<p><b>ABSTRACT:</b> Photo-controlled atom transfer radical
polymerization (PhotoATRP) was implemented, for the first time, to accomplish
polymerization induced self-assembly (PISA) mediated by UV light (λ = 365 nm)
using ppm levels (ca. < 20 ppm) of copper catalyst at ambient temperature.
Using Cu<sup>II</sup>Br<sub>2</sub>/tris(pyridin-2-ylmethyl)amine (TPMA)
catalyst systems, PISA was per-formed all in one-pot starting from synthesis of
solvophilic poly(oligo(ethylene oxide) methyl ether methacrylate) (POEGMA)
blocks to core-crosslinked nanoparticles (NPs) utilizing poly(glycidyl
methacrylate) (PGMA) and N,N-cystamine bismethacrylamide (CBMA) as the
solvophobic copolymer and crosslinking agent, respectively. Sequential
chain-extensions were performed for PGMA demonstrating capabilities for
accessing multi-block copolymers with temporal control via switching the UV
light on and off. Further, core-crosslinking of PISA nanoparticles was
performed via the slow incorporation of the CBMA enabling one-pot crosslinking
during the PISA process. Finally, the disulfide installed in the CBMA
core-crosslinks allowed for the stimuli-triggered dissociation of nanoparticles
using DL-dithiothreitol at acidic pH.</p>