Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals. An experimental and theoretical study.
Axial and equatorial cyclohexylacyl and tetrahydropyranyl-2-acyl radicals gave distinct EPR spectra thanks to surprisingly large beta-hydrogen atom hyperfine splittings that enabled them to be characterized and monitored. DFT computations indicated that the axial species (X = CH(2)) had a higher barrier to rotation about the (O)C(alpha)-C(beta) bond. The computed difference Delta H degrees for the axial and equatorial radicals (R = H, X = CH(2)) was 0.8 kcal mol(-)(1).
Correction: nBu4NI-Mediated oxidation of methyl ketones to α-ketoamides: using ammonium, primary and secondary amine-salt as an amine moiety.
Correction for 'nBu4NI-Mediated oxidation of methyl ketones to α-ketoamides: using ammonium, primary and secondary amine-salt as an amine moiety' by Dan Wang et al., Org. Biomol. Chem., 2017, 15, 3427-3434.
Cross talk between redox signalling and metabolic activity of osteoblasts and fibroblasts in the presence of hydroxyapatite-based biomaterials influences bone regeneration
Regeneration of bone tissue defects that result from metabolic disorders, including periodontal diseases, can be supported by biomaterials based on hydroxyapatite. Despite of good biocompatibility of biomaterials they can cause oxidative stress and inflammatory processes as a result of mechanical interaction with surrounding tissues. Because osteoblasts are responsible for bone regeneration process in which gingival fibroblasts may also participate, the aim of the work was to investigate the influence of hydroxyapatite-based biomaterials (allogeneic and xenogeneic) and biomaterials combined with enamel matrix derivative (Emdogain) on osteoblast and fibroblast redox balance in the context of osteoblast proliferation and differentiation.
The results showed that examined substitutes were not cytotoxic in vitro, but affected redox balance of osteoblasts and fibroblasts (ROS level increase and GSH level decrease) which led to oxidative stress (MDA and protein carbonyl groups level increase) resulting in an increase of the Nrf2 and NFκB expression. The consequence of these changes was partial inhibition of proliferation and osteoblast differentiation. Emdogain alone and combined with biomaterials decreased ROS generation and increased GSH level in both osteoblasts and fibroblasts leading to reduction of transcription factors expression especially proinflammatory NFκB, which promoted osteoblast differentiation and mineralization process.