Polypeptoids bearing carboxylic acid groups on the N-substituent are useful building blocks for the construction of peptidomimetic supramolecular assemblies with stimuli-responsive properties.
The intramicellar mass heterogeneity of a series of sequence-defined
ionic peptoid block copolymers carrying a single charged monomer has
been determined through contrast variation small-angle neutron scattering
analysis. We observe that the internal micellar structure, namely,
the number density radial distributions of invasive water and peptoid
polymer, is significantly impacted by the location of the ionic monomer.
By positioning the ionic monomer progressively closer to the hydrophilic/hydrophobic
block junction, the micelles become less compact with increasing levels
of chain folding and invasive water to accommodate electrostatic repulsion
among the ionic monomers via solvation. This results in increasingly
smaller micellar aggregates with aggregation numbers (N
agg) ranging from 15.6 to 44 and micellar radii (R
b) ranging from 61 to 94 Å. This study
highlights the potential of using ionic monomer position as a design
parameter to control the internal structures of nanoscale micellar
assemblies.
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