Vanadyl cationic complexes as catalysts in olefin oxidation

Three new mononuclear oxovanadium(IV) complexes [VO(acac)(R-BIAN)]Cl (BIAN = 1,2-bis{(R-phenyl)imino} acenaphthene, R = H, 1; CH3, 2; Cl, 3) were prepared and characterized. They promoted the catalytic oxidation of olefins such as cyclohexene, cis-cyclooctene, and styrene with both tbhp (tert-butylhydroperoxide) and H2O2, and of enantiopure olefins (S(-)- and R(+)-pinene, and S(-)- and R(+)-limonene) selectively to their epoxides, with tbhp as the oxidant. The TOFs for styrene epoxidation promoted by complex 3 with H2O2 (290 mol mol(-1)V h(-1)) and for cis-cyclooctene epoxidation by 2 with tbhp (248 mol mol(V)(-1) h(-1)) are particularly good. Conversions reached 90% for several systems with tbhp, and were lower with H2O2. A preference for the internal C=C bond, rather than the terminal one, was found for limonene. Kinetic data indicate an associative process as the first step of the reaction and complex [VO(acac)(H-BIAN)](+) (1(+)) was isolated in an FTICR cell after adding tbhp to 1. EPR studies provide evidence for the presence of a V(IV) species in solution, until at least 48 hours after the addition of tbhp and cis-cyclooctene, and cyclic voltammetry studies revealed an oxidation potential above 1 V for complex 1. DFT calculations suggest that a [VO(H-BIAN)(MeOO)](+) complex is the likely active V(IV) species in the catalytic cycle from which two competitive mechanisms for the reaction proceed, an outer sphere path with an external attack of the olefin at the coordinated peroxide, and an inner sphere mechanism starting with a complex with the olefin coordinated to vanadium

Severe acute respiratory infections in the 2012/2013 season studied by the Portuguese Laboratory Network for Influenza Diagnosis

During the 2009/10 influenza pandemic, a network of 14 laboratories located in the main reference hospitals from Portugal mainland, Madeira and Azores was established for the diagnosis of the new influenza A(H1N1)2009 pandemic strain. Since then, the network performs laboratory diagnosis of influenza as well as other respiratory pathogens, thus contributing to the laboratory diagnosis of respiratory disease in Portugal. This network is a valuable complement of the National Influenza Surveillance Programme (mainly based on primary healthcare units), enabling a more accurate knowledge of the aetiology of the severe respiratory infections, especially in hospitalized cases. The present study describes the severe acute respiratory infections, in the 2012/2013 season, diagnosed by the laboratory network. From the 14 laboratories, 11 reported cases of respiratory disease during 2012/2013 season. The laboratory network performs diagnosis of influenza A and B viruses and other respiratory agents by PCR based methods, also enabling the detection of mixed infections. All 14 laboratories perform the detection of influenza A(H1)pdm09, 4 perform the influenza A(H1) seasonal and A(H3) subtyping, and 10 participants also detect influenza B. Eight laboratories implemented methodologies for the detection of other infectious agents associated with respiratory disease. The antigenic characterization of 8 isolated viruses [3 A(H1)pdm09 and 5 B/Yamagata] was performed at the National Influenza Reference Laboratory. The genetic analysis of the HA1 subunit of the haemagglutinin gene was performed in 17 viruses [7 A(H1)pdm09, 1 A(H3) and 9 B/Yamagata]. Twenty nine A(H1)pdm09 and 5 B/Yamagata were tested for antiviral susceptibility [PCR(NA)-H275Y and/or MUNANA phenotypic assays for oseltamivir and zanamivir]. The 11 laboratories reported a total of 1470 respiratory disease cases, from week 39/2012 to 21/2013 [peak of 205 (13.9%) cases during week 10/2013]. Influenza was identified in 504 cases. Influenza A was detected in 352 (70.0%) cases: 297 (59.0%) cases were A(H1)pdm09, 48 (10.0%) cases were not subtyped, and 7 (1.0%) cases were A(H3). Influenza B was identified in 152 (30%) of the influenza cases. During the 2012/2013 season, 311 (21.2%) reported cases were hospitalized in intensive care units (ICU), the majority of them had between 50-54 years (34; 10.9%), followed by the age groups 45-49 and 55-59 years old (28; 9.0% each). The causal agent was identified in 160 (51.4%) ICU cases. Influenza was identified in 120 (38.5%) patients, other respiratory agents were detected in 40 (12.8%), within these, multiple infections were present in 18 (5.7%). Bacteria were identified in 31 (10.0%) cases mainly associated with RSV and hRV. Among ICU influenza cases, the most detected virus was A(H1)pdm09 (82; 62.0%). However, cases of A(H3) (3; 2.0%), A unsubtyped (8; 7.0%) and B (27; 23.0%) were also detected. As expected, the highest number of ICU influenza positive cases was detected in week 10/2013 (18; 15.0%), coincident with the highest number of influenza cases during all season. ICU flu cases were detected predominantly in individuals between 50-54 years (18; 15.0%). From the ICU reported cases, 6 (1.9%) died. The influenza A(H1)pdm09 virus was detected in 2 man between 50-59 years old from these 6 fatal outcomes. The isolated influenza A viruses were similar to the 2012/2013 vaccine strains. The influenza B/Yamagata viruses showed a greater antigenic and genetic variability. The Portuguese Laboratory Network for Influenza Diagnosis plays a major role in the diagnosis of acute respiratory infections in Portugal, providing a more accurate knowledge of the respiratory agents involved. During the 2012/2013 season, the influenza A(H1)pdm09 virus predominated in co-circulation with influenza B virus. The A(H1)pdm09 virus was the responsible for the majority of the flu cases admitted in the ICU and may have been the cause of death in two cases. Bacterial and other viral agents have been identified in some of the severe cases reported. The majority of the characterized influenza viruses were similar to the vaccine strains and none of the virus showed reduced susceptibility to oseltamivir or zanamivir

Comentários a uma sentença anunciada : o processo Lula

“Comentários a uma sentença: o Caso Lula” é talvez o mais importante documento jurídico publicado no Brasil em décadas. A presente coletânea de artigos nasceu de um movimento espontâneo e bastante significativo de juristas brasileiros e estrangeiros que examinaram cuidadosamente a sentença proferida no âmbito do processo que tramitou na 13ª Vara Federal de Curitiba, no caso que ficou conhecido na mídia como o do “tríplex do Guarujá”. <br>De la presentación de Geraldo Prad

Comentarios a una sentencia anunciada : el proceso Lula

El centenar de textos que conforman este libro -escritos por un movimiento de prestigiosos/as juristas y abogados- desgranan el procedimiento al que fue sometido Lula. En la opinión de las y los autores de los artículos las normas no fueron observadas, y su inobservancia llevó a que se dictaminase una decisión injusta. Frases del estilo "Voy a tomar una decisión revolucionaria, dejando de lado la ley, porque por la ley no se puede condenarlo de ninguna manera”, dichas en los juicios por las más altas autoridades judiciales militares y civiles, hoy son conocidas gracias a quienes se abocaron al trabajo de escuchar los audios de aquellas sesiones, nutriendo las reflexiones que argumentan sobre el imperativo de la hora: restablecer el estado de derecho y absolver al presidente Lula Da Silva