Search

In recent years, the issue of coral bleaching has led to restrictions in some tropical locations (i.e., Palau, Hawaii, etc.) on the use of some organic UV sunscreen filters, such as oxybenzone and ethyl hexyl methoxycinnamate. In contrast, ZnO is considered safe for marine environments and thus is often used without considering its photocatalytic and oxidative activities related to the generation of O2•− and HO•. Moreover, ZnO needs to be used in combination with other filters to reach higher protection factors. Thus, the study of its interaction with formulations and with organic filters is important in sunscreen technology for the development of safer by-design products. In this work, the photocatalytic activity of zinc oxides with different surface areas (30, 25 and 9 m2/g) and their interaction with selected organic sunscreen filters were investigated. In particular, the ZnO photocatalytic kinetics were studied following the photodegradation of Acid Blue 9 (AB9) observing a first-order reaction with a chemical regime. Our evaluations of the selective inhibitions by hvb+ and HO• demonstrated a substantial predominance of the hydroxide radicals in the expression of the photocatalysis, a trend that was also confirmed by the irradiation of ZnO in an ethanolic solution. Indeed, the formulations containing both ZnO and organic filters defined as “safe” for coral reefs (i.e., Diethylamino Hydroxybenzoyl Hexyl Benzoate, DHHB, and Ethylhexyl Triazone, EHT) showed a non-negligible photocatalytic oxidation and thus the combination was underlined as safe to use.

The cobalt substituted polyoxotungstate [Co6 (H2 O)2 (α-B-PW9 O34 )2 (PW6 O26 )]17- (Co6) displays fast electron transfer (ET) kinetics to photogenerated RuIII (bpy)33+ , 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II)-OH2 and Co6(II)-OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)-OH moiety (Co6(III)-OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa , the Co6(II)-OH→RuIII (bpy)33+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH

Purpose This work deals with the application of a solidification/stabilization process with the aim to obtain safe and reusable granular materials from a polluted soil and to elucidate the mechanisms involved in the retention of several heavy metals. Materials and methods The High Performance Solidification/Stabilization (HPSS®) process was applied to the selected contaminated soil by using both ordinary Portland cement and calcium aluminate cement, as well as several binders prepared by combining these two types of cement in different proportions. Leaching and mechanical tests were carried out to evaluate the performances of the proposed binders in the pellets produced by the HPSS® process, while XRD analysis and SEM/EDX imaging were used to investigate the phase composition and internal microstructure of the treated samples. Result and discussion The examination of the obtained granular materials revealed that the immobilization of Sb was mainly related to its inclusion within calcium silicate hydrates’ structure; the immobilization of Cr, Pb, Ni, Co, Zn and Tl was associated with the eluate pH and their incorporation within ettringite structure, while for Se, Cu, Ba and V, the main retention mechanism was physical encapsulation. In addition, the application of a wet conditioning process improved the materials’ performance, leading to granules always satisfying the Italian regulatory requirements for reuse. Conclusions The findings obtained in this study were useful to better elucidate the mechanisms involved in the retention of heavy metals by several binders, contributing to the development of sustainable management strategies for contaminated soils and sediments through their transformation into reusable materials. Graphical abstract

Bone infections following open bone fracture or implant surgery remain a challenge in the orthopedics field. In order to avoid high doses of systemic drug administration, optimized local antibiotic release from scaffolds is required. 3D additive manufactured (AM) scaffolds made with biodegradable polymers are ideal to support bone healing in non-union scenarios and can be given antimicrobial properties by the incorporation of antibiotics. In this study, ciprofloxacin and gentamicin intercalated in the interlamellar spaces of magnesium aluminum layered double hydroxides (MgAl) and α-zirconium phosphates (ZrP), respectively, are dispersed within a thermoplastic polymer by melt compounding and subsequently processed via high temperature melt extrusion AM (~190 °C) into 3D scaffolds. The inorganic fillers enable a sustained antibiotics release through the polymer matrix, controlled by antibiotics counterions exchange or pH conditions. Importantly, both antibiotics retain their functionality after the manufacturing process at high temperatures, as verified by their activity against both Gram + and Gram - bacterial strains. Moreover, scaffolds loaded with filler-antibiotic do not impair human mesenchymal stromal cells osteogenic differentiation, allowing matrix mineralization and the expression of relevant osteogenic markers. Overall, these results suggest the possibility of fabricating dual functionality 3D scaffolds via high temperature melt extrusion for bone regeneration and infection prevention., Graphical abstract Image 1, Highlights • Antibiotic-eluting scaffolds are processed via melt extrusion at high temperature. • Inorganic lamellar fillers dispersed in the scaffold carry the antibiotics. • Antibiotics are released via ion-exchange in a controlled and tunable manner. • Antibiotics preserve their activity after the high temperature printing process. • Human mesenchymal stromal cells undergo osteogenic differentiation on the scaffolds.

