Supercritical CO2 extraction of secondary metabolites from Agaricus blazei: experiments and modelling

The mycelium and young fruiting bodies of Agaricus blazei were submitted to supercritical CO2 extraction, in a modified commercial flow apparatus, at temperatures from 40 to 80 ºC, pressures up to 600 bar and CO2 flow-rates from 2.0 to 9.0 g.min-1. The best extraction conditions of secondary metabolites, whereby the degree of solubilization (g extract/100 g of fungi) is the highest, was obtained with pure CO2 at 400 bar, 70 ºC and a CO2 flow rate of 5.7g.min-1. The extract in that conditions were analysed by GC-Ms. In order to increase the extraction yield of secondary metabolites, which are mostly present in glycolipid fractions, a polar compound (ethanol) was used as co-solvent in the proportions of 5 and 10 % (mol/mol). The presence of ethanol increased the yield when compared with the extraction with pure CO2. Moreover, a simple model was applied to the supercritical CO2 extraction of secondary metabolites from Agaricus blazei.

OC/EC ratio observations in Europe: Re-thinking the approach for apportionment between primary and secondary organic carbon

This study explores a large set of OC and EC measurements in PM(10) and PM(2.5) aerosol samples, undertaken with a long term constant analytical methodology, to evaluate the capability of the OC/EC minimum ratio to represent the ratio between the OC and EC aerosol components resulting from fossil fuel combustion (OC(ff)/EC(ff)). The data set covers a wide geographical area in Europe, but with a particular focus upon Portugal, Spain and the United Kingdom, and includes a great variety of sites: urban (background, kerbside and tunnel), industrial, rural and remote. The highest minimum ratios were found in samples from remote and rural sites. Urban background sites have shown spatially and temporally consistent minimum ratios, of around 1.0 for PM(10) and 0.7 for PM(2.5).The consistency of results has suggested that the method could be used as a tool to derive the ratio between OC and EC from fossil fuel combustion and consequently to differentiate OC from primary and secondary sources. To explore this capability, OC and EC measurements were performed in a busy roadway tunnel in central Lisbon. The OC/EC ratio, which reflected the composition of vehicle combustion emissions, was in the range of 03-0.4. Ratios of OC/EC in roadside increment air (roadside minus urban background) in Birmingham, UK also lie within the range 03-0.4. Additional measurements were performed under heavy traffic conditions at two double kerbside sites located in the centre of Lisbon and Madrid. The OC/EC minimum ratios observed at both sites were found to be between those of the tunnel and those of urban background air, suggesting that minimum values commonly obtained for this parameter in open urban atmospheres over-predict the direct emissions of OC(ff) from road transport. Possible reasons for this discrepancy are explored. (C) 2011 Elsevier Ltd. All rights reserved.

Desenvolvimento do sistema de protecção, monitorização e gestão de baterias de iões de lítio do tipo LiFePO4 para aplicação em veículos eléctricos

A mobilidade é considerada um dos factores chave na sustentabilidade e desenvolvimento de qualquer economia. Em Portugal essa realidade não é diferente. Em 2011 verifica-se que 41% do consumo global de combustíveis pertence ao sector rodoviário [1] o que evidencia a sua relevância na economia do país. No que concerne aos veículos de tracção eléctrica, começaram a surgir nos finais do séc. XIX, e no início do séc. XX nos Estados Unidos da América representavam 38% dos veículos [2]. Diversos factores económicos e tecnológicos conduziram a um crescente desinteresse por parte da indústria em investir na produção deste tipo de veículos. Contudo com a introdução de baterias de iões de lítio em veículos de tracção eléctrica, torna-os viáveis e competitivos. Neste trabalho é proposto o desenvolvimento de um sistema de gestão de baterias de iões de lítio do tipo LiFePO4 para aplicação em veículos eléctricos. O sistema deverá assegurar a protecção das baterias e indicar o estado de carga das mesmas. Este sistema permitirá uma optimização no uso deste género de baterias, proporcionará uma melhor utilização, aumentando a sua vida útil. O sistema irá ser aplicado e testado experimentalmente no veículo eléctrico ecológico (Veeco). No âmbito do projecto Veeco foi projectado e construído um banco de ensaios utilizado na análise do comportamento das baterias, e determinar quais os requisitos necessários para o sistema de gestão desenvolvido. Foi também projectado e realizado um sistema de aquisição e processamento de dados que permite obter informações acerca da bateria, dados que estarão disponíveis no interface Homem-máquina do Veeco.

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.