Fluorescence probes for prokaryotic and eukaryotic cells using Re(CO)3+ complexes with an electron withdrawing ancillary ligand

A. Carreño, M. Gacitúa, J. A. Fuentes, D. Páez-Hernández, J. P. Peñaloza, C. Otero, M. Preite, E. Molins, W. B. Swords, G. J. Meyer, J. Manuel Manríquez, R. Polanco, I. Chávez, R. Arratia-Pérez

Research output: Contribution to journalArticle

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Abstract

Research in fluorescence microscopy presents new challenges, especially with respect to the development of new metal-based fluorophores. In this work, new fac-[Re(CO)3(bpy)L]PF6 (C3) and fac-[Re(CO)3(dmb)L]PF6 (C4) complexes, where L is an ancillary ligand, E-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6-di-tert-butylphenol, both exhibiting an intramolecular hydrogen bond, have been synthesized for use as preliminary probes for fluorescence microscopy. The complexes were characterized using chemical techniques such as UV-vis, 1H-NMR, TOCSY, FT-IR, cyclic voltammetry, mass spectrometry (EI-MS 752.22 M+ for C3 and 780.26 M+ for C4) and DFT calculations including spin-orbit effects. The electron withdrawing nature of the ancillary ligand L in C3 and C4 explains their electrochemical behavior, which shows the oxidation of ReI at 1.84 V for C3 and at 1.88 V for C4. The UV-vis absorption and emission properties have been studied at room temperature in acetonitrile solution. The complexes show luminescent emission with a large Stokes shift (λex = 366 nm, λem = 610 nm for C3 and λex = 361 nm, λem = 560 nm for C4). The TDDFT calculations suggest that an experimental mixed absorption band at 360 nm could be assigned to MLCT (d(Re) → π∗(dmb)) and LLCT (π(L) → π∗(dmb)) transitions. We have also assessed the cytotoxicity of C3 and C4 in an epithelial cell line (T84). We found that 12.5 μg ml-1 of C3 or C4 is the minimum concentration needed to kill 80% of the cell population, as determined by neutral red uptake. Finally, the potential of C3 and C4 as biological dyes for use in fluorescent microscopy was assessed in bacteria (Salmonella enterica) and yeasts (Candida albicans and Cryptococcus spp.), and in an ovarian cancer cell line (SKOV-3). We found that in all cases, both C3 and C4 are suitable compounds to be used as fluorescent dyes for biological purposes. In addition, we present evidence suggesting that these rhenium(i) tricarbonyl complexes may be also useful as differential fluorescent dyes in yeasts (Candida albicans and Cryptococcus spp.), without the need for antibodies.

Original languageEnglish
Pages (from-to)7687-7700
Number of pages14
JournalNew Journal of Chemistry
Volume40
Issue number9
DOIs
Publication statusPublished - 1 Jan 2016

Fingerprint

Candida
Fluorescence microscopy
Carbon Monoxide
Fluorescent Dyes
Yeast
Dyes
Fluorescence
Ligands
Cells
Rhenium
Neutral Red
Salmonella
Fluorophores
Electrons
Cytotoxicity
Discrete Fourier transforms
Cyclic voltammetry
Mass spectrometry
Absorption spectra
Bacteria

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

Carreño, A. ; Gacitúa, M. ; Fuentes, J. A. ; Páez-Hernández, D. ; Peñaloza, J. P. ; Otero, C. ; Preite, M. ; Molins, E. ; Swords, W. B. ; Meyer, G. J. ; Manríquez, J. Manuel ; Polanco, R. ; Chávez, I. ; Arratia-Pérez, R. / Fluorescence probes for prokaryotic and eukaryotic cells using Re(CO)3+ complexes with an electron withdrawing ancillary ligand. In: New Journal of Chemistry. 2016 ; Vol. 40, No. 9. pp. 7687-7700.
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abstract = "Research in fluorescence microscopy presents new challenges, especially with respect to the development of new metal-based fluorophores. In this work, new fac-[Re(CO)3(bpy)L]PF6 (C3) and fac-[Re(CO)3(dmb)L]PF6 (C4) complexes, where L is an ancillary ligand, E-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6-di-tert-butylphenol, both exhibiting an intramolecular hydrogen bond, have been synthesized for use as preliminary probes for fluorescence microscopy. The complexes were characterized using chemical techniques such as UV-vis, 1H-NMR, TOCSY, FT-IR, cyclic voltammetry, mass spectrometry (EI-MS 752.22 M+ for C3 and 780.26 M+ for C4) and DFT calculations including spin-orbit effects. The electron withdrawing nature of the ancillary ligand L in C3 and C4 explains their electrochemical behavior, which shows the oxidation of ReI at 1.84 V for C3 and at 1.88 V for C4. The UV-vis absorption and emission properties have been studied at room temperature in acetonitrile solution. The complexes show luminescent emission with a large Stokes shift (λex = 366 nm, λem = 610 nm for C3 and λex = 361 nm, λem = 560 nm for C4). The TDDFT calculations suggest that an experimental mixed absorption band at 360 nm could be assigned to MLCT (d(Re) → π∗(dmb)) and LLCT (π(L) → π∗(dmb)) transitions. We have also assessed the cytotoxicity of C3 and C4 in an epithelial cell line (T84). We found that 12.5 μg ml-1 of C3 or C4 is the minimum concentration needed to kill 80{\%} of the cell population, as determined by neutral red uptake. Finally, the potential of C3 and C4 as biological dyes for use in fluorescent microscopy was assessed in bacteria (Salmonella enterica) and yeasts (Candida albicans and Cryptococcus spp.), and in an ovarian cancer cell line (SKOV-3). We found that in all cases, both C3 and C4 are suitable compounds to be used as fluorescent dyes for biological purposes. In addition, we present evidence suggesting that these rhenium(i) tricarbonyl complexes may be also useful as differential fluorescent dyes in yeasts (Candida albicans and Cryptococcus spp.), without the need for antibodies.",
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Fluorescence probes for prokaryotic and eukaryotic cells using Re(CO)3+ complexes with an electron withdrawing ancillary ligand. / Carreño, A.; Gacitúa, M.; Fuentes, J. A.; Páez-Hernández, D.; Peñaloza, J. P.; Otero, C.; Preite, M.; Molins, E.; Swords, W. B.; Meyer, G. J.; Manríquez, J. Manuel; Polanco, R.; Chávez, I.; Arratia-Pérez, R.

