Highly Selective Fluorescent Sensors: Polyethylenimine Derivatives of Triphenylamine and Coumarin for GTP and ATP Interaction via Fluorescence Lifetime Imaging Microscopy

Estefanía Delgado-Pinar; Matilde Medeiros; Telma Costa; J Sérgio Seixas de Melo

doi:10.1021/acsapm.3c00834

Highly Selective Fluorescent Sensors: Polyethylenimine Derivatives of Triphenylamine and Coumarin for GTP and ATP Interaction via Fluorescence Lifetime Imaging Microscopy

ACS Appl Polym Mater. 2023 Jul 11;5(8):6176-6185. doi: 10.1021/acsapm.3c00834. eCollection 2023 Aug 11.

Authors

Estefanía Delgado-Pinar^{1

2}, Matilde Medeiros¹, Telma Costa¹, J Sérgio Seixas de Melo¹

Affiliations

¹ CQC-IMS, Department of Chemistry, University of Coimbra, Rua Larga, Coimbra 3004-535, Portugal.
² Instituto de Ciencia, Molecular, Departamento de Química Inorgánica, Universidad de Valencia, C/Catedrático José Beltrán 2, Paterna 46980, Spain.

Abstract

Chemical derivatives of polyethylenimine (PEI) receptors with either triphenylamine (TPA) or 7-hydroxy-4-methyl-coumarin (Cou) form stable complexes with adenine and guanine nucleotides in water. The host-guest complex modulation is found to be based on noncovalent molecular interactions such as π-π stacking and hydrogen bonding, which are dependent on the aromatic moieties attached to the polyaminic (PEI) backbone. PEI-TPA acts as a chemosensor with a recognition driving force based on aggregation-induced emission (AIE), involving π-π interaction between the nucleic base and TPA. It detects GTP by a chelation enhancement quenching effect of fluorescence (CHEQ) with a measured logarithm stability constant, log β = 7.7. By varying the chemical characteristics of the fluorophore, as in the PEI-Cou system, the driving force for recognition changes from a π-π interaction to an electrostatic interaction. The coumarin derivative detects ATP with a log β value one order of magnitude higher than that for GTP, allowing for the selective recognition of the two nucleotides in a 100% aqueous solution. Furthermore, fluorescence lifetime imaging microscopy (FLIM) allows for a correlation between the selectivity of PEI-TPA toward nucleotides and the morphology of the structures formed upon ATP and GTP recognition. This study offers valuable insights into the design of receptors for the selective recognition of nucleotides in water.