An Ester‐Substituted Semiconducting Polymer with Efficient Nonradiative Decay Enhances NIR‐II Photoacoustic Performance for Monitoring of Tumor Growth

• Published in: Angewandte Chemie International Edition 2020-12, Vol.59 (51), p.23268-23276
• Main Authors: Zha, Menglei, Lin, Xiangwei, Ni, Jen‐Shyang, Li, Yaxi, Zhang, Yachao, Zhang, Xun, Wang, Lidai, Li, Kai
• Format: Article
• Language: English
• Subjects: Adiabatic; Animals; Antineoplastic Agents - chemical synthesis; Antineoplastic Agents - chemistry; Antineoplastic Agents - pharmacology; Azo Compounds - chemical synthesis; Azo Compounds - chemistry; Azo Compounds - pharmacology; Cell Line, Tumor; Cell Proliferation - drug effects; Cell Survival - drug effects; Charge transfer; Decay; Density Functional Theory; Dihedral angle; Drug Screening Assays, Antitumor; Esters - chemistry; Humans; Infrared Rays; Medical imaging; Mice; Molecular Structure; Nanoparticles; Nanoparticles - chemistry; Neoplasms - diagnostic imaging; Neoplasms - drug therapy; photoacoustic; Photoacoustic Techniques; Photothermal conversion; Photothermal Therapy; Polymers; Polymers - chemical synthesis; Polymers - chemistry; Polymers - pharmacology; Quinoxalines - chemical synthesis; Quinoxalines - chemistry; Quinoxalines - pharmacology; reorganization energy; reversed AIE; Semiconductors; Substitutes; TICT; Tumors
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202010228

Photoacoustic agents have been of vital importance for improving the imaging contrast and reliability against self‐interference from endogenous substances. Herein, we synthesized a series of thiadiazoloquinoxaline (TQ)‐based semiconducting polymers (SPs) with a broad absorption covering from NIR‐I to NIR‐II regions. Among them, the excited s‐BDT‐TQE, a repeating unit of SPs, shows a large dihedral angle and narrow adiabatic energy as well as low radiative decay, attributing to its strongly electron‐deficient ester‐substituted TQ‐segment. In addition, its more vigorous molecular motions trigger a higher reorganization energy that further yields an efficient photoinduced nonradiative decay, which has been carefully examined and understood by theoretical calculation. Thus, BDT‐TQE SP‐cored nanoparticles with twisted intramolecular charge transfer (TICT) feature exhibit a high NIR‐II photothermal conversion efficiency (61.6 %) and preferable PA tracking of in situ hepatic tumor growth for more than 20 days. This study highlights a unique strategy for constructing efficient NIR‐II photoacoustic agents via TICT‐enhanced PNRD effect, advancing their applications for in vivo bioimaging. A NIR‐II‐absorbing semiconducting polymer served as an excellent photoacoustic (PA) agent, which was constructed via substitution of strong electron‐withdrawing of ester‐groups. Such agent with TICT‐enhanced reorganization energy (Er) and nonradiative decay (kr) exhibits high photothermal conversion efficiency and PA performance, realizing in vivo long‐term monitoring of tumor growth.