The environmental residues and drug resistance resulting from antibiotic abuse urgently call for the development of efficient multicomponent detection technologies. Therefore, single-lanthanide metal-organic frameworks [Ln(BDPO)(H2O)4](H2O) (DMF): Ln = Eu, Tb, Gd, Dy; BDPO= N,N'-bis(3,5-dicarboxyphenyl)-oxalamide are designed and synthesized, and the ternary mixed-metal MOFs are constructed. Single-crystal X-ray diffraction analysis shows that the series MOFs belong to the triclinic P1̅ space group with a one-dimensional chain structure. Optical performance tests confirm that Eu-MOF and Tb-MOF exhibit ligand-to-rare-earth ion ″antenna effect″ that allows for dual-emission ratio fluorescence response. Based on this, Eu-MOF and Tb-MOF exhibit high sensitivity and quantitative detection capabilities for ciprofloxacin and ofloxacin. The multiemission centers of EuTbGd-MOF show differential responses identify seven types of antibiotics when combined with linear discriminant analysis (LDA), principal component analysis (PCA), and hierarchical cluster analysis (HCA). Real sample testing demonstrate that the sensor array can effectively identify target antibiotics even in milk and tap water matrices. This study provides a new sensing platform for the highly selective detection of multicomponent pollutants in complex systems, offering significant application prospects in environmental monitoring and food safety.
Si-Jie Wang, Bo Sun, Jin Wang et al.· Inorganic Chemistry· 0 citations
The development of fast proton-conducting materials that operate above 150°C with high chemical stability is both challenging and critically important for advancing proton-exchange membrane fuel cells (PEMFCs). In this study, we constructed two three-dimensional COFs with covalent phosphonate modification using a solvent-free, melt-phase post-synthetic modification (PSM) strategy. This approach simultaneously reduces imine to amine linkages and constructs C─P bonds, covalently anchoring phosphonate groups without disrupting crystal integrity. Single-crystal x-ray diffraction (SCXRD) analysis reveals precise geometric changes in the framework and the formation of an extended N─H···O═P hydrogen-bond network. The functionalized single-crystal COFs exhibit excellent anhydrous proton conduction along the crystallographic c-axis at exceptionally high temperatures, achieving 8.91 × 10-3 S cm-1 at 210°C for COF-300-DMP and 5.65 × 10-3 S cm-1 at 230°C for COF-300-DEP. The remarkably low activation energies (0.196‒0.229 eV) indicate a Grotthuss-type hopping mechanism. This work not only establishes a generalizable route for COF functionalization but also provides a definitive blueprint for designing advanced proton conductors for extreme environments.
Aiping Yao, Linlin Huo, Chunyi Sun et al.· Angewandte Chemie· 0 citations