Syntheses Of Acylated Bipyrroles And Development Of A Fluorescent Zn(Ⅱ) Probe Based On The Linear Oligopyrrole

Zinc ion plays significant roles in numerous physiological and pathological processes, so the detection and separation of zinc is of great theoretical and practical significance. As a kind of zinc ion detection technique, fluorescent Zn2+probes, especially fluorescence turn-on type probes have attracted extensive interest due to the advantages of easy operation, high sensitivity, and low cost, In this thesis, we designed and synthesized a new type of fluorescence enhancing Zn(II) probe based on acylated bipyrroles. The main contents are summarized as following:In chaper1, we summarized recent advances in developing fluorescent zinc probes, and proposed the research ideas of this thesis.In chaper2, the Friedel-Crafts acylation of2,2’-bipyrrole afforded six acylated products with rich a-, β-, β1-, a,a’-, a,β’-, and a,β1’-substitution modes for1-6, respectively. All of these compounds have been fully characterized by1H NMR,1H-1H COSY NMR,13C NMR and HRMS. Moreover, Crystal structures of1and4were analyzed by X-ray diffraction analyses, which show interesting supramolecular dimers formed by multiple hydrogen bonds and O...p interactions. But none of the acylated bipyrrolic compounds showed obvious binding to Zn2+.In chaper3, the a,a’-diacylated compound4was used to synthesize a prodigiosin derivative9. Crystal structure of9shows interesting supramolecular dimers formed by multiple hydrogen bonds, as well as p...p interactions. Interestingly,9shows fluorescence turn-on probing behavior towards Zn2+both in DMF and in DMF-HEPES, with high sensitivity and selectivity. The detection limit for Zn2+in DMF was calculated to be1.1x10-8M and the emission peak centered at about622nm. Based on these results,9may be developed as a novel fluorescent Zn2+probe.In chaper4, the results of this thesis were summarized with an outlook on the future researches.