Differentiation of a pair of diastereomeric tertiarybutoxycarbonylprolylproline ethyl esters by collision-induced dissociation of sodium adduct ions in electrospray ionization mass spectrometry and evidence for chiral recognition by ab initio molecular orbital calculations.
The fragmentation of the sodium adduct ions for tert-butoxycarbonyl-L-prolyl-L-proline ethyl ester (Boc-L-Pro-L-Pro-OEt) was compared with that for Boc-D-Pro-L-Pro-OEt in positive-ion electrospray ionization (ESI) mass spectrometry. In the collision-induced dissociation (CID) mass spectra of the [M + Na](+) ions, the abundance of the [M + Na - C(CH(3))(3) + H](+) ion, which is due to the loss of a tert-butyl group from the [M + Na](+) ion for Boc-D-Pro-L-Pro-OEt, was about eight times higher than that for Boc-L-Pro-L-Pro-OEt. In addition, in the CID spectra of the sodium adduct fragment ion ([M + Na - Boc + H](+)), the abundance of the [M + Na - Boc - prolylresidue + H](+) ion, which is due to the loss of prolyl residue from the [M + Na - Boc + H](+) ion for Boc-L-Pro-L-Pro-OEt, was about five times higher than that for Boc-D-Pro-L-Pro-OEt. These results indicate that Boc-L-Pro-L-Pro-OEt was distinguished from Boc-D-Pro-L-Pro-OEt by the CID mass spectra of the sodium adduct ions in ESI mass spectrometry. The optimized geometries of the [M + Na](+) and the [M + Na - Boc + H](+) ions calculated by ab initio molecular orbital calculations suggest that the chiral recognition of these diastereomers was due to the difference of the orientation of a sodium ion to the oxygen and nitrogen atoms in dipeptide derivatives, and to the difference of the total energies between them.
Tsunematsu
Hideaki
H
Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan. tsunemat@fukuoka-u.ac.jp
Ikeda
Hirohito
H
Hanazono
Hiroshi
H
Inagaki
Masanori
M
Isobe
Ryuichi
R
Higuchi
Ryuichi
R
Goto
Yoshinobu
Y
Yamamoto
Magobei
M
D004151:Dipeptides / Q000737:chemistry*; D004952:Esters; D007477:Ions / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D012964:Sodium / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
D004151:Dipeptides; D004952:Esters; D007477:Ions; C448039:prolyl-proline; D012964:Sodium