Giorgio Cini Foundation

One of the most relevant factors limiting the performance of proton-exchange membrane fuel cells (PEMFCs) is the large cathode overpotential, that is associated to the sluggishness of the oxygen reduction reaction (ORR) in an acidic environment. In conventional state-of-the-art PEMFCs the ORR is promoted by electrocatalysts (ECs) that include a very high loading of platinum-group metals in order to achieve performance and durability levels that are matching the requirements set by the applications. Indeed, Pt is the element that affords the best ORR kinetics in an acidic environment. This is a major shortcoming of today’s PEMFCs, whose large-scale rollout is hindered by the significant risk to incur in Pt supply bottlenecks [1]. This issue is addressed by developing ORR ECs that do not include platinum (“Pt-free” ECs). It is shown that the ORR can be effectively promoted by active sites that are based on a first-row transition metal (e.g., Fe, Co and Ni), that is bound on the surface of the EC by coordination interactions mediated by C and N ligand atoms. It is also revealed that the EC performance is raised significantly by the addition of another element (e.g., Sn) that acts as a “co-catalyst”. The ORR kinetics of such “Pt-free” ECs improves dramatically in an alkaline environment, where the adsorption of O2 on the active sites is more facile. Finally, the performance and the durability of the “Pt-free” ECs are strongly affected by the chemical composition, structure and morphology of the support, that must minimize the ohmic drops and facilitate the mass transport phenomena. In this framework, in principle graphene is a very attractive support for ORR ECs as it affords: (i) a very high specific area; (ii) an outstanding electron mobility; and (iii) a negligible microporosity. Hence, graphene is adopted as the main component of the support included in a several different families of “Pt-free” ORR ECs, whose development is overviewed in this work. All the ECs described here are obtained with the synthetic protocol devised in our laboratory [2], and are characterized by a “core-shell” morphology. In detail, the graphene-based support “core” is covered by a carbon nitride “shell”, that stabilizes the active sites in “coordination nests” based on C- and N- ligands. The physicochemical properties of the proposed ECs (e.g., chemical composition, morphology, porosity and structure) are correlated with the ORR performance determined both in “ex-situ” measurements carried out in half-cell configuration and in single fuel cell tested under operating conditions. It is elucidated the impact of: (i) the chemical composition of the active sites; (ii) the features of the support (e.g., size of graphene sheets, presence of spacers); and (iii) the details of the post-synthesis treatments carried out on the ECs on the ORR overpotentials and reaction pathway as a function of the pH of the environment. Acknowledgement This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 785219, and from the BIRD 2018 program of UNIPD.

The sluggishness of the kinetics of the oxygen reduction reaction (ORR) is one of the most relevant phenomena curtailing the operation capability of proton-exchange membrane fuel cells (PEMFCs)[1]. Hence, the development of advanced ORR electrocatalysts (ECs) is one of the main goals of the research in this field. The ECs described here exhibit a “core-shell” morphology: a hierarchical graphene-based support (H-GR) “core” is covered by a carbon nitride “shell” stabilizing the active sites in “coordination nests” [2]. The “core” comprises highly defected graphene nanoplatelets [3] and carbon black nanoparticles; the latter act as spacers and facilitate the charge and mass transport phenomena that take place during the EC operation. The ECs proposed here are characterized by a very low loading of platinum, on the order of ca. 5 wt%, that is the “active metal”; Ni is introduced as the “co-catalysts” to improve the ORR performance [2]. An extensive post-synthesis activation process (A) is applied to the ECs, significantly affecting their chemical composition, structure and morphology. The ORR performance of the “activated” ECs is much improved in comparison with state-of-the-art Pt/C reference ECs. This work is aimed at investigating the effect of different activation parameters on the ORR performance and reaction mechanism, aiming at a robust and reliable upscaling of the preparation process [4]. The proposed ECs are extensively characterized both before and after A to study the complex interplay between the synthetic/activation parameters, the physicochemical properties, and the electrochemical ORR performance both “ex-situ” and in single PEMFC. The bulk chemical composition of the ECs is determined by means of Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) and CHNOS microanalyses; the structure is investigated through wide-angle X-ray diffraction (WAXD) and vibrational spectroscopies (e.g., confocal micro-Raman); the surface composition and oxidation states are probed with X-ray photoelectron spectroscopy (XPS); morphology is observed by high-resolution transmission electron microscopy (HR-TEM); the details of the ORR performance and reaction pathway as a function of the pH of the environment are elucidated by cyclic voltammetry with the rotating ring-disk electrode (CV-TF-RRDE). Finally, the ECs are used to fabricate membrane-electrode assemblies (MEAs) that are tested in single PEMFC in operating conditions. Acknowledgement This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 785219, and from the BIRD 2018 program of UNIPD.

In this paper I analyze some of the effects of the recent spread of YouTube among the battenti devoted to the cult of the Madonna dell’Arco, in Naples. The music performed during the battenti’s rites (devotional songs and brass band music) is linked to devotional and identity symbolic horizons, whose manipulation is used by different groups of devotees to legitimize themselves as ritual mediators representing their local neighbourhood. One of the most relevant effects deriving from the spread of YouTube can be recognized in the exaltation of some already existent social dynamics, connected to imitation and distinction strategies. As a result of the spread of YouTube, changes in the musical phenomena connected to the rites – one of the effects of the mentioned strategies – are now happening faster than in the past, leading to radical innovations in brass band music, and to the introduction of new musical genres, such as the neomelodica pop song.

