Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines
Herein, pyridinium and 4-vinylpyridinium groups are introduced into the VIE-active <i>N</i>,<i>N</i>′-disubstituted-dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines (DPAC) framework to afford a series of D-π-A-structured dihydrodibenzo[<i>a</i>,...
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/17/6392 |
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| author | Zhaozhi Zhang Qijing Wang Xinyi Zhang Dong Mei Ju Mei |
| author_facet | Zhaozhi Zhang Qijing Wang Xinyi Zhang Dong Mei Ju Mei |
| author_sort | Zhaozhi Zhang |
| collection | DOAJ |
| description | Herein, pyridinium and 4-vinylpyridinium groups are introduced into the VIE-active <i>N</i>,<i>N</i>′-disubstituted-dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines (DPAC) framework to afford a series of D-π-A-structured dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines in consideration of the aggregation-benefited performance of the DPAC module and the potential mitochondria-targeting capability of the resultant pyridinium-decorated DPACs (DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub>). To modulate the properties and elucidate the structure–property relationship, the corresponding pyridinyl/4-vinylpyridinyl-substituted DPACs, i.e., DPAC-Py and DPAC-D-Py, are designed and studied as controls. It is found that the strong intramolecular charge transfer (ICT) effect enables the effective separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub>, which is conducive to the generation of ROS. By adjusting the electron-accepting group and the π-bridge, the excitation, absorption, luminescence, photosensitizing properties as well as the mitochondria-targeting ability can be finely tuned. Both DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub> display large Stokes shifts (70–222 nm), solvent-dependent absorptions and emissions, aggregation-induced emission (AIE), red fluorescence in the aggregated state (<i>λ</i><sub>em</sub> = 600–650 nm), aggregation-promoted photosensitizing ability with the relative singlet-oxygen quantum yields higher than 1.10, and a mitochondria-targeting ability with the Pearson coefficients larger than 0.85. DPAC-D-PyPF<sub>6</sub> shows absorption maximum at a longer wavelength, slightly redder fluorescence and better photosensitivity as compared to DPAC-PyPF<sub>6</sub>, which consequently leads to the higher photocytotoxicity under the irradiation of white light as a result of the larger π-conjugation. |
| first_indexed | 2024-03-10T23:16:52Z |
| format | Article |
| id | doaj.art-f08888c430b448b08362dad5032a380a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T23:16:52Z |
| publishDate | 2023-09-01 |
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| series | Molecules |
| spelling | doaj.art-f08888c430b448b08362dad5032a380a2023-11-19T08:35:19ZengMDPI AGMolecules1420-30492023-09-012817639210.3390/molecules28176392Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazinesZhaozhi Zhang0Qijing Wang1Xinyi Zhang2Dong Mei3Ju Mei4Key Laboratory for Advanced Materials, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, ChinaKey Laboratory for Advanced Materials, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, ChinaKey Laboratory for Advanced Materials, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, ChinaClinical Research Center, Beijing Children’s Hospital, Capital Medical University, National Center for Children’s Health, Beijing 100045, ChinaKey Laboratory for Advanced Materials, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, ChinaHerein, pyridinium and 4-vinylpyridinium groups are introduced into the VIE-active <i>N</i>,<i>N</i>′-disubstituted-dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines (DPAC) framework to afford a series of D-π-A-structured dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines in consideration of the aggregation-benefited performance of the DPAC module and the potential mitochondria-targeting capability of the resultant pyridinium-decorated DPACs (DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub>). To modulate the properties and elucidate the structure–property relationship, the corresponding pyridinyl/4-vinylpyridinyl-substituted DPACs, i.e., DPAC-Py and DPAC-D-Py, are designed and studied as controls. It is found that the strong intramolecular charge transfer (ICT) effect enables the effective separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub>, which is conducive to the generation of ROS. By adjusting the electron-accepting group and the π-bridge, the excitation, absorption, luminescence, photosensitizing properties as well as the mitochondria-targeting ability can be finely tuned. Both DPAC-PyPF<sub>6</sub> and DPAC-D-PyPF<sub>6</sub> display large Stokes shifts (70–222 nm), solvent-dependent absorptions and emissions, aggregation-induced emission (AIE), red fluorescence in the aggregated state (<i>λ</i><sub>em</sub> = 600–650 nm), aggregation-promoted photosensitizing ability with the relative singlet-oxygen quantum yields higher than 1.10, and a mitochondria-targeting ability with the Pearson coefficients larger than 0.85. DPAC-D-PyPF<sub>6</sub> shows absorption maximum at a longer wavelength, slightly redder fluorescence and better photosensitivity as compared to DPAC-PyPF<sub>6</sub>, which consequently leads to the higher photocytotoxicity under the irradiation of white light as a result of the larger π-conjugation.https://www.mdpi.com/1420-3049/28/17/6392aggregation-induced emissionvibration-induced emissionphotodynamic therapymitochondria-specific imagingphotosensitizing propertiesdihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| spellingShingle | Zhaozhi Zhang Qijing Wang Xinyi Zhang Dong Mei Ju Mei Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines Molecules aggregation-induced emission vibration-induced emission photodynamic therapy mitochondria-specific imaging photosensitizing properties dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title | Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title_full | Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title_fullStr | Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title_full_unstemmed | Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title_short | Modulating the Luminescence, Photosensitizing Properties, and Mitochondria-Targeting Ability of D-π-A-Structured Dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| title_sort | modulating the luminescence photosensitizing properties and mitochondria targeting ability of d π a structured dihydrodibenzo i a i i c i phenazines |
| topic | aggregation-induced emission vibration-induced emission photodynamic therapy mitochondria-specific imaging photosensitizing properties dihydrodibenzo[<i>a</i>,<i>c</i>]phenazines |
| url | https://www.mdpi.com/1420-3049/28/17/6392 |
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