Mixed HMW-GS stimulate T-cell lines from some coeliac patients and exacerbate coeliac disease in vivo, inducing expression, within 2 h, of IL-15. This suggests an innate immune response to these proteins.

New asymmetric (salen)Mn III and UO 2 complexes containing a calix [4]arene unit in the ligand framework were synthesized. The UO 2 complexes were characterized by 1 H-, 13 C-, 2D TOCSY and T-ROESY NMR spectroscopy. Furthermore, the structure of one UO 2 complex was determined by singlecrystal X-ray analysis. The data showed that UO 2 complexes, which can be considered in first approximation models of the Mn=O oxidant active species, possess a chiral pocket and

H and 19 F NMR measurements on aqueous solutions of sodium perfluorooctanoate (SPFO) and sodium dodecanoate (SD) mixtures are reported. The surfactant concentration ranged from ∼0.3 to 10 times the critical micelle concentration (cmc = 0.03 mol L -1 ). The cmc of the SD/SPFO/water mixed system obtained from NMR data was in good agreement with that previously obtained by conductivity measurements. Below the cmc, the experimental chemical shift (δ) was independent of the total concentration for both surfactants. Above the cmc, however, the δ values for 19 F varied linearly with concentration, whereas the values for the hydrogenated surfactant deviated from linearity. These observations indicate that below the cmc each monomer is not affected by the presence of the others. Above the cmc, on increasing the total concentration, the chemical shift trends indicate that the fluorinated chains begin to aggregate, forming islands among hydrocarbon chain domains. Since the extended chain of the fluorinated surfactant is shorter than the inner micelle radius, some methyl groups of the longer SD must be segregated within the micelle. This patchwork distribution, involving an intramicellar phase separation, prevents the computation of the micelle composition; however, NMR data give information complementary to that obtained by a previous SANS study indicating the existence of mixed micelles having the same composition. Information on the structure of micelles and on the mean distribution of the two components in the system are obtained by SANS, while the NMR technique suggests details on the chemical environment of a single monomer and on the structural organization of the molecules within a micelle. Thus, the patchwork model here proposed is able to explain apparently conflicting data obtained from different techniques.

19 F NMR measurements on lithium perfluorononanoate [LiPFN] in D 2 O and in solutions of D 2 O with poly- (vinylpyrrolidone) [PVP] at different molecular weights have been carried out. A careful study of literature data and COSY maps allowed the full assignment of the 19 F resonances as a function of concentration and composition of the systems. For the LiPFN/D 2 O system, analysis of the chemical shifts of the fluorine atoms bound to the different carbons of the LiPFN backbone reveals significant variations correlated to the LiPFN concentration. Such a finding has been explained in terms of the changes in the local dielectric constant caused by the surfactant self-aggregation process. The presence of PVP in solution strongly modifies the trend of the 19 F chemical shifts observed in the binary LiPFN/D 2 O system. Such a feature, depending both on the position of the fluorine atoms along the surfactant backbone and on the LiPFN concentration, indicates the presence of strong polymer-surfactant interactions. The line width analysis of selected 19 F resonances as a function of the surfactant concentration shows, in addition, the presence of an equilibrium among different species of LiPFN in solution (i.e., free monomers, bound monomers, free micelles, bound micelles). The extreme spread of 19 F chemical shifts allow the spectroscopic observation of separate resonances for free and bound micelles at low temperature. Combining the 19 F NMR results with other detailed information derived from previous 1 H NMR, surface tension, viscosity, and conductometric studies, a structural model for the micelle-polymer supramolecular aggregates has been formulated.

A series of new compounds containing a benzimidazole, benzothiazole, or benzoxazole nucleus linked to an arylpiperazine by different thioalkyl chains was prepared. They were tested in radioligand binding experiments to evaluate their affinity for 5-HT 1A and 5-HT 2A serotonergic, alpha 1 adrenergic, D1, and D2 dopaminergic receptors. Many of tested compounds showed an interesting binding profile; in particular, 36 displayed very high 5-HT 1A receptor affinity and selectivity over all the other investigated receptors. Selected compounds, evaluated in functional assays, showed antagonistic or partial agonistic activity at 5-HT 1A receptor. An extensive conformational research using both NMR and modeling techniques indicated that extended conformations predominated in vacuum, in solution and during interactions with 5-HT 1A receptor. Finally, the elaborated binding mode of selected compounds at 5-HT 1A receptor was used to explain the influence of spacer length on ligands affinity.