Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Bioconversion of D-glucose into D-glucosone by Glucose 2-oxidase from Coriolus versicolor at Moderate Pressures

Glucose 2-oxidase (pyranose oxidase, pyranose: oxygen-2-oxidoreductase, EC 1.1.3.10) from Coriolus versicolor catalyses the oxidation of D-glucose at carbon 2 in the presence of molecular O(2) producing D-glucosone (2-keto-glucose and D-arabino-2-hexosulose) and H(2)O(2). It was used to convert D-glucose into D-glucosone at moderate pressures (i.e. up to 150 bar) with compressed air in a modified commercial batch reactor. Several parameters affecting biocatalysis at moderate pressures were investigated as follows: pressure, [enzyme], [glucose], pH, temperature, nature of fluid and the presence of catalase. Glucose 2-oxidase was purified by immobilized metal affinity chromatography on epoxy-activated Sepharose 6B-IDA-Cu(II) column at pH 6.0. The rate of bioconversion of D-glucose increased with the pressure since an increase in the pressure with compressed air resulted in higher rates of conversion. On the other hand, the presence of catalase increased the rate of reaction which strongly suggests that H(2)O(2) acted as inhibitor for this reaction. The rate of bioconversion of D-glucose by glucose 2-oxidase in the presence of either nitrogen or supercritical CO(2) at 110 bar was very low compared with the use of compressed air at the same pressure. The optimum temperature (55 degrees C) and pH (5.0) of D-glucose bioconversion as well as kinetic parameters for this enzyme were determined under moderate pressure. The activation energy (E(a)) was 32.08 kJmol(-1) and kinetic parameters (V(max), K(m), K(cat) and K(cat)/K(m)) for this bioconversion were 8.8 Umg(-1) protein, 2.95 mM, 30.81 s(-1) and 10,444.06 s(-1)M(-1), respectively. The biomass of C. versicolor as well as the cell-free extract containing glucose 2-oxidase activity were also useful for bioconversion of D-glucose at moderate pressures. The enzyme was apparently stable at moderate pressures since such pressures did not affect significantly the enzyme activity.

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.

On the solubility of three disperse anthraquinone dyes in supercritical carbon dioxide: new experimental data and correlation

Solubility measurements of quinizarin. (1,4-dihydroxyanthraquinone), disperse red 9 (1-(methylamino) anthraquinone), and disperse blue 14 (1,4-bis(methylamino)anthraquinone) in supercritical carbon dioxide (SC CO2) were carried out in a flow type apparatus, at a temperature range from (333.2 to 393.2) K and at pressures from (12.0 to 40.0) MPa. Mole fraction solubility of the three dyes decreases in the order quinizarin (2.9 x 10(-6) to 2.9.10(-4)), red 9 (1.4 x 10(-6) to 3.2 x 10(-4)), and blue 14 (7.8 x 10(-8) to 2.2 x 10(-5)). Four semiempirical density based models were used to correlatethe solubility of the dyes in the SC CO2. From the correlation results, the total heat of reaction, heat of vaporization plus the heat of solvation of the solute, were calculated and compared with the results presented in the literature. The solubilities of the three dyes were correlated also applying the Soave-Redlich-Kwong cubic equation of state (SRK CEoS) with classical mixing rules, and the physical properties required for the modeling were estimated and reported.

Solubility of red 153 and blue 1 in supercritical carbon dioxide

Solubilities of red 153, (3-[[4-[[5,6(or 6,7)-dichloro-2-benzothiazolyl]azo]phenyl]ethylamino]propanenitrile), an azo compound, and disperse blue1 (1,4,5,8-tetraaminoantraquinone) in supercritical carbon dioxide (SC CO(2)) were measured at T = (333.2 to 393.2) K over the pressure range (12.0 to 40.0) MPa by a flow type apparatus. The solubility of red 153 (0.985. 10(-6) to 37.2. 10(-6)) in the overall region of measurements is found to be significantly higher than that of disperse blue 1 (1.12.10(-7) to 4.89.10(-7)). The solubility behavior of disperse red 153 follows the general solubility trend displayed by disperse dyes with a crossover pressure at about 20 MPa. On the other hand, blue 1, which is a disperse anthraquinone dye, exhibits unexpected behavior not recorded previously there is no crossover pressure at the temperature and pressure ranges studied, and the dye's solubility at T = 333.2 K practically does not increase with pressure. To the best of our knowledge, there are no previous measurements of blue 1 solubility in SC CO(2) reported in the literature. The experimental data were correlated by using the Soave Redlich Kwong equation of state (EoS) with the one-fluid van der Waals mixing rule, and an acceptable correlation of the solubility data for both dyes was obtained.

