Clickable Pyclen‐Based Luminescent Lanthanide Complexes: Application to Two‐Photon Microscopy
Lanthanide luminescent bioprobes incorporating a reactive group for the functionalization of biomolecules via click chemistry are of high interest for the straightforward preparation of smart luminescent tools for biological imaging and sensing applications. This article describes the synthesis and the photophysical properties of two lanthanide complexes based on the pyclen macrocycle bearing a terminal alkyne group on its pyridine moiety and a 4-(4-alkylthiophenyl)picolinate charge transfer chromophore to sensitize the lanthanide luminescence. The Eu<sup>3+</sup> and Sm<sup>3+</sup> complexes show excellent two-photon absorption and emission properties. These complexes were conjugated to a cell penetrating peptide bearing an azide via copper-catalyzed azide-alkyne cycloaddition. The resulting conjugates exhibit luminescence properties comparable to those of the parent alkyne-complex. Two-photon microscopy imaging of live HeLa cells was performed with both the Eu<sup>3+</sup> and the Sm<sup>3+</sup> conjugates. These bioprobes are efficiently delivered to the cytosol of the living cells. The Eu<sup>3+</sup> luminescence was detected in cells even at very low incubation concentration (50 nM) and the Sm<sup>3+</sup> complex gave excellent quality images despite a low emission quantum yield (< 1 %).
Authors
- Alexeï Grichine (ORCID: https://orcid.org/0000-0002-7335-9706)
- Raphaël Tripier
- Guillaume Micouin (ORCID: https://orcid.org/0000-0003-1229-1071)
- Maryline Beyler (ORCID: https://orcid.org/0000-0002-6540-970X)
- Olivier Sénèque (ORCID: https://orcid.org/0000-0002-0633-5528)
- Sule Erbek (ORCID: https://orcid.org/0000-0002-4427-0841)
- Véronique Martel‐Frachet (ORCID: https://orcid.org/0000-0001-6739-7901)
- Annika Sickinger (ORCID: https://orcid.org/0000-0001-8394-985X)
- Nadège Hamon (ORCID: https://orcid.org/0000-0002-5794-0488)
- Ákos Bányász (ORCID: https://orcid.org/0000-0002-2412-3019)
- Olivier Maury (ORCID: https://orcid.org/0000-0002-4639-643X)
- Dina Akl (ORCID: https://orcid.org/0009-0005-0611-1654)
- Baptiste Chartier
- Léo Corne
Institutions
- École Normale Supérieure de Lyon (FR)
- Centre National de la Recherche Scientifique (FR)
- Inserm (FR)
- École Pratique des Hautes Études (FR)
- Université de Bretagne Occidentale (FR)
- Commissariat à l'Énergie Atomique et aux Énergies Alternatives (FR)
- Université Paris Sciences et Lettres (FR)
- CEA Grenoble (FR)
- Institut de Recherche Interdisciplinaire de Grenoble (FR)
- Laboratoire de Physique de l'ENS de Lyon (FR)
- Laboratoire Chimie Electrochimie Moléculaires et Chimie Analytique (FR)
- Laboratoire des Sciences et Techniques de l’Information de la Communication et de la Connaissance (FR)
- Laboratoire de Chimie et Biologie des Métaux (FR)
- Laboratoire de Chimie (FR)
- Université Grenoble Alpes (FR)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-07-24
- DOI
- https://doi.org/10.1002/chem.202502044
- Citations
- 6
- Primary Topic
- Lanthanide and Transition Metal Complexes
- Type
- article
- Field-Weighted Citation Impact
- 3.11
Funders
- LABoratoires d’EXcellence ARCANE
- Infrastructures en Biologie Santé et Agronomie
- Agence Nationale de la Recherche
- Institut National de la Santé et de la Recherche Médicale
- Centre National de la Recherche Scientifique
- Commissariat à l'Énergie Atomique et aux Énergies Alternatives