We have prepared self-assembled monolayers (SAMs) of 4-aminothiophenol (4-ATP) and 1-(4-mercaptophenyl)-2,6-diphenyl-4-(4-pyridyl)pyridinium tetrafluoroborate (MDPP) functionalized with iron phthalocyanine (FePc) and copper phthalocyanine (CuPc) adsorbed on gold (111) electrodes. The catalytic activity of these SAMs/MPc was examined for the reduction of O 2 in aqueous solutions and compared to that of bare gold and with gold coated directly with preadsorbed MPc molecules. Scanning tunneling microscopy (STM) studies confirm the functionalization of the 4-ATP by MPc. STM images reveal that iron phthalocyanine molecules are chemically anchored to 4-aminothiophenol organic monolayers, probably having an "umbrella" type orientation with regards to the surface. The electrocatalytic studies carried out with Au/4-ATP/FePc and Au/ MDPP/FePc electrodes show that the O 2 reduction takes place by the transfer of 4-electron to give water in contrast to a 2-electron transfer process observed for the bare gold. The modified electrode obtained by simple adsorption of FePc directly to the Au(111) surface still promotes the 4-electron reduction process, but it shows a lower activity than the electrodes involving SAMs with FePc molecules positioned at the outmost portion of the selfassembled monolayers. The activity of the electrodes increases as follow: Au < Au/FePc < Au/4-ATP/FePc < Au/MDPP/FePc with the highest activity when FePc molecules are more separated from the Au surface. In contrast, the less active CuPc shows almost the same activity in all three configurations. Theoretical calculations suggest the importance of the back-bonding into the adduct formation, showing the relevance of the supporting gold surface on the electron-transfer process mediated by anchoring ligands.
An analysis of the antibacterial activities of 15 terpenoids, eleven of which were previously described by us and four were extracted from the literature, suggested two structural requirements for activity of these and related compounds: a hydrophobic moiety, consisting of a substituted decalin skeleton, and a hydrophilic region possessing one hydrogen-bond-donor group. These structural requirements are responsible for an optimal insertion of these and related compounds into cell membranes, as suggested by the results of docking some of these compounds into a model phospholipid bilayer.
We
have been able to “tune” the electrocatalytic
activity of iron phthalocyanine (FePc) and iron hexadodecachlorophthalocyanine
(16(Cl)FePc) for the oxygen reduction reaction (ORR) by manipulating
the “pull effect” of pyridinium molecules axially bounded
to the phthalocyanine complexes (FePcs). These axial ligands play
both the role of molecular anchors and also of molecular wires. The
axial ligands also affect the reactivity of the Fe metal center in
the phthalocyanine. The “pull effect” originates from
the positive charge located on the pyridinium core. We have explored
the influence of the core positions (Up or Down), in two structural
pyridiniums isomers on the activity of FePc and 16(Cl)FePc for the
ORR. Of all self-assembled catalysts tested, the highest catalytic
activity was exhibited by the Au(111)/Up/FePc system. XPS measurements
and DFT calculations showed that it is possible to tailor the FePc–N(pyridiniums)
Fe–O2 binding energies, by changing the core positions
and affecting the “pull effect” of pyridiniums. This
affects directly the catalytic activity of FePcs. The plot of activity
as (log I)E versus the calculated Fe–O2 binding energies gives an activity volcano correlation, indicating
that an optimum binding energy of O2 with the Fe center
provides the highest activity.
An attempt has been made in order to unify the three types of solvatochromisms (negative, positive and inverted) of phenolate betaine dyes by a working model which describes them as particular cases of a general behavior. The model, based on the calculation (gas phase) of the chemical hardness of donor and acceptor fragments, was applied to 56 examples from the literature. As a result, the investigated compounds were grouped according to the sum of the hardnesses of their (non-interacting) fragments, this sum being larger for a negative, intermediate for an inverted, and smaller for a positive solvatochromic behavior.
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