The Synthesis Of Boron-Fluorine Fluorescent Material And Its Application On Labeling Natural Products

The Boron-dipyrromethene fluorescent dye (known as BODIPY) is a class of uniquefluorescent dye with many advantages, such as narrow absorption and emission, highmolar absorptivity and fluorescence quantum yield, excellent optical and chemical stability.As traditional BODIPY fluorescent dyes have the limitations of small Stokes shift andconcentration-induced fluorescence, we adopted multi-heterocyclic rings to substitutepyrrole, focusing on synthesis of Boron-Fluorine dyes with high fluorescent quantum yield,large Stokes shift, solid emission. And then these dyes were applied for labeling naturalproducts. These dyes were characterized by NMR,Ms,UV-vis and fluorescent measure-ments. Through the study of their photochemical and photophysical properties, theinfluence of different substituents on the fluorescence properties was investigated.The synthesized dyes demonstrates the following fluorescence characteristics: highfluorescence quantum yield, larger Stokes shifts (over70nm), and excellent fluorescencein solution, solid, and crystal states. To promote the application of such dyes in the fieldsof chemical analysis and bio-labeling, we designed and synthesized the Boron-Fluorinefluorescent probes bearing long-chain side alkynyl (unilateral and bilateral), andsuccessfully realized the fluorescent labeling of the two fluorescent dyes with the naturalproduct oleanolic acid. Meanwhile, we connected the terminal alkynyl fluorescent dyeswith a long chain ending amino group; facilitating the Boron-Fluorine dyes’ fluorescentlabeling of natural products or drugs.The work of this dissertation is concluded as following:Chapter: Commonly used fluorescent dyes were summarized, including the researchof the BODIPY fluorescent dye, biological labeling and solid-emissive fluorescent dyes.Chapter Π: The synthesis, characterization, crystal structures and spectroscopicproperties of the new Boron-Fluorine intermediates with large stokes shifts. Thephotophysical properties were studied in different solvents. And the mechanism of solidemission properties was discussed.Chapter III: A new series Boron-Fluorine fluorescent dyes with a novel chromophorecore were designed and synthesized; and then we study the influence of the substituent’seffect (push-pull electronic and steric effects) on the dyes’ photophysical properties.Through X-ray single-crystal diffraction, we explained the mechanism of compounds’solid-state fluorescence emission concerning three-dimensional packing, intermolecularnon-covalent interactions. Chapter IV: The synthesis of functional Boron-Fluorine fluorescent dyes and itsfluorescent labeling of the natural product oleanolic acid.