Polymerization-induced photothermy: A non-donor-acceptor approach to highly effective near-infrared photothermal conversion nanoparticles

Photothermal conversion nanoagents based on conjugated polymers (CPs) are attracting increasing attention for in vivo disease theranostics and high-performing ones are in urgent pursuit. Herein, we report a new and non-donor-acceptor approach to photothermal conversion CPs that combine several merits including low bandgaps, strong near-infrared absorption, low intersystem crossing rate and non-emissive nature. Three CPs based on 6,7; 6′,7′-fused isoindigos (nIIDs), i.e., P2IIDV, P3IIDV and P4IIDV that have optical bandgaps of 1.30, 1.22 and 1.17 eV, respectively, are synthesized. The nanoparticles (NPs) of the CPs in water are prepared via nanocoprecipitation, which are non-fluorescent due to the rapid intramolecular twisting in the CP backbone within NPs, enabling most of the excitation energy flow to generate heat. The photothermal conversion efficiencies of the NPs as measured under irradiation at 808, 880 and 980 nm are 62.4%, 40.5% and 15.8% for P2IIDV, 65.1%, 41.0% and 38.9% for P3IIDV and 71.5%, 48.9% and 41.7% for P4IIDV, which are significantly higher than indocyanine green and many popularly reported photothermal conversion materials. In vivo studies using xenograft 4T1 tumor-bearing mouse model demonstrate that the P4IIDV NPs can serve as a rather effective photothermal conversion nanoagent for enhanced photoacoustic imaging and photothermal therapy of tumors.