Fluorescence-oriented Synthesis And Properties Study Of Calixarene

The calixarene is a cyclic oligomer having a cavity structure formed by the condensation of p-tert-butylphenol and formaldehyde under basic conditions.The calixarene has both a hydrophobic?-cavity and a hydrophilic end surrounded by a cyclic phenolic hydroxyl group.It has an inclusion ability for neutral molecules and ions,and the lower rim of the calixarene and the methylene group of the bridge chain can beenchemical modification,synthesis with various functional groups and?cavity can adjust the calixarene derivatives.The fluorescence sensor is composed of three parts:identification group,fluorescence group and connection arm,due to its characteristics of high sensitivity,high selectivity,real-time,in-situ response,no damage to samples and easy to control,it has been widely used in biochemistry,analytical chemistry,medical science and other fields in recent years.Therefore,based on the calix[4]arene platform,this paper selects the appropriate connection arm,introduces cheap and easy fluorescent groups with superior fluorescence properties,and constructs fluorescent calix[4]arene with high sensitivity and selectivity,so as to conduct identification and detection research and its application in cells.An cucurbit[8]uril?Q[8]?and its supramolecular self-assembly were selected to explore the construction modes of the two rings.The main contents are as follows:1.Five calix[4]arene derivatives with fluorescent groups were synthesized based on calix[4]arene platform.The calix[4]arene are detert-butylated.The water-soluble fluorescein calix[4]arene derivatives 4 with cone-shaped configurations were obtained by modifying the upper and lower rim.Different fluorescence calix[4]arene derivatives5 and 6 were obtained by attaching different groups to hydroxyl groups at the lower rim.1,4,5,8-naphthalene tetraacetic anhydride was modified by 1,3 hydroxyl groups at the lower rim to obtain"2+2"bridged fluorescence bis-calixarene 7.Its structure was characterized by NMR and MS.2.The recognition properties of fluorescent calix[4]arene 4 on cations were studied by UV absorption spectroscopy,FL spectroscopy and NMR titration.Fluorescent calix[4]arene 4 exhibited in DMF/H₂O?v/v,9/1?,Selective recognition of cations Ca²⁺,Sr²⁺,and Ba²⁺under conditions of pH=8.5)has high sensitivity and low detection limit.The detection method not only has spectral detection,but also visual colorimetric rapid detection;Microamounts of Ca²⁺,Sr²⁺and Ba²⁺in cancer cells can be detected by single channel fluorescence imaging.3.The interaction between host and guest was carried out with the fluorescent calix[4]arene 5?6 as the guest and the cucurbit[8]uril?Q[8]?.The two were studied by UV,FL,1H NMR and DOSY-NMR.Supramolecular polymerization process,mechanism and construction mode;preparation of supramolecular oligomers.On the basis of this,since both have ethylene double bonds,whether light can make the double bond photodimerize is also investigated.