Nanomaterials

The laser energy per unit surface, necessary to trigger material removal, decreases with the pulse shortening, becoming pulse–time independent in the sub-picosecond range. These pulses are shorter than the electron-to-ion energy transfer time and electronic heat conduction time, minimising the energy losses. Electrons receiving an energy larger than the threshold drag the ions off the surface in the mode of electrostatic ablation. We show that a pulse shorter than the ion period (Shorter-the-Limit (StL)) ejects conduction electrons with an energy larger than the work function (from a metal), leaving the bare ions immobile in a few atomic layers. Electron emission is followed by the bare ion’s explosion, ablation, and THz radiation from the expanding plasma. We compare this phenomenon to the classic photo effect and nanocluster Coulomb explosions, and show differences and consider possibilities for detecting new modes of ablation experimentally via emitted THz radiation. We also consider the applications of high-precision nano-machining with this low intensity irradiation. Full article

Zinc oxide (ZnO) nanoparticles have shown great potential because of their versatile and promising applications in different fields, including solar cells. Various methods of synthesizing ZnO materials have been reported. In this work, controlled synthesis of ZnO nanoparticles was achieved via a simple, cost-effective, and facile synthetic method. Using transmittance spectra and film thickness of ZnO, the optical band gap energies were calculated. For as-synthesized and annealed ZnO films, the bandgap energies were found to be 3.40 eV and 3.30 eV, respectively. The nature of the optical transition indicates that the material is a direct bandgap semiconductor. Spectroscopic ellipsometry (SE) analysis was used to extract dielectric functions where the onset of optical absorption of ZnO was observed at lower photon energy due to annealing of the nanoparticle film. Similarly, X-ray diffraction (XRD) and scanning electron microscopy (SEM) data revealed that the material is pure and crystalline in nature, with the average crystallite size of ~9 nm. Full article

Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities, and MW of the organic matrix, was investigated to determine the optimum formulation for water purification under these conditions. This was attained with the aid of UV-visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential, liquid nitrogen (LN₂) porosimetry, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Results highlighted that both adsorbents have extraordinary sorption capacities. Xerogels are cost-effective since they approximate the performance of nanoparticles with much less organic content. Both adsorbents could be used in the form of dispersions. The xerogels, though, are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor gel-forming solution, producing composite purification devices. Full article

The UiO-6x family of metal-organic frameworks has been extensively studied for applications in chemical warfare agent (CWA) capture and destruction. An understanding of intrinsic transport phenomena, such as diffusion, is key to understanding experimental results and designing effective materials for CWA capture. However, the relatively large size of CWAs and their simulants makes diffusion in the small-pored pristine UiO-66 very slow and hence impractical to study directly with direct molecular simulations because of the time scales required. We used isopropanol (IPA) as a surrogate for CWAs to investigate the fundamental diffusion mechanisms of a polar molecule within pristine UiO-66. IPA can form hydrogen bonds with the ${\mu }_3$-OH groups bound to the metal oxide clusters in UiO-66, similar to some CWAs, and can be studied by direct molecular dynamics simulations. We report self, corrected, and transport diffusivities of IPA in pristine UiO-66 as a function of loading. Our calculations highlight the importance of the accurate modeling of the hydrogen bonding interactions on diffusivities, with about an order of magnitude decrease in diffusion coefficients when the hydrogen bonding between IPA and the ${\mu }_3$-OH groups is included. We found that a fraction of the IPA molecules have very low mobility during the course of a simulation, while a small fraction are highly mobile, exhibiting mean square displacements far greater than the ensemble average. Full article

This study is focused on the preparation, characterization, and multifunctional properties of intelligent hybrid nanopigments. The hybrid nanopigments with excellent environmental stability and antibacterial and antioxidant properties were fabricated based on natural Monascus red, surfactant, and sepiolite via a facile one-step grinding process. The density functional theory calculations demonstrated that the surfactants loaded on sepiolite were in favor of enhancing the electrostatic, coordination, and hydrogen bonding interactions between Monascus red and sepiolite. Thus, the obtained hybrid nanopigments exhibited excellent antibacterial and antioxidant properties, with an inhibition effect on Gram-positive bacteria that was superior to that of Gram-negative bacteria. In addition, the scavenging activity on DPPH and hydroxyl free radicals as well as the reducing power of hybrid nanopigments were higher than those of hybrid nanopigments prepared without the addition of the surfactant. Inspired by nature, gas-sensitive reversible alochroic superamphiphobic coatings with excellent thermal and chemical stability were successfully designed by combining hybrid nanopigments and fluorinated polysiloxane. Therefore, intelligent multifunctional hybrid nanopigments have great application foreground in related fields. Full article

