Synthesis And Photophysical Properties Of Nanparticles Based Functionalized Phthalocyanine Complexes

In this paper, a novel series of phthalocyanines zinc/silicon bearing different functionalized groups(morpholine, thiophene, alkynyl and pyrrolidinyl) were synthesized. They were bis-(2-morpholinoethoxy) silicon phthalocyanine [MSiPc], tetra-((2-morpholinoethoxy) zinc phthalocyanines [MZnPc], tetra-(2-thienyl) phthalocyanine zinc [TZnPc], bis-(3,5-(prop-2-ynyloxy)phenyl) silicon phthalocyanine [YSiPc] and tetra-(3,5-(prop-2-ynyloxy)phenyl) phthalocyanine zinc [YZnPc], bis-4-(2-oxopyrrolidin-l-yl)ethoxy) silicon phthalocyanine [Py-SiPc], and tetra-4-(2-oxopyrrolidin-1-yl)ethoxy) metallated phthalocyanines [metal=zinc(Ⅱ), copper(Ⅱ), cobalt(Ⅱ),nickel(Ⅱ)]. The structure of phthalocyanines were characterized by elemental analysis, 1H NMR, IR and ESI-MS.The photophysical properties of phthalocyanines bearing different functionalized substituent groups (morpholine, thiophene, alkynyl, pyrrolidinyl) were studied by UV/Vis, steady-state and time-resolved fluorescence spectroscopic methods. The effect of functionalized substituent groups, substituent position and central ions on the UV/Vis, fluorescence spectra, fluorescence quantum yields, fluorescence lifetimes and singlet. oxygen quantum yield of phthalocyanine complexes were compared. The photophysical properties of functionalized phthalocyanine complexes was related to the electron withdrawing group ability of substituents and the paramagnetic behavior of central ions. The electrochemical of different functionalized phthalocyanines were studied by cyclic voltammery(CV) method. The difference between second and third potential of phthalocyanines (HOMO-LUMO) is basically identical to the change of the intensity of fluorescence.Gold nanoparticles were prepared reduction of HAuCl4 by citrate. The MPEG-SH was employed to capped gold nanoparticles for interacting with Py-ZnPc, Py-NiPc, Py-CoPc, Py-CuPc to prepare composite nanoparticles MPEG-SH-Au-Py-MPc (M=Zn, Co, Cu and Ni). The morphologies, particle sizes and photophysical properties of gold nanoparticles and composite nanoparticles were characterized by TEM, UV/Vis and fluorescence spectra. Compared with gold nanoparticles, the size of composite nanoparticles increased slightly. Compared with the corresponding free phthalocyanines, the maximum Q band and the emission peak position of composite nanoparticles are red-shifted, and the fluorescence intensities of composite nanoparticles are decreased, but lifetimes are increased.The amphiphilic diblock copolymer polyethylene glycol monomethyl ether-polycaprolactone (MPEG5000-PCL2000) was selected as drug carriers to load YSiPc/YZnPc and curcumin. The polymeric nanoparticles loaded with YSiPc/CUR and YZnPc/CUR were prepared using water/DMF as cosolvent. The morphologies and particle sizes of polymeric nanoparticles (YSiPc/BCUR@MPEG5000-PCL2000, YSiPc@MPEGsooo-PCL2ooo, YZnPc/BCUR@MPEG5000-PCL2000, YZnPc@ MPEG5000-PCL2000)were studied by TEM. They were sphere with the diameter about 90 nm and 62 nm for nanparticles load with YSiPc and YZnPc,100 nm and 110 nm for co-load YSiPc/CUR and YZnPc/CUR. The size of co-load phthalocyanine and curcumin were increased, which was the nanoparticles with curcumin increasing more drugs into the micelles, leading to the size of micelles increased. The photophysical properties of polymeric nanoparticles were studied by UV/Vis and fluorescence spectroscopic methods. Compared to nanopaerticles load with YSiPc and YZnPc only, the intensity and position of Q band of co-load YSiPc/CUR and YZnPc/CUR nanoparticles were basically remain unchanged, the fluorescence intensity and lifetime were decreased.Using seeding growth method, gold nanoparticles (AuNP) and gold nanorods (AuNR) with different nanosized were prepared. The composite nanoparticles were synthesized by electrostatic interactions between the negatively charged 1-2 generation of water soluble dendritic phthalocyanines with carboxyl teminal groups and positively charged gold nanoparticles. The morphologies, particle sizes of composite nanoparticles were studied by TEM. The result indicated that the composite nanoparticles were sphere with the diameter were ranging from 8.2 nm to 50 nm. Compared to gold nanoparticles, the size of composite nanoparticles was increased indicating that phthalocyanines were dispersed on the surface of gold nanoparticles by electrostatic interaction. The photophysical property of composite nanoparticles were characterized by UV/Vis and fluorescence spectra. Compared with free phthalocyanines, the absorbance and fluorescence intensity of composite nanoparticles were increased. This is due to the phthalocyanines interacted with spherical gold nanoparticles, which can effectively dispersed phthalocyanine complexes, reducing aggregation degree. The existence of gold nanoparticles can effectively sensitizing the photophysical properties of phthalocyanines. Compared with the phthalocyanines that combining to gold nanoparticles(AuNP), the fluorescence intensity of phthalocyanines combining to gold nanorods(AuNR) was increased more obviously. This maybe because the gold nanorods have two major plasma resonance absorption peak. This study could provide theoretical and experimental foundation for developing of new nanoparticle based photosensitizer.