Research on the vocal culture of Orcinus orca in the Loro Parque, Tenerife: a pilot study

This research is focussed on the study of Orcinus orca's communication system. The analysis of vocalizations emitted by marine mammals has started in the '80s and most studies have been carried out in the wild. In this regard the most studied animal has been common dolphin (Tursiops truncatus) as the numerous presence of captive individuals worldwide made researches easier to be carried out. Studies about Orcinus orca's vocalizations have mainly been carried out in the wild (most in British Columbia) because its maintenance in a controlled environment results to be very difficult, only 17 among parks and oceanaria worldwide have some Orcinus orca (45 overall among which 64% born in captivity). These researches showed that Orcinus orca emit three main different types of sounds, classified as: whistles, clicks and calls. Besides, it was discovered that different groups (pods) produce sounds belonging only to the relevant pod (dialects). It is rare to find two pods sharing some calls. The two pods usually live in adjacent areas and can form a clan. This study was carried out in a controlled environment in the Orca ocean structure (Loro Parque, Tenerife, Spain) where, at the moment (March 2012) 6 individuals are hosted. Here it was developed an automatic sound recording system. Thanks to the use of suitable mathematical algorithms that allow to isolate only "interesting" sound events that differ from the "background noise", it was possible to create a database. The visualization of the sound events collected in the database is carried out with the use of a software. By looking at this output and at the observation register we could match the animal to the sound produced. Three situations were detected and studied: 1) Chosen alone: the animal chooses to go to the recording pool but it is free to move to another pool with other individuals. 2) Put alone: the animal is put alone in the recording pool. 3) With other orcas: more animals are together in the recording pool. The statistic analysis show that animals emit more vocalizations when they are in the situation "Chosen alone". The research will continue in order to observe eventual differences in the individual repertoire of each Orcinus orca.

The effect of poly(lactide)-poly(carbonate) based block copolymers on the morphology and crystallization of double crystalline poly(lactide)/poly(ε-caprolactone) blends

Block copolymers of poly(lactide) and poly(carbonate) were synthetized in three different compositions and characterized by 1H-NMR and ATR analyses. The compatibilization effect of this copolymers on 80/20 (w/w%) PLA/PCL blend was evaluated. SEM micrographs show that all the blends exhibit the typical sea-island morphology characteristic of immiscible blends with PCL finely dispersed in droplets on a PLA matrix. Upon the addiction of the copolymers a reduction on PCL droplets size is observable. At the same time, a Tg depression of the PLA phase is detected when the copolymers are added in the blend. These results indicate that these copolymers are effective as compatibilizers. The copolymer that acts as the best compatibilizer is the one characterized by the same amount of PLA and PC as repeating units. As result, in the blend containing this copolymer PLA phase exhibits the highest spherulitic growth rate. An analyses on PLA phase crystallization behaviour from the glassy state within the blends was evaluated by DSC experiments. Isothermal cold crystallization of the PLA phase is enhanced up an order of magnitude upon the blending with PCL. Annealing experiments demonstrated that the crystallization of the PCL phase induces the formation of active nuclei in PLA when cooled above cooled below Tg. When the crystallization rate of PCL is retarded, a reduction on PLA nucleation is observed.

Theoretical and experimental study on the role of benzoquinone in the Guerbet reaction catalyzed by a ruthenium complex

The benzoquinone was found as an effective co-catalyst in the ruthenium/NaOEt-catalyzed Guerbet reaction. The co-catalyst behavior has therefore been investigated through experimental and computational methods. The reaction products distribution shows that the reaction speed is improved by the benzoquinone supplement since the beginning of the process, having a minimal effect on the selectivity toward alcoholic species. DFT calculations were performed to investigate two hypotheses for the kinetic effects: i) a hydrogen storage mechanism or ii) a basic co-catalysis of 4-hydroxiphenolate. The most promising results were found for the latter hypothesis, where a new mixed mechanism for the aldol condensation step of the Guerbet process involves the hydroquinone (i.e. the reduced form of benzoquinone) as proton source instead of ethanol. This mechanism was found to be energetically more favorable than an aldol condensation in absence of additive, suggesting that the hydroquinone derived from benzoquinone could be the key species affecting the kinetics of the overall process. To verify this theoretical hypothesis, new phenol derivatives were tested as additives in the Guerbet reaction. The outcomes confirmed that an aromatic acid (stronger than ethanol) could improve the reaction kinetics. Lastly, theoretical products distributions were simulated and compared to the experimental one, using the DFT computations to build the kinetic models.