The vehicle braking systems as main source of inhalable airborne magnetite particles in trafficked areas.

Magnetite (Fe3O4) nano-particles (MNPs) have been found in human tissues and causally linked to serious illnesses. The possible negative role of MNPs has been not still fully ascertained even though MNPs might cause health effects due to their magnetic property, redox activity and surface charge. The origin of MNPs in human tissues still remains to be unambiguously identified since biological processes, natural phenomena and anthropogenic production have been proposed. According to this latter increasingly convincing hypothesis, anthropogenic MNPs might enter mainly in the human body via inhalation, penetrate deeply into the lungs and in the alveoli and also migrate into the blood circulation and gather in the extrapulmonary organs and central nervous system. In order to identify the releasing source of the potentially inhalable MNPs, we pioneered an innovative approach to rapidly investigate elemental profile and morphology of a large number of airborne micron and sub-micron-sized Fe-bearing particles (FePs). The study was performed by collecting a large amount of micron and sub-micron sized inhalable airborne FePs in trafficked and densely frequented areas of Rome (Italy). Then, we have investigated individually the elemental profile and morphology of the collected particles by means of high-spatial resolution scanning electron microscopy, energy dispersive spectroscopy and an automated software purposely developed for the metal-bearing particles analysis. On the basis of specific elemental tracing features, the investigation reveals that almost the total amount of the airborne FePs is released by the vehicle braking systems mainly in the form of magnetite. Furthermore, we point out that our approach might be more generally used to identify the releasing sources of different inorganic airborne particles and to contribute to establish more accurately the impact of specific natural or anthropogenic particles on the environment and human health.

Rebuilding of the Burial Environment from the Chemical Biography of Archeological Copper-Based Artifacts.

The long-term interaction between Cu-based alloys and environmental species gives rise to the formation of different and sometimes unusual compounds (i.e., the patina) with distinctive chemical and structural features as a function of the peculiar characteristics of the context. In this paper, we describe some representative case studies concerning degraded bronze Roman valuable or common use objects, and we show that an attentive study at a microscale level, as for forensic analysis, allows one to understand the chemical processes that underlie the formation of the surface alteration products. The achieved information describe fragments of chemical life and disclose the complex chemical changes suffered by the artifacts, allowing one to write their chemical biography. This challenging approach expands the panorama of available information and demonstrates that it is possible to reconstruct the different modes through which the bronze surfaces and interfaces have interacted with environmental species, organic matter, and microorganisms, opening up a new possibility to describe complex environmental chemical stories, in certain cases interrelated.

Long-Lasting Efficacy of Coatings for Bronze Artwork Conservation: The Key Role of Layered Double Hydroxide Nanocarriers in Protecting Corrosion Inhibitors from Photodegradation.

The photodegradation kinetics of 2-mercaptobenzothiazole (MBT), a corrosion inhibitor for copper-based alloys, is studied in high amorphous polyvinyl alcohol coatings subjected to either UV irradiation or indoor light exposure. The photodegradation process proceeds rapidly, thus compromising the anticorrosion ability of the coating. The encapsulation of MBT into layered double hydroxide (LDH) nanocarriers slows down its decomposition kinetics by a factor of three. Besides preserving the corrosion inhibitor, such a strategy allows a controlled release of MBT triggered by corrosion-related stimuli, for example, presence of chloride species and acid pH. The developed coating guarantees long-lasting corrosion protection even at low amounts of inhibitor-loaded LDH nanocarriers (ca. 5 wt %). This also reflects in a high transparency, which makes the protective coating suitable for demanding applications, such as the conservation of high-value metal works of art.

Highly efficient photoanodes for dye solar cells with a hierarchical meso-ordered structure.

An engineered bi-layered photoelectrode for dye solar cells has been developed which profitably employs two synergistic meso-ordered components, namely a thin meso-ordered TiO2 film and a main microparticles-based photoelectrode. The former has been deposited as an interfacial layer at the FTO-coated substrate and suppresses the back-transport reaction by blocking direct contact between the electrolyte and conductive oxide. The latter is made of hierarchical micro- and nano-structured building blocks prepared by template synthesis, which permits efficient light scattering without sacrificing the internal surface area. The optimization of light harvesting and charge recombination dynamics allowed us to achieve as high energy conversion efficiency as 9.7%.

Green synthesis of gold-chitosan nanocomposites for caffeic acid sensing.

In this work, colloidal gold nanoparticles (AuNPs) stabilized into a chitosan matrix were prepared using a green route. The synthesis was carried out by reducing Au(III) to Au(0) in an aqueous solution of chitosan and different organic acids (i.e., acetic, malonic, or oxalic acid). We have demonstrated that by varying the nature of the acid it is possible to tune the reduction rate of the gold precursor (HAuCl(4)) and to modify the morphology of the resulting metal nanoparticles. The use of chitosan, a biocompatible and biodegradable polymer with a large number of amino and hydroxyl functional groups, enables the simultaneous synthesis and surface modification of AuNPs in one pot. Because of the excellent film-forming capability of this polymer, AuNPs-chitosan solutions were used to obtain hybrid nanocomposite films that combine highly conductive AuNPs with a large number of organic functional groups. Herein, Au-chitosan nanocomposites are successfully proposed as sensitive and selective electrochemical sensors for the determination of caffeic acid, an antioxidant that has recently attracted much attention because of its benefits to human health. A linear response was obtained over a wide range of concentration from 5.00 × 10(-8) M to 2.00 × 10(-3) M, and the limit of detection (LOD) was estimated to be 2.50 × 10(-8) M. Moreover, further analyses have demonstrated that a high selectivity toward caffeic acid can be achieved without interference from catechin or ascorbic acid (flavonoid and nonphenolic antioxidants, respectively). This novel synthesis approach and the high performances of Au-chitosan hybrid materials in the determination of caffeic acid open up new routes in the design of highly efficient sensors, which are of great interest for the analysis of complex matrices such as wine, soft drinks, and fruit beverages.