Grazina, R, de Sousa PM, Brondino CD, Carepo MS, Moura I, Moura JJ.
2011.
Structural redox control in a 7Fe ferredoxin isolated from Desulfovibrio alaskensis, Aug. Bioelectrochemistry. 82:22-8., Number 1
AbstractThe redox behaviour of a ferredoxin (Fd) from Desulfovibrio alaskensis was characterized by electrochemistry. The protein was isolated and purified, and showed to be a tetramer containing one [3Fe-4S] and one [4Fe-4S] centre. This ferredoxin has high homology with FdI from Desulfovibrio vulgaris Miyazaki and Hildenborough and FdIII from Desulfovibrio africanus. From differential pulse voltammetry the following signals were identified: [3Fe-4S](+1/0) (E(0')=-158+/-5mV); [4Fe-4S](+2/+1) (E(0')=-474+/-5mV) and [3Fe-4S](0/-2) (E(0')=-660+/-5mV). The effect of pH on these signals showed that the reduced [3Fe-4S](0) cluster has a pK'(red)(')=5.1+/-0.1, the [4Fe-4S](+2/+1) centre is pH independent, and the [3Fe-4S](0/-2) reduction is accompanied by the binding of two protons. The ability of the [3Fe-4S](0) cluster to be converted into a new [4Fe-4S] cluster was proven. The redox potential of the original [4Fe-4S] centre showed to be dependent on the formation of the new [4Fe-4S] centre, which results in a positive shift (ca. 70mV) of the redox potential of the original centre. Being most [Fe-S] proteins involved in electron transport processes, the electrochemical characterization of their clusters is essential to understand their biological function. Complementary EPR studies were performed.
Avo, J, Parola AJ, Lima JC, Pina F, Cunha-Silva L.
2011.
Phase transition thermochromism based on C-H acidity of 4-alkylflavylium compounds in Pluronic F-127, 2011. Journal of Materials Chemistry. 21:16628-16637.
AbstractIn moderately acidic water/ethanol solutions, 7-(naphthalen-2-ylmethyl)-5,6-dihydrobenzo[c]xanthen12-ium perchlorate shows C-H proton acidity giving rise to an ethylenic base species, instead of the hydration products of the typical flavylium network of chemical reactions, hemiketal, cis-chalcone and trans-chalcone. The kinetics of this acid-base process is much slower, k(obs)(s(-1)) = 3.5 x 10(-3) + 0.16[H(+)], than those commonly observed for O-H deprotonation. In the presence of the triblock copolymer Pluronic F-127, the ethylenic base is dramatically stabilized shifting the pK(a) from 1.35 (in ethanol : water (1 : 1) to -0.35. Taking profit from the well-described temperature dependence of this polymer, a phase transition thermochromic system was achieved. The system was cycled between 5 and 35 degrees C with negligible changes in absorbance after 20 cycles.
Leydet, Y, Gavara R, Cunha-Silva L, Parola AJ, Pina F.
2011.
Phase-Dependent Photochromism of a Lactone-Stabilized Chromene from a Flavylium Reaction Network, 2011. Chemistry-a European Journal. 17:3663-3671.
AbstractNew trans-2-hydroxychalcones bearing a carboxylate group at position 2' (Ct(-)) were synthesized (compounds 2 and 3). These compounds lead to a network of chemical reactions depending on pH value, light, and solvent. In water, when the pH value is lowered, the ionized trans-chalcone is protonated and the flavylium cation AH(+) is formed at very acidic pH values through hemiketal B and cis-chalcone Cc, with global acidity constants of pK'(a) <= -1 and approximate to 0.1, respectively, for 2 and 3. The electron-acceptor character of the carboxylic substituent not only increases the observed acidity of the flavylium cation, but also decreases the rate of the ring-opening/closing from a subsecond timescale to hours relative to model compound 1 (without carboxylate). The photochemistry of the network was studied in detail by means of continuous irradiation, monitored by UV/Vis absorption and H-1 and C-13 NMR spectroscopic analysis. Although compound 3 is only slightly photoactive, compound 2 (Ct(-)) reacts in aqueous solutions (lambda(irr) = 313 nm) to form B- and Cc(-), with a global quantum yield of 0.15, and fully reverts back to Ct(-) with a rate constant of k = 6.7 x 10(-5) s(-1). The flavylium cation is no longer formed in methanol, and irradiation of Ct(-) leads to the formation of B- and the new lactone-trapped chromene species La. The formation of La takes place through a sequence of three photochemical steps: photoisomerization of Ct(-), photo-ring-closing reaction of Cc , and photolactonization of B-. Only the cis/trans isomerization and ring-closing reactions are thermally reversible on a timescale of seconds and hours, respectively. A photochromic system was achieved in rigid matrices of methanol (at 77 K) and 1-dodecanol (5 degrees C) by irradiating lactone La to give a red ortho-quinone allide through a photo-ring-opening reaction; the color disappears with a rate constant of k = 1.25 x 10(-2) s(-1) in 1-dodecanol at 5 degrees C.
Lopes, T, Amado M, Correia de Freitas J.
2011.
Green Build Design Process, 18 Oct. SB11 World Sustainable Building Conference. , Helsinki
AbstractAll the buildings promote impacts on the environmental and in human health who impose more attention in the evaluation of sustainable performance in building design. The difficulty to identify the better design process to answer to all conflicting factors in special the economical and environmental performance impose the research of the issue. To assist the research in the way to find the best process to the promotion of design alternatives the life cycle analysis methodology is the more adapted the deal with all the three factors of sustainable development. The promotion of a new process to design phase of green build is the goal of this paper.
Amado, M, Lopes T, Correia de Freitas J.
2011.
Indicators to measure sustainability in urban developments, 18 Oct. SB11 World Sustainable Building Conference. , Helsinki
AbstractThe use of indicators to measure sustainability in urban development’s is the most efficient tool to help local authorities in the regulation of new and existing urban areas. The demographic grow in developing countries impose a utilization of a tool who make possible have a clear image of the process of land use change and the evaluation of the capacity of charge is the way to archive a effective sustainable development of the urban areas and regions. The selection of the correct indicators to apply to the process of land use transformation in Cabo Verde is the objective of the paper.
Baptista, PV, Doria G, Quaresma P, Cavadas M, Neves CS, Gomes I, Eaton P, Pereira E, Franco R.
2011.
Nanoparticles in molecular diagnostics. Nanoparticles in Translational Science and Medicine. 104(11)(
Villaverde, Antoni, Ed.).:427-488.: Academic Press Co., Elsevier Publishing Services