Improvement of Catalytic Performance of Perovskites by Partial Substitution of Cations and Supporting on High Surface Area Materials

In this chapter, we present two relevant strategies to improve the activity and selectivity of perovskite-mixed oxides ABO3 in heterogeneous catalytic reactions such as the oxidation of hydrocarbons, soot combustion and CO selective oxidation, for which the surface sites and lattice oxygen species play important roles for the chemical transformations. Besides, we focus on synthesis of higher alcohols, partial oxidation of methane, oxidative reforming of diesel and dry reforming of methane for which the perovskite is a precursor that leads to a dispersed metal active phase over an oxide matrix. But which strategies are we talking about? First, the partial substitution of cations A and B by different elements, which change atomic distances, causes unit cell distortions, stabilizes multiple oxidation states or induces cationic or anionic vacancies within the lattice. And all these new features perturb the solid reactivity by changing the reaction mechanism on the catalyst surface. Thus, appropriate cations substitutions may lead to better catalysts. The second strategy comprises supporting the perovskite, which usually presents low surface area, on high surface area materials to maximize the exposed surface sites

Performance of the new ACR/EULAR classification criteria for systemic sclerosis in clinical practice

Objective. The preliminary classification criteria for SSc lack sensitivity for mild/early SSc patients, therefore, the new ACR/EULAR classification criteria for SSc were developed. The objective of this study was to evaluate the performance of the new classification criteria for SSc in clinical practice in a cohort of mild/early patients. Methods. Consecutive patients with a clinical diagnosis of SSc, based on expert opinion, were prospectively recruited and assessed according to the EULAR Scleroderma Trials and Research group (EUSTAR) and very early diagnosis of SSc (VEDOSS) recommendations. In some patients, missing values were retrieved retrospectively from the patient's records. Patients were grouped into established SSc (fulfilling the old ACR criteria) and mild/early SSc (not fulfilling the old ACR criteria). The new ACR/EULAR criteria were applied to all patients. Results. Of the 304 patients available for the final analysis, 162/304 (53.3%) had established SSc and 142/304 (46.7%) had mild/early SSc. All 162 established SSc patients fulfilled the new ACR/EULAR classification criteria. The remaining 142 patients had mild/early SSc. Eighty of these 142 patients (56.3%) fulfilled the new ACR/EULAR classification criteria. Patients with mild/early SSc not fulfilling the new classification criteria were most often suffering from RP, had SSc-characteristic autoantibodies and had an SSc pattern on nailfold capillaroscopy. Taken together, the sensitivity of the new ACR/EULAR classification criteria for the overall cohort was 242/304 (79.6%) compared with 162/304 (53.3%) for the ACR criteria. Conclusion. In this cohort with a focus on mild/early SSc, the new ACR/EULAR classification criteria showed higher sensitivity and classified more patients as definite SSc patients than the ACR criteri

Protophormia terraenovae (Robineau-Desvoidy, 1830) (Diptera, Calliphoridae) A new forensic indicator to south-western Europe

Protophormia terraenovae larvae are found frequently on corpses in central and northern Europe but are scarce in the Mediterranean area. We present the first case in the Iberian Peninsula where P. terraenovae was captured during autopsies in Madrid (Spain). In the corpse other necrophagous flies were found, Lucilia sericata, Chrysomya albiceps and Sarcophaga argyrostoma. To calculate the posmortem interval, the life cycle of P. terraenovae was studied at constant temperature, room laboratory and natural fluctuating conditions. The total developmental time was 16.61±0.09 days, 16.75±4.99 days in the two first cases. In natural conditions, developmental time varied between 31.22±0.07 days (average temperature: 15.6oC), 15.58±0.08 days (average temperature: 21.5oC) and 14.9±0.10 days (average temperature: 23.5oC). Forensic importance and the implications of other necrophagous Diptera presence is also discussed.Las larvas de Protophormia terraenovae se encuentran con frecuencia asociadas a cadáveres en el centro y norte de Europa pero son raras en el área Mediterránea. Presentamos el primer caso en la Península Ibérica donde se han recolectado larvas de P. terraenovae en autopsias efectuadas en Madrid (Spain). Otras especies necrófagas fueron recolectadas del cadáver, Lucilia sericata, Chrysomya albiceps y Sarcophaga argyrostoma. Para estimar el intervalo postmortem, se estudió el ciclo biológico de P. terraenovae a temperatura constante, en condiciones de laboratorio y bajo condiciones naturales variables. El tiempo total de desarrollo fue 16.61±0.09 días, 16.75±4.99 días para los dos primeros casos. En condiciones naturales, el tiempo total de desarrollo varió entre 31.22±0.07 días (temperatura media: 15.6oC), 15.58±0.08 días (temperatura media: 21.5oC) y 14.9±0.10 días (temperatura media: 23.5oC). Se discuten tanto la importancia forense como las implicaciones de otros dípteros necrófagos presentes en el estudio.Partial financial support was partially provided by the European Commission [LIFE05 ENV/E/000302], University of Alicante [GRE09-27] and the Regional Ministry of the Generalitat Valenciana [GV/2011/039]

The cost-effectiveness of influenza vaccination for people aged 50 to 64 years: An international model

