ClimateFish: A Collaborative Database to Track the Abundance of Selected Coastal Fish Species as Candidate Indicators of Climate Change in the Mediterranean Sea

Under the effects of global warming, many animals and plants are undergoing rapid distribution shifts. These changes can be particularly rapid in marine fishes, and many species have responded markedly to recent increases in sea temperature. ClimateFish is an open-access database, which collates abundance data for 7 Mediterranean indigenous and 8 non-indigenous fishes, proposed as candidate indicators of climate change. These species have been selected by a network of Mediterranean scientists based on their wide distribution, responsiveness to temperature conditions and easy identification. Data are periodically collected according to a standard visual census protocol in four different depth layers. At present, the database collates data on a total number of 101'771 observed individuals belonging to the 15 target species. Counts were realized along 3142 transects carried out in 7 Mediterranean countries between 2009 and 2021. This database, associated with climate data, offers new opportunities to investigate spatiotemporal effects of climate change and to test the effectiveness of each selected indicator. Data are available at https://doi.org/10.17882/86784.The Mediterranean ClimateFish initiative was initially conceived by the international basin wide monitoring program CIESM Tropical Signals (funded by the Albert II of Monaco Foundation) and subsequently supported by the Interreg Med Programme (Projects: MPA-ADAPT, grant number 1MED15_3.2_M2_337 and MPA Engage, grant number 5MED18_3.2_M23_007), 85% co funded by the European Regional Development Fund

Sintesi di derivati SAHA-like utilizzati per indagare sulla selettività verso le diverse isoforme HDAC

Lo studio dell’inibizione della famiglia di enzimi istone deacetilasi (HDAC) riveste un’elevata importanza nell’ambito dell’individuazione di nuove terapie epigenetiche atte a curare diversi stati patologici come il cancro, infiammazione, malattie neurodegenerative, diabete ecc. È oramai noto che l’individuazione di inibitori HDAC punta a molecole selettive verso una particolare isoforma enzimatica. SCOPO di questo lavoro è stato quello di sintetizzare derivati SAHA-like (suberoylanilide hydroxamic acid, vorinostat approvato in terapia nel 2006 per il linfoma cutaneo a cellule T) utilizzati come tools per indagare sulla selettività verso le undici isoforme HDAC. METODI. Le molecole sintetizzate rispettano i punti farmacoforici descritti dal classico modello di inibizione HDAC mantenendo invariata la porzione che lega un atomo di zinco presente nel sito catalitico (ZBG di tipo idrossammico) e il linker, mentre viene rielaborata la porzione che si adagia all’esterno del sito stesso (cap group). In questa porzione, infatti, l’anello aromatico presente nel SAHA è stato diversamente funzionalizzato con diversi gruppi progettati per poter dare interazioni aggiuntive con i residui amminoacidici presenti nelle porzioni adiacenti a quelle del cap. Per l’ottenimento di questa classe di molecole SAHA-like, a struttura fenilammidica, sono stati messi a punto due strategie sintetiche ed in particolare è stato sviluppato un approccio metodologico di ottimizzazione della reazione di Baeyer-Villiger, assistita dalle microonde, che ha permesso di ottenere, in eccellente resa ed in tempi brevissimi, l’intermedio chiave utilizzato poi durante le diverse strategie sintetiche. RISULTATI. Le molecole così ottenute sono state sottoposte a test biochimici d’inibizione enzimatica in modo da valutarne la selettività verso gli isozimi HDAC. Tali test hanno evidenziato che alcuni composti della serie sintetizzata possiedono una selettività dell’ordine sub-micromolare per l’isozima HDAC6. CONCLUSIONI. In considerazione del fatto che in letteratura è presente un numero limitatissimo di inibitori selettivi HDAC6 (tubacina), queste strutture possono costituire degli interessanti e promettenti lead compounds da ottimizzare per migliorare sia il profilo di selettività sia la capacità di interazione con i siti di interazione addizionale

A Practical, Enantioselective Synthesis of the Fragrances Canthoxal and Silvial (R), and Evaluation of Their Olfactory Activity

The fragrances (S)-(+)- and (R)-(-)-canthoxal [(S)-(+)- and (R)-(-)-3-(4-methoxyphenyl)-2-methylpropanal] and (+)- and (-)-Silvial® [(+)- and (-)-3-(4-isobutylphenyl)-2-methylpropanal] have been synthesized in high enantiopurity via a simple four-step strategy starting from the commercially available 4-substituted benzaldehydes. The key synthetic step is the catalytic asymmetric hydrogenation of the appropriate 3-aryl-2-methylacrylic acid which has been carried out employing an in situ prepared ruthenium/axially chiral phosphine catalyst (up to 98% ee). The olfactory activity of the single enantiomers has been evaluated.The fragrances (S)-(+)- and (R)-(-)-canthoxal [(S)-(+)- and (R)-(-)-3-(4-methoxyphenyl)-2-methylpropanal] and (+)- and (-)-Silvial® [(+)- and (-)-3-(4-isobutylphenyl)-2-methylpropanal] have been synthesized in high enantiopurity via a simple four-step strategy starting from the commercially available 4-substituted benzaldehydes. The key synthetic step is the catalytic asymmetric hydrogenation of the appropriate 3-aryl-2-methylacrylic acid which has been carried out employing an in situ prepared ruthenium/axially chiral phosphine catalyst (up to 98% ee). The olfactory activity of the single enantiomers has been evaluated

Therapy of endocrine disease. Effects of chronic use of phosphodiesterase inhibitors on endothelial markers in type 2 diabetes mellitus: a meta-analysis.

