Although the brain controls all main metabolic pathways in the whole organism, its lipid metabolism is partially separated from the rest of the body. Circulating lipids and other metabolites are taken up into brain areas like the hypothalamus and are locally metabolized and sensed involving several hypothalamic cell types. In this study we show that saturated and unsaturated fatty acids are differentially processed in the murine hypothalamus. The observed differences involve both lipid distribution and metabolism. Key findings were: (i) hypothalamic astrocytes are targeted by unsaturated, but not saturated lipids in lean mice; (ii) in obese mice labeling of these astrocytes by unsaturated oleic acid cannot be detected unless β-oxidation or ketogenesis is inhibited; (iii) the hypothalamus of obese animals increases ketone body and neutral lipid synthesis while tanycytes, hypothalamic cells facing the ventricle, increase their lipid droplet content; and (iv) tanycytes show different labeling for saturated or unsaturated lipids. Our data support a metabolic connection between tanycytes and astrocytes likely to impact hypothalamic lipid sensing. GLIA 2017;65:231-249.
The singlet oxygen reaction with trisubstituted E‐allylic alcohols resulted in the unselective formation of regioisomeric secondary and tertiary allylic hydroperoxides. Increasing the steric demand at the allylic hydroxymethyl group leads to a moderate large‐group effect that can be strongly enhanced by deprotonation of a dimethylated allylic alcohol and even more pronounced by cation complexation. The presence of alkoxide groups did additionally alter the diastereoselectivity of the singlet oxygen ene reactions with chiral allylic alcohols. The molecular combination of Michael ester and enol ether in α‐alkoxy ester substrates made possible the design of chemoselective substrates for singlet oxygen ene versus [2+2] cycloaddition, e. g. a 3,3‐dimethylated Michael ester as a selective substrate for the ene reaction and an adamantyl analogue as a selective 2+2 substrate. The Z/E‐monomethylated substrates as probes for cis regioselectivity revealed that there is no site preference for Z‐alkoxy hydrogen transfer on the way to the corresponding ene product.
The Front Cover shows a cartoon of the hydrogen‐transfer process initiating the singlet oxygen ene reaction with several strong regio‐ and stereodirecting effects following the rule of thumb: If you give singlet oxygen your little finger it will soon have your whole hand (as adapted from a quote by Sigmund Freud). More information can be found in the Article by M. Kleczka et al on page 964 in Issue 11, 2018 (DOI: 10.1002/cptc.201800133).
The front cover artwork is provided by Axel Griesbeck and Diana But at the University of Cologne (Germany). The image shows a cartoon of the hydrogen‐transfer process initiating the singlet oxygen ene reaction with several strong regio‐ and stereodirecting effects following the rule of thumb: If you give singlet oxygen your little finger it will soon have your whole hand (as adapted from a quote by Sigmund Freud). Read the full text of the Article athttps://doi.org/10.1002/cptc.201800133.
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