Gold nanostar as an ultrasensitive colorimetric probe for picomolar detection of lead ion

The sensitivity for analytes of interest is vital for environment protection and food safety. Here, we propose an extremely sensitive assay toward Pb²⁺ by using gold nanostars (GNSs) as probes based on the catalytic activity of Pb on etching gold atoms after being reduced in the presence of 2-mercaptoethanol (2-ME) and sodium thiosulfate. GNSs were prepared by using 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid as both the reducing and capping agents, enabling high stability and sensitivity for quantitation of Pb²⁺. Upon increasing Pb²⁺ concentration over the range of 0-10 μM, GNS solution color changed from greenish-blue to blue to purple to red, and eventually to colorless. The color change can be distinguished by naked eye at the Pb²⁺ concentration as low as 200 pM. Through monitoring longitudinal localized surface plasmon of GNSs, Pb²⁺ could be detected with a limit of detection of 1.5 pM, and the working range is 2 pM-1 μM. The ultra-high sensitivity of our assay stems from the high catalysis of Pb on etching gold on tips and branches in the presence of 2-ME and sodium thiosulfate, leading to the shape deformation to spherical gold nanoparticle and the corresponding significant changes in their optical properties. The assay provides high selectivity of Pb²⁺ over the tested interfering metal ions like Cu²⁺. With high sensitivity and selectivity, the assay was efficiently validated by analyzing water samples and monitoring the migration of Pb²⁺ from the tested container to water.