Engineered bio-scaffolds for wound healing provide an attractive treatment option for tissue engineering and traumatic skin injuries since they can reduce dependence on donors and promote faster repair through strategic surface engineering. Current scaffolds present limitations in handling, preparation, shelf life, and sterilization options. In this study, bio-inspired hierarchical all-carbon structures comprising carbon nanotube (CNT) carpets covalently bonded to flexible carbon fabric have been investigated as a platform for cell growth and future tissue regeneration applications. CNTs are known to provide guidance for cell growth, but loose CNTs are susceptible to intracellular uptake and are suspected to cause in vitro and in vivo cytotoxicity. This risk is suppressed in these materials due to the covalent attachment of CNTs on a larger fabric, and the synergistic benefits of nanoscale and micro-macro scale architectures, as seen in natural biological materials, can be obtained. The structural durability, biocompatibility, tunable surface architecture, and ultra-high specific surface area of these materials make them attractive candidates for wound healing. In this study, investigations of cytotoxicity, skin cell proliferation, and cell migration were performed, and results indicate promise in both biocompatibility and directed cell growth. Moreover, these scaffolds provided cytoprotection against environmental stressors such as Ultraviolet B (UVB) rays. It was seen that cell growth could also be tailored through the control of CNT carpet height and surface wettability. These results support future promise in the design of hierarchical carbon scaffolds for strategic wound healing and tissue regeneration applications. Full article

Although radiotherapy is one of the most important curative treatments for cancer, its clinical application is associated with undesired therapeutic effects on normal or healthy tissues. The use of targeted agents that can simultaneously achieve therapeutic and imaging functions could constitute a potential solution. Herein, we developed 2-deoxy-d-glucose (2DG)-labeled poly(ethylene glycol) (PEG) gold nanodots (2DG-PEG-AuD) as a tumor-targeted computed tomography (CT) contrast agent and radiosensitizer. The key advantages of the design are its biocompatibility and targeted AuD with excellent sensitivity in tumor detection via avid glucose metabolism. As a consequence, CT imaging with enhanced sensitivity and remarkable radiotherapeutic efficacy could be attained. Our synthesized AuD displayed linear enhancement of CT contrast as a function of its concentration. In addition, 2DG-PEG-AuD successfully demonstrated significant augmentation of CT contrast in both in vitro cell studies and in vivo tumor-bearing mouse models. In tumor-bearing mice, 2DG-PEG-AuD showed excellent radiosensitizing functions after intravenous injection. Results from this work indicate that 2DG-PEG-AuD could greatly potentiate theranostic capabilities by providing high-resolution anatomical and functional images in a single CT scan and therapeutic capability. Full article

Lithium metal batteries (LMBs) are a dazzling star in electrochemical energy storage thanks to their high energy density and low redox potential. However, LMBs have a deadly lithium dendrite problem. Among the various methods for inhibiting lithium dendrites, gel polymer electrolytes (GPEs) possess the advantages of good interfacial compatibility, similar ionic conductivity to liquid electrolytes, and better interfacial tension. In recent years, there have been many reviews of GPEs, but few papers discussed the relationship between GPEs and solid electrolyte interfaces (SEIs). In this review, the mechanisms and advantages of GPEs in inhibiting lithium dendrites are first reviewed. Then, the relationship between GPEs and SEIs is examined. In addition, the effects of GPE preparation methods, plasticizer selections, polymer substrates, and additives on the SEI layer are summarized. Finally, the challenges of using GPEs and SEIs in dendrite suppression are listed and a perspective on GPEs and SEIs is considered. Full article

