TiO2-MoS2-PMMA Nanocomposites for an Efficient Water Remediation.

An improvement of water supply and sanitation and better management of water resources, especially in terms of water reuse, is one of the priorities of the European Green Deal. In this context, it is crucial to find new strategies to recycle wastewater efficiently in a low-cost and eco-friendly manner. The immobilization of inorganic nanomaterials on polymeric matrices has been drawing a lot of attention in recent years due to the extraordinary properties characterizing the as-obtained nanocomposites. The hybrid materials, indeed, combine the properties of the polymers, such as flexibility, low cost, mechanical stability, high durability, and ease of availability, with the properties of the inorganic counterpart. In particular, if the inorganic fillers are nanostructured photocatalysts, the materials will be able to utilize the energy delivered by light to catalyze chemical reactions for efficient wastewater treatment. Additionally, with the anchoring of the nanomaterials to the polymers, the dispersion of the nanomaterials in the environment is prevented, thus overcoming one of the main limits that impede the application of nanostructured photocatalysts on a large scale. In this work, we will present nanocomposites made of polymers, i.e., polymethyl methacrylate (PMMA), and photocatalytic semiconductors, i.e., TiO2 nanoparticles (Evonik). MoS2 nanoflakes were also added as co-catalysts to improve the photocatalytic performance of the TiO2. The hybrid materials were prepared using the sonication and solution casting method. The nanocomposites were deeply characterized, and their remarkable photocatalytic abilities were evaluated by the degradation of two common water pollutants: methyl orange and diclofenac. The relevance of the obtained results will be discussed, opening the route for the application of these materials in photocatalysis and especially for novel wastewater remediation.

Titanium Dioxide Nanoparticles: Effects on Development and Male Reproductive System.

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.

Sulfonated Pentablock Copolymer Coating of Polypropylene Filters for Dye and Metal Ions Effective Removal by Integrated Adsorption and Filtration Process.

In this work, we coated polypropylene (PP) fibrous filters with sulfonated pentablock copolymer (s-PBC) layers and tested them for the removal of cationic organic dyes, such as methylene blue (MB), and heavy metal ions (Fe3+ and Co2+) from water by adsorption and filtration experiments. Some of the coated filters were irradiated by UV light before being exposed to contaminated water and then were tested with unirradiated filters in the same adsorption and filtration experiments. Polymer-coated filters showed high efficiency in removing MB from an aqueous solution in both absorption and filtration processes, with 90% and 80% removal, respectively. On the other hand, for heavy metal ions (Fe3+ and Co2+), the coated filters showed a better removal performance in the filtration process than for the adsorption one. In fact, in the adsorption process, controlled interaction times allow the ionic species to interact with the surface of the filters leading to the formation and release of new species in solution. During filtration, the ionic species are easily trapped in the filters, in particular by UV modified filters, and we observed for Fe3+ ions a total removal (>99%) in a single filtration process and for Co2+ ions a larger removal with respect to the untreated filter. The mechanisms involved in the removal of the contaminants processes were investigated by characterizing the filters before and after use by means of scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis and Fourier transform infrared spectroscopy (FT-IR).

New Approaches and Understandings in the Growth of Cubic Silicon Carbide.

In this review paper, several new approaches about the 3C-SiC growth are been presented. In fact, despite the long research activity on 3C-SiC, no devices with good electrical characteristics have been obtained due to the high defect density and high level of stress. To overcome these problems, two different approaches have been used in the last years. From one side, several compliance substrates have been used to try to reduce both the defects and stress, while from another side, the first bulk growth has been performed to try to improve the quality of this material with respect to the heteroepitaxial one. From all these studies, a new understanding of the material defects has been obtained, as well as regarding all the interactions between defects and several growth parameters. This new knowledge will be the basis to solve the main issue of the 3C-SiC growth and reach the goal to obtain a material with low defects and low stress that would allow for realizing devices with extremely interesting characteristics.

Synthesis and Photochemical Properties of Monolithic TiO2 Nanowires Diode.

