Trifluoromethyl substitution enhances photoinduced activity against breast cancer cells but reduces ligand exchange in Ru(ii) complex.
Trifluoromethyl substitution enhances photoinduced activity against breast cancer cells but reduces ligand exchange in Ru(ii) complex.
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DOI：
10.1039/d1sc03213e
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发表时间：
2021-09-22
期刊：
影响因子：
8.4
通讯作者：
Turro C
中科院分区：
文献类型：
--
作者：
Lanquist AP;Gupta S;Al-Afyouni KF;Al-Afyouni M;Kodanko JJ;Turro C
合成并表征了一系列含有三苯基膦基团的五种钌配合物顺式-[Ru(bpy)2(P(P -R- ph)3)(CH3CN)]2+，其中bpy = 2,2 ' -联吡啶和P(P -R- ph)3代表R = - och3 (1), - ch3 (2) - h (3), - f(4)和- cf3(5)的对取代三苯基膦配体。在可见光（λirr≥395 nm）下，1-5在水中光解导致配位的乙腈被溶剂分子取代，生成相应的水络合物作为单个光产物。在400 nm辐照下测量了量子产率的3倍变化，Φ400，其中1是最有效的，Φ400 = 0.076(2)， 5是最不具有光活性的配合物，Φ400 = 0.026(2)。基于1的金属到配体电荷转移（MLCT）吸收比5的红移，这种趋势是意料之外的，但可以与取代基Hammett参数和辅助膦配体的pKa值相关。复合物1-5在黑暗中对三阴性乳腺癌细胞系MDA-MB-231没有毒性，但在蓝光照射下，复合物3和复合物5的细胞毒性分别提高了>4.2倍和>19倍。许多实验表明，细胞凋亡，而不是坏死或坏死下垂，是辐照后细胞死亡的机制。这些发现为理解膦配体在光诱导配体取代中的作用提供了基础，并显示了-CF3基团对光化学疗法的增强作用，这将有助于未来光化学疗法药物递送光笼的设计。Ru（ii）配合物表现出光诱导的CH3CN交换和对乳腺癌细胞的光细胞毒性，高度依赖于辅助三苯基膦配体的取代基。
A series of five ruthenium complexes containing triphenyl phosphine groups known to enhance both cellular penetration and photoinduced ligand exchange, cis-[Ru(bpy)2(P(p-R-Ph)3)(CH3CN)]2+, where bpy = 2,2′-bipyridine and P(p-R-Ph)3 represent para-substituted triphenylphosphine ligands with R = –OCH3 (1), –CH3 (2) –H (3), –F (4), and –CF3 (5), were synthesized and characterized. The photolysis of 1–5 in water with visible light (λirr ≥ 395 nm) results in the substitution of the coordinated acetonitrile with a solvent molecule, generating the corresponding aqua complex as the single photoproduct. A 3-fold variation in quantum yield was measured with 400 nm irradiation, Φ400, where 1 is the most efficient with a Φ400 = 0.076(2), and 5 the least photoactive complex, with Φ400 = 0.026(2). This trend is unexpected based on the red-shifted metal-to-ligand charge transfer (MLCT) absorption of 1 as compared to that of 5, but can be correlated to the substituent Hammett para parameters and pKa values of the ancillary phosphine ligands. Complexes 1–5 are not toxic towards the triple negative breast cancer cell line MDA-MB-231 in the dark, but 3 and 5 are >4.2 and >19-fold more cytotoxic upon irradiation with blue light, respectively. A number of experiments point to apoptosis, and not to necrosis or necroptosis, as the mechanism of cell death by 5 upon irradiation. These findings provide a foundation for understanding the role of phosphine ligands on photoinduced ligand substitution and show the enhancement afforded by –CF3 groups on photochemotherapy, which will aid the future design of photocages for photochemotherapeutic drug delivery. Ru(ii) complexes exhibit photoinduced exchange of coordinated CH3CN and photocytotoxicity against breast cancer cells highly dependent on the substituents of the ancillary triphenylphospine ligand.
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影响因子：
20.6
作者：
Knoll JD;Turro C
通讯作者：
Turro C
影响因子：
4.6
作者：
Acharya, Sourav;Maji, Moumita;Mukherjee, Arindam
通讯作者：
Mukherjee, Arindam
影响因子：
4.9
作者：
Knoll, J. D.;Albani, B. A.;Turro, C.
通讯作者：
Turro, C.
影响因子：
15
作者：
Arora K;Herroon M;Al-Afyouni MH;Toupin NP;Rohrabaugh TN Jr;Loftus LM;Podgorski I;Turro C;Kodanko JJ
通讯作者：
Kodanko JJ
影响因子：
8.4
作者：
Al-Afyouni MH;Rohrabaugh TN Jr;Al-Afyouni KF;Turro C
通讯作者：
Turro C