OBJECTIVE: Diabetes mellitus (DM) is associated with endothelial dysfunction, reducing nitric oxide-dependent vasodilation, and increasing production of pro-inflammatory factors, leading to an increased risk of long-term cardiovascular disease. As the effects of phosphodiesterase 5 inhibitors (PDE5i) on endothelial function have not been systematically investigated, we conducted a meta-analysis of available randomized clinical trials (RCTs). DESIGN: A thorough search of the literature was carried out. Relevant studies were considered according to RCT study design, enrollment of men with type 2 DM, chronic administration of PDE5i, and evaluation of endothelial function through both hemodynamic and endothelial inflammation-related parameters. RESULTS: Fifteen studies fulfilled the eligibility criteria but only six RCTs met the inclusion criteria and were analyzed for 476 diabetic men, 239 randomized to Sildenafil, and 237 to placebo respectively. Four RCTs evaluated flow-mediated dilation (FMD), demonstrating a weighted mean increase of 2.19% (95% CI 0.48 to 3.90). This result showed a high heterogeneity (I(2): 98%). Thus, a further sub-group meta-analysis was performed and this analysis confirmed a significant, Sildenafil-related FMD improvement. Sildenafil improved endothelin 1 and high sensitivity C-reactive protein by ∼-0.94 pg/ml and -0.36 mg/l, respectively, not reaching statistical significance (P=0.69 and P=0.22 respectively). Finally, Sildenafil administration significantly reduced serum levels of interleukin 6 (IL6, -0.82 pg/ml; 95% CI -1.58 to -0.07). CONCLUSION: This meta-analysis suggests a beneficial effect of chronic PDE5i administration on endothelial function. Chronic Sildenafil administration seems to improve hemodynamic (FMD) and serum pro-inflammatory makers (IL6) in diabetic men. Larger studies are needed to confirm the effects of chronic PDE5i on endothelial function

Preparation, Characterization and Optical properties of a Dendritic Dye Sensitizer DDS-TiO2 hybrid material

We report a new triphenylamine-based dye having a dendritic structure (DDS) with one OH-ending able to interact with the surface hydroxyl moieties of a porous TiO2.We present the optical properties of the dye-titania composite showing that the dye performs more efficiently on a pure anatase TiO2 than on the commercial Degussa P25. The synthesized organic molecule and the hybrid material obtained by impregnation of DDS on the TiO2 porous structures were characterized by different techniques including 1H NMR, XPS, XRD, SEM and TEM. XRD confirms that the synthesized TiO2[1] is composed of pure anatase phase, whereas the commercial Degussa P25 contains a 20% of rutile phase. SEM and TEM show that the building blocks of the porous structure are nanoparticles of 20-30 nm in size. Physisorption measurements indicate that both the porous structure are quite disordered, and that the specific surface areas are similar. Optical measurements (Figure) show that the absorption of the dye in the pure anatase sample is more efficient than that in P25. The presence of DDS in pure anatase extends the spectral region resulting for example potentially useful for conversion of photons into electrical current in a DSSC [2] making it a promising candidate as a metal-free dye for DSSCs

Preparation, Characterization and Optical properties of a Dendritic Dye Sensitizer DDS-TiO2 hybrid material

We report a new triphenylamine-based dye having a dendritic structure (DDS) with one OH-ending able to interact with the surface hydroxyl moieties of a porous TiO2.We present the optical properties of the dye-titania composite showing that the dye performs more efficiently on a pure anatase TiO2 than on the commercial Degussa P25. The synthesized organic molecule and the hybrid material obtained by impregnation of DDS on the TiO2 porous structures were characterized by different techniques including 1H NMR, XPS, XRD, SEM and TEM. XRD confirms that the synthesized TiO2[1] is composed of pure anatase phase, whereas the commercial Degussa P25 contains a 20% of rutile phase. SEM and TEM show that the building blocks of the porous structure are nanoparticles of 20-30 nm in size. Physisorption measurements indicate that both the porous structure are quite disordered, and that the specific surface areas are similar. Optical measurements (Figure) show that the absorption of the dye in the pure anatase sample is more efficient than that in P25. The presence of DDS in pure anatase extends the spectral region resulting for example potentially useful for conversion of photons into electrical current in a DSSC [2] making it a promising candidate as a metal-free dye for DSSCs

A novel triphenylamine-based dye sensitizer supported on titania nanoparticles and the effect of titania fabrication on its optical properties

A new synthesised triphenylamine-based dye having a branched structure with one OH-ending branch able to interact with the surface hydroxyl moieties of mesoporous TiO2 is reported. Optical properties of the dye-titania hybrid material are presented and the higher efficiency of the dye on pure anatase TiO2 compared to the commercial Degussa P25, which contains a rutile phase component, is confirmed. The optical and chemical properties of the dye make it a promising candidate as a metal-free dye for DSSCs or as a host for a variety of transition or main group metal ions for different applications.A new synthesised triphenylamine-based dye having a branched structure with one OH-ending branch able to interact with the surface hydroxyl moieties of mesoporous TiO2 is reported. Optical properties of the dye-titania hybrid material are presented and the higher efficiency of the dye on pure anatase TiO2 compared to the commercial Degussa P25, which contains a rutile phase component, is confirmed. The optical and chemical properties of the dye make it a promising candidate as a metal-free dye for DSSCs or as a host for a variety of transition or main group metal ions for different applications