The interaction of melatonin with water containing either sodium bis (2-ethylhexyl) sulfosuccinate (AOT) or soybean phosphatidylcholine (lecithin) reversed micelles has been investigated by UV absorption spectroscopy, at a molar ratio of melatonin:surfactant 1:800 for AOT and 1:400 for lecithin reversed micelles, and by varying the water:surfactant molar ratio (R). Our results suggest that in the presence of domains from apolar organic solvent to surfactant and to water, melatonin positions itself in the micellar phase, with a preferential location in the surfactant polar head group domain, independent of the nature of the surfactant and the amount of water encapsulated into the micellar core. Effects are due to the hydrophilic and lipophilic moieties of melatonin. The effectiveness of melatonin as an electron donor and free radical scavenger has been recently recognized. While supporting the hypothesis that melatonin may provide antioxidant protection without the benefit of receptors, present findings may suggest that the molecule could easily scavenge aqueous as well as lipophilic radicals.

The state of melatonin confined in dry cholesterol/lecithin mixed reversed micelles dispersed in CCl4 was investigated using 1H-NMR and FT-IR spectroscopies as a function of the melatonin to lecithin molar ratio (R(MLT)) and of the cholesterol to lecithin molar ratio (R(CHL)). An analysis of experimental results leads to the hypothesis that, independent of R(MLT) and as a consequence of anisotropic melatonin/lecithin, melatonin/cholesterol and cholesterol/lecithin interactions, melatonin is totally solubilized in reversed micelles. Melatonin is mainly located in and oriented in the nanodomain constituted by the hydrophilic groups of cholesterol and lecithin. A competition of melatonin and cholesterol for the hydrophilic binding sites of the reversed micelles was observed by changing the R(CHL). Some possible biological implications of the specific interactions governing the solubilization process, the preferential location and the peculiar properties of melatonin confined in cholesterol/lecithin mixed reversed micelles are discussed.

Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by ESI mass spectrometry, energy resolved mass spectrometry and density functional theory calculations. The negatively charged aggregates are found to be less stable than their positive counterparts. The results are consistent with a self-assembling pattern dominated by electrostatic interactions involving the counterions and head groups of the investigated amphiphilic compounds while the alkyl chains point outwards, protecting the aggregates from unlimited growth processes.

The hydrogen-carbon, carbon-carbon double rearrangement, responsible for the formation of benzyl or tropylium ions previously observed in the electron ionization mass spectra of several substituted 1,lbis(dimethoxydipheny1)methanes bearing an ortho methoxy group, also occurs for 2-methoxydiphenylmethane (1) itself, the simplest compound of the series. It was shown using deuterium and ''C labelled 2methoxydiphenylmethanes (2, 3) that in this instance benzyl or tropilium ions are also formed through two alternative fragmentation routes.

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Fourier transform infrared spectrometry (FT-IR) and X-Ray diffraction (XRD) investigations were carried out on MLT plus α-, β-and γ-CD physical mixtures and lyophilized or crystalline MLT/α-, β-, γ-CD complexes. Inclusion complexes formation between MLT and cyclodextrins in solid phase has been emphasized by the significant differences between IR and XRD spectra of physical mixtures with respect to those of the complexes. The structure of MLT CDs complexes in the solid state as well as the biochemical and pharmaceutical implications are discussed.

It has been shown by exact mass measurements and collision-induced dissociation mass-analysed ion kinetic energy spectra that the structure of the m/z 124 ion observed in the mass spectra of N-(4-methoxyphenyl)thiophene-2-carboxamide, N-(4-methoxyphenyl)thiophene-3-carboxamide, N-(4-methoxyphenyl)-5-nitrothiophene-3-carboxamide and N-(4-methoxyphenyl)bnzamide is identical with that of the molecular ion of 4-methoxyphenol. This ion becomes abundant in metastable energy window reactions. A probable mechanism for its formation is discussed.