Pedro Barrulas

Stereoselective Reduction of Imines with Trichlorosilane Using Solid-Supported Chiral Picolinamides

The stereoselective reduction of imines with trichlorosilane catalyzed by chiral Lewis bases is a well-established procedure for the synthesis of enantio-enriched amines. Five supported cinchona-based picolinamides have been prepared and their activity tested in a model reaction. The comparison of different supporting materials revealed that polystyrene gave better results than silica in terms of stereoselectivity. The applicability of the solid-supported catalyst of choice to the reduction of different imines was also demonstrated. Additionally, for the first time, a catalytic reactor containing a polymer-immobilized chiral picolinamide has been employed for the stereoselective reduction of imines with trichlorosilane under continuous flow conditions.

Classification of wines according to several factors by ICP-MS multi-element analysis

Wines from different grape varieties, geographical zones, soil types, foliar N application, SO2 addition and oak ageing were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). For this purpose, ICP-MS methodology was optimized. The elements which allowed differentiate wines from studied grape varieties were Sr, Ca, Mg and Mn. Geographical zones were classified according to Sr, Ba, Ni, and Cu. Cs and Pb were the main elements to discriminate the wines from the 3 soil types. Wines from several N foliar doses application were classified by Pb, Ni, Mn and Zn. The content of Cs, Mg, Cu and Pb in wines characterized the SO2 addition. Finally, wines storage in barrels were differentiate by Na and Cs concentration. The discriminant functions classify 100% of the wines, with the exception of grape variety (97.0%) and oak ageing (95.8%). Consequently, ICP-MS can be applied to classified wines according to viticultural and oenological factors.

Natural limestone discolouration triggered by microbial activity—a contribution

Colour is a major argument that drives the decision of an architect in a specific architecture project and one of the most important characteristics and perceptible aspects of natural building stones. “Blue” limestones are building rocks, with different geological ages, typically used in several countries, and are known for their vulnerability to alteration, which causes colour change and the occurrence of unaesthetic patterns. Owing to this vulnerability, the conservation-restoration works in monuments, or new buildings constructed with “blue” limestone is extremely costly. Considering that the main limitation of this lithological variation is the chromatic change, a multidisciplinary approach was envisaged in this study to allow a closer insight into the chemical and mineralogical alterations and the microbial communities. Results obtained suggest that the inorganic alteration in the “blue” limestone may create favourable conditions for microbial growth and could lead to an increment in deterioration process.

Mesolithic human occupation and seasonality: sclerochronology, δ18O isotope geochemistry, and diagenesis verification by Raman and LA-ICP-MS analysis of Argyrosomus regius (meagre) sagittae otoliths from layer 1 of Cabeço da Amoreira Mesolithic shell midden (Muge, Portugal)

We present preliminary sclerochronological analysis on 15 Argyrosomus regius (meagre) otoliths collected from two different human occupation levels from the Cabeço da Amoreira shell midden (Muge valley, Portugal). The otoliths were sectioned and observed under a reflected light stereomicroscope to examine seasonal growth rings. Carbonates collected from individual growth rings subsampled with a micromill sampling device were analyzed for their stable oxygen isotope content with the objective of determining the predominant season of capture and therefore season of site use, environmental conditions, and sites of resource procurement (local versus regional). The otoliths’ stable isotope records show clear seasonality and a season of capture estimate that seems consistent with a “good season” (warmer season, i.e., from spring to late summer/beginning of autumn in this area) site use in the last occupation layer (the great majority of otoliths are from layer 1), except for four samples giving heaver oxygen isotope (δ18O) values that suggest colder conditions and only one with markedly positive δ18O values. Potential effect of diagenesis on the otolith records was also assessed through coupled laser ablation–inductively coupled plasma mass spectrometry (LA-ICP-MS) and by micro-X-Ray diffraction (μ-XRD). Results revealed the presence of only aragonite and no traces of calcite, providing no evidence of diagenesis that could significantly alter isotope results and lead to erroneous interpretations. The implications of these results are discussed and compared with data from other archeological sites, as well as data from micromorphology regarding continuity or interruption of site use and other faunal remains.