Guest-to-host proton transfer in melatonin-beta-cyclodextrin inclusion complex by ionspray, fast atom bombardment and tandem mass spectrometry.

Ionspray (IS) and fast atom bombardment (FAB) positive ionization mass spectrometry (MS) of 1 : 1 beta-cyclodextrin (beta-CD)-melatonin (MLT) host-guest complex allowed the detection of gaseous protonated 1 : 1 beta-CD-MLT. Tandem MS collision-induced dissociation (CID) of such protonated 1 : 1 beta-CD-MLT species showed the proton (charge) to be retained to a significant extent by the host and by its cage fragmentation products, in spite of the higher proton affinity of MLT with respect to that of beta-CD. This requires an endothermic guest-to-host proton transfer to occur within the gaseous association. Collisional activation could be accounted for by the promotion of such an endothermic process; however, the proton affinity decrease of the guest determined by the loss of the elements of acetamide, which is a dominant MS dissociation reaction of pure protonated MLT, could also provide a rationale for such an endothermic guest-to-host proton transfer. This proposal parallels the reaction scheme we had previously formulated for the analogous MS and tandem MS behaviour of 1 : 1 beta-CD-5-methoxytryptamine inclusion complex with the protonated 5-methoxytryptamine guest undergoing deamination.

Interactions of tryptophan and serotonin with biomembrane models: binding to reversed micellar systems of ionic and non ionic surfactants.

The interactions of Tryptophan (TRP) and Serotonin (5-HT), with water-containing sodium bis (2-ethylhexyl) sulfosuccinate (AOT), didodecyldimethylammonium bromide (DDAB) and tetraethylene glycol monododecyl ether (C12E4) reversed micelles have been investigated by UV absorption spectroscopy. Our results suggest that independently of the nature of the surfactant and the amount of the water encapsulated into the micellar core, TRP and 5-HT are solubilized in the micellar phase, preferring to be located in a shallow region constituted by the hydrated surfactant head groups. This is due to the amphiphilic nature of TRP and 5-HT and the biological implications are discussed.