Spherical
surfaces bearing mobile, solvophilic chains are ubiquitous.
These systems are found in nature in the form of biological cells
bearing carbohydrate chains, or glycans, or in drug delivery systems
such as vesicles bearing polyethylene glycol chains and carrying therapeutic
molecules. The self-organization of the chains on the spherical surface
dictates the stability and functionality of the latter and is determined
by key factors such as the interchain, chain–surface interactions,
excluded volume, concentration of the chains, and external environment.
This study develops a fundamental understanding of how these factors
control the organization of mobile, solvophilic chains while preserving
the stability of the spherical surface. To that end, the study focuses
on the organization of polyamidoamine dendrons on the surface of a
dipalmitoylphosphatidylcholine-based vesicle. The excluded volume
of the chains and the external environment are, respectively, controlled
via the dendron generation and the pH. For acidic and basic pH environments,
the dendrons are extended away from the surface. As a consequence,
the vesicles are able to accommodate significantly higher concentration
of dendrons on their surface without rupturing. For acidic pH, the
dendrons change their conformation to avoid intermeshing. However
for basic pH, the dendrons only change their conformation at extremely
high concentrations due to excluded volume effects. These conformational
changes are attributed to the number of protonated dendron residues
that vary as a function of pH. The results from this study will advance
diverse subdisciplines within cell biology, biomedicine, and pharmaceuticals.