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A novel synthetic procedure for the functionalisation of styrenic cross-linked polymers with perfluorinated acyl chains has been reported. The effective significant grafting of the fluorinated moieties is supported by {1H}-13C and {19F}-13C NMR characterisations. This kind of polymer appears promising as catalytic support for a variety of reactions requiring a highly lipophilic catalyst. Indeed, the improved lipophilicity of the materials resulted in enhanced catalytic properties of the corresponding sulfonic materials in the reaction of esterification of a solution in a vegetable oil of stearic acid with methanol.

We employed oxygen- and nitrogen-functionalized mesoporous carbons (OMC and N-OMC) as supports for Pd nanoparticles pre-formed via a modified colloidal method. In the direct synthesis of hydrogen peroxide (H2O2) from H2 and O2, the prepared Pd/OMC catalyst outperformed a commercial Pd catalyst supported on activated carbon (Pd/AC) and a Pd catalyst on oxygen-functionalized carbon nanotubes (Pd/OCNT) in terms of H2O2 productivity, emphasizing the advantage of mesoporous carbon support. An even higher H2O2 productivity was obtained over Pd catalyst supported on N-OMC with 2.72 at.% nitrogen on the surface. However, a further increase of surface nitrogen content to 13.26 at.%, as the case of mesoporous carbon directly grown using N-containing carbon precursor (NMC), led to increased activity (in terms of H2 consumption) but poor H2O2 productivity. X-ray photoelectron spectroscopy analyses of the Pd/MC catalysts suggest that a suitable amount of N groups (ca. 2.72 at.%) on the MC surface led to a high fraction of Pd2+ in the Pd/MC catalyst, which is believed to be important for achieving high selectivity in direct H2O2 synthesis. These results highlight that tuning the surface properties of carbon supports is a versatile approach to fabricate highly selective supported Pd catalysts for the sustainable direct synthesis of H2O2 from H2 and O2.

Background The effectiveness of implantable cardioverter-defibrillator (ICD) in the elderly is uncertain, given their competing risk of nonarrhythmic death. Guidelines state that an ICD should be implanted if the expectation of survival is at least 1 year. However, survival is not easy to predict in elderly patients with severe cardiac disease. Aim To assess 12-month survival after ICD implantation in patients aged ≥75 years, to identify predictors of 12-month mortality, and to evaluate the incidence of ICD therapy during follow-up. Methods We retrospectively analyzed all clinical, instrumental, and survival data of patients ≥75 years old who received an ICD in our center from 2000 to 2013. Results We included 127 patients (mean age 78 years). ICD was implanted for primary prevention in 61%. The 12-month survival rate was 87.4%. At both univariate and multivariate analyses, left ventricular ejection fraction (EF) ≤ 25%, and moderate to severe impaired renal function (IRF) independently predicted 12-month mortality that was as high as 45.5% in patients with both risk factors. During a median follow-up of 38 months, 30 patients (23.6%) received ≥1 appropriate ICD interventions, but only 3.1% of shocks occurred during the first year, and none in the subgroup of patients with EF ≤ 25% and IRF. Conclusion Twelve-month survival in elderly patients after ICD implantation is good and the indication for ICD should not be based on age alone. However, the subgroup with EF ≤ 25% and IRF showed a high 12-month nonarrhythmic mortality and did not benefit from ICD implantation.

The chemical structure and morphology of a set of sulfonic gel-type poly(styrene-divinylbenzene) resins (2 mol% DVB) prepared with different synthetic approaches were investigated by solid state NMR, Inverse Size Exclusion Chromatography (ISEC), FT-IR and elemental analysis to compare their swollen state structure. FT-IR and solid state NMR clearly show that the sulfonation mainly occurs in the para- position with respect the main polymer chain. Sensible proportions of sulfone bridges were found in the materials obtained with oleum and chlorosulfonic acid. With oleum, the presence of the sulfone bridges is clearly associated to a reduced ability to swell in the water medium relative to the proton exchange capacity. This highlights the cross-linking action of the sulfone bridges according to ISEC results, showing a high proportion of a dense polymer fraction in the swollen material. An even higher degree of sulfone-bridging, lower swelling ability, and a high proportion of a dense polymer fraction in the swollen material are found in the resin obtained with chlorosulfonic acid. As a matter of fact, Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP-MAS 13C-NMR), elemental analysis, and ion exchange capacity, show that oleum and chlorosulfonic acid produced resins with remarkably smaller pores and lower swollen gel volume in polar solvents, with respect to concentrated sulfuric acid.

