Dual-emission ciprofloxacin-gold nanoclusters enable ratiometric sensing of Cu2+, Al3+, and Hg2

Abstract

An innovative triple optical sensor is presented that utilizes gold nanoclusters (GNCs) stabilized with ciprofloxacin (CIP) and bovine serum albumin (BSA). The sensor is designed to identify three critical metal ions, namely Cu²⁺, Al³⁺, and Hg²⁺. Under 360 nm excitation, the synthesized CIP-BSA-GNCs demonstrate dual fluorescence emission with peaks at 448 nm (blue) and 612 nm (red). The red emission is associated with the interior of the CIP-BSA-GNCs, whereas the blue emission results from the surface-bound CIP molecules. The sensitive and selective fluorescent nanosensor CIP-BSA-GNCs were employed to detect Cu²⁺, Al³⁺, and Hg²⁺ ions. Cu²⁺ effectively quenched the fluorescence intensity of the CIP-BSA-GNCs at both peaks via the internal charge transfer mechanism (ICT). Cu²⁺ could be detected within the concentration range 1.13 × 10^-3 to 0.05 µM, with a detection limit of 0.34 nM. Al³⁺ increased the intensity of CIP fluorescence at 448 nm via the chelation-induced fluorescence enhancement mechanism. The fluorescence intensity of the core CIP-BSA-GNCs at 612 nm was utilized as a reference signal. Thus, the ratiometric detection of Al³⁺ succeeded with a limit of detection of 0.21 nM within the dynamic range 0.69 × 10^-3 to 0.07 µM. Hg²⁺ effectively quenched the fluorescence intensity of the CIP-BSA-GNCs at 612 nm via the metallophilic interaction mechanism. The fluorescence intensity of CIP molecules at 448 nm was utilized as a reference signal. This allowed for the ratiometric detection of Hg²⁺ with a detection limit of 0.7 nM within the concentration range 2.3 × 10^-3 to 0.1 µM.

Keywords: BSA; Ciprofloxacin; Fluorescent nanosensor; Gold nanocluster; Heavy metals detection; Metal nanoparticles.