In the present work, we provide evidence for visible light irradiation of the Au/TiO₂ nanoparticles' surface plasmon resonance band (SPR) leading to electron injection from the Au nanoparticles to the conduction band of TiO₂. The Au/TiO₂ SPR band is shown to greatly enhance the light absorption of TiO₂ in the visible region. Evidence is presented for the light absorption by the Au/TiO₂ plasmon bands leading to the dissolution of Au nanoparticles. This dissolution occurs concomitantly with the injection of the hot electrons generated by the Au plasmon into the conduction band of TiO₂. The electron injection from the Au nanoparticles into TiO₂ was followed by femtosecond spectroscopy. The formation of Au ions was further confirmed by the spectral shift of the transient absorption spectra of Au/TiO₂. The spectral changes of the SPR band of Au/TiO₂ nanoparticles induced by visible light were detected by spectrophotometer, and the morphological transformation of Au/TiO₂ was revealed by electron microscopy techniques as well. Subsequently, the fate of the Au ions was sorted out during the growth and biofilm formation for some selected Gram-negative bacteria. This study compares the bactericidal mechanism of Au ions and Ag ions, which were found to be substantially different depending on the selected cell used as a probe.

Metallic nanoparticles show plasmon resonance phenomena when irradiated with electromagnetic radiation of a suitable wavelength, whose value depends on their composition, size, and shape. The damping of the surface electron oscillation causes a release of heat, which causes a large increase in local temperature. Furthermore, this increase is enhanced when nanoparticle aggregation phenomena occur. Local temperature increase is extensively exploited in photothermal therapy, where light is used to induce cellular damage. To activate the plasmon in the visible range, we synthesized 50 nm diameter spherical gold nanoparticles (AuNP) coated with polyethylene glycol and administered them to an E. coli culture. The experiments were carried out, at different gold nanoparticle concentrations, in the dark and under irradiation. In both cases, the nanoparticles penetrated the bacterial wall, but a different toxic effect was observed; while in the dark we observed an inhibition of bacterial growth of 46%, at the same concentration, under irradiation, we observed a bactericidal effect (99% growth inhibition). Photothermal measurements and SEM observations allowed us to conclude that the extraordinary effect is due to the formation, at low concentrations, of a light-induced cluster of gold nanoparticles, which does not form in the absence of bacteria, leading us to the conclusion that the bacterium wall catalyzes the formation of these clusters which are ultimately responsible for the significant increase in the measured temperature and cause of the bactericidal effect. This photothermal effect is achieved by low-power irradiation and only in the presence of the pathogen: in its absence, the lack of gold nanoparticles clustering does not lead to any phototoxic effect. Therefore, it may represent a proof of concept of an innovative nanoscale pathogen responsive system against bacterial infections.

Development of a rapid, sensitive and cost-effective method for toxicity assessment of commonly used nanoparticles is urgently needed for the sustainable development of nanotechnology. A neural cell with high sensitivity and conductivity has become a potential candidate for a cell chip to investigate toxicity of environmental influences. A neural cell immobilized on a conductive surface has become a potential tool for the assessment of nanotoxicity based on electrochemical methods. The effective electrochemical monitoring largely depends on the adequate attachment of a neural cell on the chip surfaces. Recently, establishment of integrin receptor specific ligand molecules arginine-glycine-aspartic acid (RGD) or its several modifications RGD-Multi Armed Peptide terminated with cysteine (RGD-MAP-C), C(RGD)₄ ensure farm attachment of neural cell on the electrode surfaces either in their two dimensional (dot) or three dimensional (rod or pillar) like nano-scale arrangement. A three dimensional RGD modified electrode surface has been proven to be more suitable for cell adhesion, proliferation, differentiation as well as electrochemical measurement. This review discusses fabrication as well as electrochemical measurements of neural cell chip with particular emphasis on their use for nanotoxicity assessments sequentially since inception to date. Successful monitoring of quantum dot (QD), graphene oxide (GO) and cosmetic compound toxicity using the newly developed neural cell chip were discussed here as a case study. This review recommended that a neural cell chip established on a nanostructured ligand modified conductive surface can be a potential tool for the toxicity assessments of newly developed nanomaterials prior to their use on biology or biomedical technologies.

Dielectric layers are widely used in ferroelectric applications such as memory and negative capacitance devices. The wake-up and the split-up phenomena in the ferroelectric hafnia are well-known challenges in early-stage device reliability. We found that the phenomena even occur in the bilayer, which is composed of the hafnia and the dielectrics. The phenomena are known to be affected mainly by oxygen vacancies of hafnia. Dielectric layers, which are often metal oxides, are also prone to be affected by oxygen vacancies. To study the effect of the dielectric layer on the wake-up and the split-up phenomena, we fabricated ferroelectric thin-film capacitors with dielectric layers of various thicknesses and measured their field-cycling behaviors. We found that the movement of oxygen vacancies in the dielectric layer was predominantly affected by the polarization state of the ferroelectric layer. In addition, the mechanism of the field-cycling behavior in the bilayer is similar to that in ferroelectric thin films. Our results can be applied in ferroelectric applications that use dielectric layers.