Palladium catalysts supported by a mesoporous form of sulfonated poly-divinylbenzene, Pd/&micro, S-pDVB10 (1%, w/w) and Pd/&micro, S-pDVB35 (3.6% w/w), were applied to the direct synthesis of hydrogen peroxide from dihydrogen and dioxygen. The reaction was carried for 4 h out in a semibatch reactor with continuous feed of the gas mixture (H2/O2 = 1/24, v/v, total flow rate 25 mL&middot, min&minus, 1), at 25 &deg, C and 101 kPa. The catalytic performances were compared with those of a commercial egg-shell Pd/C catalyst (1%, w/w) and of a palladium catalyst supported by a macroreticular sulfonated ion-exchange resin, Pd/mS-pSDVB10 (1%, w/w). Pd/&micro, S-pDVB10 and Pd/C showed the highest specific activity (H2 consumption rate of about 75&ndash, 80 h&minus, 1), but the resin supported catalyst was much more selective (ca 50% with no promoters). The nanoparticles (NP) size was somewhat larger in Pd/&micro, S-pDVB10, showing that either the reaction was structure insensitive or diffusion limited to some extent over Pd/C, in which the support is microporous. The open pore structure of Pd/&micro, S-pDVB10, possibly ensuring the fast removal of H2O2 from the catalyst, could also be the cause of the relatively high selectivity of this catalyst. In summary, Pd/&micro, S-pDVB10 was the most productive catalyst, forming ca 375 molH2O2&middot, kgPd&minus, 1&middot, h&minus, 1, also because it retained a constant selectivity, while the other ones underwent a more or less pronounced loss of selectivity after 80&ndash, 90 min. Ageing experiments showed that for a palladium catalyst supported on sulfonated mesoporous poly-divinylbenzene storage under oxidative conditions implied some deactivation, but a lower drop in the selectivity, regeneration upon a reductive treatment or storage under strictly anaerobic conditions (dry-box) lead to an increase of the activity but to both a lower initial selectivity and a higher drop of selectivity with time.

Axillary vein puncture is an effective method for pacemaker lead insertion with less complications compared with subclavian vein puncture; however, there are limited data on implantable cardioverter defibrillator (ICD) implantation with this technique. We reported our experience with a blind axillary vein puncture using fluoroscopic landmarks consisting of the outer edge of the first rib and the body surface of the second rib for ICD lead implantation. The study population included 103 consecutive patients (mean age 59 ± 9 years) referred for ICD implantation using axillary vein puncture without contrast venography. An 18-gauge needle was advanced toward the outer edge of the fist rib below the clavicle or the body surface of the second rib. If the vein was not entered, the needle was withdrawn and the puncture was repeated with slight variations of needle direction for a maximum of four times, then contrast-guided vein puncture was performed. The total implanted leads were 152 including 103 right ventricular leads, 35 right atrial leads, and 14 left ventricular epicardial leads. Blind axillary vein puncture was successful obtained in 96 (93.2 %) patients. The rate of success was higher using the body surface of the second rib compared with the outer edge of the first rib (88.7 vs. 100 %; p = 0.04).Contrast venography was required in seven (6.8 %) patients because of vein course abnormality (n = 5) or vasospasm (n = 2). No acute complications or device-related complications were recorded during a mean follow-up of 12 ± 5 months. Axillary vein access using fluoroscopic landmarks, especially the body surface of the second rib, is an effective approach for ICD implantation and offers the potential to avoid complications usually observed with traditional subclavian vein approach

The habitat weighting method, the Simpson diversity index and the mutual climatic range method are applied to the small-mammal assemblage of Grotta del Romito (southern Italy) in order to reconstruct the environmental and climatic fluctuations that occurred during the latest Pleistocene–Holocene sequence of the cave. The analysed strata have a discontinuous chronological range from the middle-late Gravettian (ca. 24 ka uncal. BP) to the Mesolithic–Sauveterrian (still radiometrically undated). Gravettian and Epigravettian layers were excavated inside the cave, Mesolithic layers in the rockshelter outside the cave. The small-mammal assemblage shows significant differences along the sequence; a turning point is detected in strata D29-D11, coinciding with the end of Heinrich Event 1 (H1) and the beginning of the Bolling–Allerod interstadial (between ca. 14.9–14 ka cal. BP). These data are in accordance with the previously obtained environmental data for Grotta del Romito, as well as with other continental climatic and environmental changes detected at a regional scale.

The occurrence of the genus Iberomys is testified in Italy and the Iberian Peninsula from the Early Pleistocene on. The genus comprises two extinct voles: I. huescarensis from the Early Pleistocene to the early Middle Pleistocene and I. brecciensis (=mediterraneus) from the Middle to the early Late Pleistocene. I. cabrerae, has been present in Spain from the early Late Pleistocene, enduring right through to today. The fossil record of Iberomys in Italy is poor in comparison with those in the Iberian Peninsula and southern France. I. huescarensis has been identified in Italy at the Rifreddo and Spessa sites, while I. brecciensis has been recognized at Zoppega 2, Montagnola Senese II, Isernia, Valdemino, Polledrara di Cecanibbio and Paglicci. A revision of the specimens of the genus Iberomys in Italy and a comparison with the fossil records of southern France and the Iberian Peninsula show that the origin of the Early Pleistocene species (I. huescarensis) is clearly in the Iberian Peninsula, where the species having evolved from ancient populations of Allophaiomys nutiensis. The origin of the species I. brecciensis is still unknown. It seems to appear at the same time in Italy and in the Iberian Peninsula, and its extinction occurred during the late Middle Pleistocene-early Late Pleistocene in Italy, France and Iberia simultaneously.

