Highly Selective Detection of Hypochlorous Acid by a Bis-heteroleptic Ru(II) Complex of Pyridyl-1,2,3-triazole Ligand via C(sp2)–H Hydroxylation
| Autor: | Snehadrinarayan Khatua, Sumit Kumar Patra, Sanjoy Kumar Sheet, Bhaskar Sen, Debaprasad Koner, Nirmalendu Saha |
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| Rok vydání: | 2019 |
| Předmět: |
1
2 3-Triazole Hypochlorous acid 010405 organic chemistry Stereochemistry Ligand 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Hydroxylation Cell membrane chemistry.chemical_compound medicine.anatomical_structure chemistry medicine Proton NMR Stereoselectivity Titration Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 58:9982-9991 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | A Ru(II) complex (Ru-1) of a substituted pyridyl-1,2,3-triazole ligand (BtPT) for highly selective "light-up" detection of hypochlorous acid is presented. An unusual anti-Markovnikov HOCl addition to the C═C bond of 1,2,3-triazole and a highly specific C(sp2)-H hydroxylation over epoxidation made Ru-1 a highly selective luminescent HOCl probe. The abnormal regio- and stereoselective HOCl addition and subsequent hydroxylation mechanism in detail is supported by the combination of ESI-MS, 1H/13C NMR spectroscopy, and 1H NMR titration. The hydroxylation at the C5 center in 1,2,3-triazole increases the electron density and makes BtPT a better σ-donor as well as π-donor, which in turn increases the 3MC-3MLCT energy gap and inhibits the nonradiative decay from the excited state of Ru-1 and is the key reason for luminescence light-up. Most importantly, the exogenous and endogenous HOCl imaging in the living HEK293T cells is also demonstrated. The probe showed low cytotoxicity and efficiently permeated the cell membrane. The cell-imaging experiments revealed rapid staining of the extranuclear region of HEK293T cells which clearly indicates the presence of cytoplasmic HOCl. The endogenous HOCl generation and imaging, stimulated by lipopolysaccharides (LPS) and paraquat in the HEK293T cells, is also demonstrated. |
| Databáze: | OpenAIRE |
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