Effect of Gas Atmosphere on Catalytic Behaviour of Zirconia, Ceria and Ceria Zirconia Catalysts in Valeric Acid Ketonization

[EN] Ketonization of valeric acid, which can be obtained by lignocellulosic biomass conversion, was carried out in a fixed bed flow reactor over ZrO2, 5-20 % CeO2/ZrO2 and CeO2 both under hydrogen and nitrogen stream at 628 K and atmospheric pressure. Regardless gas-carrier 10 wt% CeO2/ZrO2 was found to show higher catalytic activity compared to zirconia per se as well as other ceria modified zirconia while ceria per se exhibited very low catalytic activity. All catalysts provided higher acid conversion in H-2 than in N-2 whereas selectivity to 5-nonanone was insensitive to gas atmosphere. XRD, FTIR, UV-Vis DRS, XPS, HRTEM methods were applied to characterize catalysts in reduced and unreduced states simulating corresponding reaction conditions during acid ketonization. XRD did not reveal any changes in zirconia and ceria/zirconia lattice parameters as well as crystalline phase depending on gas atmosphere while insertion of ceria in zirconia caused notable increase in lattice parameter indicating some distortion of crystalline structure. According to XPS, FTIR and UV-Vis methods, the carrier gas was found to affect catalyst surface composition leading to alteration in Lewis acid sites ratio. Appearance of Zr3+ cations was observed on the ZrO2 surface after hydrogen pretreatment whereas only Zr4+ cations were determined using nitrogen as a gas-carrier. These changes of catalyst's surface cation composition affected corresponding activity in ketonization probably being crucial for reaction mechanism involving metal cations catalytic centers for acid adsorption and COO- stabilization at the initial step.Financial support from the Russian Foundation of Basic Research (RFBR Grant No 11-03-94001-CSIC) is gratefully acknowledged. This work was supported by the Federal Program "Scientific and Educational Cadres of Russia'' (Grant No 2012-1.5-12-000-1013-002). The authors also wish to thank Dr. Evgeniy Gerasimov, Dr. Igor Prosvirin, Dr. Demid Demidov from the Department of Physicochemical Methods at the Boreskov Institute of Catalysis for TEM and XPS measurements.Zaytseva, YA.; Panchenko, VN.; Simonov, MN.; Shutilov, AA.; Zenkovets, GA.; Renz, M.; Simakova, IL.... (2013). Effect of Gas Atmosphere on Catalytic Behaviour of Zirconia, Ceria and Ceria Zirconia Catalysts in Valeric Acid Ketonization. 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Association of Calcineurin with the COPI Protein Sec28 and the COPII Protein Sec13 Revealed by Quantitative Proteomics

Calcineurin is a calcium-calmodulin-dependent serine/threonine specific protein phosphatase operating in key cellular processes governing responses to extracellular cues. Calcineurin is essential for growth at high temperature and virulence of the human fungal pathogen Cryptococcus neoformans but the underlying mechanism is unknown. We performed a mass spectrometry analysis to identify proteins that associate with the calcineurin A catalytic subunit (Cna1) in C. neoformans cells grown under non-stress and high temperature stress conditions. A novel prioritization strategy for mass spectrometry data from immunoprecipitation experiments identified putative substrates and proteins potentially operating with calcineurin in common pathways. Cna1 co-purified with proteins involved in membrane trafficking including the COPI component Sec28 and the COPII component Sec13. The association of Cna1 with Sec28 and Sec13 was confirmed by co-immunoprecipitation. Cna1 exhibited a dramatic change in subcellular localization during high temperature stress from diffuse cytoplasmic to ER-associated puncta and the mother-bud neck and co-localized with Sec28 and Sec13

Aspectos psicossociais em cirurgia bariátrica: a associação entre variáveis emocionais, trabalho, relacionamentos e peso corporal Psychosocial aspects in bariatric surgery: the association among emotional variables, job, relationships and body weight

RACIONAL: Operações bariátricas têm sido consideradas alternativa para o tratamento de obesidade mórbida. Alguns eventos adversos que as pessoas experimentam após o tratamento frequentemente são consequência da falta de conhecimento consistente associada a fatores psicossociais que estão relacionadas ao status pré-operatório dos pacientes. OBJETIVO: Avaliar as variáveis ?psicossociais de 414 candidatos ? cirurgia bari?trica do Hospital de Cl?nicas da Faculdade de Medicina da Universidade de S?o Paulo, Ribeir?o Preto, SP, Brasil. psicossociais de 414 candidatos à cirurgia bariátrica do Hospital de Clínicas da Faculdade de Medicina da Universidade de São Paulo, Ribeirão Preto, SP, Brasil. MÉTODOS: Foram utilizados entrevista semi-estruturada, Inventário de Depressão de Beck (BDI), Inventário de Ansiedade de Beck (BAI) e Binge Eating Scale (BES). RESULTADOS: IMC foi maior entre os pacientes que não tinham emprego (p = 0,019), do sexo feminino, os que tinham um parceiro e os pacientes com IMC <50 kg / m², todos eles desejando ter peso menor (p<0,001). Escores do BAI foram maiores entre os pacientes que não tinham emprego (p <0,05) e maior naqueles com IMC> 50 kg / m² (p <0,05). BDI foram mais altos entre as mulheres (p <0,05) e menores entre aqueles que tinham um emprego (p <0,01). Nenhuma diferença no BES foi encontrada. CONCLUSÕES: Os dados sugerem que as mulheres apresentaram indicadores mais elevados de ansiedade e depressão, sugerindo que elas tinham funcionamento psicológico mais frágil com dificuldades em lidar com a angústia. Auto-percepção, assim como competências e habilidades, podem refletir aspectos internos da personalidade do indivíduo. Pacientes que tiveram um emprego antes da operação parecia ter mais recursos emocionais. Assim, eles podiam sentir menos sofrimento, porque o emprego podia protegê-los. Mulheres e aqueles que não tinham emprego eram mais propensos a apresentar sintomas de depressão. Além disso, pacientes que não tinham emprego e aqueles com IMC> 50 kg / m² foram mais propensos a apresentar sintomas de ansiedade.<br>BACKGROUND: Bariatric surgeries have been considered an alternative for treatment of morbid obesity. Some adverse events that people experience after the treatment frequently are the consequence of the lack of consistent knowledge associated with psychosocial factors that are related to the pre-surgery status of the patients. AIM: To evaluate psychosocial variables of 414 candidates for bariatric surgery from Clinical Hospital of Medical School at University of São Paulo, Ribeirão Preto, SP, Brazil. METHODS: Semi-structured interview, Beck Depression Inventory (BDI), Beck Anxiety Inventory (BAI) and Binge Eating Scale (BES) were used. RESULTS: BMI was higher among patients who had no employment (p = 0.019). Female, patients who had a partner and patients with a BMI < 50 kg/m², all of them desired have a lower weight (p < 0.001). BAI scores were higher among patients who had no employment (p < 0.05) and higher among those with a BMI > 50 kg/m² (p < 0.05). BDI scores were higher among women (p < 0.05) and lower among those who had an employment (p < 0.01). No difference in BES was found. CONCLUSIONS: The data suggest that women showed higher indicators of anxiety and depression, suggesting that they had a more fragile psychological functioning with difficulties in coping with distress. Self-perception as well as skills and abilities, may reflect internal aspects of individual's personality. Patients who had an employment before surgery seemed have more emotional resources. So, they may feel less distress because the employment may protect them. Women and those who did not have an employment were more likely to experience depression symptoms. Furthermore, patients who did not have an employment and those with BMI> 50 kg / m² were more likely to experience anxiety symptoms