Synthesis And Photophysical Properties Of A Series Of Functional Phthalocyanines Nanoparticles Composites

A series of phthalocyanines bearing different functional substituent groups(bromophenyl thiophenol,methyl morpholine,adamantane)were synthesized.They were tetra-(4-bromophenyl thiophenol)zinc(Ⅱ)phthalocyanine(ZnPcBr),tetra-(4-bromophenyl thiophenol)magnesium(Ⅱ)phthalocyanine(MgPcBr),tetra-{3,5-di-[4-(N-morpholinyl ethoxy)methoxycarbonyl benzyloxy]benzyloxy zinc(Ⅱ)phthalocyanine(ME-ML-ZnPc),di-[3,5-di(4-methoxycarbonyl benzyloxy)benzyloxy]silicon(Ⅳ)phthalocyanine(ME-SiPc),di-{3,5-di-[4-(N-morpholinyl ethoxy)methoxycarbonyl benzyloxy]benzyloxy silicon(IV)phthalocyanine(ME-ML-SiPc),di-{3,5-di-[4-(N-methyliodide morpholinyl ethoxy)methoxycarbonyl benzyloxy]benzyloxy silicon(Ⅳ)phthalocyanine(ME-ML-SiPcI4),di-(2-adamantane ethoxy)silicon(Ⅳ)phthalocyanine(ADiSiPc)and di-(2-adamantane ethoxy tetraethyl glycol)silicon(Ⅳ)phthalocyanine(ADnSiPc).The structures of these phthalocyanines were characterized by elemental analysis,IR,1H NMR,ESI-MS and MALDI-TOF-MS methods.The photophysical properties of phthalocyanines bearing functional substituent groups(bromophenyl thiophenol,methyl morpholine,adamantane)were studied by UV-Vis,fluorescence spectroscopic analyses.It was found that,phthalocyanines bearing different functional substituent groups(bromophenyl thiophenol,methyl morpholine,adamantane)(ZnPcBr,MgPcBr,ME-ML-ZnPc,ME-SiPc,ME-ML-SiPc,ME-ML-SiPcI4,ADiSiPc and ADnSiPc)exist as monomer in origanic solvents.As the water-soluble phthalocyanine,ME-ML-SiPcI4 exists mainly as monomer in water,but ME-ML-ZnPc exists mainly as aggregate.The maximum absorption,fluorescence intensity and singlet oxygen quantum yield of ZnPcBr were higher than that of MgPcBr.But the lifetime and fluorescence quantum yield of MgPcBr was higher than that of ZnPcBr,which may be associated with the shell structure of central metal ions.The amphiphilic diblock copolymer polyethylene glycol monomethyl ether-polycaprolactone(MPEG5000-PCL2000)was selected as drug carriers to load ZnPcBr/Cur/Au or MgPcBr/Cur/Au.The polymeric nanoparticles were prepared using water/DMF as cosolvent.The morphologies and particle sizes of ZnPcBr/Cur/Au@PP and MgPcBr/Cur/Au@PP were studied by TEM.They were sphere and with the diameter from 16 nm to 67 nm.EDS elemental analysis results confirmed that MgPcBr,ZnPcBr,Cur and Au havs been successfully loaded on the polymeric nanoparticles.The photophysical properties were studied by UV-Vis,fluorescence and Raman spectrum.Au nanoparticles enhanced the surface enhanced Raman scattering(SERS)of ZnPcBr/Cur/Au and MgPcBr/Cur/Au,indicating that ZnPcBr and MgPcBr combined on the surface of gold nanoparticles through Au-S bonds.Compared to ZnPcBr@PP and MgPcBr@PP,the intensity of Q-band absorption peak co-load ZnPcBr/Cur/Au@PP and MgPcBr/Cur/Au@PP increased.The results showed that Cur and Au had a disaggregation effect on ZnPcBr and MgPcBr.The nanoparticles loaded with ZnPcBr/Cur/Au showed lower fluorescent lifetime,higher fluorescent intensity,higher singlet oxygen quantum yield and enhanced DNA degradation ability.The nanoparticle loaded with MgPcBr/Cur/Au showed lower fluorescent intensity and fluorescent lifetime,higher singlet oxygen quantum yield and DNA degradation ability than that of MgPcBr@PP.The results showed that Cur and Au could enhance the photoactivity of ZnPcBr and MgPcBr.Besides,molar absorption coefficient,fluorescence intensity,quantum yield and lifetime of silicon(Ⅳ)phthalocyanine(ME-ML-SiPc)of significantly longer than the periphery substituent zinc(Ⅱ)phthalocyanine(ME-ML-ZnPc)at the same concentration in DMF,but the corresponding singlet oxygen quantum yield exhibited exactly the opposite rule,which may be related to the shell structure of central ions and the aggregation behavior.Molar absorption coefficient,fluorescence intensity,fluorescence quantum yield,fluorescence lifetime and singlet oxygen quantum yield of methylation silicon(Ⅳ)phthalocyanine(ME-ML-SiPcI4)was significantly lower than the corresponding non-ionic silicon(IV)phthalocyanine(ME-ML-SiPc)at the same concentration in DMF.This results showed that ME-ML-SiPc exhibited less aggragation than that of ME-ML-SiPcI4 in DMF,which may be related to the degree of polarity.In the same concentration,molar absorption coefficient,fluorescence intensity,fluorescence quantum yield and fluorescence lifetime of methylation silicon(Ⅳ)phthalocyanine(ME-ML-SiPcI4)in pure water was lower than the corresponding phthalocyanine in DMF,but the singlet oxygen quantum yield exhibited exactly the opposite rule.The water-soluble phthalocyanine would be a promising photosensitizer(PS)for PDT.At the same concentration,the absorbance and fluorescence intensity of ADiSiPc were significantly higher than that of ADnSiPc in DMF.The fluorescent lifetime,fluorescence quantum yield and singlet oxygen quantum yield were lower than that of ADnSiPc.This may be related to the length of the axial glycol chain which lead to the aggregation behavior.The electrochemical of ZnPcBr,MgPcBr,ME-ML-ZnPc,ME-SiPc,ME-ML-SiPc,ME-ML-SiPcI4,ADiSiPc and ADnSiPc was studied by cyclic voltammery(CV)and square wave voltammetry(SWV)methods.The difference of phthalocyanines between the absorbance and fluorescence intensity was basically accordance with the second and third potential(HOMO-LUMO)of phthalocyanines.