Phosphorescent sensor for biological mobile zinc
A new phosphorescent zinc sensor (ZIrF) was constructed, based on an Ir(III) complex bearing two 2-(2,4-difluorophenyl)pyridine (dfppy) cyclometalating ligands and a neutral 1,10-phenanthroline (phen) ligand. A zinc-specific di(2-picolyl)amine (DPA) receptor was introduced at the 4-position of the p...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2012
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| Online Access: | http://hdl.handle.net/1721.1/74071 https://orcid.org/0000-0002-2693-4982 |
| _version_ | 1811081687505829888 |
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| author | You, Youngmin Lee, Sumin Kim, Tae Hee Ohkubo, Kei Chae, Weon-Sik Fukuzumi, Shunichi Jhon, Gil-Ja Nam, Wonwoo Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry You, Youngmin Lee, Sumin Kim, Tae Hee Ohkubo, Kei Chae, Weon-Sik Fukuzumi, Shunichi Jhon, Gil-Ja Nam, Wonwoo Lippard, Stephen J. |
| author_sort | You, Youngmin |
| collection | MIT |
| description | A new phosphorescent zinc sensor (ZIrF) was constructed, based on an Ir(III) complex bearing two 2-(2,4-difluorophenyl)pyridine (dfppy) cyclometalating ligands and a neutral 1,10-phenanthroline (phen) ligand. A zinc-specific di(2-picolyl)amine (DPA) receptor was introduced at the 4-position of the phen ligand via a methylene linker. The cationic Ir(III) complex exhibited dual phosphorescence bands in CH[subscript 3]CN solutions originating from blue and yellow emission of the dfppy and phen ligands, respectively. Zinc coordination selectively enhanced the latter, affording a phosphorescence ratiometric response. Electrochemical techniques, quantum chemical calculations, and steady-state and femtosecond spectroscopy were employed to establish a photophysical mechanism for this phosphorescence response. The studies revealed that zinc coordination perturbs nonemissive processes of photoinduced electron transfer and intraligand charge-transfer transition occurring between DPA and phen. ZIrF can detect zinc ions in a reversible and selective manner in buffered solution (pH 7.0, 25 mM PIPES) with K[subscript d] = 11 nM and pK[subscript a] = 4.16. Enhanced signal-to-noise ratios were achieved by time-gated acquisition of long-lived phosphorescence signals. The sensor was applied to image biological free zinc ions in live A549 cells by confocal laser scanning microscopy. A fluorescence lifetime imaging microscope detected an increase in photoluminescence lifetime for zinc-treated A549 cells as compared to controls. ZIrF is the first successful phosphorescent sensor that detects zinc ions in biological samples. |
| first_indexed | 2024-09-23T11:50:31Z |
| format | Article |
| id | mit-1721.1/74071 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:50:31Z |
| publishDate | 2012 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/740712022-10-01T06:24:16Z Phosphorescent sensor for biological mobile zinc You, Youngmin Lee, Sumin Kim, Tae Hee Ohkubo, Kei Chae, Weon-Sik Fukuzumi, Shunichi Jhon, Gil-Ja Nam, Wonwoo Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Lippard, Stephen J. You, Youngmin Lippard, Stephen J. A new phosphorescent zinc sensor (ZIrF) was constructed, based on an Ir(III) complex bearing two 2-(2,4-difluorophenyl)pyridine (dfppy) cyclometalating ligands and a neutral 1,10-phenanthroline (phen) ligand. A zinc-specific di(2-picolyl)amine (DPA) receptor was introduced at the 4-position of the phen ligand via a methylene linker. The cationic Ir(III) complex exhibited dual phosphorescence bands in CH[subscript 3]CN solutions originating from blue and yellow emission of the dfppy and phen ligands, respectively. Zinc coordination selectively enhanced the latter, affording a phosphorescence ratiometric response. Electrochemical techniques, quantum chemical calculations, and steady-state and femtosecond spectroscopy were employed to establish a photophysical mechanism for this phosphorescence response. The studies revealed that zinc coordination perturbs nonemissive processes of photoinduced electron transfer and intraligand charge-transfer transition occurring between DPA and phen. ZIrF can detect zinc ions in a reversible and selective manner in buffered solution (pH 7.0, 25 mM PIPES) with K[subscript d] = 11 nM and pK[subscript a] = 4.16. Enhanced signal-to-noise ratios were achieved by time-gated acquisition of long-lived phosphorescence signals. The sensor was applied to image biological free zinc ions in live A549 cells by confocal laser scanning microscopy. A fluorescence lifetime imaging microscope detected an increase in photoluminescence lifetime for zinc-treated A549 cells as compared to controls. ZIrF is the first successful phosphorescent sensor that detects zinc ions in biological samples. National Institute of General Medical Sciences (U.S.) (Grant GM065519) Ewha Woman's University (Korea) (RP-Grant 2010) 2012-10-18T14:39:46Z 2012-10-18T14:39:46Z 2011-10 2011-07 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/74071 You, Youngmin et al. “Phosphorescent Sensor for Biological Mobile Zinc.” Journal of the American Chemical Society 133.45 (2011): 18328–18342. https://orcid.org/0000-0002-2693-4982 en_US http://dx.doi.org/10.1021/ja207163r Journal of the American Chemical Society Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf American Chemical Society (ACS) Prof. Lippard via Erja Kajosalo |
| spellingShingle | You, Youngmin Lee, Sumin Kim, Tae Hee Ohkubo, Kei Chae, Weon-Sik Fukuzumi, Shunichi Jhon, Gil-Ja Nam, Wonwoo Lippard, Stephen J. Phosphorescent sensor for biological mobile zinc |
| title | Phosphorescent sensor for biological mobile zinc |
| title_full | Phosphorescent sensor for biological mobile zinc |
| title_fullStr | Phosphorescent sensor for biological mobile zinc |
| title_full_unstemmed | Phosphorescent sensor for biological mobile zinc |
| title_short | Phosphorescent sensor for biological mobile zinc |
| title_sort | phosphorescent sensor for biological mobile zinc |
| url | http://hdl.handle.net/1721.1/74071 https://orcid.org/0000-0002-2693-4982 |
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