Removal of As(III) from Biological Fluids: Mono- versus Dithiolic Ligands.

Arsenic is one of the inorganic pollutants typically found in natural waters, and its toxic effects on the human body are currently of great concern. For this reason, the search for detoxifying agents that can be used in a so-called "chelation therapy" is of primary importance. However, to the aim of finding the thermodynamic behavior of efficient chelating agents, extensive speciation studies, capable of reproducing physiological conditions in terms of pH, temperature, and ionic strength, are in order. Here, we report on the acid-base properties of meso-2,3-dimercaptosuccinic acid (DMSA) at different temperatures (i.e., T = 288.15, 298.15, 310.15, and 318.15 K). In particular, its capability to interact with As(III) has been investigated by experimentally evaluating some crucial thermodynamic parameters (ΔH and TΔS), stability constants, and its speciation model. Additionally, in order to gather information on the microscopic coordination modalities of As(III) with the functional groups of DMSA and, at the same time, to better interpret the experimental results, a series of state-of-the-art ab initio molecular dynamics simulations have been performed. For the sake of completeness, the sequestering capabilities of DMSA-a simple dithiol ligand-toward As(III) are directly compared with those recently emerged from similar analyses reported on monothiol ligands.

Functionalization of silicon nanowire arrays by silver nanoparticles for the laser desorption ionization mass spectrometry analysis of vegetable oils.

In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications. Copyright © 2016 John Wiley & Sons, Ltd.