Surface-enhanced vibrational techniques for the detection of synthetic organic colorants

The research project object of this thesis is focused on the development of an advanced analytical system based on the combination of an improved thin layer chromatography (TLC) plate coupled with infrared (FTIR) and Raman microscopies for the detection of synthetic dyes. Indeed, the characterization of organic colorants, which are commonly present in mixtures with other components and in a very limited amount, still represents a challenging task in scientific analyses of cultural heritage materials. The approach provides selective spectral fingerprints for each compound, foreseeing the complementary information obtained by micro ATR-RAIRS-FTIR and SERS-Raman analyses, which can be performed on the same separated spot. In particular, silver iodide (AgI) applied on a gold coated slide is proposed as an efficient stationary phase for the discrimination of complex analyte mixtures, such as dyes present in samples of art-historical interest. The gold-AgI-TLC plate shows high performances related both to the chromatographic separation of analytes and to the spectroscopic detection of components. The use of a mid-IR transparent inorganic salt as the stationary phase avoids interferences of the background absorption in FTIR investigations. Moreover, by ATR microscopy measurements performed on the gold-AgI surface, a considerable enhancement in the intensity of spectra is observed. Complementary information can be obtained by Raman analyses, foreseeing a SERS activity of the AgI substrate. The method has been tested for the characterization of a mixture of three synthetic organic colorants widely used in dyeing processes: Brilliant Green (BG1), Rhodamine B (BV10) and Methylene Blue (BB9).

Seasonality and diel variation in blue whale D calls recorded in the Southern California Bight

Passive acoustic data have been collected using HARPs (High-frequency Acoustic Recording Packages) and were used to assess (1) the seasonality of blue whale D calls in the Southern California Bight, (2) their interannual abundance during 2007-2012 and (3) their diel variation. This goal has been achieved running the GPL (Generalized Power-Law) automated detector. (1) Blue whale D calls were detected in the Southern California Bight from May through November with a peak in July, even though few detections were from December to April as well. A key predictor for blue whale distribution and movement in the California Current region has been identified with zooplankton aggregations, paying a particular attention to those euphausiid species, such as E. pacifica and T. spinifera, which are blue whale favorite krill. The Southern California Bight experiences seasonal upwelling, resulting in an increase of productivity and prey availability. The summer and early fall have been marked as the most favorable periods. This supports the presence of blue whales in the area at that time, supposing these marine mammals exploit the region as a feeding ground. (2) As to the interannual abundance during 2007-2012, I found a large variability. I observed a great increase of vocalizations in 2007 and 2010, whereas a decrease was shown in the other years, which is well marked in 2009. It is my belief that these fluctuations in abundance of D calls detections through the deployed period are due to the alternation of El Nino and La Nina events, which occurred in those years. (3) The assessment of the daily timing of D calls production shows that D calls are more abundant during the day than during the night with a peak at 12:00 and 13:00. Assuming that D calling is associated with feeding, the daily pattern of D calls may be linked to the prey availability. E. pacifica and T. spinifera are among those species of krill which undertake daily vertical migrations, remaining at depth during the day and slowly coming up towards the surface at night. Because of some anatomical arrangements, these euphausiids are very sensitive to the light. Given that we believe D calls have a social function, I hypothesize that blue whales may recognize the hours at the highest solar incidence as the best moment of the day in terms of prey availability, exploiting this time window to advert their conspecifics.