Alloy-based catalysts with high corrosion resistance and less self-aggregation are essential for oxygen reduction/evolution reactions (ORR/OER). Here, via an in situ growth strategy, NiCo alloy-inserted nitrogen-doped carbon nanotubes were assembled on a three-dimensional hollow nanosphere ([email protected]/HN) using dicyandiamide. [email protected]/HN exhibited better ORR activity (half-wave potential (E_1/2) of 0.87 V) and stability (E_1/2 shift of only −13 mV after 5000 cycles) than commercial Pt/C. [email protected]/HN displayed a lower OER overpotential (330 mV) than RuO₂ (390 mV). The [email protected]/HN-assembled zinc–air battery exhibited high specific-capacity (847.01 mA h g⁻¹) and cycling-stability (291 h). Synergies between NiCo alloys and NCNTs facilitated the charge transfer to promote 4e⁻ ORR/OER kinetics. The carbon skeleton inhibited the corrosion of NiCo alloys from surface to subsurface, while inner cavities of CNTs confined particle growth and the aggregation of NiCo alloys to stabilize bifunctional activity. This provides a viable strategy for the design of alloy-based catalysts with confined grain-size and good structural/catalytic stabilities in oxygen electrocatalysis. Full article

Plasmonic nanomaterials have attracted great attention in the field of catalysis and sensing for their outstanding electrical and optical properties. Here, a representative type of nonstoichiometric Cu_2−xSe nanoparticles with typical near-infrared (NIR) localized surface plasma resonance (LSPR) properties originating from their copper deficiency was applied to catalyze the oxidation of colorless TMB into their blue product in the presence of H₂O₂, indicating they had good peroxidase-like activity. However, glutathione (GSH) inhibited the catalytic oxidation of TMB, as it can consume the reactive oxygen species. Meanwhile, it can induce the reduction of Cu(II) in Cu_2−xSe, resulting in a decrease in the degree of copper deficiency, which can lead to a reduction in the LSPR. Therefore, the catalytic ability and photothermal responses of Cu_2−xSe were decreased. Thus, in our work, a colorimetric/photothermal dual-readout array was developed for the detection of GSH. The linear calibration for GSH concentration was in the range of 1–50 μM with the LOD as 0.13 μM and 50–800 μM with the LOD as 39.27 μM. To evaluate the practicability of the assay, tomatoes and cucumbers were selected as real samples, and good recoveries indicated that the developed assay had great potential in real applications. Full article

Transistor scaling has become increasingly difficult in the dynamic random access memory (DRAM). However, vertical devices will be good candidates for 4F² DRAM cell transistors (F = pitch/2). Most vertical devices are facing some technical challenges. For example, the gate length cannot be precisely controlled, and the gate and the source/drain of the device cannot be aligned. Recrystallization-based vertical C-shaped-channel nanosheet field-effect transistors (RC-VCNFETs) were fabricated. The critical process modules of the RC-VCNFETs were developed as well. The RC-VCNFET with a self-aligned gate structure has excellent device performance, and its subthreshold swing (SS) is 62.91 mV/dec. Drain-induced barrier lowering (DIBL) is 6.16 mV/V. Full article

Optimization of equipment structure and process conditions is essential to obtain thin films with the required properties, such as film thickness, trapped charge density, leakage current, and memory characteristics, that ensure reliability of the corresponding device. In this study, we fabricated metal–insulator–semiconductor (MIS) structure capacitors using HfO₂ thin films separately deposited by remote plasma (RP) atomic layer deposition (ALD) and direct-plasma (DP) ALD and determined the optimal process temperature by measuring the leakage current and breakdown strength as functions of process temperature. Additionally, we analyzed the effects of the plasma application method on the charge trapping properties of HfO₂ thin films and properties of the interface between Si and HfO₂. Subsequently, we synthesized charge-trapping memory (CTM) devices utilizing the deposited thin films as charge-trapping layers (CTLs) and evaluated their memory properties. The results indicated excellent memory window characteristics of the RP-HfO₂ MIS capacitors compared to those of the DP-HfO₂ MIS capacitors. Moreover, the memory characteristics of the RP-HfO₂ CTM devices were outstanding as compared to those of the DP-HfO₂ CTM devices. In conclusion, the methodology proposed herein can be useful for future implementations of multiple levels of charge-storage nonvolatile memories or synaptic devices that require many states. Full article

