DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)

Abstract

Perfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, 19F nuclear magnetic resonance (NMR 19F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of 19F NMR was performed. In this study we have determined the shielding constant (σ) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The σ calculations were made at vacuum and in presence of a solvent. The values of chemical shifts (δ), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl3), acetone (CH3COCH3) and methanol (CH3OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS). © 2011 Sociedade Brasileira de Química.