La popolazione di Blue Straggler Stars in due ammassi globulari della Grande Nube di Magellano

Le Blue Straggler Stars (BSS) sono la popolazione di oggetti esotici piu' comune e numerosa negli ammassi globulari. Nel diagramma colore-magnitudine le BSS definiscono una sequenza più brillante e blu del punto di turn-off della Sequenza Principale, simulando una popolazione più giovane delle stelle dell'ammasso.  Osservazioni hanno dimostrato che le BSS hanno una massa significativamente più grande (1.2-1.7 Msun) di quella delle stelle di un ammasso globulare. Per questa proprietà, la distribuzione radiale delle BSS e' un utile strumento per tracciare empiricamente lo stato di evoluzione dinamica degli ammassi stellari. Il lavoro di tesi si è concentrato sullo studio della popolazione di BSS di due ammassi globulari della Grande Nube di Magellano: NGC2257 e NGC1754. Applicando metodi di indagine già usati per sistemi stellari della Via Lattea, abbiamo derivato le eta' dinamiche di questi due sistemi e le abbiamo confrontate con stime teoriche.

First assessment on genetic structure and phylogeography of Mediterranean blue shark (prionace glauca, L. 1758) population using mitochondrial gene variation: a comparison with the Atlantic.

The blue shark, Prionace glauca, is one of the most vagile shark species worldwide distributed. The particular body shape allows blue sharks make transoceanic movements, leading to a circumglobal distribution. Due to its reproductive cycle, an extraordinarily high number of specimens is globally registered but, even if it is still a major bycatch of longline fishery rather than a commercial target, it is characterized by a high vulnerability. In this perspective it is important to increase the amount of informations regarding its population extent in the different worldwide areas, evaluating the possible phylogeographic patterns between different locations. This study, included in the "MedBlueSGen" European project, aims exactly at filling a gap in knowledges regarding the genetic population structure of the Mediterranean blue sharks, which has never been investigated before, with a comparison with the North-Eastern Atlantic blue shark population. To reach this objective, we used a dataset of samples from different Mediterranean areas implementing it with some samples from North-Eastern Atlantic. Analyzing the variability of the two mitochondrial markers control region and cytochrome b, with the design of new species-specific primer pairs, we assessed the mitochondrial genetic structure of Mediterranean and North-Eastern Atlantic samples, focusing on the analysis of their possible connectivity, and we tried to reconstruct their demographic history and population size. Data analyses highlighted the absence of a genetic structuring within the Mediterranean and among it and North-Eastern Atlantic, suggesting that the Strait of Gibraltar doesn't represent a phylogeographic barrier. These results are coherent to what has been found in similar investigations on other worldwide blue shark populations. Analysis of the historical demographic trend revealed a general stable pattern for the cytochrome-b and a slightly population expansion for the control region marker.

Un nuovo indicatore di segregazione radiale delle blue stragglers

Le blue straggler stars (BSS) sono un importante strumento osservativo per gli studi mirati alla determinazione dell'evoluzione dinamica degli ammassi globulari. La loro distribuzione radiale, influenzata dal fenomeno di segregazione di massa, costituisce un efficace strumento per la determinazione dello stato di rilassamento del sistema. In questo lavoro di tesi sono esplorate le potenzialità di un nuovo indicatore di segregazione centrale delle BSS: la cosiddetta "Area Positiva (A+)", definita come la differenza tra l'area sottesa dalla distribuzione radiale cumulativa delle BSS e quella di una popolazione di riferimento. Per costruzione, questo parametro e` indicatore sensibile del livello di segregazione delle BSS. Il campione di ammassi e` costituito da 18 oggetti di bassa densità e concentrazione recentemente osservati nell'ambito di una survey ultravioletta con la camera WFC3/UVIS (Piotto et al. 2015) e 8 sistemi di densità più elevata, analizzati in lavori precedenti. Per ciascun ammasso sono state selezionate le popolazioni di BSS e di stelle di riferimento lungo la sequenza principale o il ramo delle giganti e sono state costruite le rispettive distribuzioni radiali cumulative, da cui e` stata poi determinata l'Area Positiva. Sono state infine individuate forti correlazioni tra A+ e alcuni parametri strutturali/dinamici degli ammassi, in particolare col tempo di rilassamento e la densita` centrali. Questi risultati dimostrano che il parametro A+ e` un buon misuratore del grado di evoluzione dinamica degli ammassi globulari.