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Mass spectral study of alkali-cationized Boc-carbo-beta3-peptides by electrospray tandem mass spectrometry.
Rapid Commun Mass Spectrom. 2004; 18(24):3041-50.RC

Abstract

Electrospray tandem mass spectrometry was used to study the dissociation reactions of [M+Cat]+ (Cat = Na+ and Li+) of Boc-carbo-beta3-peptides. The collision-induced dissociation (CID) spectra of [M+Cat-Boc]+ of these peptides are found to be significantly different from those of [M+H-Boc]+ ions. The spectra are more informative and display both C- and N-terminus metallated ions in addition to characteristic fragment ions of the carbohydrate moiety. Based on the fragmentations observed in the CID spectra of the [M+Cat-Boc]+ ions, it is suggested that the dissociation involves complexes in which the metal ion is coordinated in a multidentate arrangement involving the carbonyl oxygen atoms. The CID spectra of [M+Cat-Boc]+ ions of the peptide acids show an abundant N-terminal rearrangement ion [b(n)+17+Cat]+ which is absent for esters. Further, two pairs of positionally isomeric Boc-carbo-beta3-peptide acids, Boc-NH-Caa(S)-beta-hGly-OH (11) and Boc-NH-beta-hGly-Caa(S)-OH (12), and [Boc-NH-Caa(S)-beta-hGly-Caa(S)-beta-hGly-OH] (13) and [Boc-NH-beta-hGly-Caa(S)-beta-hGly-Caa(S)-OH] (14), were differentiated by the CID of [M+Cat-Boc]+ ions. The CID spectra of compounds 11 and 13 are significantly different from those of 12 and 14, respectively. The abundance of [b(n)+17+Cat]+ ions is higher for peptide acids 12 and 14 with a sugar group at the C-terminus when compared to 11 and 13 which contain a sugar moiety at the N-terminus. The observed differences between the CID spectra of these isomeric peptides are attributed to the difference in the preferential site of metal ion binding and also on the structure of the cyclic intermediate involved in the formation of the rearrangement ion.

Authors+Show Affiliations

National Centre for Mass Spectrometry, Indian Institute of Chemical Technology, Hyderabad 500 007, India.No 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

15543549

Citation

Srikanth, R, et al. "Mass Spectral Study of Alkali-cationized Boc-carbo-beta3-peptides By Electrospray Tandem Mass Spectrometry." Rapid Communications in Mass Spectrometry : RCM, vol. 18, no. 24, 2004, pp. 3041-50.
Srikanth R, Reddy PN, Srinivas R, et al. Mass spectral study of alkali-cationized Boc-carbo-beta3-peptides by electrospray tandem mass spectrometry. Rapid Commun Mass Spectrom. 2004;18(24):3041-50.
Srikanth, R., Reddy, P. N., Srinivas, R., Sharma, G. V., Reddy, K. R., & Krishna, P. R. (2004). Mass spectral study of alkali-cationized Boc-carbo-beta3-peptides by electrospray tandem mass spectrometry. Rapid Communications in Mass Spectrometry : RCM, 18(24), 3041-50.
Srikanth R, et al. Mass Spectral Study of Alkali-cationized Boc-carbo-beta3-peptides By Electrospray Tandem Mass Spectrometry. Rapid Commun Mass Spectrom. 2004;18(24):3041-50. PubMed PMID: 15543549.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mass spectral study of alkali-cationized Boc-carbo-beta3-peptides by electrospray tandem mass spectrometry. AU - Srikanth,R, AU - Reddy,P Nagi, AU - Srinivas,R, AU - Sharma,G V M, AU - Reddy,K Ravinder, AU - Krishna,Palakodety Radha, PY - 2004/11/16/pubmed PY - 2005/3/19/medline PY - 2004/11/16/entrez SP - 3041 EP - 50 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 18 IS - 24 N2 - Electrospray tandem mass spectrometry was used to study the dissociation reactions of [M+Cat]+ (Cat = Na+ and Li+) of Boc-carbo-beta3-peptides. The collision-induced dissociation (CID) spectra of [M+Cat-Boc]+ of these peptides are found to be significantly different from those of [M+H-Boc]+ ions. The spectra are more informative and display both C- and N-terminus metallated ions in addition to characteristic fragment ions of the carbohydrate moiety. Based on the fragmentations observed in the CID spectra of the [M+Cat-Boc]+ ions, it is suggested that the dissociation involves complexes in which the metal ion is coordinated in a multidentate arrangement involving the carbonyl oxygen atoms. The CID spectra of [M+Cat-Boc]+ ions of the peptide acids show an abundant N-terminal rearrangement ion [b(n)+17+Cat]+ which is absent for esters. Further, two pairs of positionally isomeric Boc-carbo-beta3-peptide acids, Boc-NH-Caa(S)-beta-hGly-OH (11) and Boc-NH-beta-hGly-Caa(S)-OH (12), and [Boc-NH-Caa(S)-beta-hGly-Caa(S)-beta-hGly-OH] (13) and [Boc-NH-beta-hGly-Caa(S)-beta-hGly-Caa(S)-OH] (14), were differentiated by the CID of [M+Cat-Boc]+ ions. The CID spectra of compounds 11 and 13 are significantly different from those of 12 and 14, respectively. The abundance of [b(n)+17+Cat]+ ions is higher for peptide acids 12 and 14 with a sugar group at the C-terminus when compared to 11 and 13 which contain a sugar moiety at the N-terminus. The observed differences between the CID spectra of these isomeric peptides are attributed to the difference in the preferential site of metal ion binding and also on the structure of the cyclic intermediate involved in the formation of the rearrangement ion. SN - 0951-4198 UR - https://www.unboundmedicine.com/medline/citation/15543549/Mass_spectral_study_of_alkali_cationized_Boc_carbo_beta3_peptides_by_electrospray_tandem_mass_spectrometry_ L2 - https://doi.org/10.1002/rcm.1730 DB - PRIME DP - Unbound Medicine ER -