Manganese oxides occur typically as cryptocrystalline and fine-grained mixtures of different Mn-phases, carbonates, silicates, and Fe oxides/hydroxides; thus their characterization by standard methods, such as X-ray diffraction, is extremely challenging. These materials have been widely used in various applications over the millennia, for example, in art works as pigments for pottery, mural paintings, stained glass, and recently, as nanostructured materials with very attractive physicochemical properties. Furthermore, they are important geomaterials that could play a key role in environmental applications, by controlling the partitioning of arsenic and heavy metals between rocks, soils, and aqueous systems. Raman spectroscopy, which is a punctual and nondestructive technique, has been widely used to characterize these materials. However, literature data are often conflicting and contradictory, usually not allowing a proper identification of the Mn species. In this work, we characterize the most common natural manganese oxides by combining X-ray powder diffraction, Fourier-transform infrared spectroscopy, and Raman spectroscopy. Our data show that some manganese oxides have characteristic Raman spectra and can be easily recognized by using Raman spectroscopy alone, whereas integration of Raman data with other techniques is mandatory to characterize minerals that have almost identical Raman spectra. With this respect, Raman spectroscopy is the only technique allowing an easy discrimination between hollandite [Ba(Mn 4+ 6 ,Mn 3+ 2 )O 16 ] and cryptomelane [K(Mn 4+ 7 ,Mn 3+ )O 16 ]. The final goal of this work is to provide reference Raman spectra, acquired on previously well-characterized Mn samples to facilitate the application of Raman spectroscopy in the study of these geomaterials.

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SummaryThe inventory of microorganisms responsible for biological deterioration of ancient paintings has become an integral part of restoration activities. Here, the microbial agent of rosy discoloration on medieval frescoes in the Crypt of the Original Sin (Matera, Italy) was investigated by a combination of microscopic, molecular and spectroscopic approaches. The bacterial community from three rosy-discoloured painting sites was characterized by 16S rRNA gene-based techniques. The eubacterial population was prevalently composed of Actinobacteria, among which Rubrobacter radiotolerans-related bacteria accounted for 63-87% of the 16S rRNA gene pool per sampled site. Archaea, with prevalence of Haloarchaea-related species, were detected in one of the three sites where they accounted for < 0.1% of the total 16S rRNA gene pool. Raman spectroscopy confirmed the identity between R. radiotolerans carotenoids (bacterioruberins) and pigments responsible for colour alteration of frescoes. This investigation provides the first evidence of a causal relationship between heavy contamination by Rubrobacter-related bacterioruberinproducing bacteria and rosy discoloration of ancient wall paintings.

Water-peptide interactions play an important role in determining peptide structure and function. Nevertheless, a microscopic description of these interactions is still incomplete. In this study we have investigated at the atomic scale length the interaction between water and the tripeptide glutathione. The rationale behind this work, based on the combination between a neutron diffraction experiment and a computer simulation, is twofold. It extends previous studies on amino acids, addressing issues such as the perturbation of the water network brought by a larger biomolecule in solution. In addition, and more importantly, it seeks a possible link between the atomic length scale description of the glutathione-water interaction with the specific biological functionality of glutathione, an important intracellular antioxidant. Results indicate a rather weak hydrogen bond between the thiol (-SH) group of cysteine and its first neighbor water molecule. This -SH group serves as a proton donor, is responsible for the biological activity of glutathione, and it is involved in the formation of glutathione disulfide, the oxidized form of glutathione. Moreover, the hydration shell of the chemically identical carboxylate group on the glutamic acid residue and on the glycine residue shows an intriguing different spatial location of water molecules and coordination numbers around the two CO2(-) groups.