Disfavoring Macrocycle b Fragments by Constraining Torsional Freedom: The "Twisted" Case of QWFGLM b(6)

TitleDisfavoring Macrocycle b Fragments by Constraining Torsional Freedom: The "Twisted" Case of QWFGLM b(6)
Publication TypeJournal Article
Year of Publication2012
AuthorsM. Tirado, J. Rutters, X. Chen, A. Yeung, J. van Maarseveen, J.R Eyler, G. Berden, J. Oomens, N.C Polfer
JournalJournal of the American Society for Mass Spectrometry
Volume23
Number3
Pagination475-482
Date PublishedMar
Type of ArticleArticle
ISBN Number1044-0305
Keywords4-Aminomethylbenzoic acid, ACID-RESIDUES, COLLISION-INDUCED DISSOCIATION, CYCLIZATION, GAS-PHASE, H/D EXCHANGE, HYDROGEN/DEUTERIUM EXCHANGE, INFRARED-SPECTROSCOPY, IR spectroscopy, LEU-ENKEPHALIN, macrocycle, METAL-CATIONIZED PEPTIDES, OXAZOLONE, Peptide rearrangement, PROLINE, PROTONATED PEPTIDES, RESONANCE MASS-SPECTROMETRY, SORI CID, TRYPTIC PEPTIDES
Abstract

While recent studies have shown that for some peptides, such as oligoglycines and Leu-enkephalin, mid-sized b fragment ions exist as a mixture of oxazolone and macrocycle structures, other primary structure motifs, such as QWFGLM, are shown to exclusively give rise to macrocycle structures. The aim of this study was to determine if certain amino acid residues are capable of suppressing macrocycle formation in the corresponding b fragment. The residues proline and 4-amino-methylbenzoic acid (4AMBz) were chosen because of their intrinsic rigidity, in the expectation that limited torsional flexibility may impede "head-to-tail" macrocycle formation. The presence of oxazolone versus macrocycle b(6) fragment structures was validated by infrared multiple photon dissociation (IRMPD) spectroscopy, using the free electron laser FELIX. It is confirmed that proline disfavors macrocycle formation in the cases of Q (P) under bar WFGLM b(7) and in Q (P) under bar FGLM b(6). The 4AMBz substitution experiments show that merely QWFG(4AMBz) M b(6), with 4AMBz in the fifth position, exhibits a weak oxazolone band. This effect is likely ascribed to a stabilization of the oxazolone structure, due to an extended oxazolone ring-phenyl p-electron system, not due to the rigidity of the 4AMBz residue. These results show that some primary structures have an intrinsic propensity to form macrocycle structures, which is difficult to disrupt, even using residues with limited torsional flexibility.

URLhttp://rodgers.chem.wayne.edu/pire/publications/Tirado_JASMS.pdf
DOI10.1007/s13361-011-0315-5
Division

GUTHz

Department

Moldyn

PID

4d15e2c96389a466a5c984b0e2bba9ab

Alternate TitleJ. Am. Soc. Mass Spectrom.

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