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131.
Dean A Ferlin MG Brun P Castagliuolo I Badocco D Pastore P Venzo A Bombi GG Di Marco VB 《Dalton transactions (Cambridge, England : 2003)》2008,(13):1689-1697
In view of a possible application to Fe and Al chelation therapy, 2-methyl-3-hydroxy-4-pyridinecarboxylic acid (DT2) was synthesised, and its complex formation, electrochemical and cytotoxic properties were studied. The complexing properties of DT2 towards Fe(III) and Al(III) were investigated in aqueous 0.6 m (Na)Cl at 25 degrees C by means of potentiometric titrations, UV-vis spectrophotometry, and 1H NMR spectroscopy. DT2 is a triprotic acid (H3L+) having pKa1 = 0.47, pKa2 = 5.64 and pKa3 = 11.18. The metal-ligand complexes observed in solution and their corresponding stability constants (log beta values) are the following: FeLH (19.38), FeL (16.01), FeLH(-1) (12.28), FeL2H2 (37.29), FeL3H3 (53.41), FeL3H2 (47.99), FeL3H (41.21) and FeL3 (34.1); AlLH (17.43), AlL2H2 (33.74), AlL2H (27.6), AlL3H3 (48.72), AlL3H2 (42.67), AlL3H (35.8) and AlL3 (27.92). The complex formation between DT2 and Fe(II) was studied by UV-vis: the weak complex FeLH (log beta = 15.8) was detected. DT2 shows a lower complexation efficiency with Fe(III) and Al(III) than that of other available chelators, but higher than that of its non-methylated analogue 3-hydroxy-4-pyridinecarboxylic acid (DT0). The electrochemical behaviour of DT2 was investigated by means of cyclic voltammetry, indicating that the oxidation of the ligand proceeds through a two electron process with a CECE mechanism. Voltammetric curves suggest that the oxidation or the reduction of DT2 in vivo is unlikely. According to the thermodynamic data, also the Fe(III)-DT2 complexes do not undergo redox cycling at physiological pH. Amperometric titrations of solutions containing Fe(III) and DT2 at pH = 5 indicated the same Fe(III) : ligand stoichiometric ratio as calculated from potentiometric data. The toxicity of DT2 and of other simple hydroxypyridinecarboxylic acids was investigated in vitro and no cytotoxic activity was observed (IC50 > 0.1 mM) on cancer cell lines and also on primary human cells, following a three day exposure. 相似文献
132.
We present a Density Functional Theory investigation aimed to model the possible adsorption modes to the TiO(2) surface of two representative TPA-based dyes, termed L0 and rh-L0, having the two mostly employed anchoring groups, namely the cyanoacrylic and rhodanine-3-acetic acids respectively. The bidentate coordination with proton transfer to a nearby surface oxygen is found to be the energetically favored anchoring mode for both dyes. The calculations show that the different dye anchoring groups give rise to a very different electronic coupling between the dye and the manifold of unoccupied semiconductor states, thus implying different electron injection mechanisms. The strongly coupled L0 dye possibly shows an adiabatic electron injection mechanism, while a non-adiabatic electron injection can be foreseen for the weakly coupled rh-L0 dye. The different orientation with respect to the TiO(2) surface for the two classes of dyes, implying different distances of the donor group from the oxide surface, together with the different electron injection mechanisms might account for the faster recombination reaction measured for the rhodanine-based dyes. 相似文献
133.
Couallier EM Payot T Bertin AP Lameloise ML 《Applied biochemistry and biotechnology》2006,133(3):217-238
In beet distilleries, condensates arising from stillage concentration could be recycled as dilution water for the fermentation step, thus preserving groundwater resources and ensuring a quality-controlled water supply. However, the recycling of condensates has been found to cause a significant reduction in fermentation activity. This study aimed to verify that condensates are toxic to alcoholic fermentation. Ten compounds found in condensates (formic, acetic, propionic, butyric, valeric, and hexanoic acids; 2,3-butanediol, furfuryl alcohol, furfural, and 2-phenyl-ethyl-alcohol) were tested. With the exception of 2,3-butanediol, they all proved to be inhibitors. At the same molar concentration, the longer the carbonaceous chain, the stronger the inhibition by fatty acids. An experimental design was used to study the inhibitory characteristics of the 10 compounds at the concentrations found in condensates. Synergistic effects were also confirmed. In real effluents, acetic acid was so highly concentrated that it became the strongest inhibitor. It is therefore necessary to eliminate it before recycling, as well as less concentrated compounds that may accumulate, as illustrated by the simulation. 相似文献
134.
