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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.
J Mass Spectrom. 2003 Feb; 38(2):188-95.JM

Abstract

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.

Authors+Show Affiliations

Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan. tsunemat@fukuoka-u.ac.jpNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

12577285

Citation

Tsunematsu, Hideaki, et al. "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." Journal of Mass Spectrometry : JMS, vol. 38, no. 2, 2003, pp. 188-95.
Tsunematsu H, Ikeda H, Hanazono H, et al. 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. J Mass Spectrom. 2003;38(2):188-95.
Tsunematsu, H., Ikeda, H., Hanazono, H., Inagaki, M., Isobe, R., Higuchi, R., Goto, Y., & Yamamoto, M. (2003). 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. Journal of Mass Spectrometry : JMS, 38(2), 188-95.
Tsunematsu H, et al. 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. J Mass Spectrom. 2003;38(2):188-95. PubMed PMID: 12577285.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - 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. AU - Tsunematsu,Hideaki, AU - Ikeda,Hirohito, AU - Hanazono,Hiroshi, AU - Inagaki,Masanori, AU - Isobe,Ryuichi, AU - Higuchi,Ryuichi, AU - Goto,Yoshinobu, AU - Yamamoto,Magobei, PY - 2003/2/11/pubmed PY - 2003/4/10/medline PY - 2003/2/11/entrez SP - 188 EP - 95 JF - Journal of mass spectrometry : JMS JO - J Mass Spectrom VL - 38 IS - 2 N2 - 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. SN - 1076-5174 UR - https://www.unboundmedicine.com/medline/citation/12577285/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_ L2 - https://doi.org/10.1002/jms.428 DB - PRIME DP - Unbound Medicine ER -