Mechanism of Self‐Oxidative Copolymerization and its Application with Polydopamine‐pyrrole Nano‐copolymers

Abstract Currently, the copolymer of dopamine (DA) and pyrrole (PY) via chemical and electrochemical oxidation usually requires additional oxidants, and lacks flexibility in regulating the size and morphology, thereby limiting the broad applications of DA‐PY copolymer in biomedicine. Herein, the semiquinone radicals produced by the self‐oxidation of DA is ingeniously utilized as the oxidant to initiate the following copolymerization with PY, and a series of quinone‐rich polydopamine‐pyrrole copolymers (PDA m ‐nPY) with significantly enhanced absorption in near‐infrared (NIR) region without any additional oxidant assistance is obtained. Moreover, the morphology and size of PDA m ‐nPY can be regulated by changing the concentration of DA and PY, thereby optimizing nanoscale PDA 0.05 ‐0.15PY particles (≈ 150 nm) with excellent NIR absorption and surface modification activity are successfully synthesized. Such PDA 0.05 ‐0.15PY particles show effective photoacoustic (PA) imaging and photothermal therapy (PTT) against 4T1 tumors in vivo. Furthermore, other catechol derivatives can also copolymerize with PY under the same conditions. This work by fully utilizing the semiquinone radical active intermediates produced through the self‐oxidation of DA reduces the dependence on external oxidants in the synthesis of composite materials and predigests the preparation procedure, which provides a novel, simple, and green strategy for the synthesis of other newly catechol‐based functional copolymers.