O'Sullivan Stephen, Tabrizi Leila, Turzańska Kaja, Clark Ian P, Fitzgerald-Hughes Deirdre, Pryce Mary T
School of Chemical Sciences, Dublin City University, D09W6Y4 Dublin, Ireland.
Department of Clinical Microbiology, Royal College of Surgeons in Ireland, RCSI Education and Research, Beaumont Hospital, Beaumont, D09YD60 Dublin, Ireland.
Molecules. 2025 Jun 25;30(13):2727. doi: 10.3390/molecules30132727.
This work presents the synthesis, characterisation, photophysical properties, time-resolved spectroscopic behaviour, and biological evaluation of two structurally distinct heavy-atom-free BODIPY-anthracene dyads () and the newly designed 2,6-bis[1-(tert-butyl) 4-(prop-2-yn-1-yl) piperazine-1,4-dicarboxylate] BODIPY-anthracene (), incorporating 2,6-alkynyl-piperazine substituents for potential application in antimicrobial photodynamic therapy. exhibits absorption and emission maxima at 507 nm and 516 nm, respectively, with a Stokes shift of 344 cm in dichloromethane (DCM), characteristic of unsubstituted BODIPYs. In contrast, undergoes a red-shift in the absorption maximum to 552 nm (Stokes shift of 633 cm), which is attributed to the extended conjugation from the introduction of the alkyne groups. Time-resolved infrared spectroscopy confirmed efficient spin-orbit charge transfer intersystem crossing, and nanosecond transient absorption studies confirmed the formation of a long-lived triplet state for (up to 138 µs in MeCN). A binding constant (K) of 9.6 × 10 M was obtained for when titrated with bovine serum albumin (BSA), which is higher than comparable BODIPY derivatives. displayed improved hemocompatibility compared to (<5% haemolysis of human erythrocytes up to 200 μg·mL). Antimicrobial activity of and was most potent when irradiated at 370 nm compared to the other wavelengths employed. However, did not retain the potent (6 log) and rapid (within 15 min) eradication of achieved by under irradiation at 370 nm. These findings demonstrate the rational design of as a biocompatible, and heavy-atom-free BODIPY offering promise for targeted antimicrobial photodynamic therapeutic applications.
本研究展示了两种结构不同的无重原子硼二吡咯-蒽二元化合物（）以及新设计的2,6-双[1-(叔丁基)-4-(丙-2-炔-1-基)哌嗪-1,4-二羧酸酯]硼二吡咯-蒽（）的合成、表征、光物理性质、时间分辨光谱行为和生物学评价，该化合物引入了2,6-炔基哌嗪取代基，具有在抗菌光动力疗法中的潜在应用价值。在二氯甲烷（DCM）中，分别在507 nm和516 nm处呈现吸收和发射最大值，斯托克斯位移为344 cm，这是未取代硼二吡咯的特征。相比之下，吸收最大值发生红移至552 nm（斯托克斯位移为633 cm），这归因于炔基引入导致的共轭扩展。时间分辨红外光谱证实了有效的自旋-轨道电荷转移系间窜越，纳秒瞬态吸收研究证实了形成了长寿命三重态（在乙腈中长达138 μs）。用牛血清白蛋白（BSA）滴定得到的结合常数（K）为9.6×10 M，高于同类硼二吡咯衍生物。与相比，显示出改善的血液相容性（在高达200 μg·mL时人红细胞溶血率<5%）。与其他使用的波长相比，和在370 nm照射时抗菌活性最强。然而，在370 nm照射下，没有保持所实现的强效（6 log）和快速（15分钟内）根除效果。这些发现证明了作为一种生物相容性无重原子硼二吡咯的合理设计，为靶向抗菌光动力治疗应用带来了希望。
