“Grafting
to” polymeric nanostructures or surfaces
is a simple and versatile approach to achieve functionalization. Herein,
we describe the formation of mixed polymer-grafted nanoparticles through
a supramolecular “grafting to” method that exploits
multiple hydrogen-bonding interactions between the thymine (T)-containing
cores of preformed micelles and the complementary nucleobase adenine
(A) of added diblock copolymers. To demonstrate this new “grafting
to” approach, mixed-corona polymeric nanoparticles with different
sizes were prepared by the addition of a series of complementary diblock
copolymers containing thermoresponsive poly(N-isopropylacrylamide)
(PNIPAM) to a preformed micelle with a different coronal forming block,
poly(4-acryloylmorpholine) (PNAM). PNIPAM chains were distributed
throughout the corona and facilitated a fast and fully reversible
size change of the resulting mixed-corona micelles upon heating. Through
the introduction of an environmentally sensitive fluorophore, the
reversible changes in nanoparticle size and coronal composition could
be easily probed. Furthermore, preparation of mixed-corona micelles
also enabled ligands, such as d-mannose, to be concealed
and displayed on the micelle surface. This supramolecular “grafting
to” approach provides a straightforward route to fabricate
highly functionalized mixed polymeric nanostructures or surfaces with
potential applications in targeted diagnosis or therapy and responsive
surfaces.