Study On The Properties Of Thoracic And Triazine Calixarene Fluorescent Probes

The design and synthesis of fluorescent probes are one of the important research topics of analytical chemistry and supramolecular chemistry. Fluorescence probes were widely applied in industry, agriculture, medicine, archeology, mineralogy, environmental and other field due to its high sensitivity, high selectivity, rapid in situ, the identification for variety of cations and anions, and which can realize real-time analysis. In recent years, with the application of fluorescent probes in vivo samples as well as the detection in living cells, make the study of fluorescent probes into a new boom.With thiacalix[4]arene as structure platform, select the three kinds of fluorescent groups, respectively designed and synthesized 1,3-alternate thiacalix[4]arenequinoline derivatives fluorescence probe s1, 1,2-alternate thiacalix[4]arene-coumarin derivatives fluorescent probe s2, get has specific structure, and has probe nature of compounds. A disubstituted phthalimide-based thiacalix[4]arene derivative(s3) was synthesized by our research team from cone 1,3-thiacalix[4]arene and hydroxyethyl phthalimide, with benzyl appended the lower edge of thiacalix[4]-arene by triazole ring in the 2,4 position. Including N, O atom of acridine-triazine type of heteroatomic calixarenes(s4) and N atoms of acridine-triazine type of heteroatomic calixarenes(s5). The recognition and sensing properties of these probes to metal ions and anions were investigated by UV-vis spectrum and fluorescent spectrum and the recognition mechanism was investigated by IR, ITC, 1H NMR and ES-MS. We investigated the recognition properties of the target compounds to metal ions and anions by fluorescence and visible absorption spectra, and discussed the recognition mechanism, composition, sites and control conditions of the complexation including probe s1、s3、s4、s5. Because of the different structures, the results showed that the compounds have specific optical probe properties toward different metal ions or anions.Probe s1 can be used for detecting La3+ and Lu3+ by the method of fluorescent spectrum with enhanced fluorescence significantly, which were not reported in the previous literature. Probe s3 showed excellent selectivity and sensitivity for the recognition of Fe3+ and I-, can be used as fluorescence quenching probe. IR spectrum showed that the nitrogen atoms of triazole groups are involved in the complexation with Fe3+, while the hydrogen atoms of triazole groups were complexed with I- by hydrogen bonding. Probe s4 showed good fluorescent recognition ability to Cu2+ and I-. Probe s5 similar with the probe s4, also showed the high selectivity to Cu2+ and I-. Fluorescent quantum yield and ion recognition performance are weaker than s4 because of the difference of heteroatomic.Design and synthesis of series 1,3-alternate thiacalix[4]arene-quinoline derivatives s1, disubstituted phthalimide-based thiacalix[4]arene derivative s3, and triazine type of heteroatomic calixarenes s4、s5 derivatives response to proper metal ions and anions as high selectivity and high sensitivity chomosensor. So we can conclude that this derivatives have the value for determining metal ions and anions. The investigation enriched the study of fluorescent probe, fluorescence materials and electrochemical sensor materials.