Supercritical carbon dioxide extraction of bioactive compounds from microalgae and volatile oils from aromatic plants

A discussion of the most interesting results obtained in our laboratories, during the supercritical CO(2) extraction of bioactive compounds from microalgae and volatile oils from aromatic plants, was carried out. Concerning the microalgae, the studies on Botryococcus braunii and Chlorella vulgaris were selected. Hydrocarbons from the first microalgae, which are mainly linear alkadienes (C(23)-C(31)) with an odd number of carbon atoms, were selectively extracted at 313 K increasing the pressure up to 30.0 MPa. These hydrocarbons are easily extracted at this pressure, since they are located outside the cellular walls. The extraction of carotenoids, mainly canthaxanthin and astaxanthin, from C. vulgaris is more difficult. The extraction yield of these components at 313 K and 35.0 MPa increased with the degree of crushing of the microalga, since they are not extracellular. On the other hand, for the extraction of volatile oils from aromatic plants, studies on Mentha pulegium and Satureja montana L were chosen. For the first aromatic plant, the composition of the volatile and essential oils was similar, the main components being the pulegone and menthone. However, this volatile oil contained small amounts of waxes, which content decreased with decreasing particle size of the plant matrix. For S. montana L it was also observed that both oils have a similar composition, the main components being carvacrol and thymol. The main difference is the relative amount of thymoquinone, which content can be 15 times higher in volatile oil. This oxygenated monoterpene has important biological activities. Moreover, experimental studies on anticholinesterase activity of supercritical extracts of S. montana were also carried out. The supercritical nonvolatile fraction, which presented the highest content of the protocatechuic, vanilic, chlorogenic and (+)-catechin acids, is the most promising inhibitor of the enzyme butyrylcholinesterase. In contrast, the Soxhlet acetone extract did not affect the activity of this enzyme at the concentrations tested. (C) 2011 Elsevier B.V. All rights reserved.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

Carbon footprint of the academic community of Lisbon School of Health Technology, Portugal

According to the Intergovernmental Panel on Climate Change, the average temperature of the Earth's surface has risen about 1º C in the last 100 years and will increase, depending on the scenario emissions of Greenhouse Gases. The rising temperatures could trigger environmental effects like rising sea levels, floods, droughts, heat waves, hurricanes. With growing concerns about different environmental issues and the need to address climate change, institutions of higher education should create knowledge and integrate sustainability into teaching programs and research programs, as well as promoting environmental issues for society. The aim of this study is to determine the carbon footprint of the academic community of Lisbon School of Health Technology (ESTeSL) in 2013, identifying possible links between the Carbon Footprint and the different socio-demographic variables.

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.

Cooperative effects in the detection of a nitroaliphatic liquid explosive and na explosive taggant in the vapor phase by calix[4]arene-based carbazole-containing conjugated polymers

Two fluorescent molecular receptor based conjugated polymers were used in the detection of a nitroaliphatic liquid explosive (nitromethane) and an explosive taggant (2,3-dimethyl-2,3-dinitrobutane) in the vapor phase. Results have shown that thin films of both polymers display remarkably high sensitivity and selectivity toward these analytes. Very fast, reproducible, and reversible responses were found. The unique behavior of these supramolecular host systems is ascribed to cooperativity effects developed between the calix[4] arene hosts and the phenylene ethynylene-carbazolylene main chains. The calix[4]-arene hosts create a plethora of host-guest binding sites along the polymer backbone, either in their bowl-shaped cavities or between the outer walls of the cavity, to direct guests to the area of the transduction centers (main chain) at which favorable photoinduced electron transfer to the guest molecules occurs and leads to the observed fluorescence quenching. The high tridimensional porous nature of the polymers imparted by the bis-calixarene moieties concomitantly allows fast diffusion of guest molecules into the polymer thin films.

