2 research outputs found
Electrostatic Control of Peptide Side-Chain Reactivity Using Amphiphilic Homopolymer-Based Supramolecular Assemblies
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<i>K</i><sub>a</sub> 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
Electrostatic Control of Peptide Side-Chain Reactivity Using Amphiphilic Homopolymer-Based Supramolecular Assemblies
Supramolecular assemblies formed by amphiphilic homopolymers with negatively charged groups in the hydrophilic segment have been designed to enable high labeling selectivity towards 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 non-protonated 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 pK(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