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3+ (n = 18-41) ions (ref 12), we have placed protons only on -NH groups of the peptide backbone. In general, coulomb repulsion between charge sites is a dominant factor in determining overall conformation in these multiply charged systems. Although we note that theoretical studies of triglycine have suggested that the backbone -C=O groups are more basic than backbone -NH groups (Zhang, K.; Cassady, C.J.; Chung-Phillips, A. J. Am. Chem. Soc. 1994, 116, 11512), these were not considered as protonation sites due to limitations of the available force fields. Because the electronegativity of carbonyl groups engages them in hydrogen-bonding interactions with the protonation site, it is unlikely that formally placing the proton on the -NH portion of the backbone will significantly affect the molecular modeling results.
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z+ parents).
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|