In: New Journal of Chemistry, Vol. 40, No. 9, 01.01.2016, p. 7687-7700.

Research output: Contribution to journalArticle

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T1 - Fluorescence probes for prokaryotic and eukaryotic cells using Re(CO)3+ complexes with an electron withdrawing ancillary ligand

AU - Carreño, A.

AU - Gacitúa, M.

AU - Fuentes, J. A.

AU - Páez-Hernández, D.

AU - Peñaloza, J. P.

AU - Otero, C.

AU - Preite, M.

AU - Molins, E.

AU - Swords, W. B.

AU - Meyer, G. J.

AU - Manríquez, J. Manuel

AU - Polanco, R.

AU - Chávez, I.

AU - Arratia-Pérez, R.

PY - 2016/1/1

Y1 - 2016/1/1

N2 - Research in fluorescence microscopy presents new challenges, especially with respect to the development of new metal-based fluorophores. In this work, new fac-[Re(CO)3(bpy)L]PF6 (C3) and fac-[Re(CO)3(dmb)L]PF6 (C4) complexes, where L is an ancillary ligand, E-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6-di-tert-butylphenol, both exhibiting an intramolecular hydrogen bond, have been synthesized for use as preliminary probes for fluorescence microscopy. The complexes were characterized using chemical techniques such as UV-vis, 1H-NMR, TOCSY, FT-IR, cyclic voltammetry, mass spectrometry (EI-MS 752.22 M+ for C3 and 780.26 M+ for C4) and DFT calculations including spin-orbit effects. The electron withdrawing nature of the ancillary ligand L in C3 and C4 explains their electrochemical behavior, which shows the oxidation of ReI at 1.84 V for C3 and at 1.88 V for C4. The UV-vis absorption and emission properties have been studied at room temperature in acetonitrile solution. The complexes show luminescent emission with a large Stokes shift (λex = 366 nm, λem = 610 nm for C3 and λex = 361 nm, λem = 560 nm for C4). The TDDFT calculations suggest that an experimental mixed absorption band at 360 nm could be assigned to MLCT (d(Re) → π∗(dmb)) and LLCT (π(L) → π∗(dmb)) transitions. We have also assessed the cytotoxicity of C3 and C4 in an epithelial cell line (T84). We found that 12.5 μg ml-1 of C3 or C4 is the minimum concentration needed to kill 80% of the cell population, as determined by neutral red uptake. Finally, the potential of C3 and C4 as biological dyes for use in fluorescent microscopy was assessed in bacteria (Salmonella enterica) and yeasts (Candida albicans and Cryptococcus spp.), and in an ovarian cancer cell line (SKOV-3). We found that in all cases, both C3 and C4 are suitable compounds to be used as fluorescent dyes for biological purposes. In addition, we present evidence suggesting that these rhenium(i) tricarbonyl complexes may be also useful as differential fluorescent dyes in yeasts (Candida albicans and Cryptococcus spp.), without the need for antibodies.

AB - Research in fluorescence microscopy presents new challenges, especially with respect to the development of new metal-based fluorophores. In this work, new fac-[Re(CO)3(bpy)L]PF6 (C3) and fac-[Re(CO)3(dmb)L]PF6 (C4) complexes, where L is an ancillary ligand, E-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6-di-tert-butylphenol, both exhibiting an intramolecular hydrogen bond, have been synthesized for use as preliminary probes for fluorescence microscopy. The complexes were characterized using chemical techniques such as UV-vis, 1H-NMR, TOCSY, FT-IR, cyclic voltammetry, mass spectrometry (EI-MS 752.22 M+ for C3 and 780.26 M+ for C4) and DFT calculations including spin-orbit effects. The electron withdrawing nature of the ancillary ligand L in C3 and C4 explains their electrochemical behavior, which shows the oxidation of ReI at 1.84 V for C3 and at 1.88 V for C4. The UV-vis absorption and emission properties have been studied at room temperature in acetonitrile solution. The complexes show luminescent emission with a large Stokes shift (λex = 366 nm, λem = 610 nm for C3 and λex = 361 nm, λem = 560 nm for C4). The TDDFT calculations suggest that an experimental mixed absorption band at 360 nm could be assigned to MLCT (d(Re) → π∗(dmb)) and LLCT (π(L) → π∗(dmb)) transitions. We have also assessed the cytotoxicity of C3 and C4 in an epithelial cell line (T84). We found that 12.5 μg ml-1 of C3 or C4 is the minimum concentration needed to kill 80% of the cell population, as determined by neutral red uptake. Finally, the potential of C3 and C4 as biological dyes for use in fluorescent microscopy was assessed in bacteria (Salmonella enterica) and yeasts (Candida albicans and Cryptococcus spp.), and in an ovarian cancer cell line (SKOV-3). We found that in all cases, both C3 and C4 are suitable compounds to be used as fluorescent dyes for biological purposes. In addition, we present evidence suggesting that these rhenium(i) tricarbonyl complexes may be also useful as differential fluorescent dyes in yeasts (Candida albicans and Cryptococcus spp.), without the need for antibodies.

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