the low-k hydroxides generated by moisture absorption of the gate oxide and greatly optimizes the gate dielectric properties. Electrical performance measurements of metal oxide semiconductor (MOS) capacitors with different gate stack order have revealed that the lowest leakage current density of 4.57 × 10⁻⁹ A/cm² and the smallest interfacial density of states (Dit) of 2.38 × 10¹² cm⁻² eV⁻¹ have been achieved in the Al₂O_3/Er₂O₃/Si MOS capacitor, which can be attributed to the optimized interface chemistry. Further electrical measurements of annealed Al₂O_3/Er₂O₃/Si gate stacks at 450 °C have demonstrated superior dielectric properties with a leakage current density of 1.38 × 10⁻⁹ A/cm². At the same, the leakage current conduction mechanism of MOS devices under various stack structures is systematically investigated. Full article

In this work, we present a comprehensive theoretical and computational investigation of exciton fine structures of WSe${}_2$-monolayers, one of the best-known two-dimensional (2D) transition-metal dichalcogenides (TMDs), in various dielectric-layered environments by solving the first-principles-based Bethe–Salpeter equation. While the physical and electronic properties of atomically thin nanomaterials are normally sensitive to the variation of the surrounding environment, our studies reveal that the influence of the dielectric environment on the exciton fine structures of TMD-MLs is surprisingly limited. We point out that the non-locality of Coulomb screening plays a key role in suppressing the dielectric environment factor and drastically shrinking the fine structure splittings between bright exciton (BX) states and various dark-exciton (DX) states of TMD-MLs. The intriguing non-locality of screening in 2D materials can be manifested by the measurable non-linear correlation between the BX-DX splittings and exciton-binding energies by varying the surrounding dielectric environments. The revealed environment-insensitive exciton fine structures of TMD-ML suggest the robustness of prospective dark-exciton-based optoelectronics against the inevitable variation of the inhomogeneous dielectric environment. Full article

Mesoporous silica engineered nanomaterials are of interest to the industry due to their drug-carrier ability. Advances in coating technology include using mesoporous silica nanocontainers (SiNC) loaded with organic molecules as additives in protective coatings. The SiNC loaded with the biocide 4,5-dichloro-2-octyl-4-isothiazolin-3-one (DCOIT), i.e., SiNC-DCOIT, is proposed as an additive for antifouling marine paints. As the instability of nanomaterials in ionic-rich media has been reported and related to shifting key properties and its environmental fate, this study aims at understanding the behaviour of SiNC and SiNC-DCOIT in aqueous media with distinct ionic strengths. Both nanomaterials were dispersed in (i) low- (ultrapure water—UP) and (ii) high- ionic strength media—artificial seawater (ASW) and f/2 medium enriched in ASW (f/2 medium). The morphology, size and zeta potential (ζP) of both engineering nanomaterials were evaluated at different timepoints and concentrations. Results showed that both nanomaterials were unstable in aqueous suspensions, with the initial ζP values in UP below −30 mV and the particle size varying from 148 to 235 nm and 153 to 173 nm for SiNC and SiNC-DCOIT, respectively. In UP, aggregation occurs over time, regardless of the concentration. Additionally, the formation of larger complexes was associated with modifications in the ζP values towards the threshold of stable nanoparticles. In ASW, SiNC and SiNC-DCOIT formed aggregates (<300 nm) independently of the time or concentration, while larger and heterogeneous nanostructures (>300 nm) were detected in the f/2 medium. The pattern of aggregation detected may increase engineering nanomaterial sedimentation rates and enhance the risks towards dwelling organisms. Full article

We present a study with a numerical model based on $\overrightarrow{k}·\overrightarrow{p}$, including electromechanical fields, to evaluate the electromechanical and optoelectronic properties of single GaAs quantum dots embedded in direct band gap AlGaAs nanowires. The geometry and the dimensions of the quantum dots, in particular the thickness, are obtained from experimental data measured by our group. We also present a comparison between the experimental and numerically calculated spectra to support the validity of our model. Full article