Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications
The design, synthesis, and investigation of new molecular oxygen probes for bioimaging, based on phosphorescent transition metal complexes are among the topical problems of modern chemistry and advanced bioimaging. Three new iridium [Ir(N^C)<sub>2</sub>(N^N)]<sup>+</sup> comp...
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MDPI AG
2023-04-01
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| Series: | Chemosensors |
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| Online Access: | https://www.mdpi.com/2227-9040/11/5/263 |
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| author | Mozhgan Samandarsangari Ilya S. Kritchenkov Daria O. Kozina Anastasia D. Komarova Marina V. Shirmanova Sergey P. Tunik |
| author_facet | Mozhgan Samandarsangari Ilya S. Kritchenkov Daria O. Kozina Anastasia D. Komarova Marina V. Shirmanova Sergey P. Tunik |
| author_sort | Mozhgan Samandarsangari |
| collection | DOAJ |
| description | The design, synthesis, and investigation of new molecular oxygen probes for bioimaging, based on phosphorescent transition metal complexes are among the topical problems of modern chemistry and advanced bioimaging. Three new iridium [Ir(N^C)<sub>2</sub>(N^N)]<sup>+</sup> complexes with cyclometallating 4-(pyridin-2-yl)-benzoic acid derivatives and different di-imine chelate ligands have been synthesized and characterized by mass spectrometry and NMR spectroscopy. The periphery of these complexes is decorated with three relatively small “double-tail” oligo(ethylene glycol) fragments. All these complexes exhibit phosphorescence; their photophysical properties have been thoroughly studied, and quantum chemical calculations of their photophysical properties were also performed. It turned out that the changes in the nature of the di-imine ligand greatly affected the character of the electronic transitions responsible for their emission. Two complexes in this series show the desired photophysical characteristics; they demonstrate appreciable quantum yield (14–15% in degassed aqueous solutions) and a strong response to the changes in oxygen concentration, ca. three-fold increase in emission intensity, and an excited state lifetime upon deaeration of the aqueous solution. The study of their photophysical properties in model biological systems (buffer solutions containing fetal bovine serum—FBS) and cytotoxicity assays (MTT) showed that these complexes satisfy the requirements for application in bioimaging experiments. It was found that these molecular probes are internalized into cultured cancer cells and localized mainly in mitochondria and lysosomes. Phosphorescent lifetime imaging (PLIM) experiments showed that under hypoxic conditions in cells, a 1.5-fold increase in the excitation state lifetime was observed compared to aerated cells, suggesting the applicability of these complexes for the analysis of hypoxia in biological objects. |
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| last_indexed | 2024-03-11T03:51:14Z |
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| spelling | doaj.art-ead2e59f2d6b4d5ca7e8586a24d328692023-11-18T00:53:47ZengMDPI AGChemosensors2227-90402023-04-0111526310.3390/chemosensors11050263Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging ApplicationsMozhgan Samandarsangari0Ilya S. Kritchenkov1Daria O. Kozina2Anastasia D. Komarova3Marina V. Shirmanova4Sergey P. Tunik5Institute of Chemistry, St. Petersburg State University, Universitetskaya Embankment 7-9, 199034 St. Petersburg, RussiaInstitute of Chemistry, St. Petersburg State University, Universitetskaya Embankment 7-9, 199034 St. Petersburg, RussiaInstitute of Chemistry, St. Petersburg State University, Universitetskaya Embankment 7-9, 199034 St. Petersburg, RussiaInstitute of Experimental Oncology and Biomedical Technologies, Privolzhskiy Research Medical University, Minin and Pozharsky sq. 10/1, 603005 Nizhny Novgorod, RussiaInstitute of Experimental Oncology and Biomedical Technologies, Privolzhskiy Research Medical University, Minin and Pozharsky sq. 10/1, 603005 Nizhny Novgorod, RussiaInstitute of Chemistry, St. Petersburg State University, Universitetskaya Embankment 7-9, 199034 St. Petersburg, RussiaThe design, synthesis, and investigation of new molecular oxygen probes for bioimaging, based on phosphorescent transition metal complexes are among the topical problems of modern chemistry and advanced bioimaging. Three new iridium [Ir(N^C)<sub>2</sub>(N^N)]<sup>+</sup> complexes with cyclometallating 4-(pyridin-2-yl)-benzoic acid derivatives and different di-imine chelate ligands have been synthesized and characterized by mass spectrometry and NMR spectroscopy. The periphery of these complexes is decorated with three relatively small “double-tail” oligo(ethylene glycol) fragments. All these complexes exhibit phosphorescence; their photophysical properties have been thoroughly studied, and quantum chemical calculations of their photophysical properties were also performed. It turned out that the changes in the nature of the di-imine ligand greatly affected the character of the electronic transitions responsible for their emission. Two complexes in this series show the desired photophysical characteristics; they demonstrate appreciable quantum yield (14–15% in degassed aqueous solutions) and a strong response to the changes in oxygen concentration, ca. three-fold increase in emission intensity, and an excited state lifetime upon deaeration of the aqueous solution. The study of their photophysical properties in model biological systems (buffer solutions containing fetal bovine serum—FBS) and cytotoxicity assays (MTT) showed that these complexes satisfy the requirements for application in bioimaging experiments. It was found that these molecular probes are internalized into cultured cancer cells and localized mainly in mitochondria and lysosomes. Phosphorescent lifetime imaging (PLIM) experiments showed that under hypoxic conditions in cells, a 1.5-fold increase in the excitation state lifetime was observed compared to aerated cells, suggesting the applicability of these complexes for the analysis of hypoxia in biological objects.https://www.mdpi.com/2227-9040/11/5/263oxygen sensingiridium complexesphosphorescencehypoxiabioimagingphosphorescence lifetime imaging |
| spellingShingle | Mozhgan Samandarsangari Ilya S. Kritchenkov Daria O. Kozina Anastasia D. Komarova Marina V. Shirmanova Sergey P. Tunik Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications Chemosensors oxygen sensing iridium complexes phosphorescence hypoxia bioimaging phosphorescence lifetime imaging |
| title | Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications |
| title_full | Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications |
| title_fullStr | Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications |
| title_full_unstemmed | Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications |
| title_short | Phosphorescent O<sub>2</sub>-Probes Based on Ir(III) Complexes for Bioimaging Applications |
| title_sort | phosphorescent o sub 2 sub probes based on ir iii complexes for bioimaging applications |
| topic | oxygen sensing iridium complexes phosphorescence hypoxia bioimaging phosphorescence lifetime imaging |
| url | https://www.mdpi.com/2227-9040/11/5/263 |
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