In this paper, the structural and photochemical properties of a monolithic photochemical diode are discussed. The present structure is composed, from the top to the bottom, of a TiO2 nanowire layer, a TiO2 film, a Ti foil, and a porous layer made of Pt nanoparticles. The synthesis of the nanowires was simply carried out by Au-catalysed-assisted process; the effects of the annealing temperature and time were deeply investigated. Morphological and structural characterizations were performed by scanning electron microscopy and Raman spectroscopy. The analyses showed the rutile structure of the TiO2 nanowires. The photocatalytic properties were studied through the degradation of methylene blue (MB) dye under UV light irradiation. The nanowires induced an enhancement of the photo-degradation rate, compared to TiO2 in a bulk form, due to an increase in the surface area. Moreover, the presence of a nano-porous Pt layer deposited on the rear side of the samples provided a further increase in the MB degradation rate, related to the scavenging effect of Pt nanoparticles. The overall increment of the photo-activity, due to the nano-structuration of the TiO2 and to the presence of the Pt layer, resulted a factor 7, compared to the bulk reference. In addition, photovoltage measurements allowed to assess the effects of TiO2 nano-structuration and Pt nanoparticles on the electron accumulation.

Correlation between Defects and Electrical Performances of Ion-Irradiated 4H-SiC p-n Junctions.

In this study, 4H-SiC p-n junctions were irradiated with 700 keV He+ ions in the fluence range 1.0 × 1012 to 1.0 × 1015 ions/cm2. The effects of irradiation were investigated by current-voltage (I-V) and capacitance-voltage (C-V) measurements, while deep-level transient spectroscopy (DLTS) was used to study the traps introduced by irradiation defects. Modifications of the device's electrical performances were observed after irradiation, and two fluence regimes were identified. In the low fluence range (≤1013 ions/cm2), I-V characteristics evidenced an increase in series resistance, which can be associated with the decrease in the dopant concentration, as also denoted by C-V measurements. In addition, the pre-exponential parameter of junction generation current increased with fluence due to the increase in point defect concentration. The main produced defect states were the Z1/2, RD1/2, and EH6/7 centers, whose concentrations increased with fluence. At high fluence (>1013 ions/cm2), I-V curves showed a strong decrease in the generation current, while DLTS evidenced a rearrangement of defects. The detailed electrical characterization of the p-n junction performed at different temperatures highlights the existence of conduction paths with peculiar electrical properties introduced by high fluence irradiation. The results suggest the formation of localized highly resistive regions (realized by agglomeration of point defects) in parallel with the main junction.

Artemia salina: A microcrustacean to assess engineered nanoparticles toxicity.

The focus of this work was to investigate the toxicity of different metal nanoparticles (gold nanoparticles [AuNPs], silver nanoparticles [AgNPs], titanium dioxide nanoparticles [TiO2 NPs]) on brine shrimp Artemia salina. We investigated if nanoparticles could have an influence on hatching of cysts and on mortality of larvae. Larvae (also called nauplii) and cysts were exposed to NPs for 24 hr in artificial seawater on microplates. At the end of the test, we assessed the endpoint (immobility/death) for the larvae by a stereomicroscope. Nauplii that appeared completely motionless, were counted as dead, and the percentages of mortality were calculated for each treatment. Instead for the cysts, the percentages of not-hatched nauplii for each concentration considered were calculated by counting the number of whole cysts. Currently, nanoparticles toxicity has been investigated in several research; in our study we highlighted the nontoxicity of TiO2 NPs on A. salina nauplii as shown by low percentages of immobilization and on cysts because TiO2 NPs do not affect their hatching. Despite AuNPs exerted toxic effects on hatching, they did not affect larvae development as well as TiO2 NPs. Otherwise, AgNPs induced mortality of the larvae and inhibited cysts hatching.

Ovarian aging increases small extracellular vesicle CD81+ release in human follicular fluid and influences miRNA profiles.

Ovarian aging affects female reproductive potential and is characterized by alterations in proteins, mRNAs and non-coding RNAs inside the ovarian follicle. Ovarian somatic cells and the oocyte communicate with each other secreting different molecules into the follicular fluid, by extracellular vesicles. The cargo of follicular fluid vesicles may influence female reproductive ability; accordingly, analysis of extracellular vesicle content could provide information about the quality of the female germ cell.In order to identify the most significant deregulated microRNAs in reproductive aging, we quantified the small extracellular vesicles in human follicular fluid from older and younger women and analyzed the expression of microRNAs enclosed inside the vesicles. We found twice as many small extracellular vesicles in the follicular fluid from older women and several differentially expressed microRNAs. Correlating microRNA expression profiles with vesicle number, we selected 46 deregulated microRNAs associated with aging. Bioinformatic analyses allowed us to identify six miRNAs involved in TP53 signaling pathways. Specifically, miR-16-5p, miR214-3p and miR-449a were downregulated and miR-125b, miR-155-5p and miR-372 were upregulated, influencing vesicle release, oocyte maturation and stress response. We believe that this approach allowed us to identify a battery of microRNAs strictly related to female reproductive aging.

