Estimation of standard reduction potentials of alkyl radicals involved in atom transfer radical polymerization

The redox properties of some alkyl radicals, which are important in atom transfer radical polymerization both as initiators and mimics of the propagating radical chains, have been investigated in CH₃CN by an indirect electrochemical method based on homogeneous redox catalysis involving alkyl halides (RX) and electrogenerated aromatic or heteroaromatic radical anions (D⁻). Dissociative electron transfer between RX and D⁻ yields an intermediate radical (R), which further reacts with D⁻ either by radical coupling or by electron transfer. Examination of the competition between these reactions, which depends on ED/D−°, allows determination of the standard reduction potential of R as well as the self-exchange reorganization energy λR/R⁻. The standard reduction potentials obtained for the radicals CH₂CN, CH₂CO₂Et and CH(CH₃)CO₂Me are −0.72 ± 0.06, −0.63 ± 0.07 and −0.66 ± 0.07 V vs. SCE, respectively. Quite high values of λR/R⁻ (from 122 to 164 kJ mol⁻¹) were found for all radicals, indicating that a significant change of structure accompanies electron transfer to R.     

Diffusivity of anion vacancies in WO3 passive films

The WO₃ films were grown in 0.1 M HClO₄ aqueous solution, at different formation potentials (E_f) in the range of 2.0-7.0 V versus sce, on W electrode. The anion diffusion coefficient (DO) of WO₃ films was calculated from EIS spectra, following the surface charge approach (at high-field limit approximation), the Point Defect Model and the Mott-Shottky analysis. Among the parameters necessary to evaluate DO, the half-jump distance (a) is very relevant, given that a small variation in a has a great impact in the calculation of DO. In this work, it is proposed the half-jump distance (a) should be evaluated from spectroscopic data (available in the literature). The value of a (∼1.9 Å) is taken from lattice constants of a-WO₃ (amorphous-WO₃), with different values of N (coordination number), and the lattice constants of m-WO₃ (monoclinic-WO₃). The calculated value of DO was ∼3 × 10⁻¹⁷ cm²/s.     

Electrochemical investigation of superoxide anion scavenging ability of 1,2,3-triketohydrindene hydrate in aprotic solvents

1,2,3-Triketohydrindene hydrate (NHy) shows well-defined redox electrochemistry in the formation of monoanionic radical (NHy⁻) and dianion (NHy²⁻) in nitrogen saturated aprotic solvents such as acetonitrile and dimethylsulfoxide. Cyclic voltammetry reveals that in an oxygen-saturated solution of DMSO, the oxidation peak of superoxide anion (O₂⁻) at −0.7 V versus Ag/AgCl wire electrode, decreases systematically with increasing NHy concentration. The similar behaviour is observed in the rotating disk voltammetry. On Pt disk, oxygen is reduced to O₂⁻ at a constant potential of −0.8 V and at Pt ring, O₂⁻ is oxidised to oxygen and the corresponding limiting current plateau in the ring voltammogram is decreased linearly as [NHy] is increased. In aqueous solutions, NHy is found to exhibit completely different redox chemistry due to its structural changes and hence showed no favourable redox potentials for efficient quenching of O₂⁻.     

In situ ESR spectroscopic evidence of the spin-trapped superoxide radical, O2, electrochemically generated in DMSO at room temperature

Superoxide radical (O₂⁻) was both electrochemically generated and detected at room temperature. In situ ESR spectroelectrochemistry with spin trapping was used for the radical detection. That is, the O₂⁻ radical was obtained in a DMSO solution under cyclic voltammetry conditions as soon as the potential of the dioxygen electroreduction was reached. This radical reacted then with a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) spin-trap reagent present in solution to form the DMPO-OOH adduct. The hyperfine coupling constants determined for the adduct were a_N = 1.285 mT, and in accord to those reported in literature.     

Study on the oxidation of C4-phenolic-1,4-dihydropyridines and its reactivity towards superoxide radical anion in dimethylsulfoxide

Electrochemical characterization on glassy carbon electrode (GCE) and reactivity with superoxide radical anion in aprotic medium of three new synthesized C4-phenolic-1, 4-dihydropyridines is reported.Voltammetry, coulometry, controlled-potential electrolysis (CPE), UV-vis spectroscopy, ¹H NMR techniques were employed for the characterization of title compounds.The oxidation mechanism involves initially an oxidation process on the phenol moiety with the formation of the corresponding quinone followed by a second one affecting the dihydropyridine ring to give the pyridine derivative. Both processes appeared irreversible in character.Cyclic voltammetry was used to generate O₂⁻ by reduction on GCE of molecular oxygen in DMSO. The reactivity of DHPs towards O₂⁻ was directly measured by the anodic current decay of the radical in the presence of increasing concentration of tested 1,4-dihydropyridines and compared with the reaction of the reference antioxidant, Trolox. The linear correlations obtained between the anodic current of O₂⁻ and compound concentrations in the range between 0.01 mM and 1.00 mM allowed the determination of both the DHP antioxidant index (AI) and the concentrations needed to consume 50% of O₂⁻. Synthesized C4-phenolic 1,4-dihydropyridines exhibited significant scavenging capacity towards superoxide radical anion higher than Trolox and tested commercial 1,4-dihydropyridines.     

ESR spectra of spin probe in PPO membrane

Poly(phenylene oxide) (PPO) polymer's membranes (dense) were prepared by blending spin probes (TEMPO, 5-, 12- and 16-doxylstearic aid) in the casting solution used for the preparation of membranes. It was noticed that the shape and size of the probe influence the ESR spectra of the NO radical in the poly(phenylene oxide)membrane. Unexpectedly, from the shape of the ESR signal it was noticed that of the NO radical of TEMPO in PPO membrane was more mobile than in water media. However, the motion of the NO radical of 16-doxylstearic acid was higher than NO of 5- and 12-doxylstearic acid when the radicals were in the PPO membrane. This could be due to the inductive effect from COOH group. The Hamiltonian parameters of the ESR signal indicated that all the probes were not randomly distributed in PPO membrane, but some probes were in orderly fashion.