Wang Yang, Sun Qinning, Xie Lei, Chen Long, Zhu Fengrong, Liu Liang
School of Physical Science and Technology, Southwest Jiaotong University, Chengdu 611756, China.
School of Materials Science & Engineering, Jiangsu University, Zhenjiang 212013, P. R. China.
ACS Omega. 2023 Jul 26;8(31):28376-28386. doi: 10.1021/acsomega.3c02452. eCollection 2023 Aug 8.
Boron dipyrromethene (BODIPY)-derived dyes are generally superior emitters, but their absorption and emission fail to match the bio-active optical window (650-900 nm). In this work, we explored four bisBODIPY dyes (PB1-PB4) with easy-to-go synthesis, good solubility, high photostability, and high emission quantum yield in the deep-red region. Methyl and ethyl groups were introduced in these BODIPY dyes to improve their solubility. PB4 having a fused coplanar plane was synthesized and compared to PB1-PB3 having a non-fused structure. Their geometric structure was confirmed by single-crystal analysis, and their electronic structure, along with one-photon and two-photon absorptions, was analyzed by time-dependent functional theory calculation. Their absorption/emission spectra, emission quantum yields, and lifetimes were compared. It was found that the fused coplanar structure successfully red shifted PB4 absorption/emission to the deep-red region (698/720 nm), with a quantum yield of 0.58. PB4 showed an amplified spontaneous emission effect with an output efficiency of 6.0% at a pumping power of 3000 μJ. An improved photodynamic therapy (PDT) performance was observed from PB4 via in vitro and in vivo experiments. The practical PDT performance was evaluated by cell availability. Upon a 980 nm laser radiation of 5 min, the cell viability was decreased to ∼15%.
硼二吡咯亚甲基（BODIPY）衍生染料通常是优异的发光体，但它们的吸收和发射未能与生物活性光学窗口（650 - 900纳米）匹配。在这项工作中，我们探索了四种双BODIPY染料（PB1 - PB4），它们具有易于合成、良好的溶解性、高光稳定性以及在深红色区域具有高发射量子产率的特点。在这些BODIPY染料中引入了甲基和乙基以提高其溶解性。合成了具有稠合共面平面的PB4，并将其与具有非稠合结构的PB1 - PB3进行比较。通过单晶分析确认了它们的几何结构，并通过含时密度泛函理论计算分析了它们的电子结构以及单光子和双光子吸收。比较了它们的吸收/发射光谱、发射量子产率和寿命。发现稠合共面结构成功地将PB4的吸收/发射红移至深红色区域（698/720纳米），量子产率为0.58。PB4在3000 μJ的泵浦功率下表现出放大自发辐射效应，输出效率为6.0%。通过体外和体内实验观察到PB4具有改善的光动力疗法（PDT）性能。通过细胞存活率评估了实际的PDT性能。在980纳米激光照射5分钟后，细胞存活率降至约15%。