The cooperative interaction of triplex forming oligonucleotides on DNA-triplex formation at electrode surface: Molecular dynamics studies and experimental evidences.

An extensive study on cooperative interaction of Triplex Forming Oligonucleotides (TFOs) with a double strand DNA, to form a triplex-DNA structure at electrode surface, is here reported. The cooperative effect on triplex structure formation was assumed by the higher binding enthalpy value, calculated for the interaction between the duplex DNA structure and the TFO1 and TFO2 probes (-67.3 KJ/mol), respect the sum of the single duplex-TFO1 and duplex-TFO2 interactions (-47.0 kJ/mol). The formation of triplex-DNA structure was proven by kinetic modelling study performed using the Luzar and Chandler model. The results indicate that after 500 ns from interaction, H-bonds between the base pairs in the double strand DNA are weaken while new H-bonds between the TFOs and duplex DNA are formed. Molecular dynamic (MD) simulations indicate that the TFOs sequence distance (138 bps) and the amount of TA*T triplet units are the keystones for the effectiveness of the cooperative effect, reaching for the selected target a minimum of energy value of -19452.6 kJ/mol. The MD data were experimentally corroborated by electrochemical measurements, detecting a HBV-clone genome at TFOs modified electrode surface. The interaction was electrochemical transduced by an intercalative Osmium based compound. The Langmuir isotherm model reports for the forming triplex DNA an association constant value of about 2.9 × 1016M-1, this high value could be attributed to the synergic contribution of the TFOs cooperative effect and to the rigid circular duplex structure. Finally, AFM and SEM investigations suggest the formation of a triplex-DNA structure at electrode surface, consisting in circles of about 1.5 um in diameter with asymmetric stranded thickness. This finding data paving the way to future development of advanced miniaturized DNA computing and biosensors.

Temperature Investigation on 3C-SiC Homo-Epitaxy on Four-Inch Wafers.

In this work, results related to the temperature influence on the homo-epitaxial growth process of 3C-SiC is presented. The seed for the epitaxial layer was obtained by an innovative technique based on silicon melting: after the first step of the hetero-epitaxial growth process of 3C-SiC on a Si substrate, Si melts, and the remaining freestanding SiC layer was used as a seed layer for the homo-epitaxial growth. Different morphological analyses indicate that the growth temperature and the growth rate play a fundamental role in the stacking faults density. In details, X-ray diffraction and micro-Raman analysis show the strict relationship between growth temperature, crystal quality, and doping incorporation in the homo-epitaxial chemical vapor deposition CVD growth process of a 3C-SiC wafer. Furthermore, photoluminescence spectra show a considerable reduction of point defects during homo-epitaxy at high temperatures.

Laser Annealing of P and Al Implanted 4H-SiC Epitaxial Layers.

This work describes the development of a new method for ion implantation induced crystal damage recovery using multiple XeCl (308 nm) laser pulses with a duration of 30 ns. Experimental activity was carried on single phosphorus (P) as well as double phosphorus and aluminum (Al) implanted 4H-SiC epitaxial layers. Samples were then characterized through micro-Raman spectroscopy, Photoluminescence (PL) and Transmission Electron Microscopy (TEM) and results were compared with those coming from P implanted thermally annealed samples at 1650-1700-1750 °C for 1 h as well as P and Al implanted samples annealed at 1650 °C for 30 min. The activity outcome shows that laser annealing allows to achieve full crystal recovery in the energy density range between 0.50 and 0.60 J/cm2. Moreover, laser treated crystal shows an almost stress-free lattice with respect to thermally annealed samples that are characterized by high point and extended defects concentration. Laser annealing process, instead, allows to strongly reduce carbon vacancy (VC) concentration in the implanted area and to avoid intra-bandgap carrier recombination centres. Implanted area was almost preserved, except for some surface oxidation processes due to oxygen leakage inside the testing chamber. However, the results of this experimental activity gives way to laser annealing process viability for damage recovery and dopant activation inside the implanted area.

