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. 2009 Dec 9;131(48):17528-9.
doi: 10.1021/ja9054542.

Evidence of diketopiperazine and oxazolone structures for HA b2+ ion

Brittany R Perkins  1 , Julia Chamot-Rooke, Sung Hwan Yoon, Ashley C Gucinski, Arpád Somogyi, Vicki H Wysocki
Affiliations

Evidence of diketopiperazine and oxazolone structures for HA b2+ ion

Brittany R Perkins et al. J Am Chem Soc. .

Abstract

Peptide fragmentation can lead to an oxazolone or diketopiperazine b(2)(+) ion structure. IRMPD spectroscopy combined with computational modeling and gas-phase H/D exchange was used to study the structure of the b(2)(+) ion from protonated HAAAA. The experimental spectrum of the b(2)(+) ion matches both the experimental spectrum for the protonated cyclic dipeptide HA (a commercial diketopiperazine) and the theoretical spectrum for a diketopiperazine protonated at the imidazole pi nitrogen. A characteristic band at 1875 cm(-1) and increased abundance of the peaks at 1619 and 1683 cm(-1) indicate a second population corresponding to an oxazolone species. H/D exchange also shows a mixture of two populations consistent with a mixture of b(2)(+) ion diketopiperazine and oxazolone structures.

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Figures

FIGURE 1
FIGURE 1
IRMPD spectra (fragmentation efficiency vs. wavenumber) of a) the b2+ ion produced by CID fragmentation of protonated HA4 and b) protonated cyclic HA dipeptide. Calculated spectra for selected c) diketopiperazine and d) oxazolone structures. Arrows indicate protonation site.
FIGURE 2
FIGURE 2
H/D exchange of a) protonated cHA and b) HA b2+ ion with increasing exchange time.
See this image and copyright information in PMC

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References

    1. Yalcin T, et al. J. Am. Soc. Mass Spectrom. 1995;6:1165–1174. - PubMed
    2. Nold MJ, et al. Int. J. Mass Spectrom. Ion Proc. 1997;164:137–153.
    3. Vaisar T, Urban J. European Mass Spectrom. 1998;4:359–364.
    4. Haselmann KF, et al. Rapid Commun. Mass Spectrom. 2000;14:2242–2246. - PubMed
    5. Paizs B, et al. Int. J. Mass Spectrom. 2002;219:203–232.
    6. Riba-Garcia I, et al. J. Am. Soc. Mass Spectrom. 2008;19:609–613. - PubMed
    1. Savitski MM, Hith M, Fung YME, Adams CM, Zubarev RA. J. Am. Soc. Mass Spectrom. 2008;19:1755–1763. - PubMed
    1. Eckart K, et al. J. Am. Soc. Mass Spectrom. 1998;9:1002–1011.
    2. Harrison AG, et al. J. Am. Soc. Mass Spectrom. 2000;11:427–436. - PubMed
    3. Paizs B, Suhai S. Rapid Commun. Mass Spectrom. 2002;16:375–389. - PubMed
    4. Paizs B, Suhai S. J. Am. Soc. Mass Spectrom. 2003;14:1454–1469. - PubMed
    5. El Aribi H, et al. J. Am. Chem. Soc. 2003;125:9229–9236. - PubMed
    6. El Aribi H, et al. J. Phys. Chem. B. 2004;108:18743–18749.
    7. Bythell BJ, et al. J. Am. Soc. Mass Spectrom. 2007;18:1291–1303. - PubMed
    1. Farrugia JM, O'Hair RAJ, Reid GE. Int. J. Mass Spectrom. 2001;210:71–87.
    1. Farrugia JM, Taverner T, O'Hair RAJ. Int. J. Mass Spectrom. 2001;209:99–112.

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