Bridging D-A type photosensitizers with the azo group to boost intersystem crossing for efficient photodynamic therapy.
Bridging D-A type photosensitizers with the azo group to boost intersystem crossing for efficient photodynamic therapy.
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DOI：
10.1039/d2sc00381c
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发表时间：
2022-04-06
期刊：
影响因子：
8.4
通讯作者：
Zhu C
中科院分区：
文献类型：
--
作者：
Hao B;Wang J;Wang C;Xue K;Xiao M;Lv S;Zhu C
光动力疗法（PDT）在疾病治疗中受到广泛关注。然而，探索一种新的方法来构建具有刺激响应性的优秀光敏剂（ps）仍然具有挑战性。在这项研究中，我们首次报道了一种新颖有效的策略，通过桥接供体-受体（D-A）型ps与偶氮基团来促进活性氧（ROS）的产生。与没有偶氮桥接的ps相比，偶氮桥接的ps在i型和ii型光化学反应中都表现出显著增强的ROS生成。理论计算表明，偶氮桥接导致ΔEST的显著减少，从而通过有效的系统间交叉（ISC）增强ROS的产生。得到的偶氮桥接PS（用Azo-TPA-Th（+）表示）对临床相关耐药菌具有特别强的杀菌作用，在白光照射下杀灭效率可达99.999999%。由于偶氮桥接产生偶氮苯结构，Azo-TPA-Th（+）在紫外线照射下可以通过关闭ISC通道进行反式到顺式异构化，形成发射聚集体。利用未结合偶氮- tpa - th（+）的荧光开启特性，我们提出了一种直接识别有效光动力杀菌剂量的简单方法，而无需进行繁琐的平板计数试验。本研究为设计ROS生成强、刺激反应性强的高级PSs开辟了全新的途径，在高质量PDT和快速预测治疗结果方面具有很大的潜力。通过将D-A型光敏剂与偶氮基团桥接，开发了一种新的有效的增强光敏的策略，在高质量的光动力治疗中具有很大的潜力，并且可以快速预测治疗结果。
Photodynamic therapy (PDT) has attracted much attention in disease treatments. However, the exploration of a novel method for the construction of outstanding photosensitizers (PSs) with stimuli-responsiveness remains challenging. In this study, we, for the first time, report a novel and effective strategy to boost reactive oxygen species (ROS) generation by bridging donor–acceptor (D–A) type PSs with the azo group. In contrast to the counterpart without azo-bridging, the azo-bridged PSs exhibit remarkably enhanced ROS generation via both type-I and type-II photochemical reactions. Theoretical calculations suggest that azo-bridging leads to a prominent reduction in ΔEST, thereby enabling enhanced ROS generation via efficient intersystem crossing (ISC). The resulting azo-bridged PS (denoted as Azo-TPA-Th(+)) exhibits a particularly strong bactericidal effect against clinically relevant drug-resistant bacteria, with the killing efficiency up to 99.999999% upon white light irradiation. Since azo-bridging generates an azobenzene structure, Azo-TPA-Th(+) can undergo trans-to-cis isomerization upon UV irradiation to form emissive aggregates by shutting down the ISC channel. By virtue of the fluorescence turn-on property of unbound Azo-TPA-Th(+), we propose a straightforward method to directly discern the effective photodynamic bactericidal dose without performing the tedious plate-counting assay. This study opens a brand-new avenue for the design of advanced PSs with both strong ROS generation and stimuli-responsiveness, holding great potential in high-quality PDT with rapid prediction of the therapeutic outcome. A novel and effective strategy is developed for enhanced photosensitization by bridging D–A type photosensitizers with the azo group, holding great potential in high-quality photodynamic therapy with rapid prediction of the therapeutic outcome.
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