3C-SiC Growth on Inverted Silicon Pyramids Patterned Substrate.

This work reports on the properties of cubic silicon carbide (3C-SiC) grown epitaxially on a patterned silicon substrate composed of squared inverted silicon pyramids (ISP). This compliant substrate prevents stacking faults, usually found at the SiC/Si interface, from reaching the surface. We investigated the effect of the size of the inverted pyramid on the epilayer quality. We noted that anti-phase boundaries (APBs) develop between adjacent faces of the pyramid and that the SiC/Si interfaces have the same polarity on both pyramid faces. The structure of the heterointerface was investigated. Moreover, due to the emergence of APB at the vertex of the pyramid, voids buried on the epilayer form. We demonstrated that careful control of the growth parameters allows modification of the height of the void and the density of APBs, improving SiC epitaxy quality.

Fast and Efficient Sun Light Photocatalytic Activity of Au_ZnO Core-Shell Nanoparticles Prepared by a One-Pot Synthesis.

Gold nanostructures absorb visible light and show localized surface plasmon resonance bands in the visible region. Semiconducting ZnO nanostructures are excellent for ultraviolet detection, thanks to their wide band gap, large free exciton binding energy, and high electron mobility. Therefore, the coupling of gold and ZnO nanostructures represents the best-suited way to boost photodetection. With the above perspective, we report on the high photocatalytic activity of some Au_ZnO core-shell nanoparticles (NPs) recently prepared by a one-pot synthesis in which a [zinc citrate]- complex acted as the ZnO precursor, a reducing agent for Au3+, and a capping anion for the obtained Au NPs. The overall nanostructures proved to be Au(111) NPs surrounded by a thin layer of [zinc citrate]- that evolved to Au_ZnO core-shell nanostructures. Worthy of note, with this photocatalyst, sun light efficiently decomposes a standard methylene blue solution according to ISO 10678:2010. We rationalized photodetection, reaction rate, and quantum efficiency.

Biocompatibility between Silicon or Silicon Carbide surface and Neural Stem Cells.

Silicon has been widely used as a material for microelectronic for more than 60 years, attracting considerable scientific interest as a promising tool for the manufacture of implantable medical devices in the context of neurodegenerative diseases. However, the use of such material involves responsibilities due to its toxicity, and researchers are pushing towards the generation of new classes of composite semiconductors, including the Silicon Carbide (3C-SiC). In the present work, we tested the biocompatibility of Silicon and 3C-SiC using an in vitro model of human neuronal stem cells derived from dental pulp (DP-NSCs) and mouse Olfactory Ensheathing Cells (OECs), a particular glial cell type showing stem cell characteristics. Specifically, we investigated the effects of 3C-SiC on neural cell morphology, viability and mitochondrial membrane potential. Data showed that both DP-NSCs and OECs, cultured on 3C-SiC, did not undergo consistent oxidative stress events and did not exhibit morphological modifications or adverse reactions in mitochondrial membrane potential. Our findings highlight the possibility to use Neural Stem Cells plated on 3C-SiC substrate as clinical tool for lesioned neural areas, paving the way for future perspectives in novel cell therapies for neuro-degenerated patients.

Evaluation of the effects of silver nanoparticles on Danio rerio cornea: Morphological and ultrastructural analysis.

Although in recent years there has been intensification in the use of nanoparticles (NPs) for the production of many commercial products, few studies have been carried out to assess the risks associated with its use. Among the most used NPs, silver nanoparticles (AgNPs) have a preponderant position as they have various applications. In this study, 40 adult zebrafish were exposed to increasing concentrations of AgNPs (8, 45, and 70 µg/L) for 30 days to evaluate the effects on eyes after chronic exposure to AgNPs with an average diameter of 50 nm. From the morphological and ultrastructural analysis performed, no alteration or lesions of the corneal epithelium were detected.

SiCILIA-Silicon Carbide Detectors for Intense Luminosity Investigations and Applications.

Silicon carbide (SiC) is a compound semiconductor, which is considered as a possible alternative to silicon for particles and photons detection. Its characteristics make it very promising for the next generation of nuclear and particle physics experiments at high beam luminosity. Silicon Carbide detectors for Intense Luminosity Investigations and Applications (SiCILIA) is a project starting as a collaboration between the Italian National Institute of Nuclear Physics (INFN) and IMM-CNR, aiming at the realization of innovative detection systems based on SiC. In this paper, we discuss the main features of silicon carbide as a material and its potential application in the field of particles and photons detectors, the project structure and the strategies used for the prototype realization, and the first results concerning prototype production and their performance.

