Novel V-shaped D-π-A-π-D two-photon absorption compounds with large Stokes shifts: Synthesis, optical properties, selective detection of cysteine, and imaging in living cells

Abstract

The novel V-shaped donor-π-acceptor-π-donor compounds bearing an aldehyde group (1Pip, 2EtO, and 3TEG) were designed, synthesized, and evaluated as the two-photon excited fluorescence probes for the selective detection of cysteine (Cys). Their structures were fully characterized by 1H NMR, 13C NMR, FT-IR, and HRMS. The optical properties of the target compounds in various solvents were studied in details and the time-dependent density functional theory calculations were performed to shed light on their electronic structures. It is found that all of them exhibit large Stokes shifts (6331-10047 cm−1). 1Pip and 3TEG are capable of detecting Cys with high selectivity, good anti-interference ability, and favorable two-photon absorption performance. The limits of detection were determined to be equal to 0.15 μM for 1Pip and 0.73 μM for 3TEG. The possible recognition mechanism was also validated by 1H NMR and HRMS. One- and two-photon fluorescence imaging experiments indicate that 3TEG shows more satisfactory cellular membrane permeability than 1Pip, and it can successfully visualize the endogenous and exogenous Cys in living cells. These results imply that 3TEG has potential as a two-photon fluorescence probe for detecting Cys in biological samples.