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 μ3-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 μ3-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.

A better understanding of the compatibility of water-soluble semiconductor quantum dots (QDs) upon contact with the bloodstream is important for biological applications, including biomarkers working in the first therapeutic spectral window for deep tissue imaging. Herein, we investigated the conformational changes of blood plasma proteins during the interaction with near-infrared light-emitting nanoparticles, consisting of Pluronic F127 shells and cores comprised of assembled silicon QDs terminated with decane monolayers. Albumin and transferrin have high quenching constants and form a hard protein corona on the nanoparticle. In contrast, fibrinogen has low quenching constants and forms a soft protein corona. A circular dichroism (CD) spectrometric study investigates changes in the protein's secondary and tertiary structures with incremental changes in the nanoparticle concentrations. As expected, the addition of nanoparticles causes the denaturation of the plasma proteins. However, it is noteworthy that the conformational recovery phenomena are observed for fibrinogen and transferrin, suggesting that the nanoparticle does not influence the ordered structure of proteins in the bloodstream. In addition, we observed enabled cellular uptake (NIH3T3 Fibroblasts) and minimal cytotoxicity using different cell lines (HeLa, A549, and NIH3T3). This study offers a basis to design QDs without altering the biomacromolecule's original conformation with enabled cellular uptake with minimal cytotoxicity.

Memristive devices are highly promising for implementing neuromorphic functionalities in future electronic hardware, and direct insights into memristive phenomena on the nanoscale are of fundamental importance to reaching this. Conductive atomic force microscopy (cAFM) has proven to be an essential tool for probing memristive action locally on the nanoscale, but the significance of the acquired data frequently suffers from the nonlocality associated with the thermal drift of the tip in ambient conditions. Furthermore, comparative studies of different configurations of filamentary devices have proven to be difficult, because of an immanent variability of the filament properties between different devices. Herein, these problems are addressed by constraining the memristive action directly at the apex of the probe through functionalization of a cAFM tip with an archetypical memristive stack, which is comprised of Ag/Si3N4. The design of such functionalized cantilevers (entitled here as "memtips") allowed the capture of the long-term intrinsic current response, identifying temporal correlations between switching events, and observing emerging spiking dynamics directly at the nanoscale. Utilization of an identical memtip for measurements on different counter electrodes made it possible to directly compare the impact of different device configurations on the switching behavior of the same filament. Such an analytical approach in ambient conditions will pave the way towards a deeper understanding of filamentary switching phenomena on the nanoscale.

Molecular diagnostics have significantly advanced the early detection of diseases, where the electrochemical sensing of biomarkers (e.g., DNA, RNA, proteins) using multiple electrode arrays (MEAs) has shown considerable promise. Nanostructuring the electrode surface results in higher surface coverage of capture probes and more favorable orientation, as well as transport phenomena unique to nanoscale, ultimately leading to enhanced sensor performance. The central goal of this study is to investigate the influence of electrode nanostructure on electrically-guided immobilization of DNA probes for nucleic acid detection in a multiplexed format. To that end, we used nanoporous gold (np-Au) electrodes that reduced the limit of detection (LOD) for DNA targets by two orders of magnitude compared to their planar counterparts, where the LOD was further improved by an additional order of magnitude after reducing the electrode diameter. The reduced electrode diameter also made it possible to create a np-Au MEA encapsulated in a microfluidic channel. The electro-grafting reduced the necessary incubation time to immobilize DNA probes into the porous electrodes down to 10 min (25-fold reduction compared to passive immobilization) and allowed for grafting a different DNA probe sequence onto each electrode in the array. The resulting platform was successfully used for the multiplexed detection of three different biomarker genes relevant to breast cancer diagnosis.

Electrospun polymer fibers can be used as templates for the stabilization of metallic nanostructures, but metallic species and polymer macromolecules generally exhibit weak interfacial adhesion. We have investigated the adhesion of model copper nanocubes on chemically treated aligned electrospun polyacrylonitrile (PAN) fibers based on the introduction of interfacial shear strains through mechanical deformation. The composite structures were subjected to distinct macroscopic tensile strain levels of 7%, 11%, and 14%. The fibers exhibited peculiar deformation behaviors that underscored their disparate strain transfer mechanisms depending on fiber size; nanofibers exhibited multiple necking phenomena, while microfiber deformation proceeded through localized dilatation that resulted in craze (and microcrack) formation. The copper nanocubes exhibited strong adhesion on both fibrous structures at all strain levels tested. Raman spectroscopy suggests chemisorption as the main adhesion mechanism. The interfacial adhesion energy of Cu on these treated PAN nanofibers was estimated using the Gibbs-Wulff-Kaischew shape theory giving a first order approximation of about 1 J/m2. A lower bound for the system's adhesion strength, based on limited measurements of interfacial separation between PAN and Cu using mechanically applied strain, is 0.48 J/m2.

