Fine-tuning the Photochemistry of Sulfur-Based Linkages with Ruthenium(II) Polypyridyl Complexes for Optimal PACT Application.

IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Ramranjan Mishra, Pritha Chatterjee, Madhu Verma, Sri Sivakumar, Ashis K Patra
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引用次数: 0

Abstract

The thioether-based monodentate ligands are reported to be efficient photoreleasable groups from Ru(II)-photocages designed for photoactivated chemotherapy (PACT). However, the direct comparison and systematic studies of the photochemical behavior of sulfur linkages of varied electronic/oxidation states, i.e., sulfoxides, thioethers, or thiols coordinated with Ru(II)-polypyridyls, remain unexplored. To delve into the intricate photochemistry of Ru(II)-S linkages, two Ru(II)-polypyridyls: [Ru(ttpy)(phen)(DMSO)](PF6)2 [1](PF6)2 and [Ru(ttpy)(phen)(DAS)](PF6)2 [2](PF6)2, [ttpy = 4'-tolyl-2,2':6',2″-terpyridine, phen = 1,10-phenanthroline, DAS = diallyl sulfide, DMSO = dimethyl sulfoxide] were synthesized. Here, we used DMSO for the typical sulfoxide linkage, while DAS a biologically potent phytochemical, probed as a thioether linkage with Ru(II). The photosolvolysis monitored by UV/Vis and 1H NMR studies with white LED in CH3CN indicated more facile substitution of DAS than that of DMSO. The water-soluble [1](NO3)2 and [2](NO3)2 exhibited facile photorelease of DAS than DMSO from {Ru(ttpy)(phen)}2+-photocages in water. The cytotoxicity and photocytotoxicity studies with HeLa and Caco2 cells showed that [2](PF6)2 and [2](NO3)2 were more photocytotoxic with higher photoindices (PI) compared to [1](PF6)2 and [1](NO3)2. This apparently led to the conclusion that markedly facile photorelease of DAS resulted in higher photocytotoxicity of the DAS-based complexes. Therefore, thioether-based Ru(II)-polypyridyls portray better options for photocaging of prodrugs and PACT applications.

钌(II)聚吡啶配合物与硫基键的光化学微调,以获得最佳的PACT应用。
据报道,硫醚基单齿配体是为光活化化疗(PACT)设计的Ru(II)光笼的有效光释放基团。然而,对不同电子/氧化态的硫键,即与Ru(II)-聚吡啶配位的亚砜、硫醚或硫醇的光化学行为的直接比较和系统研究仍未得到探索。为了深入研究Ru(II)-S键复杂的光物理和光化学,合成了两个Ru(II)-多吡啶基:[Ru(ttpy)(phen)(DMSO)](PF6)2 [1](PF6)2, [Ru(ttpy)(phen)(DAS)](PF6)2 [2](PF6)2, [ttpy = 4'-甲苯基-2,2':6',2″-三吡啶,phen = 1,10-菲罗啉,DAS =二烯丙基硫化物,DMSO =二甲亚砜]。在这里,我们使用DMSO作为典型的亚砜连接,而DAS是一种具有生物效力的植物化学物质,作为与Ru(II)的硫醚连接进行探测。用白光LED对MeCN的光溶解度进行了紫外可见和核磁共振监测,结果表明DMSO的取代速度比DAS慢。在水中,水溶性[1](NO3)2和[2](NO3)2在{Ru(ttpy)(phen)}2+-光笼中比DMSO更容易释放DAS。HeLa和Caco2细胞的细胞毒性和光毒性研究表明,[2](PF6)2和[2](NO3)2比[1](PF6)2和[1](NO3)2具有更强的光毒性和更高的光指数。这显然可以得出结论,DAS的明显易光释放导致DAS基复合物具有较高的光细胞毒性。因此,基于硫醚的Ru(II)-聚吡啶基为前药和PACT应用提供了更好的选择。
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来源期刊
Chemistry - A European Journal
Chemistry - A European Journal 化学-化学综合
CiteScore
7.90
自引率
4.70%
发文量
1808
审稿时长
1.8 months
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.
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