The paper presents a simple, fast, and cost-effective method for creating metal/SU-8 nanocomposites by applying a metal precursor drop onto the surface or nanostructure of SU-8 and exposing it to UV light. No pre-mixing of the metal precursor with the SU-8 polymer or pre-synthesis of metal nanoparticles is required. A TEM analysis was conducted to confirm the composition and depth distribution of the silver nanoparticles, which penetrate the SU-8 film and uniformly form the Ag/SU-8 nanocomposites. The antibacterial properties of the nanocomposites were evaluated. Moreover, a composite surface with a top layer of gold nanodisks and a bottom layer of Ag/SU-8 nanocomposites was produced using the same photoreduction process with gold and silver precursors, respectively. The reduction parameters can be manipulated to customize the color and spectrum of various composite surfaces. Full article

Titanium dioxide nanoparticles (TiO₂-NPs) are used intensively. Thanks to their extremely small size (1–100 nm), TiO₂-NPs are more absorbable by living organisms; consequently, they can cross the circulatory system and then be distributed in various organs including the reproductive organs. We have evaluated the possible toxic effect of TiO₂-NPs on embryonic development and the male reproductive system using Danio rerio as an organism model. TiO₂-NPs (P25, Degussa) were tested at concentrations of 1 mg/L, 2 mg/L, and 4 mg/L. TiO₂-NPs did not interfere with the embryonic development of Danio rerio, however, in the male gonads the TiO₂-NPs caused an alteration of the morphological/structural organization. The immunofluorescence investigation showed positivity for biomarkers of oxidative stress and sex hormone binding globulin (SHBG), both confirmed by the results of qRT-PCR. In addition, an increased expression of the gene responsible for the conversion of testosterone to dihydrotestosterone was found. Since Leydig cells are mainly involved in this activity, an increase in gene activity can be explained by the ability of TiO₂-NPs to act as endocrine disruptors, and, therefore, with androgenic activity. Full article

Gene delivery has emerged as a promising alternative to conventional treatment approaches, allowing for the manipulation of gene expression through gene insertion, deletion, or alteration. However, the susceptibility of gene delivery components to degradation and challenges associated with cell penetration necessitate the use of delivery vehicles for effective functional gene delivery. Nanostructured vehicles, such as iron oxide nanoparticles (IONs) including magnetite nanoparticles (MNPs), have demonstrated significant potential for gene delivery applications due to their chemical versatility, biocompatibility, and strong magnetization. In this study, we developed an ION-based delivery vehicle capable of releasing linearized nucleic acids (tDNA) under reducing conditions in various cell cultures. As a proof of concept, we immobilized a CRISPR activation (CRISPRa) sequence to overexpress the pink1 gene on MNPs functionalized with polyethylene glycol (PEG), 3-[(2-aminoethyl)dithio]propionic acid (AEDP), and a translocating protein (OmpA). The nucleic sequence (tDNA) was modified to include a terminal thiol group and was conjugated to AEDP’s terminal thiol via a disulfide exchange reaction. Leveraging the natural sensitivity of the disulfide bridge, the cargo was released under reducing conditions. Physicochemical characterizations, including thermogravimetric analysis (TGA) and Fourier-transform infrared (FTIR) spectroscopy, confirmed the correct synthesis and functionalization of the MNP-based delivery carriers. The developed nanocarriers exhibited remarkable biocompatibility, as demonstrated by the hemocompatibility, platelet aggregation, and cytocompatibility assays using primary human astrocytes, rodent astrocytes, and human fibroblast cells. Furthermore, the nanocarriers enabled efficient cargo penetration, uptake, and endosomal escape, with minimal nucleofection. A preliminary functionality test using RT-qPCR revealed that the vehicle facilitated the timely release of CRISPRa vectors, resulting in a remarkable 130-fold overexpression of pink1. We demonstrate the potential of the developed ION-based nanocarrier as a versatile and promising gene delivery vehicle with potential applications in gene therapy. The developed nanocarrier is capable of delivering any nucleic sequence (up to 8.2 kb) once it is thiolated using the methodology explained in this study. To our knowledge, this represents the first MNP-based nanocarrier capable of delivering nucleic sequences under specific reducing conditions while preserving functionality. Full article

