Boosting effect of ortho-propenyl substituent on the antioxidant activity of natural phenols.

Seven new antioxidants derived from natural or synthetic phenols have been designed as alternatives to BHT and BHA antioxidants. Influence of various substituents at the ortho, meta and para positions of the aromatic core of phenols on the bond dissociation enthalpy of the ArO-H bond was evaluated using a DFT method B3LYP/6-311++G(2d,2p)//B3LYP/6-311G(d,p). This prediction highlighted the ortho-propenyl group as the best substituent to decrease the bond dissociation enthalpy (BDE) value. The rate constants of hydrogen transfer from these phenols to DPPH radical in a non-polar and non-protic solvent have been measured and were found to be in agreement with the BDE calculations. For o-propenyl derivatives from 2-tert-butyl-4-methylphenol, BHA, creosol, isoeugenol and di-o-propenyl p-cresol, fewer radicals were trapped by a single phenol molecule, i.e. a lower stoichiometric number. Reaction mechanisms involving the evolution of the primary phenoxyl radical ArO are proposed to rationalise these effects.

A glimpse into the early origins of medieval anatomy through the oldest conserved human dissection (Western Europe, 13(th) c. A.D.).

INTRODUCTION: Medieval autopsy practice is very poorly known in Western Europe, due to a lack of both descriptive medico-surgical texts and conserved dissected human remains. This period is currently considered the dark ages according to a common belief of systematic opposition of Christian religious authorities to the opening of human cadavers. MATERIAL AND METHODS: The identification in a private collection of an autopsied human individual dated from the 13(th) century A.D. is an opportunity for better knowledge of such practice in this chrono-cultural context, i.e. the early origins of occidental dissections. A complete forensic anthropological procedure was carried out, completed by radiological and elemental analyses. RESULTS: The complete procedure of this body opening and internal organs exploration is explained, and compared with historical data about forensic and anatomical autopsies from this period. During the analysis, a red substance filling all arterial cavities, made of mercury sulfide (cinnabar) mixed with vegetal oil (oleic and palmitic acids) was identified; it was presumably used to highlight vascularization by coloring in red such vessels, and help in the preservation of the body. CONCLUSIONS: Of particular interest for the description of early medical and anatomical knowledge, this "human preparation" is the oldest known yet, and is particularly important for the fields of history of medicine, surgery and anatomical practice.

Dramatic solvent effect on the synergy between α-tocopherol and BHT antioxidants.

During the DPPH scavenging assay carried out in non polar and non protic solvents, such as toluene, BHT regenerates α-tocopherol from tocopheryl radical, whereas in polar and protic solvents, like methanol, no regeneration is observed due to a fast electron transfer reaction from the tocopheryl radical to the reactive DPPH radical. Surprisingly, in the presence of a small amount of alcohol, the synergy is exalted and BHT regenerates twice as much α-tocopherol due to a nucleophilic addition of short alcohols on the BHT oxidation product, giving a new phenolic co-antioxidant.

The embalmed heart of Richard the Lionheart (1199 A.D.): a biological and anthropological analysis.

During the Middle Ages, the partition of the cadaver of the elite members was a current practice, with highly technical treatment given to symbolic organs such as the heart. Considered mostly from a theoretical point of view, this notion of dilaceratio corporis has never been biologically explored. To assess the exact kind of embalming reserved to the heart, we performed a full biomedical analysis of the mummified heart of the English King Richard I (1199 A.D.). Here we show among other aspects, that the organ has been embalmed using substances inspired by Biblical texts and practical necessities of desiccation. We found that the heart was deposed in linen, associated with myrtle, daisy, mint, frankincense, creosote, mercury and, possibly, lime. Furthermore, the goal of using such preservation materials was to allow long-term conservation of the tissues, and good-smelling similar to the one of the Christ (comparable to the odor of sanctity).