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Isotope effects in peptide group hydrogen exchange
Abstract
Kinetic and equilibrium isotope effects in peptide group hydrogen exchange reactions were evaluated. Unlike many other reactions, Kinetic isotope effects in amide hydrogen exchange are small because exchange pathways are not limited by bondbreaking steps. Rate constants for the acid‐cat‐alyzed exchange of peptide group NH, ND, and NT in H 2 O are essentially identical, but a solvent esotope effect doubles the rate in D 2 O. Rate constants for base‐catalyzed exchange in H 2 O decrease slowly in the order NH > ND > NT. The alkaline rate constant in D 2 O is very close to that in H 2 O when account is taken of the glass electrode pH artifact and the difference in solvent ionization constant. Small equilibrium isotope effects lead to an excess equilibrium accumulation of the heavier isotopes by the peptide group. Results obtained are expressed in terms of rate constants for the random coil polypeptide, poly‐DL‐alanine, to provide reference rates for protein hydrogen exchange studies as described in Bai et al. [preceding paper in this issue]. © 1993 Wiley‐Liss, Inc.
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Cited by
Protein Folding Intermediates: Native-State Hydrogen Exchange
Bai, Y., Sosnick, T. R., Mayne, L., & Englander, S. W. (1995) · Science · doi:10.1126/science.7618079 · Cited by 990
Self-citationMacromolecular Crowding and Protein Stability
Wang, Y., Sarkar, M., Smith, A. E., Krois, A. S., & Pielak, G. J. (2012) · Journal of the American Chemical Society · doi:10.1021/ja305300m · Cited by 346
Protein folding: The stepwise assembly of foldon units
Maity, H., Maity, M., Krishna, M. M. G., Mayne, L., & Englander, S. W. (2005) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0501043102 · Cited by 300
Self-citationThe Structural and Dynamic Basis of Ets-1 DNA Binding Autoinhibition
Lee, G. M., Donaldson, L. W., Pufall, M. A., Kang, H.-S., Pot, I., Graves, B. J., & McIntosh, L. P. (2005) · Journal of Biological Chemistry · doi:10.1074/jbc.m410722200 · Cited by 95
Lee, G. M., Pufall, M. A., Meeker, C. A., Kang, H.-S., Graves, B. J., & McIntosh, L. P. (2008) · Journal of Molecular Biology · doi:10.1016/j.jmb.2008.07.064 · Cited by 58
Metadata
- Authors
- Connelly, G. P., Bai, Y., Jeng, M., & Englander, S. W.
- Venue
- Proteins: Structure, Function, and Bioinformatics
- Publisher
- Wiley
- Published
- 1993-09
- Volume
- 17
- Issue
- 1
- Pages
- 87-92
- ISSN
- 0887-3585 (ISSN-L)
- 1097-0134
- OpenAlex
- W2131625617
- Cited by
- 376
- References
- 0
- FWCI
- 7.03
- Type
- journal article
- Language
- en
- Open access
- closed
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- Connelly, G. P., Bai, Y., Jeng, M., & Englander, S. W. (1993). Isotope effects in peptide group hydrogen exchange. Proteins: Structure, Function, and Bioinformatics. https://doi.org/10.1002/prot.340170111
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