Effects of oxidante acid treatments on carbon-templated hierarchical SAPO-11 materials: synthesis, characterization and catalytic evaluation in n-decane hydroiosomerization

Hierarchical SAPO-11 was synthesized using a commercial Merck carbon as template. Oxidant acid treatments were performed on the carbon matrix in order to investigate its influence on the properties of SAPO-11. Structural, textural and acidic properties of the different materials were evaluated by XRD, SEM, N-2 adsorption, pyridine adsorption followed by IR spectroscopy and thermal analyses. The catalytic behavior of the materials (with 0.5 wt.% Pt, introduced by mechanic mixture with Pt/Al2O3), were studied in the hydroisomerization of n-decane. The hierarchical samples showed higher yields in monobranched isomers than typical microporous SAPO-11, as a direct consequence of the modification on both porosity and acidity, the later one being the most predominant. (C) 2014 Elsevier B.V. All rights reserved.

Low-carbon cement with waste oil-craking catalyst incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Calix[4]arene-carbazole-containing polymers: synthesis and properties

New highly fluorescent calix[4]arene-containing phenylene-alt-ethynylene-3,6- and 2,7-carbazolylene polymers (CALIX-PPE-CBZs) have been synthesized for the first time and their photophysical properties evaluated. Both polymers were obtained in good isolated yields (70-84%), having M-w ranging from 7660-26,700 g mol(-1). It was found that the diethynyl substitution (3,6- or 2,7-) pattern on the carbazole monomers markedly influences the degree of polymerization. The amorphous yellow polymers are freely soluble in several nonprotic organic solvents and have excellent film forming abilities. TG/DSC analysis evidences similar thermal behaviors for both polymers despite their quite different molecular weight distributions and main-chain connectivities (T-g, in the range 83-95 degrees C and decomposition onsets around 270 degrees C). The different conjugation lengths attained by the two polymers dictates much of their photophysical properties. Thus, whereas the fully conjugated CALIX-PPE-2,7-CBZ has its emission maximum at 430 nm (E-g = 2.84 eV; Phi(F) = 0.62, CHCl3), the 3,6-linked counterpart (CALIX-PPE-3,6-CBZ) fluoresces at 403 nm with a significant lower quantum yield (E-g = 3.06 eV; Phi(F) = 0.31, CHCl3). The optical properties of both polymers are predominantly governed by the intrachain electronic properties of the conjugated backbones owing to the presence of calix[4]arenes along the polymer chain which disfavor significant interchain interactions, either in fluid- or solid-state.

Extraction of volatile oil from aromatic plants with supercritical carbon dioxide: experiments and modeling

An overview of the studies carried out in our laboratories on supercritical fluid extraction (SFE) of volatile oils from seven aromatic plants: pennyroyal (Mentha pulegium L.), fennel seeds (Foeniculum vulgare Mill.), coriander (Coriandrum sativum L.), savory (Satureja fruticosa Beguinot), winter savory (Satureja montana L.), cotton lavender (Santolina chamaecyparisus) and thyme (Thymus vulgaris), is presented. A flow apparatus with a 1 L extractor and two 0.27 L separators was built to perform studies at temperatures ranging from 298 to 353 K and pressures up to 30.0 MPa. The best compromise between yield and composition compared with hydrodistillation (HD) was achieved selecting the optimum experimental conditions of extraction and fractionation. The major differences between HD and SFE oils is the presence of a small percentage of cuticular waxes and the relative amount of thymoquinone, an oxygenated monoterpene with important biological properties, which is present in the oils from thyme and winter savory. On the other hand, the modeling of our data on supercritical extraction of volatile oil from pennyroyal is discussed using Sovova's models. These models have been applied successfully to the other volatile oil extractions. Furthermore, other experimental studies involving supercritical CO2 carried out in our laboratories are also mentioned.