Using Native Chemical Ligation for Site-specific Synthesis of Hetero- bis-lanthanide Peptide Conjugates: Application to Ratiometric Visible or Near-infrared Detection of Zn 2+

Céline Cepeda (1, 2) , Laurent Raibaut (1) , Guillaume Fremy (1, 2) , Svetlana Eliseeva (3) , Anthony Romieu (4) , Jacques Pécaut (5) , Didier Boturyn (6) , Stéphane Petoud (3) , Olivier Sénèque (1)

1 PMB - Physiochimie des Métaux
2 DCM - Département de Chimie Moléculaire
3 CBM - Centre de biophysique moléculaire
4 ICMUB - Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon]
5 CIBEST - Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie
6 DCM - I2BM - Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires

The interest for ratiometric luminescent probes that detect and quantify a specific analyte is growing. Due to their special luminescence properties, lanthanide(III) cations offer attractive opportunities for the design of dual-color ratiometric probes. Here, we describe the design principle of hetero-bis-lanthanide peptide conjugates using native chemical ligation for a perfect control of the localization of each lanthanide cation within the molecule. Two zinc-responsive probes, r-LZF1 Tb|Cs124|Eu and r-LZF1 Eu|Cs124|Tb are described on the basis of a zinc finger peptide and two DOTA complexes of terbium and europium. Both display dual-color ratiometric emission responding to the presence of Zn 2+. Using a screening approach, anthracene was identified for the sensitization of the luminescence of two near infrared-emitting lanthanides, Yb 3+ and Nd 3+. Thus, two novel zinc-responsive hetero-bis-lanthanide probes, r-LZF3 Yb|Anthra|Nd and r-LZF3 Nd|Anthra|Yb were assembled, the former offering a neat ratiometric response to Zn 2+ with emission in the near-infrared around 1000 nm, which is unprecedented.

Domaines: Chimie de coordination; Chimie organique; Chimie inorganique

Céline Cepeda, Laurent Raibaut, Guillaume Fremy, Svetlana Eliseeva, Anthony Romieu, et al.. Using Native Chemical Ligation for Site-specific Synthesis of Hetero- bis-lanthanide Peptide Conjugates: Application to Ratiometric Visible or Near-infrared Detection of Zn 2+. Chemistry - A European Journal, 2020, 26 (59), ⟨10.1002/chem.202002708⟩. ⟨hal-02944087⟩