Changes of the Membrane Lipid Organization Characterized by Means of a New Cholesterol-Pyrene Probe

We synthesized 3β-hydroxy-pregn-5-ene-21-(1-methylpyrenyl)-20-methylidene (Py-met-chol), consisting of cholesterol steroid rings connected to a pyrene group via a linker without polar atoms. This compound has interesting spectroscopic properties when probing membranes: 1), The pyrene has hypochromic properties resulting from probe self-association processes in membranes. Using liposomes of various lipid compositions, we determined the association constants of the probe (K): KDOPC ≫ KPOPC ≫ KDMPC > KDMPC/15 mol % Chol > KDMPC/30 mol % Chol. This indicates a better probe solvation in saturated than in unsaturated lipids, and this effect is enhanced as the cholesterol concentration increases. 2), The pyrene fluorophore is characterized by monomer (I1–I5) and excimer (IE) emission bands. In model membranes, I1/I3 and IE/I3 ratios revealed a correlation between the polarity of the lipid core of the membrane and the amount of cholesterol. 3), Using this probe, we monitored the first steps of the signaling pathway of the mouse δ-opioid receptor, a G-protein-coupled receptor. The thickness of the membrane around this receptor is known to change after agonist binding. Fluorescence spectra of living Chinese hamster ovary cells overexpressing mouse δ-opioid receptor specifically revealed the agonist binding. These results indicate that Py-met-chol may be useful for screening ligands of this family of receptors

Bismuth(III) chloride catalyzed cycloisomerization of enynes

Several simple bismuth(III) salts were screened for the suitability to catalyze the cycloisomerization of enynes. Among them, BiCl3 gave the best results. Under the optimized reaction conditions, eight substrates were studied, and acceptable to excellent isolated yields were obtained. Consistent with data in the literature, electron-deficient alkynes were found to be better substrates for the reaction than electronrich ones. Because BiCl3 is readily available, inexpensive and environmentally benign, this soft Lewis acid catalyzed isomerization reaction is expected to be a good choice for organic chemists to prepare pyrrolidine derivatives

Bismuth(III) Reagents in Steroid and Terpene Chemistry

Steroid and terpene chemistry still have a great impact on medicinal chemistry. Therefore, the development of new reactions or “greener” processes in this field is a contemporaneous issue. In this review, the use of bismuth(III) salts, as “ecofriendly” reagents/catalysts, on new chemical processes involving steroids and terpenes as substrates will be focused. Special attention will be given to some mechanistic considerations concerning selected reactions