Girlanda L Kievsky A Marcucci LE Pastore S Schiavilla R Viviani M 《Physical review letters》2010,105(23):232502
We report on a study of the nd and n(3)He radiative captures at thermal neutron energies, using wave functions obtained from either chiral or conventional two- and three-nucleon realistic potentials with the hyperspherical-harmonics method, and electromagnetic currents derived in chiral effective field theory up to one loop. The predicted nd and n(3)He cross sections are in good agreement with data, but exhibit a significant dependence on the input Hamiltonian. A comparison is also made between these and new results for the nd and n(3)He cross sections obtained in the conventional framework for both potentials and currents. 相似文献
135.
Protein aggregation and misfolding have important implications in an increasing number of fields ranging from medicine to biology to nanotechnology and material science. The interest in understanding this field has accordingly increased steadily over the last two decades. During this time the number of publications that have been dedicated to protein aggregation has increased exponentially, tackling the problem from several different and sometime contradictory perspectives. This review is meant to summarize some of the highlights that come from these studies and introduce this topical issue on the subject. The factors that make a protein aggregate and the cellular strategies that defend from aggregation are discussed together with the perspectives that the accumulated knowledge may open. 相似文献
136.
The existence of a length threshold, of about 35 residues, above which polyglutamine repeats can give rise to aggregation and to pathologies, is one of the hallmarks of polyglutamine neurodegenerative diseases such as Huntington's disease. The reason why such a minimal length exists at all has remained one of the main open issues in research on the molecular origins of such classes of diseases. Following the seminal proposals of Perutz, most research has focused on the hunt for a special structure, attainable only above the minimal length, able to trigger aggregation. Such a structure has remained elusive and there is growing evidence that it might not exist at all. Here we review some basic polymer and statistical physics facts and show that the existence of a threshold is compatible with the modulation that the repeat length imposes on the association and dissociation rates of polyglutamine polypeptides to and from oligomers. In particular, their dramatically different functional dependence on the length rationalizes the very presence of a threshold and hints at the cellular processes that might be at play, in vivo, to prevent aggregation and the consequent onset of the disease. 相似文献
137.
In living systems, proteins are surrounded by many other macromolecules of different nature, at high total concentrations. In the last few years, there has been an increasing effort to study biological macromolecules directly in natural crowded environments, such as in intact bacterial cells or by mimicking natural crowding by adding proteins, polysaccharides or even synthetic polymers. We have recently proposed hen egg white (HEW) as a suitable, natural medium to study macromolecules in crowding conditions. Here, we show that HEW can increase dramatically the aggregation kinetics of proteins with an in-built tendency to associate. By dissecting the mechanism we demonstrate that only part of this effect is due to crowding, while another factor playing an important role is the interaction with proteins from the milieu. High molecular weight glycoproteins present in HEW act as efficient molecular seeds for aggregation. Our results bear important consequences for in-cell NMR studies and suggest a role of glycosylated proteins in aggregation. 相似文献
138.
Anna Maria Pastore 《Rendiconti del Circolo Matematico di Palermo》1980,29(3):369-410
A principal fibre bundle≈P of 2-osculating frames is constructed on a differentiable manifold, and the connections on≈P are studied. 相似文献
139.
Silvia Capuani Marco Palombo Andrea Gabrielli Augusto Orlandi Bruno Maraviglia Francesco S. Pastore 《Magnetic resonance imaging》2013
Recently, we measured two anomalous diffusion (AD) parameters: the spatial and the temporal AD indices, called γ and α, respectively, by using spectroscopic pulse gradient field methods. We showed that γ quantifies pseudo-superdiffusion processes, while α quantifies subdiffusion processes. Here, we propose γ and α maps obtained in a controlled heterogeneous phantom, comprised of packed micro-beads in water and in excised human meningiomas. In few words, α maps represent the multi-scale spatial distribution of the disorder degree in the system, while γ maps are influenced by local internal gradients, thus highlighting the interface between compartments characterized by different magnetic susceptibility. γ maps were already obtained by means of AD stretched exponential imaging and α-type maps have been recently achieved for fixed rat brain with the aim of highlighting the fractal dimension of specific brain regions. However, to our knowledge, the maps representative of the spatial distribution of α and γ obtained on the same controlled sample and in the same excised tissue have never been compared. Moreover, we show here, for the first time, that α maps are representative of the spatial distribution of the disorder degree of the system. 相似文献
140.
Il Nuovo Cimento D - Electron-electron and electron-ion structural correlations in simple liquid metals are treated by using effective pair potentials to incorporate quantal effects into a... 相似文献