Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals.
View Article and Find Full Text PDFContact with nature can contribute to health and wellbeing, but knowledge gaps persist regarding the environmental characteristics that promote these benefits. Understanding and maximising these benefits is particularly important in urban areas, where opportunities for such contact is limited. At the same time, we are facing climate and ecological crises which require policy and practice to support ecosystem functioning.
View Article and Find Full Text PDFWe demonstrate here through molecular simulations and mutational studies the origin of the enantioselectivity in the photoinduced radical cyclization of α-chloroacetamides catalyzed by ene-reductases, in particular the ene-reductase and the Old Yellow Enzyme 1, which show opposite enantioselectivity. Our results reveal that neither the π-facial selectivity model nor a protein-induced selective stabilization of the transition states is able to explain the enantioselectivity of the radical cyclization in the studied flavoenzymes. We propose a new enantioinduction scenario according to which enantioselectivity is indeed controlled by transition-state stability; however, the relative stability of the prochiral transition states is not determined by direct interaction with the protein but is rather dependent on an inherent degree of freedom within the substrate itself.
View Article and Find Full Text PDFBackground/objectives: Sinonasal inverted papilloma (IP) is a rare but serious diagnosis, with a paucity of patient-centred information regarding this condition. As more patients are seeking healthcare information online, the quality and comprehensibility of this information becomes ever more important. The aim of the study was to investigate the readability and quality of websites on inverted papilloma.
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