The cobalt substituted polyoxotungstate [Co6(H2O)2(α‐B‐PW9O34)2(PW6O26)]17− (Co6) displays fast electron transfer (ET) kinetics to photogenerated RuIII(bpy)3 3+, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one‐electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II)−OH2 and Co6(II)−OH, respectively, whose speciation in aqueous solution is associated to a pKa of 7.6), and generates a Co(III)−OH moiety (Co6(III)−OH), as proven by transient absorption spectroscopy; (ii) at pH>pKa, the Co6(II)−OH→RuIII(bpy)3 3+ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH, Kinetic investigation by laser flash photolysis supports the occurrence of a concerted proton electron transfer (CPET) from a CoII−OH2 unit embedded in a polyoxotungstate to photogenerated RuIII(bpy)3 3+, with water acting as the base within a hydrogen bonding network.

SPR, E/121504 Copper oxide nanoparticles (CuO NPs) have previously been shown to cause dose-dependent pulmonary toxicity following inhalation. Here, CuO NPs (10 nm), coated with polyethylenimine (PEI) or ascorbate (ASC) resulting in positively or negatively charged NPs, respectively, were evaluated. Rats were exposed nose-only to similar exposure dose levels of ASC or PEI coated CuO NPs for 5 consecutive days. On day 6 and day 27 post-exposure, pulmonary toxicity markers in bronchoalveolar lavage fluid (BALF), lung histopathology and genome-wide transcriptomic changes in lungs, were assessed. BALF analyses showed a dose-dependent pulmonary inflammation and cell damage, which was supported by the lung histopathological findings of hypertrophy/hyperplasia of bronchiolar and alveolar epithelium, interstitial and alveolar inflammation, and paracortical histiocytosis in mediastinal lymph nodes for both types of CuO NPs. Transcriptomics analysis showed that pathways related to inflammation and cell proliferation were significantly activated. Additionally, we found evidence for the dysregulation of drug metabolism-related genes, especially in rats exposed to ASC-coated CuO NPs. Overall, no differences in the type of toxic effects and potency between the two surface coatings could be established, except with respect to the (regional) dose that initiates bronchiolar and alveolar hypertrophy. This disproves our hypothesis that differences in surface coatings affect the pulmonary toxicity of CuO NPs. publishersversion published

A pentacyclic quinoid dye, KuQ(O)3OH, combining (i) extended visible absorption up to 600 nm, (ii) excited state reduction potential >2 V vs. NHE, and (iii) a photoinduced proton-coupled electron transfer mechanism, has been used for the fabrication of dye-sensitized SnO2 photoanodes integrating a ruthenium polyoxometalate water oxidation catalyst. The resulting photoelectrode SnO2|KuQ(O)3OH|Ru4POM displays a light harvesting efficiency up to 90% in the range 500–600 nm, an onset potential as low as 0.2 V vs. NHE at pH 5.8, photoinduced oxygen evolution with a faradaic efficiency of 70 ± 15% and an absorbed-photon-to-current efficiency up to 0.12 ± 0.01%.

Anaerobic digestate supernatant can be used as a nutrient source for microalgae cultivation, thus integrating phytoremediation processes with high value products storage in microalgae biomass. Microalgae are able to use nitrogen and phosphorous from digestate, but high nutrient concentration can cause growth inhibition. In this study, two microalgae strains (C. vulgaris and S. obliquus) were cultivated on the anaerobic co-digestion supernatant (obtained from the organic fraction of municipal solid waste (OFMSW) and waste activated sludge (WAS)) in a preliminary Petri plate screening at different dilutions (1:10 and 1:5) using a synthetic medium (ISO) and tap water (TW). Direct Nile red screening was applied on colonies to preliminarily identify hydrophobic compound storage and then a batch test was performed (without air insufflation). Results show that C. vulgaris was able to grow on digestate supernatant 1:5 diluted, while Nile red screening allowed the preliminary detection of hydrophobic compound storage in colonies. The analysis carried out at the end of the test on ammonia, phosphate, nitrate and sulphate showed a removal percentage of 47.5 &plusmn, 0.8%, 65.0 &plusmn, 6.0%, 95.0 &plusmn, 3.0% and 99.5 &plusmn, 0.1%, respectively.

