Theoretical Studies on Two-Photon Fluorescent Hg2+ Probes Based on the Coumarin-Rhodamine System

Abstract

The development of fluorescent sensors for Hg²⁺ has attracted much attention due to the well-known adverse effects of mercury on biological health. In the present work, the optical properties of two newly-synthesized Hg²⁺ chemosensors based on the coumarin-rhodamine system (named Pro1 and Pro2) were systematically investigated using time-dependent density functional theory. It is shown that Pro1 and Pro2 are effective ratiometric fluorescent Hg²⁺ probes, which recognize Hg²⁺ by Förster resonance energy transfer and through bond energy transfer mechanisms, respectively. To further understand the mechanisms of the two probes, we have developed an approach to predict the energy transfer rate between the donor and acceptor. Using this approach, it can be inferred that Pro1 has a six times higher energy transfer rate than Pro2. Thus the influence of spacer group between the donor and acceptor on the sensing performance of the probe is demonstrated. Specifically, two-photon absorption properties of these two probes are calculated. We have found that both probes show significant two-photon responses in the near-infrared light region. However, only the maximum two-photon absorption cross section of Pro1 is greatly enhanced with the presence of Hg²⁺, indicating that Pro1 can act as a potential two-photon excited fluorescent probe for Hg²⁺. The theoretical investigations would be helpful to build a relationship between the structure and the optical properties of the probes, providing information on the design of efficient two-photon fluorescent sensors that can be used for biological imaging of Hg²⁺ in vivo.

Keywords: fluorescent Hg2+ probe; time-dependent density functional theory; two-photon absorption.

Figure 1

Molecular structures of Pro1, Pro1 + Hg²⁺, Pro2 and Pro2 + Hg²⁺.

Figure 2

Optimized ground state geometries of Pro1, Pro1 + Hg²⁺, Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 3

The OPA spectra of (a) Pro1 and Pro1 + Hg²⁺, (b) Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 4

Molecular orbitals involved in the transition of the OPA peaks for (a) Pro1 and Pro1 + Hg²⁺; (b) Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 5

Optimized first excited state geometries of Pro1, Pro1 + Hg²⁺, Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 6

The OPE spectra of (a) Pro1 and Pro1 + Hg²⁺, (b) Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 7

Molecular orbitals involved in the transition of the OPE peaks for (a) Pro1 and Pro1 + Hg²⁺; (b) Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.

Figure 8

Schematic of coordinate direction.

Figure 9

Molecular orbitals involved in the transition of the TPA peaks for (a) Pro1 and Pro1 + Hg²⁺, (b) Pro2 and Pro2 + Hg²⁺ with PCM simulating the dielectric of water.