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1.
Inorg Chem ; 57(23): 14484-14488, 2018 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-30354096

RESUMO

We report here the remarkable catalytic efficiency observed for two Pd(II) azamacrocyclic complexes supported on multiwalled carbon nanotubes (MWCNTs) toward oxygen reduction reactions. Beyond a main (>90%) 4e- process and an onset potential close to or better than those of commercial Pt electrodes, the MWCNTs functionalization strategy, aimed at chemically defined Pd(II)-based catalytic centers, allowed the half-cell to exceed the proton-exchange-membrane fuel-cell reference/target mass activity efficiency set by the U.S. Department of Energy for 2020 (440 mA/mgPGM at 0.9 V vs reversible hydrogen electrode).

2.
Phys Chem Chem Phys ; 18(48): 33142-33151, 2016 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-27892575

RESUMO

This paper focuses on studying the influence of the heat treatment on the structure and activity of carbon supported Fe(ii)phthalocyanine (FePc/C) oxygen reduction reaction (ORR) catalysts under alkaline conditions. The FePc macrocycle was deposited onto ketjen black carbon and heated treated for 2 hours under inert atmosphere (Ar) at different temperatures (400, 500, 600, 700, 800, 900 and 1000 °C). The atomic structure of Fe in each sample has been determined by XAS and correlated to the activity and ORR mechanisms determined in electrochemical half cells and in a complete H2/O2 anion exchange membrane fuel cells (AEM-FC). The results show that the samples prepared at 600 and 700 °C have the highest electrochemical catalytic activity for the ORR, consistent with the findings that the FeN4 active sites are thermally stable up to 700 °C, confirmed by both XANES linear combination fittings and EXAFS fittings. Upon annealing at temperatures above 800 °C, the FeN4 structure partially decomposes to small iron nanoparticles. The transition from the FeN4 structure to metallic Fe results in a significant loss in ORR activity and an increase in the production of undesirable HO2- during catalysis.

3.
J Enzyme Inhib Med Chem ; 30(4): 586-91, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25373500

RESUMO

Carbonic anhydrases (CAs) are widespread metalloenzymes in higher vertebrates including humans. A series of phenolic compounds, including guaiacol, 4-methylguaiacol, 4-propylguaiacol, eugenol, isoeugenol, vanillin, syringaldehyde, catechol, 3-methyl catechol, 4-methyl catechol and 3-methoxy catechol were investigated for their inhibition of all the catalytically active mammalian isozymes of the Zn(2+)-containing CA (EC 4.2.1.1). All the phenolic compounds effectively inhibited human carbonic anhydrase isoenzymes (hCA I, II, IX and XII), with Kis in the range of 2.20-515.98 µM. The various isozymes showed diverse inhibition profiles. Among the tested phenolic derivatives, compounds 4-methyl catechol and 3-methoxy catechol showed potent activity as inhibitors of the tumour-associated transmembrane isoforms (hCA IX and XII) in the submicromolar range, with high selectivity. The results obtained from this research may lead to the design of more effective carbonic anhydrase isoenzyme inhibitors (CAIs) based on such phenolic compound scaffolds.


Assuntos
Inibidores da Anidrase Carbônica/farmacologia , Catecóis/farmacologia , Guaiacol/farmacologia , Isoenzimas/antagonistas & inibidores , Catecóis/química , Guaiacol/química , Humanos
4.
Mar Environ Res ; 65(4): 349-57, 2008 May.
Artigo em Inglês | MEDLINE | ID: mdl-18281086

RESUMO

The present paper assesses the use of the supralittoral amphipod Talitrus saltator as a bioindicator of the effects of human trampling on the supralittoral sandy band. Samplings in delimited areas were carried out at sites subjected to different human impact. The results showed a strong negative correlation between the number of swimmers and the sandhopper population density, while there was no clear relationship between sandhopper abundance and the other factors considered: granulometry, compactness and organic carbon content of the sand, and trace metal contents in the sand and sandhoppers. A field test of trampling conducted in a confined space showed its direct negative effect on sandhopper survival. However, trace metal analysis confirmed the ability of T. saltator to bioaccumulate some elements (Hg, Zn, Cu, Cd). Our study demonstrates that T. saltator is a good bioindicator of human impact in the supralittoral zone of sandy shores.


Assuntos
Anfípodes/fisiologia , Praias , Ecossistema , Atividades Humanas , Dióxido de Silício , Caminhada , Animais , Carbono/análise , Humanos , Metais Pesados/análise , Tamanho da Partícula , Densidade Demográfica , Dióxido de Silício/química , Análise de Sobrevida
5.
Materials (Basel) ; 11(8)2018 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-30110888

RESUMO

The Electrochemical Atomic Layer Deposition (E-ALD) technique is used for the deposition of ultrathin films of bismuth (Bi) compounds. Exploiting the E-ALD, it was possible to obtain highly controlled nanostructured depositions as needed, for the application of these materials for novel electronics (topological insulators), thermoelectrics and opto-electronics applications. Electrochemical studies have been conducted to determine the Underpotential Deposition (UPD) of Bi on selenium (Se) to obtain the Bi2Se3 compound on the Ag (111) electrode. Verifying the composition with X-ray Photoelectron Spectroscopy (XPS) showed that, after the first monolayer, the deposition of Se stopped. Thicker deposits were synthesized exploiting a time-controlled deposition of massive Se. We then investigated the optimal conditions to deposit a single monolayer of metallic Bi directly on the Ag.

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