The application of an innovative solidification/stabilization (S/S) process was investigated for the remediation of Pb contaminated soil. The performance of Pb stabilization was evaluated by comparing the use of calcium aluminate cement (CAC) and an alkali activated metakaolin binder vs the Ordinary Portland Cement (OPC). The phase composition of the stabilized products was investigated by XRD and correlated to the internal microstructure obtained by SEM-EDX imaging. Leaching tests were performed to ascertain the effectiveness of the proposed binders in the S/S of the contaminated soil, and Pb release was evaluated for each binding system. The overall results proved that multiple mechanisms are involved in Pb retention and that key parameters regulating the stabilization performance are strongly dependent on the type of applied binder system. Pb was found to be associated to C-S-H in the case of OPC, whereas ettringite played a key role in the retention of this contaminant using the CAC binder. The use of a NaOH activated metakaolin resulted in almost total retention of Pb, despite a lack of solidification, highlighting the importance of pH in the regulation of the leaching behavior.

Skin cancer is the most common malignant cancer with an incidence of 1 million cases/year. It is well known that exposure to UV radiation from sunlight leads the most frequent risk factors for several skin disorders including skin cancer. Sunscreen filters represent a valid protection against dangerous effects derived from UV radiation, and they can be divided in organic and inorganic UV filters. Adding, at the product formulation, molecules with booster effect, or also substances that can increase the protecting effectiveness via synergic mechanisms, can further enhance their protection activity. Moreover, this approach leads to develop formulations with high SPF (Sun Protection Factor) with a reduced content of UV filters, this is in line with the recent decisions of yet a few countries (Palau, Thailand, Philippines, and Hawaii) to ban some sunscreen filters to preserve marine environments (i.e., reef). In this work, a new class of sunscreen UV filters has been synthesized, by means the combination of physical filter and Oxisol, an antioxidant molecule with booster effect. In this study, the synthesis of new physical multifunctional ingredients is reported, by means the direct surface functionalization of inorganic filters (in particular TiO2) with Oxisol. In this study, the full characterization of these multifunctional ingredients is also reported, in addition to the cytotoxicity tests, the photocatalytic activity and the rheological properties involved on skin application.

The increasing concern about antibiotic-resistance has led to the search for alternative antimicrobial agents. In this effort, different metal oxide nanomaterials are currently under investigation, in order to assess their effectiveness, safety and mode of action. This study focused on CuO nanoparticles (CuO NPs) and was aimed at evaluating how the properties and the antimicrobial activity of these nanomaterials may be affected by the interaction with ligands present in biological and environmental media. Ligands can attach to the surface of particles and/or contribute to their dissolution through ligand-assisted ion release and the formation of complexes with copper ions. Eight natural amino acids (L-Arg, L-Asp, L-Glu, L-Cys, L-Val, L-Leu, L-Phe, L-Tyr) were chosen as model molecules to investigate these interactions and the toxicity of the obtained materials against the Gram-positive bacterium Staphylococcus epidermidis ATCC 35984. A different behavior from pristine CuO NPs was observed, depending on the aminoacidic side chain. These results were supported by physico-chemical and colloidal characterization carried out by means of Fourier-Transform Infrared spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Thermo-Gravimetric Analysis (TGA), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and light scattering techniques (Dynamic Light Scattering (DLS), Electrophoretic Light Scattering (ELS) and Centrifugal Separation Analysis (CSA).

The incidence of skin cancer is increasing both because of climate change and the increase in pollution than people&rsquo, s incorrect habits of sun exposure. In these regards, sunscreen and photoprotection are essential tools in consenting the benefits induced by safe solar light exposition and skin cancer prevention. In this work, a new class of sunscreen filter was synthesized by chemical combination of a physical filter (ZnO) and Oxisol (dihydroxyphenyl benzimidazole carboxylic acid), an antioxidant molecule with booster effect. In this work, a new class of filters with new properties was achieved by direct functionalization of particles surface. A full characterization of this multifunctional ingredient (ZnO&ndash, Ox) was conducted: Compared with the simple mixture, the new filter acts as a multifunctional molecule showing a higher Sun Protection Factor (SPF), a better cytotoxic profile (MTT and NRU assay), and anti-acne activity. A strong reduction of photocatalytic activity of ZnO was observed, also improving the safety profile.

