Synthesis And Photophysicochemical Properties Of Triphenylamine Substituted Dendritic Phthalocyanine Nano-photosensitizers

A silicon phthalocyanine targeted at Golgi of cell was synthesized and characterized.It was di-（4-cholesteryl）silicon（Ⅳ）phthalocyanine（Chol-SiPc）.1,2-Distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy（polyethylene glycol）-2000](DSPE-PEG₂₀₀₀)was chosed as a drug carrier to load Chol-SiPc.The polymeric nanoparticles（DSPE@Chol-SiPc）loaded with Chol-SiPc were prepared using water/THF as co-solvent method.Chol-SiPc and DSPE@Chol-SiPc were found to be co-localized with Golgi-Tracker in MCF-7 breast cells.And the photodynamic efficacy of DSPE@Chol-SiPc against breast cells was found to be 93%.The interaction mechanism was found to lead to cell apoptosis by disrupting the function of the Golgi.Two fluorinated and non-fluorinated silicon phthalocyanines were synthesized.They were di-（4-（phenol）propane phenoxy）silicon（Ⅳ）phthalocyanine（BPA-SiPc）and di-（4-phenol）-1,1,1,3,3,3-hexafluoropropane-4-phenoxy)silicon（Ⅳ）phthalocyanine（FBPA-SiPc）.A series of triphenylamine substituted phthalocyanines were synthesized by introducing the triphenylamine（TPA）group which have aggregation-induced emission（AIE）and strong electron-donor properties into the fluorinated/non-fluorinated silicon phthalocyanines.They were di-[4-（diphenylamino）-1-biphenylyloxy]silicon（Ⅳ）phthalocyanine（TPA-SiPc）,di-[4-（diphenylamino）-1-diphenic acid-1-carbobenzoxy propanephenoxy]silicon（Ⅳ）phthalocyanine（TPA-BPA-SiPc）,di-[4-（diphenylamino）-1-diphenic acid-1-carbobenzoxy-4-（1,1,1,3,3,3-hexafluoropropane-4-phenoxy）silicon（Ⅳ）phthalocyanine（TPA-FBPA-SiPc）.The structure of these complexes was characterized.With the introduction of fluorinated groups,the peak of UV-Vis absorption of FBPA-SiPc was red-shifted and fluorescence intensity,fluorescence lifetime and quantum yield of FBPA-SiPc increased.The absorption peak was further red-shifted,and the fluorescence intensity was further enhanced when the TPA group was introduced into the FBPA-SiPc and BPA-SiPc.TPA-FBPA-SiPc has the strongest fluorescence intensity,fluorescence quantum yield and fluorescence lifetime.It is a promising second-generation photosensitizer.The two-photon fluorescence of fluorinated,non-fluorinated and a series of triphenylamine-substituted silicon phthalocyanine complexes can be detected upon 860 nm excitation.Polymeric nanoparticle loaded with different phthalocyanine was prepared by assembling DSPE-PEG₂₀₀₀000 with phthalocyanines,respectively.The morphologies and diameters of polymeric nanoparticles were studied.They were sphere with diameter in the rang of 85 to 113 nm.The photophysical properties of free phthalocyanine in water/THF mixtures and nano-micro-environment were similar.TPA-BPA-SiPc and TPA-FBPA-SiPc mainly exist as aggregates in nano-microenvironments,and exhibited as fluorescence quenching effect.No obvious aggregation induced emission is observed.While TPA-SiPc and DSPE@TPA-SiPc exhibit aggregation induced emission effect.Therefore,we could conclud that the aggregation induced emission may be related to the spatial distance between TPA（donor）and the silicon phthalocyanine（acceptor）.And the two-photon fluorescence of TPA-SiPc,TPA-FBPA-SiPc and TPA-BPA-SiPc could be detected upon excitation at 860 nm.A novel phthalocyanine with sulfonate groups which was tetra-（4-bromophenyl thiophenol）zinc（II）phthalocyanine（ZnPc-Br）wassynthesized.Tetra-{[4-（diphenylamino）-1-biphenyl]-4-sulfydryl}zinc（II）phthalocyanine（ZnPc-TPA）was obtained by coupling TPA with ZnPc-Br.The structure of these compounds was also characterized.The Q band of ZnPc-TPA were red-shifted because the conjugate length of this compound increased with the introduction of TPA into the ZnPc-Br.While the singlet oxygen quantum yield and fluorescence lifetime of ZnPc-Br are all larger than that of ZnPc-TPA.The nanoparticles loaded with ZnPc-TPA or ZnPc-Br co-loaded were synthesized using DSPE-PEG₂₀₀₀000 as carrier,respectively.The spectral properties of ZnPc-TPA in nano-environment are similar to that in water/THF mixed solvent.And the two-photon fluorescence of ZnPc-TPA also can be observed by excitation at 860 nm.A novel series of donor-acceptor-donor（D-A-D）is constructed with the triphenylamine as a electron donor,and diazabenzene,bisphenol A or fluoro-bisphenol A as a receptor,These fluorescent probes are 5,6-bis（4-（diphenylamino）-[1,1-biphenyl]-4-yl）pyrazine-2,3-dicarbonitrile（TPA-NPP-TPA）,propane-2,2-diylbis（4,1-phenylene）bis(4-（diphenylamino）-[1,1’-biphenyl]-4-carboxylate（TPA-BPA-TPA）and（perfluoropropane-2,2-diyl）bis（4,1-phenylene）bis（4’-（diphenylamino）-[1,1’-biphenyl]-4-carboxylate）（TPA-FBPA-TPA）.And their structures were characterized.TPA-NPP-TPA has strong solvation effect in water/THF mixtures with different water fractions.TPA-NPP-TPA exhibits typical aggregation-induced emission（AIE）characteristics,and its stokes shift was about 235 nm.The AIE features of TPA-BPA-TPA and TPA-FBPA-TPA are also showed but not obviously.However,their stokes were about20 to 40 nm.Nanoparticles loaded with triphenylamine probes were self-assembled by co-solvent using DSPE-PEG₂₀₀₀000 as the carrier.The polymeric nanoparticles are in a regular spherical shape and the size were found to be in the range from 49 to 64 nm.The spectral properties of triphenylamine probes in nano-environment are similar to that in water/THF mixed solvent.Moreover,the two-photon fluorescence signals of these free probes and polymeric nanoparticles could be detected upon the excitation wavelength of predecessor...