Thiol-containing hyperbranched polysiloxane for scavenging reactive oxygen species

Unconventional luminescent polymers have attracted considerable attention in the biological field due to their intrinsic fluorescence properties and excellent biocompatibility. However, exploring the luminescent properties of thiol-containing polymers and the mechanism of their scavenging of ROS remains unclear. In this work, we synthesised three kinds of hyperbranched polysiloxanes (HE, HP, and HB) with terminal thiol groups containing different chain lengths by the polycondensation reaction. Surprisingly, HP exhibits longer-wavelength emission at 480 nm with a quantum yield of 12.23% compared to HE and HB. Experiments and density functional theory (DFT) calculations have revealed that the rigidity of the conformation is enhanced by substantial hydrogen bonds and through-space O⋯O interactions in the polymer structure. These interactions, combined with the rigid carbon chains, balance the flexibility of the Si-O-C chain segments, which emerges as a critical factor contributing to the superior fluorescence performance of HP. In addition, HP exhibits excellent biocompatibility and ROS scavenging ability with a scavenging capacity of up to 35.095%. This work provides a new fluorescent polymer for scavenging ROS for the treatment of ROS-related diseases.