Introduction: the SMILE (Survival of Myocardial Infarction Long-term Evaluation) studies demonstrated that early administration of zofenopril following acute myocardial infarction (AMI) is prognostically beneficial compared to placebo or other angiotensin-converting enzyme inhibitors (ACE-inhibitors). Hypothesis: In the present meta-analysis of individual data of four SMILE studies we evaluated the cumulative efficacy of zofenopril on cardiovascular (CV) morbidity and mortality in the subgroup of hypertensive patients. Methods: 1880 (53.1%) of the 3542 patients had a positive history for hypertension. 449 hypertensives and 486 normotensives were treated with placebo (SMILE 1 and 3), 980 and 786 with zofenopril 30-60 mg/die (all four studies), 451 and 390 with lisinopril 5-10 mg/die (SMILE 2) or ramipril 10 mg/die (SMILE 4). Treatment was continued for 6 to 48 weeks. For the purpose of this pooled analysis the primary study endpoint was set to 1-year combined occurrence of death or hospitalization for CV causes. Results: the risk of CV events was significantly reduced by 35% with zofenopril vs. placebo [HR: 0.65; 95% CI: 0.49-0.86; p=0.003) in hypertensive patients and by 41% in normotensive patients (0.59; 0.44-0.79; p=0.0001). The other ACE-inhibitors reduced CV morbidity and mortality as well, though the reduction (-17%) was not statistically significant vs. placebo either in hypertensives (0.83; 0.57-1.21; p=0.338) or normotensives (reduction: -24%; HR: 0.76; 0.50-1.15; p=0.194). Treatment with zofenopril of hypertensive and normotensive patients was associated with a non-statistically significant reduction in the risk of CV outcomes as compared to the other ACE-inhibitors (hypertensives: 0.78; 0.60-1.01; p=0.062; normotensives: 0.77; 0.55-1.10; p=0.1509. Conclusions: in high-risk cardiac patients with arterial hypertension, zofenopril treatment is associated with a clinically relevant reduction in long-term CV morbidity and mortality, compared to placebo, with an efficacy similar to that of other ACE-inhibitors, such as lisinopril and ramipril.

Object In the last decade the indications for the endoscopic endonasal approach have been progressively expanded to include lesions that have not been traditionally considered amenable to resection through the transsphenoidal route. In this study, the authors analyze their experience with hypothalamic gliomas treated via the endoscopic endonasal approach. Methods Consecutive cases of hypothalamic gliomas treated since 2007 via an endoscopic endonasal approach were reviewed. Preoperative and postoperative neuroimaging as well as endocrinological, neurological, and visual symptoms were analyzed to assess the surgical outcome. Signs and symptoms of hypothalamic dysfunction including body mass index (BMI), memory, sleep-wake rhythm, and polyphagia were prospectively collected pre- and postoperatively to assess hypothalamic function. Quality of life was evaluated using the Katz scale. Results In the initial phase the endoscopic endonasal approach was adopted in 3 cases with a palliative intent, to obtain a biopsy sample or for debulking of the mass followed by radio- or chemotherapy. In 2 later cases it was successfully adopted to achieve gross-total tumor resection. Complications consisted of 2 postoperative CSF leaks, which required an endoscopic endonasal reintervention. Visual deficit improved in 3 cases and normalized in the other 2. Four patients developed diabetes insipidus, and 3 an anterior panhypopituitarism. All patients had a moderate increase in BMI. No patients presented with any other signs of hypothalamic damage, and their quality of life at follow-up is normal. Conclusions Despite the limitations of a short follow-up and small sample, the authors' early experience with the endoscopic endonasal approach has revealed it to be a direct, straightforward, and safe approach to third ventricle astrocytomas. It allowed the authors to perform tumor resection with the same microsurgical technique: dissecting the tumor with 2 hands, performing a central debulking, and controlling the bleeding with bipolar coagulation. The main limitations were represented by some anatomical conditions, such as the position of the chiasm and the anterior communicating artery complex and, finally, by the challenge of watertight plastic repair. To definitively evaluate the role of this approach in hypothalamic gliomas, a comparison with transcranial series would be necessary, but due to the rarity of these cases such a study is still lacking. The authors observed that more aggressive surgery is associated with a worse endocrinological outcome; thus they consider it to be an open question (in particular in prepubertal patients) whether radical removal is an advisable goal for hypothalamic gliomas.

Future technologies and the future of infrared 10.15 J. L. Tissot (ULIS, France) (invited lecture) IR detection with Uncooled Smart Sensors 10.45 M. Strojnik, G. Paez (Centro de Investigaciones en Optica, Mexico) Sensitivity of a temperature sensor employing ratio of fluorescence power in a band 11.05 Coffee Break Advanced Sensors, Chairman: M. Strojnik 11.20 H. Madura