Retention behaviour of polyunsaturated fatty acid methyl esters on porous graphitic carbon.
Retention with porous graphitic carbon was investigated with 25 structures of fatty acid methyl esters (FAMEs) with two different mobile phases: CH(3)CN:CHCl(3) 60:40 (v/v) and CH(3)OH:CHCl(3) 60:40 (v/v) with both 0.1% triethylamine (TEA) and an equimolar amount of HCOOH. Preliminary results showed that the use of TEA/HCOOH led to the response increase of saturated FAMEs with evaporative light scattering detection. No increase was observed for unsaturated one. These modifiers may slightly reduce the retention of FAMEs but did not significantly modify the separation factor with porous graphitic carbon. Thermodynamic parameters were calculated for each structure using Van't Hoff plot measured over the temperature range from 10 to 50 degrees C, with the both mobile phase conditions. All the studied compounds were found linked by the same retention mechanism on porous graphitic carbon. Quantitative in silico analysis of the retention using a molecular mechanics calculation demonstrated a good correlation between the retention factors and the molecular interaction energy values (r>0.93). Especially the Van der Waals energy was predominant, and the contribution of electrostatic energy was negligible for the quantitative analysis of the retention. The results indicate that Van der Waals force, hydrophobic interaction, is predominant for the retention of FAMEs on this packing material. The relative retention for highly unsaturated homologues can be changed by the selection of the weak solvent CH(3)CN or CH(3)OH. Then isomers differing only in the position of the carbon double bond on the alkyl chain can be separated and their behaviour is summarised as the closer the carbon double bonds to the FAME polar head, the more the retention decreases. Finally, the more important the number of carbon double bonds in the alkyl chain is, the smaller the retention is.
Gaudin
Karen
K
Laboratoire de Chimie Analytique, EA 3677, Bases Thérapeutiques des Inflammations et Infections, Faculté de Pharmacie, Université de Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux Cedex, France. karen.gaudin@u-bordeaux2.fr
Hanai
Toshihiko
T
Chaminade
Pierre
P
Baillet
Arlette
A
D004952:Esters; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D006108:Graphite / Q000737:chemistry*; D008958:Models, Molecular; D013816:Thermodynamics
D004952:Esters; D005231:Fatty Acids, Unsaturated; D006108:Graphite