卟吩内酯化学:区域异构效应及其在稀土化学生物学中的应用

Porpholactone Chemistry: Regioisomeric Effect of β-Substituents and Biological Applications of Rare Earth Complexes

卟啉的区域异构效应对其电子结构和生物功能产生重要影响,β位羰基取代的不饱和卟啉衍生物尤为明显。在卟吩内酯化合物中,通过引入二内酯结构和控制内酯基团的取向精准调控卟啉配体的三线态能级,实现了对Yb3+近红外发光、单线态氧敏化、光催化反应和三线态湮灭上转换等三线态能量传递过程的调控。通过芳香性的调控实现了对区域异构效应的放大,实现生物功能化的调控。并且在近期的工作中成功实现了诊(断)(治)疗一体化以及"多合一"光诊疗试剂,展现出极好的生物医学应用前景。本文综述了区域异构效应对卟啉配体的调控及其在稀土化学生物学中的研究进展,展望了其发展的方向和趋势以及在生物医学领域广阔的应用前景。

The electronic structures and biological functions of porphyrinoids depend on the regioisomeric nature of the β-pyrrolic substituents. In the past five years, we devoted to achieve the fine tuning of triplet state energy levels in porphyrin ligands through the modulation of the relative orientation of lactone groups in porphodilactone derivatives. The fine tuning of triplet state energy level can lead to a modulation of excited-state energy transfer processes in near-infrared emission of Yb3+ ion, the sensitization of singlet oxygen, photocatalytic reaction and the triplet-triplet annihilation up-conversion(TTA-UC). Moreover, we recently found the regulation of aromaticity in porphyrinoids can amplificant this regioisomeric effect, which further induce a regulation of biological functions of these rare earth porphyrinoids complexes. And in recent work, we have successfully realized the integration of diagnosis and therapy with the "all-in-one" phototheranostic reagents and regioisomers of rare earth porphyrinoids complexes, showing an excellent prospect of these rare earth complexes for biomedical applications. In this review, we summarized our recent contributions to the tunning of porphyrin ligands by regioisomeric effect with related biological applications, possible prospects and developments in the field of biomedicine.