Abstract
AbstractTwo types of gas‐phase proton transfer reactions were examined with electrospray ionization‐generated peptide and protein ions; (i) bases reacting with multiply protonated molecules and (ii) acids reacting with multiply deprotonated molecules. For reactions of type (i) with bases spanning a range of proton affinities, the proton transfer reaction rate was observed to increase with increasing proton affinity of the charge transfer reagent. Proton transfer was not observed for the low proton affinity reagents (ethyl acetate, acetonitrile and water). These studies also qualitatively measured for the first time the temperature dependences for reactions with multiply charged peptides and proteins. Negative temperature dependences were observed for the weaker bases and positive dependences for the stronger bases. A negative temperature dependence was also observed in the reaction of propionic acid with [M – nH]n− ions. Two hypotheses are proposed to explain the data. In the first, negative temperature dependences are attributed to slightly exothermic reactions, while the positive dependences may reflect contributions from a competing clustering pathway, a pathway which could be more dominant with the heavier reagents. Alternatively, the positive temperature dependences may reflect the barrier in the reaction coordinate arising from the repulsion of like‐charged ions, while negative temperature dependences could reflect a cluster‐mediated reaction in which charge delocalization lowers the barrier to proton transfer. In the latter cases, clustering is invoked with the lower proton affinity reagents because of the higher concentrations employed.
References
62
Referenced
56
10.1021/j150664a002
10.1021/j150664a046
10.1021/ac00280a023
10.1021/j100313a058
10.1007/BF01384871
10.1126/science.2675315
10.1002/mas.1280090103
10.1002/oms.1210251104
{'key': 'e_1_2_1_4_2', 'first-page': '379', 'volume': '277', 'author': 'Aleksandrov M. L.', 'year': '1984', 'journal-title': 'Dokl. Akad. Nauk. SSSR'}
/ Dokl. Akad. Nauk. SSSR by Aleksandrov M. L. (1984){'key': 'e_1_2_1_4_3', 'first-page': '710', 'volume': '10', 'author': 'Aleksandrov M. L.', 'year': '1984', 'journal-title': 'Bioorg. Khim.'}
/ Bioorg. Khim. by Aleksandrov M. L. (1984){'key': 'e_1_2_1_4_4', 'first-page': '1689', 'volume': '12', 'author': 'Aleksandrov M. L.', 'year': '1986', 'journal-title': 'Bioorg. Khim.'}
/ Bioorg. Khim. by Aleksandrov M. L. (1986){'key': 'e_1_2_1_4_5', 'first-page': '700', 'volume': '11', 'author': 'Aleksandrov M. L.', 'year': '1985', 'journal-title': 'Bioorg. Khim.'}
/ Bioorg. Khim. by Aleksandrov M. L. (1985){'key': 'e_1_2_1_4_6', 'first-page': '705', 'volume': '11', 'author': 'Aleksandrov M. L.', 'year': '1985', 'journal-title': 'Bioorg. Khim.'}
/ Bioorg. Khim. by Aleksandrov M. L. (1985){'key': 'e_1_2_1_4_7', 'first-page': '852', 'volume': '14', 'author': 'Aleksandrov M. L.', 'year': '1988', 'journal-title': 'Bioorg. Khim.'}
/ Bioorg. Khim. by Aleksandrov M. L. (1988)10.1016/1044-0305(92)87082-A
10.1021/j100170a006
10.1021/ja00170a057
- S. A.McLuckey G. J.Van BerkelandG. L.Glish in Proceedings of the 38th ASMS Conference on Mass Spectrometry and Allied Topics Tucson AZ 1990 pp.1134–1135.
10.1021/ac00018a014
- S. A.McLuckey G. L.GlishandG. J.Van Berkel in Proceedings of the 39th ASMS Conference on Mass Spectrometry and Allied Topics Nashville TN 1991 pp.901–902.
