Molecular umbrella-assisted transport of glutathione across a phospholipid membrane.

摘要: A di-walled molecular umbrella (1a) has been synthesized by acylation of the terminal amino groups spermidine with cholic acid, followed condensation bis(3-O-[N-1,2,3-benzotriazin-4(3H)-one]yl)-5,5'-dithiobis-2-nitrobenzoate (BDTNB), and displacement glutathione (gamma-Glu-Cys-Gly, GSH). Replacement sterol hydroxyls sulfate groups, prior to GSH, afforded a hexasulfate analogue 1b. Both conjugates have found enter large unilamellar vesicles (200 nm diameter, extrusion) 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), react entrapped GSH form oxidized (GSSG). Evidence for vesicular entry come from formation (GSSG) within interior vesicle, appearance thiol (USH), absence release into external aqueous phase. Results that obtained monolayer experiments, together fact heavily sulfated conjugate is able cross phospholipid bilayer, yielded strong inferential evidence an "umbrella-like" action these molecules as they lipid bilayer.