Deciphering the activation sequence of ferrociphenol anticancer drug candidates

The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions.     

Tetraferrocenylporphyrins as active components of self-assembled monolayers on gold surface

Novel tetraferrocenylporphyrins-containing self-assembled monolayers were prepared employing two different approaches. Self-assembled monolayers were characterized using UV-Vis spectroscopy and cyclic voltammetry (CV) whereas their photoelectrochemical properties were investigated by photocurrent generation (PG) experiments.     

Panchromatic Light Harvesting and Stabilizing Charge-Separated States in Corrole–Phthalocyanine Conjugates through Coordinating a Subphthalocyanine

Owing to the electron-donating and -accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively, we designed and developed two novel covalently linked Corr-Pc conjugates. The synthetic route allows the preparation of the target conjugates in satisfying yields. Comprehensive steady-state absorption, fluorescence, and electrochemical assays enabled insights into energy and electron-transfer processes upon photoexcitation. Coordinating a pyridine-appended subphthalocyanine (SubPc) to the Pc of the conjugate sets up the ways and means to realize the first example of an array composed by three different porphyrinoids, which drives a cascade of energy and charge-transfer processes. Importantly, the SubPc assists in stabilizing the charge-separated state, that is, one-electron oxidized Corr and the one electron-reduced Pc, upon photoexcitation by means of a reductive charge transfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of a Corr within electron-donor–acceptor conjugates by means of just photoexcitation. Moreover, the combination of Corr, Pc, and SubPc guarantees panchromatic absorption across the visible range of the solar spectrum, with the SubPc covering the „green gap“ that usually affects porphyrinoids.     

Doping and radiation damage profiles of P+ ions implanted in silicon along the [110] axis

Several doses of 200 KeV phosphorus ions have been implanted under channeling conditions along the [110] direction in silicon.

Range distribution has been determined for the three implant doses 10¹³, 10¹⁴, 10¹⁵ P⁺/cm² both with the electrical measurements and the neutron activation techniques.

The radiation damage distribution has been determined both with 290 KeV proton back-scattering analysis and with transmission electron microscopy (TEM) observations.

Good agreement has been found between electrical and neutron activation profiles in the samples where 100% of the implanted dose had been electrically activated by means of annealing.

Carrier concentration profiles, from samples implanted with 10¹⁵ P⁺/cm², determined after two different annealing temperatures (500°C and 700°C) have bcen compared with the radiation damage distribution and a correlation between damage and phosphorus electrical activation process seems to be possible.

Maximum damage peak, as determined by back-scattering analysis, shifts from ～0.4 μ depth in the lower dose(5 × 10¹⁴ P⁺/cm²), to ～0.22 pm depth in the higher implanted dose (4 × 10¹⁵ P⁺/cm²). Damage distribution of phosphorus ions random implanted in the same experimental conditions shows 3 peak at ～0.2 μn depth.

In accordance with the back-scattering analysis, T.E.M. observations on 10¹⁵P⁺/cm² implanted samples show the presence of amorphous regions at depth between 0.25 and 0.5 μm from the surface. In the most damaged layer ～0.3μm in depth, a surface density of ～10¹²/cm² amorphous regions 25-50 A diameter was observed.     

Unexpected one-pot synthesis of highly conjugated pentacyclic diquinoid compounds

A new class of pentacyclic diquinoid compounds has been synthesized with a facile one-pot reaction of two molecules of 2-hydroxynaphthoquinone and 1-bromoalkanes in the presence of ferrocene. These molecules were isolated as enol tautomers that exhibit intramolecular hydrogen bond and extended electronic conjugation as proved by the intense absorption spectrum with a broad band between 400 and 600 nm. The spectroscopic and electrochemical characterization of this new class of compounds has been performed. One of the synthesized diquinoid derivatives showed a significant cytotoxicity with IC(50) values of 25-50 μM against Cisplatin-Resistant SKOV3 and colon carcinoma SW480 cell lines. The results of our study provide a valuable tool to a one-pot synthesis of highly conjugated polyquinones, analogous to important biological systems, with significant antitumoral activity.     

Solvent effects of ionic liquids: investigation of ferrocenes as electrochemical probes

The redox potentials of ferrocene and decamethylferrocene were determined in a number of molecular and ionic solvents and used as a probe for polarity of room temperature ionic liquids (ILs). No macroscopic solvent property is simply related to redox potentials. Single empirical solvent parameters also are not able to describe the differences in potentials. Instead, Kamlet–Taft multiparameter relationship fits well ferrocenes redox potentials variation, with both molecular solvents and ILs, well describing specific solvent–solute interactions with the two probes. Copyright © 2010 John Wiley & Sons, Ltd.     

The first solvent-free cyclotrimerization reaction of arylethynes catalyzed by rhodium porphyrins

Different rhodium(III) porphyrin chlorides have been used as catalysts for the cyclotrimerization of several arylethynes, giving in many cases high yields in substituted benzenes and selectivities based on the steric hindrance of the macrocycles and on the substitution of the substrates.     

Franck-Condon distribution in the 226 nm band of trimethylene sulfide

The potential function for the ring-puckering vibration of trimethylene sulfide in the lowest excited singlet state is obtained, and the relative intensity distribution in the 226 nm electronic transition calculated. It is concluded that the excitation of the ring-puckering vibration by itself does not account for the intensity of the higher energy peaks that are better assigned as combination bands of ring-puckering and CS stretching modes.     

Low energy ion-beam post hydrogenation of phosphor implanted amorphous silicon films

Glow-discharge-deposited intrinsic hydrogenated amorphous silicon films have been doped by P⁺ implantation in varying doses between 10¹⁶ and 2 × 10²¹ atoms/cm³ and annealed at 260°C. Subsequent hydrogenation of the samples produces a decrease in conductivity explained by a hydrogen-induced decrease of the electrically active fraction of the dopant.