No abstract

Synthetic routes were developed to link L‐alanine methyl ester or L‐alanyl‐L‐alanine methyl ester at the upper rim of calix[4]arenes blocked in the cone conformation. Several tetra‐ (3 and 6) and difunctionalized (11 and 12) amino acids containing macrocycles were obtained. Reaction of these compounds with hydrazine gave the corresponding hydrazido derivatives 4, 13, and 14, while the hydrolysis of 3 with LiOH produced the tetraacid 5 whose lithium salt is water soluble at neutral pH. The structural properties of all amino acids containing calix[4]arenes were studied by mono‐ and bidimensional 1H NMR experiments. The X‐ray crystal structure of the difunctionalized receptor 11 shows three different conformations in the solid state, none of them having intrachain hydrogen bonding.

Three novel lower rim hexamide derivatives 5(6), 7(6), and 9(6) of p-hydroxycalix[6]arene and four octamides 5(8), 7(8)-9(8) derived from the corresponding p-hydroxycalix[8]arene were synthesized, and their potential as extractants in radioactive waste treatment was evaluated, in comparison with upper rim analogues 12(6) and 12(8) and other existing selective neutral ionophores currently used in radioactive waste treatment. Extraction of alkali and alkaline earth metal picrates from water to dichloromethane, and of the corresponding nitrates from acidic water solution simulating radioactive waste, to 2-nitrophenyl hexyl ether (NPHE), showed that the lower rim amides extract divalent cations much better than monovalent ones. The upper rim hexa-12(6) and octamide 12(8) are very inefficient ligands, hardly extracting any cation. In all cases, p-alkoxy octamides are more efficient and selective extractants than the corresponding hexamides. In the case of simulated waste solutions, the distribution coefficients for strontium removal by octamides (6.5 < D(Sr) < 30) are much higher than the corresponding value (D(Sr)) found for dicyclohexyl-18-crown-6 (DC18C6), and the same applies for the strontium/sodium selectivity, which is 6500 < D(Sr)/D(Na) < 30 000 for octamides and 47 for DC18C6. ESI-MS, UV-vis, and X-ray crystal structure studies give consistent results and indicate the formation of 2:1 (cation/ligand) strontium complexes for all octamides tested. Stability constants were determined in homogeneous methanol solution for alkali metal (log beta(11) < or = 2), calcium (4.3 < or = log beta(11) < or = 6.0; 9.4 < or = log beta(21) < or = 12.0), and strontium (5.6 < or = log beta(11) < or = 12.3) ions using a UV-vis competition method with 1-(2-pyridylazo)-2-naphthol (PAN). They confirm the high efficiency and high divalent/monovalent selectivity found in metal ion extraction experiments for the new octamide ligands. Evidence for a positive cooperative effect between the two metal ion binding sites was obtained in the case of the Ca(2+) complex of octamide 1(8).

No abstract

No abstract

No abstract

No abstract

Curosurf is a pulmonary surfactant used in the treatment or prophylaxis of neonatal respiratory distress syndrome. It contains low molecular weight hydrophobic apoproteins and a series of lipids including phosphatidylcholines, lisophosphatidylcholines, phosphatidylethanolamines, sphingomyelins, phosphatidylinositols, phosphatidylglycerols and phosphatidylserines. In the present work, a rapid method to qualitatively map the Curosurf phospholipid classes without prior derivatization or chromatographic separations is described. In particular, a series of specific electrospray tandem mass spectrometric (ES-MS/MS) experiments, i.e. product ion, precursor ion and neutral loss scans, were chosen on the basis of the chemical nature of each phospholipid class and then used to identify single components of the commercial suspension, directly infused into the ion source of the mass spectrometer.