Synthesis And Properties Of BODIPY Dyes And Porphyrins

Boron dipyrromethene （BODIPY） dyes, as an important series offluorescent dyes, contain some outstanding properties such as highfluorescence quantum yields and high absorption coefficients, narrowemission spectrum band, good stability to light, low susceptibivity tosolvent polarity and pH, max absorption and emission wavelength lyingon visible region and easy to carry out functional modification. A seriesof novel BODIPY dyes were widely used as labeling reagents, fluorescentswitches,chemosensors, anti-cancer drugs, laser dyes, photosensitizers,harvesting arrays,solar cells, energy transfer cassettes and so on.In this paper, two categories of fluorescent probes for selectiverecognition of Cys based on BODIPY were designed and synthesized.The first kind is a series of BODIPY dyes which an aldehyde group wasinstalled at α position.As a probe for detecting Cys,it shows highselectivity and sensitivety. At the same time,we successfully obtained the"turn on" and "turn off" types of fluorescent probes by controlling thesubstituent group.The other kind of probe for Cys is α, β unsaturateddiesters based on BODIPY. The probe specifically identify the aminoacids Cys containing sulfhydryl group among the common amino acids（Arg, Cys, and GSH, Hcy, Phe, Pro, Tyr, Val, Ala, Gly, Lys, Leu, Glu,Ser） with high sensitivity in CH₃CN-HEPES buffer （0.1M, pH=7.4,1:1, V/V） system.With the obvious fluorescent enhancement of the solutionafter reacting with Cys, naked-eye detection is allowed.The furtherreaction study indicates that this process goes through aβcarbon Michaeladdition to change the conjugated structure, thus to make the spectrumproperties different.A BODIPY-based fluorescent probes for detection of cyanide wasdesigned.The fluorescence enhanced obviously after reacting withcyanide due to the destruction of the intramolecular charge transfer. InTHF-H₂O system, Among commom anion (F^-, SCN^-, NO₃^-, Br^-, HSO₄^-,HPO₄^2-, H₂PO₄^-, Cl^-, ClO₄^-, AcO^-, CN^-，HSO₃^-)， the probe responsed tocyanide quickly,selectively and sensitively with detection limit of2.8×10-7M.A mitochondrial targeting photosensitizer containing triphenylphosphate salt on porphyrins was also be explored. On the one hand,porphyrin is a kind of fluorescent dyes with high molar extinctioncoefficient, high fluorescence quantum yields, large Stokes shift,relatively long excitation （>400nm） and emission （>600-nm）wavelength and is stable to light, etc. On the other hand,Triphenylphosphate salt is water soluble and can be useful as a carrier to deliver theoptical probe into mitochondria. Therefore the dyes make greatsignificance in defecting cancer cells and the treatment of the tumor cells.A series of pyrrolyldipyrrinato BF₂complexes have been developed by direct nucleophilic substitution of the3-hydrogen of BODIPY dyesThe synthesis conditions is simple and easy to control, no precious metalcatalyst （such as: palladium） is needed, representing regular and universalcharacter whether in the economy, operation or commercialization. Byintroducing smaller conjugated system pyrrol to the BODIPY corestructure of3-position, this design weakens mutually exclusiveintermolecular and interatomic force, leading to the enhancement of theplane of the whole molecule conjugation, reflecting on the spectroscopicproperties such as red shift wavelength compared with traditionalBODIPY fluorescent dye.