The effect of cyclochirality of rccc-2,8,14,20-tetra-n-decyl-4,10,16,22-tetra-O-methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano-electrospray ionization (nano-ESI)-Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton-bound [CHG]+ complexes by nano-ESI of solutions containing an equimolar amount of quasi-enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity. The kinetic results were further supported by both collision-induced dissociation experiments on some of the relevant [C2HG]+ three-body species and Density functional theory (DFT) calculations performed on the most selective systems.
Cyclochiral resorcin[4]arenes as effective enantioselectors in the gas phase / Fraschetti, Caterina; M. C., Letzel; M., Paletta; J., Mattay; Speranza, Maurizio; Filippi, Antonello; M., Aschi; A. B., Rozhenko. - In: JOURNAL OF MASS SPECTROMETRY. - ISSN 1076-5174. - STAMPA. - 47:1(2012), pp. 1038-1046. [10.1002/jms.2028]
Cyclochiral resorcin[4]arenes as effective enantioselectors in the gas phase
FRASCHETTI, CATERINA;SPERANZA, Maurizio;FILIPPI, Antonello;
2012
Abstract
The effect of cyclochirality of rccc-2,8,14,20-tetra-n-decyl-4,10,16,22-tetra-O-methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano-electrospray ionization (nano-ESI)-Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton-bound [CHG]+ complexes by nano-ESI of solutions containing an equimolar amount of quasi-enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity. The kinetic results were further supported by both collision-induced dissociation experiments on some of the relevant [C2HG]+ three-body species and Density functional theory (DFT) calculations performed on the most selective systems.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.