Near-IR nanolignin sensitizers based on pyrene-conjugated chlorin and bacteriochlorin for ROS generation, DNA intercalation and bioimaging†

Abstract

Near-infrared (NIR) fluorescent agents are extensively used for biomedical imaging due to their ability for deep tissue penetration. Tetrapyrrole-based photosensitizers are promising candidates in this regard. Further, the extended conjugation of such macromolecules with chromophores can enhance their fluorescence efficiency and DNA intercalation ability. Herein, pyrene-conjugated NIR photosensitizers, such as chlorin (PyChl) and bacteriochlorin (PyBac), were synthesized from the corresponding pyrene–porphyrin (PyP). The correlation between the theoretical and experimental optical properties (absorption and fluorescence spectroscopy results) was determined using the DFT/TD-DFT computational approach. Next, studies on the photophysical properties, reactive oxygen species (ROS) production, and DNA binding were conducted on these macrocycles to study the effect of pyrene conjugation on the pyrrolic ring. Furthermore, each photosensitizer was loaded into lignin nanoparticles (LNPs) using the solvent–antisolvent method to accomplish fluorescence-guided imaging. The developed near-IR chlorin- and bacteriochlorin-doped lignin nanocarriers (PyChl-LNCs and PyBac-LNCs) exhibited significant in vitro singlet oxygen generation upon red LED light exposure. Moreover, these macrocycle-loaded nanolignin sensitizers showed good fluorescence-guided bioimaging with fungal cells (Candida albicans). Further, the nanoprobes exhibited pH-dependent release profiles for biological applications. These nanolignin sensitizers demonstrated promising potential to be utilized in near-IR image-guided photodynamic therapy.