State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640, China.
Guangdong Provincial Key Laboratory of Medical Image Processing, School of Biomedical Engineering, Southern Medical University, Guangzhou, 510515, China.
Mater Horiz. 2023 Oct 30;10(11):4868-4881. doi: 10.1039/d3mh01263h.
Porphyrin-based photosensitizers have been widely utilized in photodynamic therapy (PDT), but they suffer from deteriorating fluorescence and reactive oxygen species (ROS) due to their close π-π stacking. Herein, a biocompatible pure organic porphyrin nanocage (Py-Cage) with enhanced both type I and type II ROS generation is reported for PDT. The porphyrin skeleton within the Py-Cage is spatially separated by four biphenyls to avoid the close π-π stacking within the nanocage. The Py-Cage showed a large cavity and high porosity with a Brunauer-Emmett-Teller surface area of over 300 m g, facilitating a close contact between the Py-Cage and oxygen, as well as the fast release of ROS to the surrounding microenvironment. The Py-Cage shows superb ROS generation performance over its precursors and commercial ones such as Chlorin E6 and Rose Bengal. Intriguingly, the cationic π-conjugated Py-Cage also shows promising type I ROS (superoxide and hydroxyl radicals) generation that is more promising for hypoxic tumor treatment. Both cell and animal experiments further confirm the excellent antitumor activity of the Py-Cage. As compared to conventional metal coordination approaches to improve PDT efficacy of porphyrin derivatives, the pure organic porous Py-Cage demonstrates excellent biocompatibility, which is further verified in both mice and rats. This work of an organic porous nanocage shall provide a new paradigm for the design of novel, biocompatible and effective photosensitizers for PDT.
基于卟啉的光敏剂已广泛应用于光动力疗法（PDT），但由于其紧密的π-π堆积，它们的荧光和活性氧物种（ROS）会恶化。在此，报道了一种具有增强的 I 型和 II 型 ROS 产生能力的生物相容性纯有机卟啉纳米笼（Py-Cage），用于 PDT。Py-Cage 中的卟啉骨架由四个联苯隔开，以避免纳米笼内的紧密 π-π 堆积。Py-Cage 具有大空腔和高孔隙率，BET 表面积超过 300 m²/g，有利于 Py-Cage 与氧气的紧密接触，以及 ROS 快速释放到周围微环境中。与前体和商业产品（如 Chlorin E6 和 Rose Bengal）相比，Py-Cage 表现出出色的 ROS 产生性能。有趣的是，带正电荷的π共轭 Py-Cage 还表现出有前途的 I 型 ROS（超氧自由基和羟基自由基）产生，这对缺氧肿瘤的治疗更有希望。细胞和动物实验进一步证实了 Py-Cage 的优异抗肿瘤活性。与传统的金属配位方法相比，提高卟啉衍生物 PDT 效果，纯有机多孔 Py-Cage 表现出优异的生物相容性，在小鼠和大鼠中得到了进一步验证。这种有机多孔纳米笼的工作为设计新型、生物相容性和有效的 PDT 光敏剂提供了一个新的范例。
