Institute of Molecular Science and Engineering, Institute of Frontier and Interdisciplinary Science, Shandong University, Qingdao, Shandong 266237, China.
College of Bioengineering, Chongqing University, Chongqing 400044, China.
J Mater Chem B. 2022 Aug 10;10(31):5968-5975. doi: 10.1039/d2tb00720g.
Due to their excellent electronic and optical properties, porphyrins are extensively studied conjugated macrocycles in supramolecular chemistry for assembling functional nanomaterials. Although the aggregation of monomers plays a significant role in driving the self-assembly process into ordered nanostructures, it remains a challenge for tuning the self-assembling behavior of porphyrins through molecular structure modifications, especially in aqueous solutions. In the present work, two novel water-soluble porphyrin derivatives were synthesized by introducing cationic linear side chains into the π-conjugated core for phosphate-templated assembly through electrostatic interactions. It was found that the stacking patterns (H- or J-type aggregation) of porphyrins could be tuned by varying the number of side chains, which are associated with dramatic morphological change. The cytotoxicity and photodynamic properties of the J-aggregation-driven nano-assemblies were also investigated for the purpose of -cancer treatment. This study demonstrates a facile and effective strategy to regulate the aqueous self-assembling behavior of porphyrins that can impact the structure and properties of assembly, which will be of great benefit to the design and synthesis of functional nanomaterials for specific applications.
由于其优异的电子和光学性能，卟啉在超分子化学中作为组装功能纳米材料的共轭大环被广泛研究。虽然单体的聚集在驱动自组装过程进入有序纳米结构中起着重要作用，但通过分子结构修饰来调节卟啉的自组装行为仍然是一个挑战，特别是在水溶液中。在本工作中，通过在π-共轭核中引入阳离子线性侧链，通过静电相互作用在磷酸盐模板组装中合成了两种新型水溶性卟啉衍生物。研究发现，通过改变侧链的数量可以调节卟啉的堆积模式（H 型或 J 型聚集），这与形态的显著变化有关。还研究了 J-聚集驱动的纳米组装体的细胞毒性和光动力性质，以用于癌症治疗。该研究展示了一种简单有效的调节卟啉在水溶液中自组装行为的策略，这可以影响组装的结构和性质，这对于设计和合成特定应用的功能纳米材料将是非常有益的。