International audience; Co3O4 nanoparticles in the spinel crystalline structure are among the most promising catalyst for water oxidation reaction, displaying remarkable activity under electrochemical and light-assisted conditions. In the presence of Ru(bpy)3 2+ as photosensitizer (bpy = 2,2'bipyridine) and Na2S2O8 as electron acceptor, 5±1 nm size Co3O4 nanoparticles show a slow primary electron transfer (ET) to photogenerated Ru(III), occurring in a timescale of tens of milliseconds. We demonstrate herein that: (i) photo-oxidation of Co3O4 NPs by Ru(III) involves transformation of surface Co(III)-OH sites to formal Co(IV)=O, along a proton-coupled electron-transfer (PCET) pathway; (ii) the rate of the process depends on pH, on the nature and concentration of the solution buffer; (iii) borate promotes general base catalysis in the PCET of Co3O4 surface sites; (iv) inhibition of the PCET mechanism is observed at high buffer concentration, due to H3BO3 poisoning of the surface Co sites, resulting in depletion of the O2 evolution activity.

Synthesis, characterization and catalytic activity of a novel tungsten(VI) amino triphenolate complex have been investigated. In particular, a tungsten(VI) amino triphenolate complex has been synthesized and tested in the oxidation of sulfides and cyclooctene, using hydrogen peroxide as terminal oxidant. The catalyst has proved to be air and water tolerant, also showing a good efficiency in terms of yields and selectivity. Moreover, an upgrade of our previous ligand synthesis is herein reported. The new developed procedure allows to obtain the triphenolamine in large scale without the use of chromatography for the intermediates purification.

The relationships between the physicochemical properties of engineered nanomaterials (ENMs) and their adverse health and environmental effects are still unclear. In order to understand key nano-bio/eco interactions and to convert this knowledge into "Safety by Design" (SbyD) strategies, it is essential to study the colloidal properties of ENMs in nano(eco)toxicology-relevant media. In the frame of such a SbyD approach, this paper investigates the dispersion stability of copper oxide NPs surface-modified by means of four stabilizing agents, namely, [polyethylenimine (PEI), sodium ascorbate (ASC), sodium citrate (CIT), and polyvinylpyrrolidone (PVP)], which were used to achieve positive (PEI), negative (ASC, CIT), and neutral (PVP) surface charging of the NPs. The effects of these four stabilizers on the CuO NPs' physicochemical properties were investigated in different biological and environmental media by combining dynamic and electrophoretic light scattering (DLS and ELS), centrifugal separation analysis (CSA) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The results showed improved dispersion stability for CuO-CIT, CuO-ASC, and CuO-PEI in both Milli-Q and phosphate buffered saline (PBS) as compared to pristine CuO and CuO-PVP. The increased ionic strength of artificial fresh (AFW) and marine (AMW) waters strongly destabilized all the CuO NP suspensions, except for CuO-PEI dispersed in AFW. The presence of proteins and amino acids in the test media had a strong influence on the colloidal stability of all the dispersions. Characterization of colloidal properties and ion release rates in (eco) toxicological testing media will help to correlate some of these properties with (eco) toxicological responses, thus enabling prediction of the behavior of NPs in real environments.

Soil and sediment contamination is recognised as one of the most relevant environmental problems caused by past industrial activities and unsustainable waste disposal practices, highlighting the need to develop or improve effective remediation techniques to support sustainable management strategies. In this context, the remediation of sediments dredged from the Mincio river (Italy) contaminated by mercury and heavy hydrocarbons (C12-40) was carried out by applying and implementing the High Performance Solidification/Stabilization technology, aimed at producing safe and reusable cement-based granular materials. The technology was improved by decreasing both the temperature and time of the thermal desorption treatment (from 280 to 110 °C and from 4-16 h to 70 min, respectively) and by including a wet conditioning step to the process. Temperature and time reduction allowed to diminish the degradation of the cementitious phases of the granules (usually related to the high temperatures employed in the process), while the wet conditioning step allowed to improve their mechanical properties, as well as to further reduce the leaching of contaminants. The physical-chemical properties of the granules and contaminant leaching in water were investigated by Inductively Coupled Plasma Mass and Optical Emission Spectrometry, Ultraviolet–Visible spectroscopy, Gas Chromatography, X-Ray Powder Diffraction, and Scanning Electron Microscopy, in order to identify the optimal parameters for both thermal and wet conditioning processes. The overall results showed that the use of consecutive thermal and wet conditioning treatment on sedimentary cementitious materials from the High Performance Solidification/Stabilization technology led to the removal of volatile pollutants and to the improvement of granule quality, thus providing a final material that satisfied all the Italian regulatory requirements for reuse. Therefore, the findings obtained in this study may contribute to the development of sustainable management strategies for contaminated soils and sediments, leading to their valorisation through the transformation into reusable materials.