Three new turn-on fluorescent sensors for the selective detection of Zn2+: Synthesis, properties and DFT studies

Abstract

The design and synthesis of three new 1,8-naphthalimide-based fluorescent sensors (1–3) for the detection of Zn2+ in aqueous solution is described. The structural architect of these sensors contains 1,8-naphthalimide scaffold as a fluorophore attached to 2,2′-dipicolylamine (DPA) and bis(2-quinolinylmethyl)amine (DQA) receptors through an amide linkage. The addition of Zn2+ to the solutions of sensors (1–3) led to enhanced fluorescence intensity, ranging between 2.5 and 14 folds. At physiological pH (pH = 7.4), these sensors exhibited high selectivities for Zn2+ over a wide range of competing metal cations, displaying high sensitivities with a limit of detections of 120, 81.7 and 79.2 nM, respectively. This suggests that these sensors can detect chronic Zn2+ concentration for freshwater (>1.84 μM), designated by the U.S. Environmental Protection Agency. DFT simulations performed on the more stable stacked conformations of unbound and Zn2+ bounded states suggested that the latter display higher density of excited states than the unbound sensors. Moreover, the stacked conformer of sensor 3 was significantly more stable as compared to sensors 1 and 2, which was attributed to a stronger Van Der Waals (VDW) interaction between DQA and 1,8-naphthalimide. The Zn2+ binding leads to enhanced electronic coupling between the HOMOs and LUMOs, making excited states more populated which then undergoes geometric relaxation before emitting light and relaxing back to the ground states. The lower energy separation (5.0 eV) between the HOMO and the first Zn2+ d-orbital in sensor 3 as compared to sensors 1 and 2 results in enhanced density of the generated states and subsequently higher intensity upon binding with Zn2+.

Keywords

• Fluorescent sensor
• 1,8-naphthalimide
• Zinc ion
• 2,2′-dipicolylamine
• Bis(2-quinolinylmethyl)amine
• DFT calculation