Appl. Nano, Volume 2, Issue 3 (September 2021) – 9 articles

A new and simple method for preparing confined copper and nickel nanoparticles by thermal treatment of their respective cations inside Mobil Composition of Matter 41 (MCM–41) hydrophobic nanopores is presented here. Surface modified MCM–41 hydrophobic materials were impregnated by using high-pressure treatment with copper II (Cu II) or nickel II (Ni II) aqueous solutions. After pressure release and washing, the remaining metal cations, confined exclusively within the nanopores, were heated, forming metallic nanoparticles. Reduction of the cations by a redox reaction between the hydrophobic organic surface and the confined metal cations is proposed. Transmission electronic microscopy (TEM), selected area electron diffraction (SAED), nitrogen (N₂) adsorption at −196 °C (77 K), Fourier transform infrared (FTIR) and thermogravimetric (TGA) analyses evidenced the identification of copper and nickel nanoparticles (NPs). Full article

Multiple heteroatom-doped graphene is of great interest for developing an efficient electrocatalyst for oxygen reduction reaction (ORR). To maximize the electrocatalytic performance of doped graphene, the competitive doping mechanism caused by the different atomic sizes of dopants should be developed. Herein, three different heteroatoms (e.g., N, P and B) are competitively introduced into reduced graphene oxide (RGO) using both single- and two-step processes. The total quantity of heteroatoms for ternary RGO synthesized using the two-step process is lower than that when using the single-step process. Higher ORR electrocatalytic activity for the two-step-synthesized RGO compared to the single-step-synthesized RGO can be explained by: (a) a high amount of P atoms; (b) the fact that B doping itself decreases the less electrocatalytic N moieties such as pyrrole and pyridine and increases the high electrocatalytic moieties such as quaternary N; (c) a high amount of B atoms itself within the RGO act as an electrocatalytic active center for O₂ adsorption; and (d) a small amount of substitutional B might increase the electrical conductivity of RGO. Our findings provide new insights into the design of heteroatom-doped carbon materials with excellent electrocatalytic performance. Full article

The treatment of coronavirus diseases (COVID-19) is a principal aim worldwide that is required restore public health in the population. To this end, we have been studied several kinds of de novo and repurposed drugs to investigate their ability to inhibit the replication of the virus which causes the current pandemic—the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). However, finding a vehicle that promotes the controlled dosage is vital for avoiding secondary effects. For this reason, the present work exposes a nanostructured carrier based on ZnO, which is coupled to three repurposed drugs (Chloroquine, Dipyridamole, and Lopinavir) to understand the chemical interaction of the formed composite. The designed composites are modeled and optimized using the DFT formalism. In obtaining exergonic adsorption energies, we found values between 0.582 to 2.084 eV, depending on the used drug. At the same time, the HOMO orbitals demonstrate the electronic overlap between the ZnO-Np and the Lopinavir, which is the molecule with the higher adsorption energy. Finally, we carried out a docking assay to investigate the interaction of free drugs and composites with the main protease of the SARS-CoV-2, finding that the coupling energy of the composites (at around to 0.03 eV) was higher, compared with the free drugs. As such, our results suggest a controlled dosage of the drug on the SARS-CoV-2 target. Full article

Surface-enhanced Raman scattering has developed into a mature analytical technique useful in various applications; however, the reproducible fabrication of a portable SERS substrate with high sensitivity and good uniformity is still an ongoing pursuit. Reported herein is a rapid fabrication method of an inexpensive SERS substrate that enables sub-nanomolar detection of molecular analytes. The SERS substrate is obtained by application of silver nanoparticles (Ag NPs)-based ink in precisely design patterns with the aid of an in-house assembled printer equipped with a user-fillable pen. Finite-difference time-domain (FDTD) simulations show a 155-times Ag NP electric field enhancement for Ag nanoparticle pairs with particle spacing of 2 nm. By comparing the SERS performance of SERS substrate made with different support matrices and fabrication methods, the PET-printed substrate shows optimal performance, with an estimated sensitivity enhancement factor of 10⁷. The quantitative analysis of rhodamine 6G absorbed on optimized SERS substrate exhibits a good linear relationship, with a correlation coefficient (R²) of 0.9998, between the SERS intensity at 610 cm⁻¹ and the concentration in the range of 0.1 nM—1μM. The practical low limit detection of R6G is 10 pM. The optimized SERS substrates show good stability (at least one month) and have been effectively tested in the detection of cancer drugs, including doxorubicin and metvan. Full article

