Developing fluorescence porous probe for detecting and eliminating Cu^(2+) contamination in water or biosystem is an essential research project that has attracted considerable attention.However,improving the fluoresce...Developing fluorescence porous probe for detecting and eliminating Cu^(2+) contamination in water or biosystem is an essential research project that has attracted considerable attention.However,improving the fluorescence detecting efficiency while enhancing the adsorption capacity of the porous probe is of great challenge.Herein,a bifunctional two-dimensional imine-based porous covalent organic framework(TTP-COF)probe was designed and synthesized from 1,3,5-tris(4-aminophenyl)benzene(TAPB)and 2,4,6-Triformylphloroglucinol(TP)ligand.TTP-COF displayed rapid detection of Cu^(2+)(limit of detection(LOD)=10 nmol·L^(−1) while achieving a high adsorption capacity of 214 mg·g^(−1)(pH=6)at room temperature with high reusability(>5 cycles).The key roles and contributions of highπ-conjugate and delocalized electrons in TABP and functional–OH groups in TP were proved.More importantly,the fluorescence quenching mechanism of TTP-COF was studied by density functional theory theoretical calculations,revealing the crucial role of intramolecular hydrogen bonds among C=N and–OH groups and the blocking of the excited state intramolecular proton transfer process in detecting process of Cu^(2+).展开更多
基金This study was financially supported by the National Natural Science Foundation of China(Nos.22001156 and 22271178)the Innovation Capability Support Program of Shaanxi(No.2022KJXX-88)the Technology Innovation Leading Program of Shaanxi(No.2020QFY07-05).
文摘Developing fluorescence porous probe for detecting and eliminating Cu^(2+) contamination in water or biosystem is an essential research project that has attracted considerable attention.However,improving the fluorescence detecting efficiency while enhancing the adsorption capacity of the porous probe is of great challenge.Herein,a bifunctional two-dimensional imine-based porous covalent organic framework(TTP-COF)probe was designed and synthesized from 1,3,5-tris(4-aminophenyl)benzene(TAPB)and 2,4,6-Triformylphloroglucinol(TP)ligand.TTP-COF displayed rapid detection of Cu^(2+)(limit of detection(LOD)=10 nmol·L^(−1) while achieving a high adsorption capacity of 214 mg·g^(−1)(pH=6)at room temperature with high reusability(>5 cycles).The key roles and contributions of highπ-conjugate and delocalized electrons in TABP and functional–OH groups in TP were proved.More importantly,the fluorescence quenching mechanism of TTP-COF was studied by density functional theory theoretical calculations,revealing the crucial role of intramolecular hydrogen bonds among C=N and–OH groups and the blocking of the excited state intramolecular proton transfer process in detecting process of Cu^(2+).