A novel flexible tripodal ligand derived from 3-methylindole, ("InTREN" L), and its mononuclear Zn(II), Cu(II), Ni(II), Hg(II) and Pd(II) complexes are described. All compounds gave analytically pure solid samples. Characterisation of the compounds was accomplished by (1)H NMR, IR and absorption spectroscopies, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and elemental analysis and their geometry optimized using density functional theory (DFT).Time-dependent-density functional theory (TD-DFT) calculations have been used to assign the lowest energy absorption bands of the free ligand and the Zn(II) complex. The system is a very good candidate for in situ recognition/coordination effects by MALDI-TOF-MS spectrometry and absorption spectroscopy. The presence of three indole groups in InTREN opens up the possibility to synthesize new three-dimensional self-assembly supramolecular structures. (C) 2008 Elsevier B.V. All rights reserved.

A presente dissertação surge pelo interesse em estudar a adequação do uso de sistemas solares fotovoltaicos na electrificação de serviços primários em povoados remotos nos países Africanos mais carenciados. A abordagem teórica tem como objectivo principal reflectir sobre a importância destas aplicações intervindo naquelas que são consideradas as maiores dificuldades dos países subdesenvolvidos, ou seja, saneamento básico, serviços de saúde e meios de comunicação adequados. Nesse contexto estuda-se a viabilidade de alimentar com energia eléctrica produzida localmente unidades sanitárias na província de Sofala (Moçambique). O trabalho exigiu por isso um estudo de caso baseado numa dessas unidades. Mediante a análise das amostras recolhidas para esta investigação elaborou-se através de ferramentas informáticas um dimensionamento e uma modelação adequadas ao sistema fotovoltaico a ser implementado. Os resultados obtidos de acordo com os requisitos da unidade sanitária permitiram dimensionar os elementos do sistema bem como, simular hora a hora o seu funcionamento diário ao longo do ano. Uma vez provada a sua viabilidade incluiuse ainda neste trabalho um anteprojecto da instalação.

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Let \(\alpha,\beta\in(0,1)\) and
\[
K^{\alpha,\beta}:=\left\{a\in L^\infty(\mathbb{T}):\
\sum_{k=1}^\infty |\widehat{a}(-k)|^2 k^{2\alpha}<\infty,\
\sum_{k=1}^\infty |\widehat{a}(k)|^2 k^{2\beta}<\infty
\right\}.
\]
Mark Krein proved in 1966 that \(K^{1/2,1/2}\) forms a Banach algebra. He also observed that this algebra is important in the asymptotic theory of finite Toeplitz matrices. Ten years later, Harold Widom extended
earlier results of Gabor Szegö for scalar symbols and established the asymptotic trace formula
\[
\operatorname{trace}f(T_n(a))=(n+1)G_f(a)+E_f(a)+o(1)
\quad\text{as}\ n\to\infty
\]
for finite Toeplitz matrices \(T_n(a)\) with matrix symbols \(a\in K^{1/2,1/2}_{N\times N}\). We show that if \(\alpha+\beta\ge 1\) and \(a\in K^{\alpha,\beta}_{N\times N}\), then the Szegö-Widom asymptotic trace formula holds with \(o(1)\) replaced by \(o(n^{1-\alpha-\beta})\).

A mixture of 70% (w/w) pine biomass and 30% (w/w) plastics (mixture of polypropylene, polyethylene, and polystyrene) was subjected to pyrolysis at 400 °C, for 15 min, with an initial pressure of 40 MPa. Part of the solid residue produced was subjected to extraction with dichloromethane (DCM). The extracted residue (residue A) and raw residue (residue B) were analyzed by weight loss combustion and submitted to the leaching test ISO/TS 21268-2 using two different leachants: DCM (0.2%, v/v) and calcium chloride (0.001 mol/L). The concentrations of the heavy metals Cd, Cr, Ni, Zn, Pb and Cu were determined in the eluates and in the two residues. The eluates were further characterized by determining their pH and the concentrations of benzene, toluene, ethylbenzene and xylenes (BTEX). The presence of other organic contaminants in the eluates was qualitatively evaluated by gas chromatography, coupled with mass spectrometry. An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Ecotoxicity (CEMWE). Residue A was not considered to be ecotoxic by the ecotoxicological criterion (EC50 (30 min) ≥10%), but it was considered to be ecotoxic by the chemical criterion (Ni ≥ 0.5 mg/L). Residue B was considered to be ecotoxic by the ecotoxicological criterion: EC50 (30 min) ≤ 10%. Besides that, residue B was considered to be hazardous according the European legislation (BTEX concentrations higher than 100 ppb). The results indicate that volatile organic contaminants can be present in sufficient amounts in these residues and their eluates to induce ecotoxicity levels. The extraction of the pyrolysis residue with DCM was an efficient method for removing lighter organic contaminants.

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The co-combustion of sewage sludge (SS) and coal is widely used for the treatment and thermal valorization of SS produced in wastewater treatment plants. The chemical and ecotoxicological properties of the ashes produced in this thermal treatment have not been fully studied. Two combustion tests were performed in a fluidized bed combustor. Colombian coal was used as fuel in test A. A blend (1 + 1) of this coal and a stabilized SS (Biogran®) was used in a second test B. Samples of the bottom and fly ashes trapped in two sequential cyclones were collected. The characterization of the ashes was focused on two main aspects: (1) the bulk content of a set of metals and (2) the characterization of eluates produced according to the European Standard leaching test EN 12457-2. The eluates were submitted to an ecotoxicological characterization for two bio-indicators. In what concerns the bulk content of ashes, both combustion tests have produced ashes with different compositions. The ashes formed during the co-combustion test have shown higher concentrations of metals, namely Cr, Cu, Ni, Pb, Zn and Fe for all ashes. The leaching test has shown low mobility of these elements from the by-products produced during the combustion and co-combustion tests. Cr and Cr(VI) were mainly detected in the eluates of the 1st cyclone ashes produced in both combustion tests and in the 2nd cyclone ashes produced in the co-combustion test.

Considering the ecotoxicity assays, the eluates of bottom and fly ashes for both combustion and co-combustion tests have shown low ecotoxic levels. The micro-crustacean Daphnia magna was generally more sensitive than the bacterium Vibrio fischeri. CEMWE criterion has allowed to classify the bottom ashes for both combustion and co-combustion tests as non-toxic residues and the fly ashes collected in both cyclones as toxic.

A method for the determination of 15 aromatic hydrocarbons in eluates from solid residues produced during the co-pyrolysis of plastics and pine biomass was developed. In a first step, several sampling techniques (headspace solid phase microextraction (HS-SPME), static headspace sampling (HS), and dispersive liquid–liquid microextraction (DLLME) were compared in order to evaluate their sensitivity towards these analytes. HS-SPME and HS sampling had the better performance, but DLLME was itself as a technique able to extract volatiles with a significant enrichment factor.

HS sampling coupled with GC–MS was chosen for method validation for the analytes tested. Calibration curves were constructed for each analyte with correlation coefficients higher than 0.999. The limits of detection were in the range of 0.66–37.85 ng/L. The precision of the HS method was evaluated and good repeatability was achieved with relative standard deviations of 4.8–13.2%. The recoveries of the analytes were evaluated by analysing fortified real eluate samples and were in the range of 60.6–113.9%.

The validated method was applied in real eluate samples. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the compounds in higher concentrations.

The DLLME technique coupled with GC–MS was used to investigate the presence of less volatile contaminants in eluate samples. This analysis revealed the presence of significant amounts of alkyl phenols and other aromatic compounds with appreciable water solubility.

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