Antioxidative Activity of Ferrocenes Bearing 2,6-Di-Tert-Butylphenol Moieties

The antioxidative activity of ferrocenes bearing either 2,6-di-tert-butylphenol or phenyl groups has been compared using DPPH (1,1-diphenyl-2-picrylhydrazyl) test and in the study of the in vitro impact on lipid peroxidation in rat brain homogenate and on some characteristics of rat liver mitochondria. The results of DPPH test at 20°C show that the activity depends strongly upon the presence of phenolic group but is improved by the influence of ferrocenyl fragment. The activity of N-(3,5-di-tert-butyl-4-hydroxyphenyl)iminomethylferrocene (1), for instance, was 88.4%, which was higher than the activity of a known antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) (48.5%), whereas the activity of N-phenyl-iminomethylferrocene 2 was almost negligible −2.9%. The data obtained demonstrate that the compounds with 2,6-di-tert-butylphenol moiety are significantly more active than the corresponding phenyl analogues in the in vitro study of lipid peroxidation in rat brain homogenate. Ferrocene 1 performs a promising behavior as an antioxidant and inhibits the calcium-dependent swelling of mitochondria. These results allow us to propose the potential cytoprotective (neuroprotective) effect of ditopic compounds containing antioxidant 2,6-di-tert-butylphenol group and redox active ferrocene fragment

Metastable phases and "metastable" phase diagrams

The work discusses specifics of phase transitions for metastable states of substances. The objects of condensed media physics are primarily equilibrium states of substances with metastable phases viewed as an exception, while the overwhelming majority of organic substances investigated in chemistry are metastable. It turns out that at normal pressure many of simple molecular compounds based on light elements (these include: most hydrocarbons; nitrogen oxides, hydrates, and carbides; carbon oxide (CO); alcohols, glycerin etc) are metastable substances too, i.e. they do not match the Gibbs' free energy minimum for a given chemical composition. At moderate temperatures and pressures, the phase transitions for given metastable phases throughout the entire experimentally accessible time range are reversible with the equilibrium thermodynamics laws obeyed. At sufficiently high pressures (1-10 GPa), most of molecular phases irreversibly transform to more energy efficient polymerized phases, both stable and metastable. These transformations are not consistent with the equality of the Gibbs' free energies between the phases before and after the transition, i.e. they are not phase transitions in "classical" meaning. The resulting polymeric phases at normal pressure can exist at temperatures above the melting one for the initial metastable molecular phase. Striking examples of such polymers are polyethylene and a polymerized modification of CO. Many of energy-intermediate polymeric phases can apparently be synthesized by the "classical" chemistry techniques at normal pressure.Comment: 5 pages, 4 figure

1-(8-Bromo-2-methyl-4-thioxo-3,4,5,6-tetra­hydro-2H-2,6-methano-1,3-benzoxazocin-11-yl)ethanone

In the title compound, C14H14BrNO2S, there are two similar non-equivalent mol­ecules in the asymmetric unit, displaying three chiral centres each. In the crystal structure, they are linked by inter­molecular N—H⋯O hydrogen bonds to form infinite chains, which are in turn connected by weak Br⋯H and S⋯H inter­actions

Control of Azomethine Cycloaddition Stereochemistry by CF<inf>3</inf> Group: Structural Diversity of Fluorinated β-Proline Dimers

© 2016 American Chemical Society.β-Proline-functionalized dimers consisting of homochiral monomeric units were synthesized by a non-peptidic coupling method for the first time. The applied synthetic methodology is based on 1,3-dipolar cycloaddition chemistry of azomethine ylides and provides absolute control over the β-proline backbone stereogenic centers. An o-(trifluoromethyl)phenyl substituent contributes to appropriate stabilization of the definite acrylamide chiral cis conformation and to achieve the dipole reactivity that is not observed for aryl groups lacking strong electronegative character

Neutral-ionic phase transition : a thorough ab-initio study of TTF-CA

The prototype compound for the neutral-ionic phase transition, namely TTF-CA, is theoretically investigated by first-principles density functional theory calculations. The study is based on three neutron diffraction structures collected at 40, 90 and 300 K (Le Cointe et al., Phys. Rev. B 51, 3374 (1995)). By means of a topological analysis of the total charge densities, we provide a very precise picture of intra and inter-chain interactions. Moreover, our calculations reveal that the thermal lattice contraction reduces the indirect band gap of this organic semi-conductor in the neutral phase, and nearly closes it in the vicinity of the transition temperature. A possible mechanism of the neutral-ionic phase transition is discussed. The charge transfer from TTF to CA is also derived by using three different technics.Comment: 11 pages, 9 figures, 7 table