Fumane cave, located at an altitude of 350 m.a.s.l. in the Monti Lessini in the Veneto Pre-Alps, northeastern Italy, is a reference site for southern Europe for the study of the behaviour of Neanderthals and Anatomically Modern Humans (AMH) from Marine Isotope Stages 5 to 2 (MIS5-MIS2). It is one of the few well-dated and closely studied sites in the Italian Peninsula, with a finely layered sedimentary sequence from the Mousterian to Gravettian. In this paper we present for the first time a palaeoenvironmental and palaeoclimatic reconstruction of the MIS3 and MIS2 sequence based on the small mammal (insectivore, bat and rodent) assemblages. The environmental and climatic results, coupled with the radiocarbon dating together with previous studies on large mammals, birds and charcoal and other studies on small mammals and pollen for the same time-span in Italy, enable us clearly to identify distinct climatic periods within our data: Heinrich Event 5 in units A7 to A6, Greenland Interstadial 12 in units A5 + A6 to A4, Heinrich Event 4 in units A3 to A1, and Heinrich Event 3 in unit D1e. Finally, the study shows that Neanderthals and Anatomically Modern Humans were well adapted to the different climatic and environmental conditions of MIS3 at the foot of the Alps.

The fossil record of the Savi vole, Microtus ( Terricola ) savii , is analyzed in terms of morphological and morphometrical variability of the first lower molar, in order to reconstruct phylogenetic relationships between insular and mainland populations and the dispersal events. The present work gives a contribution to better understand the phylogenetic history of this taxon in Sicily and Southern Italy during the interval Middle Pleistocene – Holocene, in an attempt to reconstruct the relationships between insular and continental voles and to clarify some paleobiogeographical aspects. The morphometrical data have been acquired by traditional measurements of the first lower molar and analyzed by dispersal diagrams and Principal Components Analysis. The fossil Sicilian samples have a greater size variation than extant ones. Two different morphological groups have been identified and named on the basis of the similarity with European or Italian populations: a “subterraneomorph” one (characterized by a tighter symmetric anterior cap and longer anteroconid), similar to European M. ( T. ) subterraneus species, and a “savimorph” one (more confluent and asymmetric anterior cap and shorter anteroconid), occasionally with the accentuation of morphological characters of M. ( T. ) savii . The results, in particular the differences between Pleistocene and Holocene Sicilian populations and the similarities with the mainland ones, suggest that the Savi vole dispersed at least twice in Sicily. One colonization took place likely during the cold stage MIS 6 (recorded at Isolidda 3) with dispersal events, made possible by the sea level drop and the connection with the mainland, and a second one (documented at San Teodoro cave and other Holocene assemblages) during MIS 4 (by dispersal events) or MIS 3 (by accidental transit or limited faunal exchanges).

It is well recognized that the majority of patients with heart failure (HF) are admitted to General Medicine Departments (GMDs), and that the recommendations of the international guidelines for the treatment of HF are often incorrectly applied in hospital practice. We evaluated the treatment of patients with HF discharged from a single hospital over a period of 10 years. The study population comprised two series of patients who were discharged from six GMDs of a single hospital with the diagnosis of HF in the first 2 months of 1998 and 2008. The patients were also divided in two groups on the basis of the type of HF, systolic or diastolic. In 10 years, the number of patients who were discharged with the diagnosis of HF increased, the median age rose from 79 to 82 years and diastolic has become the more common type of HF. The prevalence of comorbidities rose significantly. There was an increased use of ACE-inhibitors and betablockers, and a reduction of digoxin and nitrates. The mortality decreased from 16.7% in 1998 to 9.6% in 2008 (p < 0.02) and hospitalizations became shorter (p < 0.05) considering patients with systolic HF (EF ≤ 45%) the median age rose from 74 to 79 years old (p < 0.01). We recorded an increasing use of betablockers, a reduction in the prescription of digoxin. The percentage of Diastolic HF rose from 55.7% in 1998 to 65.0% in 2008 (p < 0.001). The median age of these patients changed from 79 to 82 years old (p < 0.05). In 10 years, the clinical characteristics and management of HF patients who are hospitalized have changed. Pharmacological treatment has improved, but it still remains far from being adequately compliant with guideline recommendations.