Photothermal motion: effect of low-intensity irradiation on the thermal motion of organic nanoparticles

Abstract

The effect of local photo-triggered heat release on the motion of organic nanopartcles (NP), a process that is itself thermal, is largely unexplored under low-intensity irradiation. Here, we develop organic NP specifically tailored for this study and demonstrate, comparing three different irradiation intensity regimes, that indeed the NP undergo “acceleration” upon light absorption (Photothermal Motion). These NP have a well-defined chemical composition and extremely high molar absorbance coefficient, and upon excitation, they deactivate mostly non radiatively with localized heat dissipation. The residual fluorescence efficiency is high enough to allow the detection of their trajectory in a simple wide field fluorescence microscope under low-intensity irradiation, a typical condition for NP bio-applications. The NP were characterized in detail from the photophysical point of view using UV-VIS absorption, steady-state and time-resolved fluorescence spectroscopy and ultra-fast transient absorption (UF-TA). A detailed analysis of the trajectories of the NP reveals a strong dependency of the diffusion coefficient on the irradiation intensity even in a low power regime. This behavior demonstrates the inhomogeneity of the environment surrounding the NP as a result of local heat generation. Upon irradiation, the effective temperature increase, that emerges from the analysis, is much larger than that expected for plasmonic NP. Anomalous diffusion object-motion analysis (ADOMA) revealed that, in the more intense irradiation regime, the motion of the NP is a fractional Brownian motion, which is a simple generalization of Brownian motion where the steps are not independent of each other.