Yttrium-doped barium cerate (BCY15) was used as ceramic matrix to obtain Ni/BCY15 anode cermet for application in proton-conducting solid oxide fuel cells (pSOFC). Ni/BCY15 cermets were prepared in two different types of medium, namely deionized water (W) and anhydrous ethylene glycol (EG) using wet chemical synthesis by hydrazine. An in-depth analysis of anodic nickel catalyst was made aiming to elucidate the effect of anode tablets’ preparation by high temperature treatment on the resistance of metallic Ni in Ni/BCY15-W and Ni/BCY15-EG anode catalysts. On purpose reoxidation upon high-temperature treatment (1100 °C for 1 h) in air ambience was accomplished. Detailed characterization of reoxidized Ni/BCY15-W-1100 and Ni/BCY15-EG-1100 anode catalysts by means of surface and bulk analysis was performed. XPS, HRTEM, TPR, and impedance spectroscopy measurements experimentally confirmed the presence of residual metallic Ni in the anode catalyst prepared in ethylene glycol medium. These findings were evidence of strong metal Ni network resistance to oxidation in anodic Ni/BCY15-EG. Enhanced resistance of the metal Ni phase contributed to a new microstructure of the Ni/BCY15-EG-1100 anode cermet getting more stable to changes that cause degradation during operation. Full article

The purpose of this study was to investigate the effect of substrate characteristics on the performance of quantum-dot light-emitting diodes (QLEDs) with the aim of developing high-performance flexible QLEDs. Specifically, we compared QLEDs made with a flexible polyethylene naphthalate (PEN) substrate to those made with a rigid glass substrate, using the same materials and structure except for the substrates. Our findings indicate that the PEN QLED had a 3.3 nm wider full width at half maximum and a 6 nm redshifted spectrum in comparison to the glass QLED. Additionally, the PEN QLED exhibited a 6% higher current efficiency, a flatter current efficiency curve, and a 2.25-V lower turn-on voltage, indicating superior overall characteristics. We attribute the spectral difference to the optical properties of the PEN substrate, such as light transmittance and refractive index. Our study also revealed that the electro-optical properties of the QLEDs were consistent with the electron-only device and transient electroluminescence results, which suggests that the improved charge injection properties of the PEN QLED were responsible. Overall, our study provides valuable insights into the relationship between substrate characteristics and QLED performance, which can be used to develop high-performance QLEDs. Full article

Telomerase is constitutively overexpressed in the majority of human cancers and telomerase inhibition provides a promising broad-spectrum anticancer therapeutic strategy. BIBR 1532 is a well-known synthetic telomerase inhibitor that blocks the enzymatic activity of hTERT, the catalytic subunit of telomerase. However, water insolubility of BIBR 1532 leads to low cellular uptake and inadequate delivery and thus, limits its anti-tumor effects. Zeolitic imidazolate framework-8 (ZIF-8) is considered as an attractive drug delivery vehicle for improved transport, release and anti-tumor effects of BIBR 1532. Herein, ZIF-8 and BIBR [email protected] were synthesized, respectively, and the physicochemical characterizations confirmed the successful encapsulation of BIBR 1532 in ZIF-8 coupled with an improved stability of BIBR 1532. ZIF-8 could alter the permeability of lysosomal membrane probably by the imidazole ring-dependent protonation. Moreover, ZIF-8 encapsulation facilitated the cellular uptake and release of BIBR 1532 with more accumulation in the nucleus. BIBR 1532 encapsulation with ZIF-8 triggered a more obvious growth inhibition of cancer cells as compared with free BIBR 1532. A more potent inhibition on hTERT mRNA expression, aggravated G0/G1 arrest accompanied with an increased cellular senescence were detected in BIBR [email protected] cancer cells. Our work has provided preliminary information on improving the transport, release and efficacy of water-insoluble small molecule drugs by using ZIF-8 as a delivery vehicle. Full article

Reducing the thermal conductivity of thermoelectric materials has been a field of intense research to improve the efficiency of thermoelectric devices. One approach is to create a nanostructured thermoelectric material that has a low thermal conductivity due to its high number of grain boundaries or voids, which scatter phonons. Here, we present a new method based on spark ablation nanoparticle generation to create nanostructured thermoelectric materials, demonstrated using Bi₂Te₃. The lowest achieved thermal conductivity was <0.1 W m${}^{-1}$ K${}^{-1}$ at room temperature with a mean nanoparticle size of $8\pm 2$ nm and a porosity of 44%. This is comparable to the best published nanostructured Bi₂Te₃ films. Oxidation is also shown to be a major issue for nanoporous materials such as the one here, illustrating the importance of immediate, air-tight packaging of such materials after synthesis and deposition. Full article