Self-assembly of colloidal monolayers represents a prominent approach to the fabrication of nanostructures. The modification of the shape of colloidal particles is essential in order to enrich the variety of attainable patterns which would be limited by the typical assembly of spherical particles in a hexagonal arrangement. Polymer particles are particularly promising in this sense. In this article, we investigate the deformation of closely-packed polystyrene particles under MeV oxygen ion irradiation at normal incidence using atomic force microscopy (AFM). By developing a procedure based on the fitting of particle topography with quadrics, we reveal a scenario of deformation more complex than the one observed in previous studies for silica particles, where several phenomena, including ion hammering, sputtering, chemical modifications, can intervene in determining the final shape due to the specific irradiation conditions. In particular, deformation into an ellipsoidal shape is accompanied by shrinkage and polymer redistribution with the presence of necks between particles for increasing ion fluence. In addition to casting light on particle irradiation in a regime not yet explored, we present an effective method for the characterization of the colloidal particle morphology which can be applied to describe and understand particle deformation in other regimes of irradiation or with different techniques.

Environmentally friendly energy storage devices have been fabricated by using functional materials obtained from completely renewable resources. Gelatin, chitosan, casein, guar gum and carboxymethyl cellulose have been investigated as sustainable and low-cost binders within the electrode active material of water-processable symmetric carbon-based supercapacitors. Such binders are selected from natural-derived materials and industrial by-products to obtain economic and environmental benefits. The electrochemical properties of the devices based on the different binders are compared by using cyclic voltammetry, galvanostatic charge/discharge curves and impedance spectroscopy. The fabricated supercapacitors exhibit series resistance lower than a few ohms and values of the specific capacitance ranged between 30 F/g and 80 F/g. The most performant device can deliver ca. 3.6 Wh/kg of energy at a high power density of 3925 W/kg. Gelatin, casein and carboxymethyl cellulose-based devices have shown device stability up to 1000 cycles. Detailed analysis on the charge storage mechanisms (e.g., involving faradaic and non-faradaic processes) at the electrode/electrolyte interface reveals a pseudocapacitance behavior within the supercapacitors. A clear correlation between the electrochemical performances (e.g., cycle stability, capacitance retention, series resistance value, coulombic efficiency) ageing phenomena and charge storage mechanisms within the porous carbon-based electrode have been discussed.

Visible-light-driven photocatalysis is one promising and efficient approach for decontaminating pollutants. Herein, we report the combination of localized surface plasmon resonance (LSPR) and p-n heterojunction structure Ag-Ag2O-ZnO nanocomposite synthesized by a hydrothermal process for the suppression of photogenerated electron-hole pair recombination rates, the extension of the absorption edge to the visible region, and the enhancement of photocatalytic efficiency. The prepared nanocomposites were investigated by standard analytical techniques and the results revealed that the synthesized powders were comprised of Ag, Ag2O, and ZnO phases. Photocatalytic activity of the photocatalyst tested for methylene blue, methyl orange, and rhodamine B showed the highest photocatalytic degradation efficiency: 97.3%, 91.1%, and 94.8% within 60 min under visible-light irradiation. The average lifetime of the photogenerated charge carriers was increased twofold in the Ag-Ag2O-ZnO photocatalyst (~10 ns) compared to the pure ZnO (~5.2 ns). The enhanced photocatalytic activity resulted from a decrease of the charge carrier recombination rate as inferred from the steady-state and time-resolved photoluminescence investigations, and the increased photoabsorption ability. The Ag-Ag2O-ZnO photocatalyst was stable over five repeated cyclic photodegradation tests without showing any significant changes in performance. Additionally, the structure indicated a potential for application in environmental remediation. The present study showcases the robust design of highly efficient and reusable visible-light-active photocatalysts via the combination of p-n heterojunction and LSPR phenomena.

We discuss the electrodeposition of two-dimensional (2D) Pt-nanostructures on Highly Oriented Pyrolytic Graphite (HOPG) achieved under constant applied potential versus a Pt counter electrode (Eappl = ca. -2.2 V vs. NHE, normal hydrogen electrode). The deposition conditions are discussed in terms of the electrochemical behavior of the electrodeposition precursor (H₂PtCl₆). We performed cyclic voltammetry (CV) of the electrochemical Pt deposit on HOPG and on Pt substrates to study the relevant phenomena that affect the morphology of Pt deposition. Under conditions where the Pt deposition occurs and H₂ evolution is occurring at the diffusion-limited rate (-0.3 V vs. NHE), Pt forms larger structures on the surface of HOPG, and the electrodeposition of Pt is not limited by diffusion. This indicates the need for large overpotentials to direct the 2D growth of Pt. Investigation of the possible effect of Cl- showed that Cl- deposits on the surface of Pt at low overpotentials, but strips from the surface at potentials more positive than the electrodeposition potential. The CV of Pt on HOPG is a strong function of the nature of the surface. We propose that during immersion of HOPG in the electrodeposition solution (3 mM H₂PtCl₆, 0.5 M NaCl, pH 2.3) Pt islands are formed spontaneously, and these islands drive the growth of the 2D nanostructures. The reducing agents for the spontaneous deposition of Pt from solution are proposed as step edges that get oxidized in the solution. We discuss the possible oxidation reactions for the edge sites.