Objectives: Routine influenza vaccination is currently recommended in several countries for people aged more than 60 or 65 years or with high risk of complications. A lower age threshold of 50 years has been recommended in the United States since 1999. To help policymakers consider whether such a policy should be adopted more widely, we conducted an economic evaluation of lowering the age limit for routine influenza vaccination to 50 years in Brazil, France, Germany, and Italy.Methods: the probabilistic model was designed to compare in a single season the costs and clinical outcomes associated with two alternative vaccination policies for persons aged 50 to 64 years: reimbursement only for people at high risk of complications (current policy), and reimbursement for all individuals in this age group (proposed policy). Two perspectives were considered: third-party payer (TPP) and societal. Model inputs were obtained primarily from the published literature and validated through expert opinion. the historical distribution of annual influenza-like illness (ILI) incidence was used to simulate the uncertain incidence in any given season. We estimated gains in unadjusted and quality-adjusted life expectancy, and the cost per quality-adjusted life-year (QALY) gained. Deterministic and probabilistic sensitivity analyses were conducted.Results: Comparing the proposed to the current policy, the estimated mean costs per QALY gained were R$4,100, 13,200, 31,400 and 15,700 for Brazil, France, Germany, and Italy, respectively, from a TPP perspective. From the societal perspective, the age-based policy is predicted to yield net cost savings in Germany and Italy, whereas the cost per QALY decreased to R$2800 for Brazil and 8000 for France. the results were particularly sensitive to the ILI incidence rate, vaccine uptake, influenza fatality rate, and the costs of administering vaccination. Assuming a cost-effectiveness threshold ratio of 50,000 per QALY gained, the probabilities of the new policy being cost-effective were 94% and 95% for France, 72% and near 100% for Germany, and 89% and 99% for Italy, from the TPP and societal perspectives, respectively.Conclusions: Extending routine influenza vaccination to people more than 50 years of age is likely to be cost-effective in all four countries studied.I3 Innovus, Uxbridge UB8 1QG, Middx, EnglandUniv Jena, Inst Virol & Antiviral Therapy, Jena, GermanyINSERM, U444, Paris, FranceUniv Genoa, Dept Hlth Sci, Genoa, ItalyUniversidade Federal de São Paulo, Reg Influenza Surveillance Grp, São Paulo, BrazilUniv York, Ctr Hlth Econ, York YO10 5DD, N Yorkshire, EnglandI3 Innovus, Medford, MA USAHarvard Univ, Sch Publ Hlth, Boston, MA 02115 USAUniversidade Federal de São Paulo, Reg Influenza Surveillance Grp, São Paulo, BrazilWeb of Scienc

Self-assembly of the toll-like receptor agonist macrophage-activating lipopeptide MALP-2 and of its constituent peptide

The self-assembly of the macrophage-activating lipopeptide MALP-2 in aqueous solution has been investigated and is compared to that of the constituent peptide GNNDESNISFKEK. MALP-2 is a toll-like receptor agonist lipopeptide with diverse potential biomedical applications and its self-assembly has not previously been examined. It is found to self-assemble, above a critical aggregation concentration (cac), into remarkable “fibre raft” structures, based on lateral aggregation of β-sheet based bilayer tapes. Peptide GNNDESNISFKEK also forms β-sheet structures above a cac, although the morphology is distinct, comprising highly extended and twisted tape structures. A detailed insight into the molecular packing within the MALP-2 raft and GNNDESNISFKEK nanotape structures is obtained through X-ray diffraction and small-angle X-ray scattering. These results point to the significant influence of the attached lipid chains on the self-assembly motif, which lead to the raft structure for the lipopeptide assemblies

Multicohort analysis of the maternal age effect on recombination

Several studies have reported that the number of crossovers increases with maternal age in humans, but others have found the opposite. Resolving the true effect has implications for understanding the maternal age effect on aneuploidies. Here, we revisit this question in the largest sample to date using single nucleotide polymorphism (SNP)-chip data, comprising over 6,000 meioses from nine cohorts. We develop and fit a hierarchical model to allow for differences between cohorts and between mothers. We estimate that over 10 years, the expected number of maternal crossovers increases by 2.1% (95% credible interval (0.98%, 3.3%)). Our results are not consistent with the larger positive and negative effects previously reported in smaller cohorts. We see heterogeneity between cohorts that is likely due to chance effects in smaller samples, or possibly to confounders, emphasizing that care should be taken when interpreting results from any specific cohort about the effect of maternal age on recombination

In the eye of the storm : the Italian economy and the eurozone crisis

The eurozone crisis had a more significant and longer-lasting impact on Italy than on virtually any other member state, with the effects still visible a decade after. The extent of the shock was surprising in view of progress Italy had apparently made in the 1990s in terms of enhancing its capacity to meet the demands of European Monetary Union. The explanation for this traumatic economic experience lies in Italy’s deep, long-term, structural tensions which were placed under severe pressure during the 1990s and which were cracked open by the 2011 sovereign debt crisis. These have had long-standing economic effects as well as political ramifications in terms of a significant change in the Italy–EU relationship

A global picture of the S-1/S-0 conical intersection seam of benzene

A global picture of the S1/S0intersection seam of benzene is presented. Eleven new conical intersection critical points were located at the CASSCF level, the connectivity was mapped and the energies refined with CASPT 2. There are two seam branches related with pairs of degenerate A1g/B2uand Egstates at D6hsymmetry, respectively, and the two branches are connected by a seam segment of Cssymmetry. The global energy minimum of the seam is the half-boat shaped intersection that leads to a pre-fulvenic intermediate [I.J. Palmer, I.N. Ragazos, F. Bernardi, M. Olivucci, M.A. Robb, J. Am. Chem. Soc. 115 (1993) 673]. Several other intersections that can lead to the same intermediate or vibrationally hot benzene lie in a range of 3.7 eV above the global seam minimum. There is a recurrent connectivity pattern where permutationally isomeric seam segments are connected by intersections of a higher symmetry point groupThis work has been supported by Grant CTQ2008-06696 from the Spanish Ministerio de Ciencia e Innovación (MICINN