Determination of Dipicolinic Acid through the Antenna Effect of Eu(III) Coordination Polymer

Abstract

Bacillus anthracis is a Gram-positive bacterium that can cause acute infection and anthracnose, which is a serious concern for human health. Determining Bacillus anthracis through its spore biomarker dipicolinic acid (DPA) is crucial, and there is a strong need for a method that is rapid, sensitive, and selective. Here, we created Eu(III)-coordination polymers (Eu-CPs) with surfaces that have abundant carboxyl and hydroxyl groups. This was achieved by using citric acid and europium nitrate hexahydrate as precursors in a straightforward one-pot hydrothermal process. These Eu-CPs were then successfully utilized for highly sensitive DPA determination. The fluorescence (FL) emission of Eu-CPs, which is typically weak due to the coordination of Eu(III) with water molecules, was significantly enhanced in the presence of DPA. This enhancement is attributed to the competitive binding between DPA’s carboxyl or hydroxyl groups and water molecules. As a result, the absorbed energy of DPA, when excited by 280 nm ultraviolet light, is transferred to Eu-CPs through an antenna effect. This leads to the emission of the characteristic red fluorescence of Eu3+ at 618 nm. A strong linear relationship was observed between the enhanced FL intensity and DPA concentration in the range of 0.5–80 μM. This relationship allowed for a limit of detection (LOD) of 15.23 nM. Furthermore, the Eu-CPs we constructed can effectively monitor the release of DPA from Bacillus subtilis spores, thereby further demonstrating the potential significance of this strategy in the monitoring and management of anthrax risk. This highlights the novelty of this approach in practical applications, provides a valuable determination technique for Bacillus anthracis, and offers insights into the development cycle of microorganisms.