Luminescent alkynyl-gold(I) coumarin derivatives and their biological activity

The synthesis and characterization of three propynyloxycoumarins are reported in this work together with the formation of three different series of gold(I) organometallic complexes. Neutral complexes are constituted by water soluble phosphines (PTA and DAPTA) which confer water solubility to them. The X-ray crystal structure of 7-(prop-2-in-1-yloxy)-1-benzopyran-2-one and its corresponding dialkynyl complex is also shown and the formation of rectangular dimers for the gold derivative in the solid state can be observed. A detailed analysis of the absorption and emission spectra of both ligands and complexes allows us to attribute the luminescent behaviour to the coumarin organic ligand. Moreover, the presence of the gold(I) metal atom seems to be responsible for an increase of coumarin phosphorescence emission. The biological activity of the complexes showed that the anionic complexes triggered strong cytotoxic effects in two different cell lines whereas the neutral gold alkynyl complexes led to lower effects against tumor cell growth. Thioredoxin reductase (TrxR) inhibition was very strong in the case of the neutral complexes (IC50 values below 0.1 μM) but moderate for the anionic complexes (IC50 values above 0.8 μM).

The potential to combine aqueous two-phase extraction (ATPE) with magnetic separation was here investigated with the aim of developing a selective non-chromatographic method for the purification of antibodies from cell culture supernatants. Aqueous two-phase systems (ATPS) composed of polyethylene glycol (PEG) and dextran were supplemented with several surface modified magnetic particles (MPs) at distinct salt concentrations. The partition of pure human IgG in the upper and lower phases as well as the amount adsorbed at the MPs surface was investigated, indicating that MPs coated with dextran and gum Arabic established the lowest amount of non-specific interactions. The binding capacity of gum arabic coated particles modified with aminophenyl boronic acid (GA-APBA-MP) was were found to be excellent in combination with the ATPS system, yielding high yields of antibody recovery (92%) and purity (98%) from cell culture supernatants. The presence of MPs in the ATPS was found to speed up phase separation (from 40 to 25 min), to consume a lower amount of MPs (half of the amount needed in magnetic fishing) and to increase the yield and purity of a mAb purified from a cell culture supernatant, when compared with ATPE or magnetic fishing processes alone.

The urgent need for non-toxic and abundant thermoelectric materials has become a significant motivation to improve the figures of merit of metal oxides in order to remove the barrier towards their widespread use for thermoelectric applications. Here we show the influence of a Cr layer in boosting the thermoelectric properties of vanadium pentoxide (V2O5) thin films, deposited by thermal evaporation and annealed at 500 °C. The Cr to V2O5 thickness ratio controls the morphological and thermoelectric properties of the thin films produced. The optimized Seebeck coefficient and power factor values at room temperature are +50 μV K−1 and 7.9 × 10−4 W m−1 K−2, respectively. The nanograin structure of the films is responsible for an improvement in the electrical conductivity up to 3 × 105 (Ω m)−1 with a typical thermal conductivity of 1.5 W m−1 K−1. These results combine to yield promising p-type thermoeletric CrV2O5 thin films with a ZT of 0.16 at room temperature.

The purple bacterium Rhodopseudomonas palustris TIE-1 expresses multiple small high-potential redox proteins during photoautotrophic growth, including two high-potential iron-sulfur proteins (HiPIPs) (PioC and Rpal_4085) and a cytochrome c2. We evaluated the role of these proteins in TIE-1 through genetic, physiological, and biochemical analyses. Deleting the gene encoding cytochrome c2 resulted in a loss of photosynthetic ability by TIE-1, indicating that this protein cannot be replaced by either HiPIP in cyclic electron flow. PioC was previously implicated in photoferrotrophy, an unusual form of photosynthesis in which reducing power is provided through ferrous iron oxidation. Using cyclic voltammetry (CV), electron paramagnetic resonance (EPR) spectroscopy, and flash-induced spectrometry, we show that PioC has a midpoint potential of 450 mV, contains all the typical features of a HiPIP, and can reduce the reaction centers of membrane suspensions in a light-dependent manner at a much lower rate than cytochrome c2. These data support the hypothesis that PioC linearly transfers electrons from iron, while cytochrome c2 is required for cyclic electron flow. Rpal_4085, despite having spectroscopic characteristics and a reduction potential similar to those of PioC, is unable to reduce the reaction center. Rpal_4085 is upregulated by the divalent metals Fe(II), Ni(II), and Co(II), suggesting that it might play a role in sensing or oxidizing metals in the periplasm. Taken together, our results suggest that these three small electron transfer proteins perform different functions in the cell.

This study addresses for the first time the issue of pigeon (genus Columba) phylogeny within the archipelagos of Madeira ( Columba trocaz) and Azores ( C. palumbus azorica), located in the singular biogeographic area of Macaronesia. The phylogeny of these endemic pigeons was inferred based on mitochondrial (cytochrome b and cytochrome c oxidase I) and nuclear ($\beta$-fibrinogen intron 7) genetic markers through multiple approaches. Despite the non-monophyletic pattern for the insular endemic species recovered in the phylogenies, topology tests presented somewhat different results. C. trocaz, the Madeiran endemic species, clustered strongly with the Canarian endemic C. bollii, and these two are thus more closely related to each other than C. bollii to C. junoniae, the other endemic species of Canary Islands, which seems to have diverged independently. Moreover, C. trocaz was found to be phylogenetically closer to C. bollii than to C. palumbus from mainland Europe and Azores Islands. No genetic differentiation was found between the continental C. p. palumbus and the endemic C. p. azorica, which suggests a relatively recent colonisation event of the Azores Islands. (English) [ABSTRACT FROM AUTHOR]

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The increase of conductivity of electrolytes favors the current production in microbial fuel cells (MFCs). Adaptation of cell cultures to higher ionic strength is a promising strategy to increase electricity production. The bacterium Geobacter sulfurreducens is considered a leading candidate for MFCs. Therefore, it is important to evaluate the impact of the ionic strength on the functional properties of key periplasmic proteins that warrants electron transfer to cell exterior. The effect of the ionic strength on the functional properties of triheme cytochrome PpcA, the most abundant periplasmic cytochrome in G. sulfurreducens, was investigated by NMR and potentiometric methods. The redox properties of heme IV are the most affected ones. Chemical shift perturbation measurements on the backbone NMR signals, at increasing ionic strength, also showed that the region close to heme IV is the most affected due to the large number of positively charged residues, which confer a highly positive electrostatic surface around this heme. The shielding of these positive charges at high ionic strength explain the observed decrease in the reduction potential of heme IV and shows that PpcA was designed to maintain its functional mechanistic features even at high ionic strength.

In this work we calculate photoionization and X-ray production cross-sections (XPCS) of M-shell vacancies in Hg at incident photon energy of 5.96 keV (low.

Responsible Research and Innovation (RRI) is a normative concept that has captured considerable attention on the Science and Technology (S&T) policy level, but also in academic discourses. It represents a new approach to how science, innovation and research can be shaped in accordance with societal values that builds directly on the concepts and methodologies of Technology Assessment (TA). The definition and operationalization aspects of RRI remain still unclear although key ingredients such as ethical acceptability are well established in S&T debates and embrace a spectrum of standard methodological approaches. In this paper we review the conceptual debate on RRI with a focus on its constituent parts. We then present a functional comparison between RRI and TA that proves the considerable conceptual overlap in the two approaches. We argue that TA methodologies and precepts should be employed as key operationalisational features in RRI. Finally we argue for a global perspective on RRI by describing a case study on global ethics in S&T that introduces an analytical framework for ethics debates.

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