Exposure to nanoparticles by various routes results in size-dependent translocation of nanoparticles to the systemic circulation and subsequent accumulation in the liver. The purpose of this study was to determine possible adverse effects in the liver of long-lasting nanoparticle presence in the organ. Mice exposed to a single dose (162 µg/animal equivalent to 9 mg/kg body weight) of TiO₂, CeO₂ or carbon black nanoparticles by intratracheal instillation or intravenous injection, resulting in relatively low or high liver burdens, were followed for 1, 28 or 180 days. Clinical appearance, feed intake, body and liver weights, hematological indices, and transaminases and alkaline phosphatase activities were unaffected by exposure. Exposure-related foreign material persisted in the liver up to 180 days after intratracheal and intravenous exposure, mainly in sinusoids, near Kupffer cells, or around blood vessels. Increased incidences of histological findings after intratracheal or intravenous exposure included: initially, prominent nuclei of Kupffer cells, the apparent increase in binucleate hepatocytes (TiO₂ and carbon black) and inflammatory infiltrations (CeO₂); later, cytoplasmic vacuolation, pyknosis and necrosis, especially for CeO₂. Thus, neither low nor high nanoparticle burden in the liver affected enzymatic markers of liver injury, but indications of exposure-related necrotic changes, particularly for CeO₂ nanoparticles, were noted. Full article

The present investigation aims to take a step forward for the transfer of a simple laboratory electrochemical method of surface nano-treatment of aluminum to industrial applications. The electrochemical method has been applied to process 1050A aluminum. Surface nano-structuring has been achieved and resulted in the formation of an organized alumina nanotubes layer on commercial aluminum plates used as adherends for the manufacturing of aluminum single-lap adhesive joints. The mechanical properties of single-lap aluminum adhesive joints constructed with both non-anodized and anodized adherends were investigated and compared. Two types of epoxy resins were used to prove that the anodization of the adherends is equally effective, independently of the adhesives’ type. Furthermore, three overlap lengths were used (7, 10, and 25 mm) to study the effect of the overlap length on the overall joint mechanical response. Results of both three-point bending and tensile–shear testing showed that there is a considerable improvement of the joints’ mechanical performance with the addition of the nanostructures, for all the overlap lengths. It was found that the anodization method greatly contributes to the strengthening of the joints, leading to a strength increase of up to 176% and 148% for the shear and three-point bending strength, respectively. Full article

Cobalt (Co) nanoparticles (NPs) may be diffusely dispersed into natural ecosystems from various anthropogenic sources such as traffic settings and eventually end up in aquatic systems. As environmentally dispersed Co NPs may be transferred through an aquatic food web, this study investigated this transfer from algae (Scendesmus sp.) to zooplankton (Daphnia magna) to fish (Crucian carp, Carassius carassius). Effects of interactions between naturally excreted biomolecules from D. magna and Co NPs were investigated from an environmental fate perspective. ATR-FTIR measurements showed the adsorption of both algae constituents and excreted biomolecules onto the Co NPs. Less than 5% of the Co NPs formed heteroagglomerates with algae, partly an effect of both agglomeration and settling of the Co NPs. The presence of excreted biomolecules in the solution did not affect the extent of heteroagglomeration. Despite the low extent of heteroagglomeration between Co NPs and algae, the Co NPs were transferred to the next trophic level (D. magna). The Co uptake in D. magna was 300 times larger than the control samples (without Co NP), which were not influenced by the addition of excreted biomolecules to the solution. Significant uptake of Co was observed in the intestine of the fish feeding on D. magna containing Co NPs. No bioaccumulation of Co was observed in the fish. Moreover, 10–20% of the transferred Co NP mass was dissolved after 24 h in the simulated gut solution of the zooplankton (pH 7), and 50–60% was dissolved in the simulated gut solution of the fish (pH 4). The results elucidate that Co NPs gain different properties upon trophic transfer in the food web. Risk assessments should hence be conducted on transformed and weathered NPs rather than on pristine particles. Full article

We reviewed some recent ideas to improve the efficiency and power output of thermoelectric nano-devices. We focused on two essentially independent aspects: (i) increasing the charge current by taking advantage of an interplay between the material and the thermodynamic parameters, which is only available in the non-linear regime; and (ii) decreasing the heat current by using nanowires with surface disorder, which helps excite localized phonons at random positions that can strongly scatter the propagating phonons carrying the thermal current. Full article

The rational synthesis of semiconducting materials with enhanced photoelectrocatalytic efficiency under visible light illumination is a long-standing issue. ZnO has been systematically explored in this field, as it offers the feasibility to grow a wide range of nanocrystal morphology; however, its wide band gap precludes visible light absorption. We report on a novel method for the controlled growth of semiconductor heterostructures and, in particular, core/sheath ZnO/MoS₂ nanowire arrays and the evaluation of their photoelectrochemical efficiency in oxygen evolution reaction. ZnO nanowire arrays, with a narrow distribution of nanowire diameters, were grown on FTO substrates by chemical bath deposition. Layers of Mo metal at various thicknesses were sputtered on the nanowire surface, and the Mo layers were sulfurized at low temperature, providing in a controlled way few layers of MoS₂, in the range from one to three monolayers. The heterostructures were characterized by electron microscopy (SEM, TEM) and spectroscopy (XPS, Raman, PL). The photoelectrochemical properties of the heterostructures were found to depend on the thickness of the pre-deposited Mo film, exhibiting maximum efficiency for moderate values of Mo film thickness. Long-term stability, in relation to similar heterostructures in the literature, has been observed. Full article