Ag-NPs induce apoptosis, mitochondrial damages and MT3/OSGIN2 expression changes in an in vitro model of human dental-pulp-stem-cells-derived neurons.

Silver nanoparticles (Ag-NPs) are one of the most popular nanotechnologies because of their unique antibacterial and antifungal properties. Given their increasing use in a wide range of commercial, biomedical and food products, exposure to Ag-NPs is now a reality in people's lives. However, there is a serious lack of information regarding their potential toxic effects in the central nervous system. In this study, we investigated the biocompatibility of "homemade" Ag-NPs in an in vitro model of human neurons derived from dental pulp mesenchymal stem cells. Our results showed that acute exposure to Ag-NPs cause cytotoxicity, by triggering cell apoptosis, damaging neuronal connections, affecting the mitochondrial activity and changing the mRNA expression level of MT3 and OSGIN2, two genes involved in heavy metals metabolism and cellular growth during oxidative stress conditions. Further studies are needed to understand the molecular mechanisms and the physiological consequences underlying Ag-NPs exposure.

Sb-Doped Titanium Oxide: A Rationale for Its Photocatalytic Activity for Environmental Remediation.

The problem of water purification is one of the most urgent issues in developing countries, where large infrastructures and energy resources are limited. Among the possibilities for a cheap route to clean water, photocatalytic materials in the form of coatings or nanostructures are among the most promising. The most widely studied photocatalytic material is titanium dioxide (TiO2). Here, we investigate the photocatalytic properties of 1.5% Sb-doped TiO2 and laser-irradiated Sb-doped TiO x . Calcined Sb-doped TiO2 was found to adopt the rutile structure, but it turned amorphous after laser irradiation. Photocatalytic tests for Sb-doped TiO2 showed an activity 1 order of magnitude higher than that of an undoped TiO2 control sample under both ultraviolet and visible irradiation. A further sizeable enhancement resulted from laser irradiation. The increased photocatalytic activity is ascribed to both enhanced visible region absorption associated with Sb-induced lone pair surface electronic states and trapping of the holes at the lone pair surface sites, thus inhibiting the recombination of the electrons and holes generated in the initial photoexcitation step. This study shows the first rationalization of the photocatalytic properties of Sb-TiO2 in terms of its electronic structure.

Optical and photocatalytic properties of TiO2 nanoplumes.

Here we report the photocatalytic efficiency of hydrogenated TiO2 nanoplumes studied by measuring dye degradation in water. Nanoplumes were synthesized by peroxide etching of Ti films with different thicknesses. Structural characterization was carried out by scanning electron microscopy and transmission electron microscopy. We investigated in detail the optical properties of the synthesized material and related them to the efficiency of UV photodegradation of methylene blue dye. The obtained results show that TiO2 nanoplumes act as an effective antireflective layer increasing the UV photocatalytic yield of the film.

Laser irradiation in water for the novel, scalable synthesis of black TiO x photocatalyst for environmental remediation.

Since 1970, TiO2 photocatalysis has been considered a possible alternative for sustainable water treatment. This is due to its material stability, abundance, nontoxicity and high activity. Unfortunately, its wide band gap (≈3.2 eV) in the UV portion of the spectrum makes it inefficient under solar illumination. Recently, so-called "black TiO2" has been proposed as a candidate to overcome this issue. However, typical synthesis routes require high hydrogen pressure and long annealing treatments. In this work, we present an industrially scalable synthesis of TiO2-based material based on laser irradiation. The resulting black TiO x shows a high activity and adsorbs visible radiation, overcoming the main concerns related to the use of TiO2 under solar irradiation. We employed a commercial high repetition rate green laser in order to synthesize a black TiO x layer and we demonstrate the scalability of the present methodology. The photocatalyst is composed of a nanostructured titanate film (TiO x ) synthetized on a titanium foil, directly back-contacted to a layer of Pt nanoparticles (PtNps) deposited on the rear side of the same foil. The result is a monolithic photochemical diode with a stacked, layered structure (TiO x /Ti/PtNps). The resulting high photo-efficiency is ascribed to both the scavenging of electrons by Pt nanoparticles and the presence of trap surface states for holes in an amorphous hydrogenated TiO x layer.