A novel multiemissive Ln/covalent-organic frameworks for ratiometric detection of 2,6-dipicolinic acid

As one of the specific biomarkers of anthrax, timely, sensitive and accurate detection of 2,6-dipicolinic acid (DPA) plays an important role in preventing biological weapons attacks and disease outbreaks. Here, multiemission Eu3+/covalent- organic framework (COFDTA-TFP) and Tb3+/COFDTA-TFP were constructed by the coordination between Eu3+ or Tb3+ with fluorescent COFDTA-TFP which was prepared by amine-aldehyde dehydration condensation between 2,5-diaminoterephthalic acid and 2,4,6-triformylphloroglucinol for the first time. The Eu3+/COFDTA-TFP and Tb3+/COFDTA-TFP can emit non-overlapping fluorescence of COFDTA-TFP and Eu3+ or Tb3+, which was used to ratiometric detection of DPA. Due to the strong coordination between the nitrogen atoms in the pyridine ring and the oxygen atoms in the carboxyl group of DPA with Eu3+ or Tb3+, DPA replaced coordinated H2O to sensitize fluorescence of Eu3+ or Tb3+ by "antenna" effect but fluorescence of COFDTA-TFP with two-dimensional lamellar structure was kept constant as a reference. The linear range and detection limit of ratiometric fluorescence sensor based on Eu3+/COFDTA-TFP for detection of DPA are 0.01–12 µM and 4.2 nM, respectively. The linear range and detection limit of ratiometric fluorescence sensor based on Tb3+/COFDTA-TFP for detection of DPA are 0.01–9.0 µM and 2.9 nM, respectively.