Affiliation:
1. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Shanghai Key Laboratory of Functional Materials Chemistry Frontiers Science Center for Materiobiology and Dynamic Chemistry Institute of Fine Chemicals School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai 200237 China
2. Department of Urology Renji Hospital School of Medicine Shanghai Jiao Tong University Shanghai 200127 China
3. Department of Pathology School of Basic Medicine Tongji Medical College Huazhong University of Science and Technology Wuhan Hubei 430074 China
4. Research Center for Marine Drugs State Key Laboratory of Oncogene and Related Genes Department of Pharmacy RenJi Hospital School of Medicine Shanghai Jiao Tong University Shanghai 200127 China
Abstract
AbstractIdentifying infected stones is crucial due to their rapid growth and high recurrence rate. Here, the calcium–magnesium dual‐responsive aggregation‐induced emission (AIE)‐active probe TCM‐5COOH (Tricyano‐methlene‐pyridine‐5COOH), distinctively engineered to distinguish high‐threat infection calculi from metabolic stones, is presented. Upon incorporation of flexible alkyl carboxyl group, TCM‐5COOH featuring five carboxyl moieties demonstrates excellent water solubility and enhanced penetration into porous infectious stones. The robust chelation of TCM‐5COOH with stone surface‐abundant Ca2+ and Mg2+ inhibits vibrational relaxation, thus triggering intense AIE signals. Remarkably, the resulting complex exhibits high insolubility, effectively anchoring within the porous structure of the infection calculi and offering prolonged illumination. Jobs’ plot method reveals similar response characteristics for Ca2+ and Mg2+, with a 1:2 coordination number for both ions. Isothermal titration calorimetry (ITC) results demonstrate higher enthalpy change (ΔH) and lower entropy change (ΔS) for the reaction, indicating enhanced selectivity compared to TCM‐4COOH lacking the alkyl carboxyl group. Synchrotron X‐ray absorption fine spectroscopy (XAFS) validates TCM‐5COOH's interaction with Ca2+ and Mg2+ at the microlevel. This dual‐responsive probe excels in identifying infectious and metabolic calculi, compatible with endoscopic modalities and laser excitation, thereby prompting clinical visualization and diagnostic assessment.
Funder
National Key Research and Development Program of China
China Postdoctoral Science Foundation