Synthesis And Photophysical Properties Of Several Thiophene And Imidazole Functional Substituted Phthalocyanine Nanoparticles

A series of axially substituted silicon phthalocyanine complexes have been synthesized.they are di-(3,5-di(thiophene-2-carboxylate)phenylmethoxy)axially substituted silicon phthalocyanine(M2SiPc),di-(4-diphenylthiophene-2-phenoxy)axially substituted silicon phthalocyanine(BBT-SiPc),and di-((3-chlorophenylthiophene-2-ester)hexafluorophenoxy)axially substituted silicon phthalocyanine(CBT-SiPc).the structure of the complexes was characterized by ~1HMR,IR,ESI-MS and MALDI-TOF-MS methods,and the effects of different substituents on the photophysical properties of the complexes were compared by measuring their UV-vis spectra,fluorescence spectra,and fluorescence lifetime.Imidazole was introduced into zinc/silicon phthalocyanine complexes to synthesize two different axially substituted silicon phthalocyanines and one peripheral substituted zinc phthalocyanine.They are di-(1-(2-hydroxyethyl)imidazole)axially substituted silicon phthalocyanine(ID-SiPc),di-(1-(3-bromopropyl)-3-(2-hydroxyethyl)-imidazole)axiallysubstitutedsiliconphthalocyanine(Br-ID-SiPc)and tetra-(4-(4-(2-diimide-1-ethoxy)-benzonitrile)zinc(II)phthalocyanine(ID-p-Zn Pc).Their structures were characterized by ~1HMR,IR,ESI-MS and MALDI-TOF-MS methods,and their photophysical properties were comprehensively evaluated by measuring their UV–vis spectra,fluorescence spectra and fluorescence lifetime.Among them Br-ID-SiPc with positive charge,it has the advantages of good water solubility and long life span.Most importantly Br-ID-SiPc can specifically target mitochondria and can be used as targeted photosensitizers for photodynamic therapy.Polyethylene glycol modified cyclodextrin supramolecular(CM-?-CD-PEG)was synthesized and cholesterol-based axially substituted silicon(IV)phthalocyanine(chol-SiPc)wasprepared.CM-?-CD-PEGself-assemblywith di-(3,5-(thiophene-2-carboxylate)phenylmethoxy)axially substituted silicon phthalocyanine(M2SiPc),cholesterol-based axially substituted silicon(IV)phthalocyanine(chol-SiPc),di-(1-(3-bromopropyl)-3-(2-hydroxyethyl)-imidazole)axially substituted silicon phthalocyanine(Br-ID-SiPc)formed CM-?-CD-PEG@M2SiPc,CM-?-CD-PEG@chol-SiPc and CM-?-CD-PEG@Br-ID-SiPc nanoparticles.The morphology and particle size of the nanoparticles were characterized by SEM and DLS,and their photophysical properties were studied by UV-vis and fluorescence spectra.Forthermore,their singlet oxygen and fluorescence lifetime were measured.The controlled release behavior of CM-?-CD-PEG@M2SiPc,CM-?-CD-PEG@chol-SiPc,CM-?-CD-PEG@Br-ID-SiPc and 1-ADH(or ATP)was studied.The fluorescence intensity decreased after self-assembly of compositions(M2SiPc,chol-SiPc,Br-ID-SiPc)and CM-?-CD-PEG to form nanoparticles.The controlled release tests were carried out with amine hydrochloride(1-ADH)and adenosine triphosphate(ATP).After the release,thefluorescenceintensityoftheCM-?-CD-PEG@M2SiPcand CM-?-CD-PEG@chol-SiPc further declined,while the fluorescence intensity of CM-?-CD-PEG@Br-ID-SiPc increased.This is because the M2SiPc and chol-SiPc are insoluble in the water system after release from cyclodextrin,and the formation of larger aggregates leads to a greater degree of quenching of fluorescence,while Br-ID-SiPc is well soluble in water after release from cyclodextrin,which makes its fluorescence intensity enhanced.This experimental result shows that CM-?-CD-PEG@Br-ID-SiPc has more application space.