String-Attached Oligothiophene Substituents Determine the Fate of Excited States in Ruthenium Complexes for Photodynamic Therapy.
String-Attached Oligothiophene Substituents Determine the Fate of Excited States in Ruthenium Complexes for Photodynamic Therapy.
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DOI：
10.1021/acs.jpca.1c04900
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发表时间：
2021-08-19
期刊：
影响因子：
--
通讯作者：
Dietzek B
中科院分区：
文献类型：
--
作者：
Chettri A;Schneider KRA;Cole HD;Roque JA 3rd;Cameron CG;McFarland SA;Dietzek B
我们探讨了Ru（II）复合物（Ru-ip-nt）的光物理特性，该特性是光动力疗法（PDT）的光敏剂。这些综合体结合了1H- imidazo [4,5-f] [1,10] - 苯磺氨酸（IP）配体附加到一个或多个噻吩环。本文研究的一种复合物是Ru-IP-3T（称为TLD1433），目前正在通过光动力疗法（PDT）治疗膀胱癌的II期临床试验中。 RU-IP-3T的有效光介毒性归因于长期寿命的内电荷转移 - 转移三重态。该状态的可访问性随着寡硫酸苯基取代基的长度（n）的变化而发生变化。在本文中，我们强调了N对Ru-ip-NT超快光诱导的动力学的影响，从而导致了函数决定的长寿命状态。飞秒时间分辨的瞬时吸收与共振拉曼数据相结合用于绘制激发态放松过程，从弗朗克 - 康登的吸收点到形成最低能量的三胞胎激发态，这是三重态至三重态的金属到钉子。 RU-IP-0T-1T的电荷转移（3MLCT）激发态和寡硫烯基 - 定位的三重态电荷转移（3ilct）RU-IP-2T-4T激发态。我们建立了激发态动力学随着噻吩链长度的函数的变化而建立的结构活性关系，从而改变了复合物的光体物理学，并可能影响了这些光激发剂的光介毒性。
We explore the photophysical properties of a family of Ru(II) complexes, Ru-ip-nT, designed as photosensitizers for photodynamic therapy (PDT). The complexes incorporate a 1H-imidazo[4,5-f][1,10]-phenanthroline (ip) ligand appended to one or more thiophene rings. One of the complexes studied herein, Ru-ip-3T (known as TLD1433), is currently in Phase II human clinical trials for treating bladder cancer by photodynamic therapy (PDT). The potent photocytotoxicity of Ru-ip-3T is attributed to a long-lived intraligand charge-transfer triplet state. The accessibility of this state changes upon varying the length (n) of the oligothiophene substituent. In this paper we highlight the impact of n on the ultrafast photoinduced dynamics in Ru-ip-nT, leading to the formation of the function-determining long-lived state. Femtosecond time-resolved transient absorption combined with resonance Raman data was used to map the excited-state relaxation processes from the Franck-Condon point of absorption to the formation of the lowest-energy triplet excited state, which is a triplet metal-to-ligand charge transfer (3MLCT) excited state for Ru-ip-0T-1T and an oligothienyl-localized triplet intraligand charge transfer (3ILCT) excited state for Ru-ip-2T-4T. We establish the structure-activity relationships with regard to changes in the excited state dynamics as a function of thiophene chain length, which alters the photophysics of the complexes and presumably impacts the photocytotoxicity of these photosensitizers.
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影响因子：
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作者：
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