10.1016/0168-1176(92)80099-M
- (a)R.FengandY.Konishi in Proceedings of the 40th ASMS Conference on Mass Spectrometry and Allied Topics Washington DC 1992 pp.1635–1636;
- (b)Y.KonishiandR.Feng in Proceedings of the 40th ASMS Conference on Mass Spectrometry and Allied Topics Washington DC 1992 pp.625–626;
- (c)R.FengandY.Konishi in Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Topics San Francisco CA 1993 p.1020a–1020b.
10.1021/ja00040a084
10.1016/1044-0305(92)85003-3
10.1002/rcm.1290060302
10.1016/1044-0305(93)85015-P
10.1016/1044-0305(94)85011-9
/ J. Am. Soc. Mass Spectrom. by Loo R. R. Ogorzalek (1994){'key': 'e_1_2_1_18_2', 'volume': '5', 'author': 'Loo R. R. Ogorzalek', 'year': '1994', 'journal-title': 'J. Amer. Soc. Mass Spectrom.'}
/ J. Amer. Soc. Mass Spectrom. by Loo R. R. Ogorzalek (1994)- (a)B.LinandJ.Sunner in Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Topics San Francisco CA 1993 pp.1058a–1058b;
10.1002/rcm.1290080515
10.1002/rcm.1290080511
10.1073/pnas.90.3.790
10.1016/1044-0305(93)85025-S
10.1016/1044-0305(94)85025-9
10.1002/rcm.1290021006
10.1002/rcm.1290030512
10.1016/1044-0305(90)80006-9
10.1021/ac00052a020
10.1126/science.2326633
{'key': 'e_1_2_1_28_2', 'first-page': '243', 'volume-title': 'Experimental Mass Spectrometry', 'author': 'Loo J. A.', 'year': '1993'}
/ Experimental Mass Spectrometry by Loo J. A. (1993)10.1021/ac00021a018
10.1021/ac00053a027
10.1002/rcm.1290071216
10.1002/rcm.1290051203
10.1021/j100185a001
10.1021/ja00012a012
10.1021/ja00070a033
10.1063/1.555719
10.1021/ja00036a062
- (a)J.WuandC. B.Lebrilla in Proceedings of the 41st ASMS Conference on Mass Spectrometry and Allied Topics San Francisco CA 1993 pp.200a–200b;
{'key': 'e_1_2_1_37_3', 'first-page': '3279', 'volume': '115', 'author': 'Wu J.', 'year': '1993', 'journal-title': 'J. Am. Chem. Soc.'}
/ J. Am. Chem. Soc. by Wu J. (1993)10.1002/rcm.1290050303
10.1021/ja00067a054
10.1021/ac00049a003
10.1007/978-94-009-7248-3_8
10.1016/B978-0-12-120801-1.50012-0
10.1007/978-94-009-3787-1_19
10.1002/oms.1210270908
{'key': 'e_1_2_1_45_2', 'first-page': '70', 'volume-title': 'Atomic and Molecular Beam Methods', 'author': 'Gentry W. R.', 'year': '1988'}
/ Atomic and Molecular Beam Methods by Gentry W. R. (1988)10.1021/ac00025a015
Dates
Type | When |
---|---|
Created | 20 years, 2 months ago (May 31, 2005, 7:48 a.m.) |
Deposited | 1 year, 9 months ago (Oct. 25, 2023, 11:45 p.m.) |
Indexed | 2 months, 4 weeks ago (May 27, 2025, 4:09 a.m.) |
Issued | 30 years, 6 months ago (Feb. 1, 1995) |
Published | 30 years, 6 months ago (Feb. 1, 1995) |
Published Online | 20 years, 4 months ago (April 14, 2005) |
Published Print | 30 years, 6 months ago (Feb. 1, 1995) |
@article{Loo_1995, title={Proton transfer reactions of multiply charged peptide and protein cations and anions}, volume={30}, ISSN={1096-9888}, url={http://dx.doi.org/10.1002/jms.1190300217}, DOI={10.1002/jms.1190300217}, number={2}, journal={Journal of Mass Spectrometry}, publisher={Wiley}, author={Loo, Rachel R. Ogorzalek and Smith, Richard D.}, year={1995}, month=feb, pages={339–347} }