Electrostatic Control of Peptide Side-Chain Reactivity Using Amphiphilic Homopolymer-Based Supramolecular Assemblies (original) (raw)

ArticleAugust 23, 2013

Electrostatic Control of Peptide Side-Chain Reactivity Using Amphiphilic Homopolymer-Based Supramolecular Assemblies

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Journal of the American Chemical Society

Cite this: J. Am. Chem. Soc. 2013, 135, 38

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Published August 23, 2013

research-article

Copyright © 2013 American Chemical Society

Abstract

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Supramolecular assemblies formed by amphiphilic homopolymers with negatively charged groups in the hydrophilic segment have been designed to enable high labeling selectivity toward reactive side chain functional groups in peptides. The negatively charged interiors of the supramolecular assemblies are found to block the reactivity of protonated amines that would otherwise be reactive in aqueous solution, while maintaining the reactivity of nonprotonated amines. Simple changes to the pH of the assemblies’ interiors allow control over the reactivity of different functional groups in a manner that is dependent on the p_K_a of a given peptide functional group. The labeling studies carried out in positively charged supramolecular assemblies and free buffer solution show that, even when the amine is protonated, labeling selectivity exists only when complementary electrostatic interactions are present, thereby demonstrating the electrostatically controlled nature of these reactions.

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Copyright © 2013 American Chemical Society

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Synthesis, other experimental details, and tandem mass spectra. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

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This article is cited by 20 publications.

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Journal of the American Chemical Society

Cite this: J. Am. Chem. Soc. 2013, 135, 38

Click to copy citationCitation copied!

Published August 23, 2013

Copyright © 2013 American Chemical Society

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