LAUSR

Controlling the internal structures of single-chain nanoparticles (SCNPs) is an important factor for their targeted chemical design and synthesis, especially in view of nanosized compartments presenting different local environments as a main feature to embed functionality. We have designed SCNPs bearing near-infrared fluorescent dyes embedded in hydrophobic compartments for use as contrast agents in pump-probe photoacoustic (PA) imaging, displaying improved properties by influencing the location of the dye in the hydrophobic particle core. Compartment formation is controlled via single-chain collapse and subsequent crosslinking of an amphiphilic polymer using external crosslinkers in reaction media of adjustable polarity. Different SCNPs with hydrodynamic diameters of 6-12 nm bearing adjustable label densities were synthesized. We find that the specific conditions for single-chain collapse have a major impact on the formation of the desired core-shell structure, in turn controlling the internal nanocompartments together with the formation of excitonic dye couples, which significantly increase their fluorescence lifetime and PA signal generation. SCNPs in which the dye molecules accumulated at the core also showed a nonlinear PA response as a function of pulse energy - a property that can be exploited as a contrast mechanism in molecular PA tomography. This article is protected by copyright. All rights reserved.