Nanoparticle and Membrane Responses in Plasmonic Polymeric Vesicles Under Distinct Pulsed Laser Irradiation Regimes

Plasmonically responsive polymersomes are promising platforms for externally triggered cargo release, particularly under pulsed laser irradiation. Incorporating gold nanoparticles (AuNPs) into the hydrophobic domain of the diblock copolymer membrane enables light‐triggered membrane disruption through plasmonic excitation. Despite the widespread use of plasmonic nanoparticles, the dependence of membrane‐incorporated AuNPs and membrane responses on pulsed laser conditions has not been systematically investigated. Here, AuNP‐loaded polymersomes (poly(butadiene) 33 ‐ b ‐poly(ethylene oxide) 20 ) were exposed to near‐resonant nanosecond (ns), picosecond (ps), and femtosecond (fs) laser irradiation. Experimental characterization combined with numerical modeling was used to correlate membrane and nanoparticle responses with AuNP photothermal dynamics. Together, these analyses indicate three distinct membrane response pathways and inferred mechanisms depending on laser pulse duration and fluence: (1) transient membrane permeabilization with minimal structural changes under ns (1.7–17 mJ cm −2 ) and low fluence ps irradiation (5.0 mJ cm −2 ); (2) complete vesicle rupture accompanied by AuNP fragmentation under medium‐ and high‐fluence ps irradiation (25–1.0 × 10 2 mJ cm −2 ); and (3) fluence‐dependent vesicle deformation with AuNP fusion and membrane restructuring under fs irradiation (2.8–10 mJ cm −2 ). These findings demonstrate that AuNP‐membrane response pathways can be tuned through laser conditions such as fluence and pulse duration, thereby altering plasmonic energy confinement and dissipation.