Study On BODIPY Fluorescent Probes And Its Application In The Detection Of Phthalates,Metal Ions And RSH

Phthalates（PAEs）existed in water have been interfered with the normal human endocrine system,resulting in disease and even cancer.Therefore,it is significant to explore PAEs detection methods.The fluorescent probe is used to realize the quantitative detection and visual detection.BODIPY equipped promising applications for their optical properties can be changed with the group modification or aggregation.Here,we introduced the application of probe BODIPY derivative and nanoassembly,which was used for non-covalent detection of phthalates;showed non-covalent molecular assemblies as drug carriers in anti-tumor.We designed and synthesized three new BODIPY,and characterized through nuclear magnetic（NMR）,mass spectrometry（ESI-MS）,ultraviolet spectroscopy（UV-vis）,infrared spectroscopy（IR）,fluorescence spectroscopy,scanning electron microscopy（SEM）and DFT calculations.Furthermore,we explored the fluorescent response mechanism of fat-soluble BODIPY-water hydrogen bond assembly to phthalates;liposome BODIPY-drug assembly;hydrogen bond competition;cancer cell imaging and recognition of imidazole-modified BODIPY on metals and sulfhydryl compounds.The main innovations are as follows:（1）The BODIPY derivative（BCNOH）were synthesized by modifying with nitrodiphenylacrylonitrile and hydroxymethylphenyl.It was found that BCNOH and water assembled to a non-fluorescent emitting BCNOH-water nanocage.What’s more,the nanocage specifically responded to PAEs in water system,but had no fluorescent response to PAEs in organic solvents.DFT calculations and other methods were used to explore the mechanism of BCNOH-water nanocage to PAEs.It was concluded that fat-soluble PAEs induced the reassembly of BCNOH-water cage by intermolecular interactions,limited the photoisomerization of BCNOH,reduced the radiant energy transfers,and turned on the fluorescence.（2）BANPs liposome was assembled with BODIPY（BCN）,andrographolide（Andro）and PEG-phospholipids.BCN modified by nitrodiphenylacrylonitrile was assembled with Andro by dipole-dipole interaction and hydrogen bond synergistically.It was found that dibutyl phthalate（DBP）was a better hydrogen bond acceptor than Andro,so BANPs can be used as fluorescent probes for DBP response.In addition,BANPs can be used to sense DBP in tumor cells,release Andro,and achieve anti-tumor effect.It indicated that BCN can be used as a drug carrier of andrographolide,and a specific probe for PAEs detection.It is a new type of drug carrier with detection capabilities.（3）A new type of water-soluble BODIPY（BIM）was designed by coupling with ether chain and imidazole group.It was found that the fluorescence emission peak of BIM was greatly red-shifted compared with the BODIPY core.BIM experted great fluorescent response to Cu（II）,Ni（II）.The coordination of BIM with Au³⁺under blue light formed a double shot phosphor（BIMAu）,which can recognize HSCH₂COOH and Na SH,while have weak effects on Glutathione（G-SH）.ESI-MS and fluorescent titration were explored to study the combination of BIMAu with HSCH₂COOH and Na SH,and it was found that BIMAu interacted with sulfhydryl small molecules would produce nano-Au.It indicates that the coordination competition between imidazole group and metal on BIM can be used as a way to detect the difference between large-molecule thiols and small-molecule thiols.