Abstract
The cationized 9-fluorenylmethoxycarbonyl (Fmoc) protected amino acids were analyzed by the electrospray ionization tandem mass spectrometry (ESI-MS/MS). A rearrangement reaction leading to the C-terminal hydroxyl group transfer was observed. The sodium adducts of Fmoc-OH was formed. A possible rearrangement mechanism was proposed. The rearrangement reaction depended on the Fmoc group, metal ions and metal ion radius. It was shown that the Fmoc group has a strong affinity to the hydroxyl group in the gas phase.
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References
Chait, B. T., Wang, R., Kent, S. B. H. et al., Protein Ladder sequencing, Science, 1993, 262: 89.
Wilm, M., Shevchenko, A., Houthaeve, T. et al., Femtomole sequencing of proteins from polyacrylamide gels by nano-electrospray mass spectrometry, Nature, 1996, 379: 466.
Sutton, C. W., Pemberton, K. S., Cottrell, J. S. et al., Identification of myocardial proteins from 2-dimensional gels by peptide mass fingerprinting, Electrophoresis, 1995, 16: 308.
Mann, M., Wilm, M., Error tolerant identification of peptides in sequence databases by peptide sequence tags, Anal. Chem., 1994, 66: 4390–4399.
Eng, J. K., Mccormack, A. L., Yates, J. R., An approach to correlate tandem mass-spectral data of peptides with amino-acid-sequences in a protein database, J. Am. Soc. Mass Spectrom., 1994, 5: 976–989.
Weng, C. C., Peter, D. W., Fmoc Solid Phase Peptide Synthesis: A Practical Approach, Oxford: University Press, 2000, 1–8.
Chen, Z. Z., Chen, S. B., Li, Y. M. et al., Negative-ion ESI mass spectrometry of N-phosphoryl amino acids and dipeptides, Rapid Commun. Mass Spectrom., 2002, 16(8): 790–796.
Chen, Z. Z., Tong, Y. F., Li, Y. M. et al., Orientation of the peptide formation of N-phosphoryl amino acids in solution, Chinese Sci. Bull. (in Chinese), 2002, 47(13): 993–997.
Chen, J., Chen, Y., Zhao, Y. F. et al., Rearrangement of P-N to P-O bonds in mass spectra of N-diisopropyloxyphosphoryl amino acids/alcohols, Rapid Commun. Mass Spectrom., 2001, 15: 1936–1940.
Atherton, E., Sheppard, R. C., Solid Phase Peptide Synthesis: A Practical Approach, Oxford: IRL Press, 1989.
Wakamiya, T., Nishida, T., Togashi, R. et al., Preparations of NαFmoc-O-[(benzyloxy)hydroxyphosphinyl] β-hydroxy α-amino acid derivatives, Bull. Chem. Soc. Jpn., 1996, 69: 465–468.
Lynn, M. T., Ronald, C. O., Jeanette, A., Location of the alkali metal ion in gas-phase peptide complexes, J. Am. Chem. Soc., 1991, 113: 3668–3675.
Tang, X. J., Werner, E., Kenneth, G. S. et al., Daughter ion mass spectra from cationized molecules of small oligopeptides in a reflecting time-of-flight mass spectrometer, Anal. Chem., 1988, 60: 1791–1789.
Kevin, D. B., Simon, J. G., Intramolecular oxygen-18 isotopic exchange in the gas phase observed during the tandem mass spectrometric analysis of peptides, J. Am. Chem. Soc., 1992, 114: 64–71.
Richard, P. G., Ronald, L. C., Michael, L. G., Metal ion-peptide interactions in the gas phase: a tandem mass spectrometry study of alkali metal cationized peptides, J. Am. Chem. Soc., 1989, 111: 2835–2842.
Chen, J., Jiang, Y., Zhao, Y. F. et al., Rearrangement with formamide extrusion in the electrospray mass spectra of aminoacylbenzylamines, Rapid Commun. Mass Spectrom., 2001, 15: 1489–1493.
Nakagawa, M., Yamagaki, T., Nakanishi, H., Fluorescent modification for peptide sequencing by postsource decay-matrix assisted laser desorption/ionization-mass spectrometry, Electrophoresis, 2000, 21: 1651–1652.
Chen, J., Li, Y. M., Zhao, Y. F. et al., Novel phosphoryl derivatization method for peptide sequencing by electrospary ionization mass spectrometry, Rapid Commun. Mass Spectrom., 2002, 16: 531–536.
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Du, J., Li, Y., Zhu, Z. et al. Rearrangement mechanism of the sodium adducts of Fmoc protected amino acids. Chin.Sci.Bull. 48, 2317–2319 (2003). https://doi.org/10.1360/03wb0093
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DOI: https://doi.org/10.1360/03wb0093