Synthesis And Photophysical Properties Of Fluorocoumarin And Tetracarboxylicdianhydride Phthalocyanine@Copper-Cysteamine Nanohybrid System

In this paper,silicon(?)phthalocyanine with fluorocoumarin-tetracarboxylicdianhydride groups and zinc(?)/silicon(IV)phthalocyanine with fluoro coumarin group were synthesized by liquid-phase condensation method.They were di-{N-[N'-(trifluoromethylcoumarin)-pery lene-3,4,9,10-tetracarboxylicdianhydride]benzene ethoxy} silicon(?)phthalocyanine(M3SiPc),di[6-(trifluoromethylcoumarin)-phenoxy]silicon(IV)phthalocyanine(coulSiP),tera[6-(trifluoromethylcoumarin)-phenoxy]zinc(?)phthalocyanine(coulZnPc),di-[7-(trifluoromethylcoumarin)-phenoxy]silicon(IV)phthalocyanine(cou2SiP)and tera[7-(trifluoromethylcoumarin)coumarin-phenoxy]zinc(?)phthalocyanine(cou2ZnPc).The structures of these phthalocyanines were characterized by elemental analysis,IR,1HNMR,ESI-MS and MALDI-TOF-MS methods.The photophysical properties of silicon(?)phthalocyanine with fluorocoumarin-tetracarboxylicdianhydride group and zinc(?)/silicon(?)phthalocyanine with fluorocoumarin group were studied by UV/Vis,steady-state and time-resolved fluorescence spectroscopic methods.Under the same concentration,absorption intensity and peak of Q-band of phthalocyaninewere significantly changed with different ligands,because ligands substituted with phthalocyanine changed the delocation of phthalocyanine.Compared with fluoro coumarin group substituted silicon(?)phthalocyanine,fluorocoumarin-tetracarboxylicdianhydride group substituted silicon(?)phthalocyanine have both a characteristic absorption band for tetracarboxylicdianhydride group at 522nm and Q band of silicon phthalocyanines at 340 and 680 nm.The fluorescence intensity and the singlet oxygen quantum yield of 7-benzyloxyl coumarin axial substituted phthalocyanine was significantly higher than that of 6-hydroxyl coumarin axial substituted phthalocyanine;The peripheral substituted zinc phthalocyanine are changed with a contrary tendency.For same ligand,the fluorescence intensity,fluorescence quantum yield and singlet oxygen quantum yield of axial substituted silicon phthalocyanine were higher than that of the peripheral substituted zinc phthalocyanine in DMF.A new PEG modified copper-cysteamine nanoparticles(PEG-Cu-Cy)was synthesis by rapid high temperature growth method.A series of fluorocoumarin group substituted silicon(IV)phthalocyanine@PEG-Cu-Cy hybrid nanocpmpositess.Transmission Electron Microscopy(TEM)showed that both copper-cysteamine nanoparticles has random mesh structure,and fluorocoumarin group substituted silicon(IV)phthalocyanine@copper-cysteamine hybrid anoparticles were lamellar single crystal with black granules on its surface.UV-vis spectra showed that PEG-Cu-Cy has an obvious absorption peak at 370nm and 600nm.The maximum absorption of Q band of phthalocyanine were red shif and the fluorescence intensity of phthalocyanine in the nanoparticle composition was significantly higher than the free phthalocyanine.This is due to the fluorescence resonance energy transfer(FRET)between phthalocyanine(donor)and PEG-Cu-Cy(acceptor).The fluorescence lifetime of phthaocyanine in hybrid nanoparticles decrease to 5.24 ns-5.96 ns compared with the free phthalocyanine,due to the interation between the phthaocyanine and PEG-Cu-Cy.Hybrid nanoparticles in DMF produced more singlet oxygen than that in water.So,coulSiPc@PEG-Cu-Cy and cou2SiPc@PEG-Cu-Cy can be very potential photosensitizer for photodynamic therapy.