Methylation Morpholine Phthalocyanine@Gold Nanorod Composite Nanoparticles Of Self-assembling,Light-activated Controlled Release And Photodegradation Of DNA

In this paper, a series of non-ionic and methylation substituted with morpholine zinc (?)/silicon(IV) phthalocyanine were synthesized. They were bis-[N-(morpholinyl)ethoxy] silicon (IV) phthalocyanine (MLSiPc), bis-[N-(methyliodide-morpholinyl)ethoxy] silicon (IV) phthalocyanine (MLSiPcI4), tetra-[N-(morpholinyl) ethoxy] zinc (II) phthalocyanine (MLZnPc), tetra-[N-(methyliodide-morpholinyl)ethoxy] zinc(II) phthalocyanine (MLZnPcI4).The structures of these phthalocyanines were characterized by elemental analysis, IR,'HNMR, ESI-MS and MALDI-TOF-MS methods.The photophysical properties of non-ionic and methylation substituted with morpholine zinc(?)/silicon (IV) phthalocyanine were studied by UV/Vis, steady-state and time-resolved fluorescence spectroscopic analyses. It was found that, non-ionic and methylation morpholino substituted phthalocyanine (MLSiPc, MLSiPcI2, MLZnPc and MLZnPcI4) are dissolved in organic solvents, exist mainly as monomer in DMF solvents. In the same concentration, no significant changes was observed for the MLSiPc and MLSiPcI4 of Q-band maximum absorption peak position and intensity in DMF, but the MLZnPcI4 of Q-band absorption intensity was significantly lower than MLZnPc. MLSiPcI4 exists mainly as monomer in water, but MLZnPcI4 exists mainly as dimeric. This results shows that an axial substituent was better than the periphery substituent inhibiting aggregation. Methylation silicon(IV) phthalocyanine(MLSiPcI2) of fluorescence intensity, the fluorescence quantum yield and singlet oxygen quantum yield was significantly higher than the corresponding non-ionic silicon(IV) phthalocyanine((MLSiPc) in DMF. While methylated zinc (?) phthalocyanine (MLZnPcI4) of fluorescence intensity, fluorescence quantum yield and singlet oxygen quantum yield were low than non-ionic zinc(II) phthalocyanine(MLZnPc) in DMF. Besides, methylation morpholine silicon (IV)phthalocyanine of fluorescence lifetime significantly longer than non-ionic silicon(IV) phthalocyanine, but the corresponding zinc (?) phthalocyanine exhibited exactly the opposite rule, which may be related to the degree of aggregation. We studied their electrochemical behavior by cyclic voltammetry. With the same central ion, methylation morpholine substituted phthalocyanines of HOMO-LUMO are smaller than the corresponding non-ionic phthalocyanine. The difference of HOMO-LUMO of morpholine substituted silicon (IV) phthalocyanines complexes is basically identical the absorption intensity, fluorescence intensity and quantum yield, but the corresponding morpholine substituted zinc(II) phthalocyanine exhibited exactly the opposite rule. It is also shown that the aggregation behavior of phthalocyanine complexes can affect their photophysical properties.Gold nanorods (GNRs) are produced by using the seed-mediated method. The GNR-PSS-MLZnPcl4 composite nanoparticles were achieved by a controllable layer-by-layer assembly of water-soluble photosensitive agent methylation morpholino substituted zinc(II) phthalocyanine (MLZnPcI4) electrostatically attracted to the polyelectrolyte-coated gold nanorods surface. TEM images of GNR-PSS-MLZnPcI4 composite nanoparticles showed a rod morphology and the aspect ratio of about 2.87. As the self-assembly proceeds were carried out, the thickness of the composite nanoparticles increased by AFM. EDS elemental analysis results confirmed that methylation morpholino zinc(II) phthalocyanine (MLZnPcI4) successfully loaded with polyelectrolyte-coated gold nanorods. When the GNR-PSS-MLZnPcI4 was irradiated by laser (670 nm,60 mW), MLZnPcI4 released from the as-synthesized GNR-PSS-MLZnPcI4 composite nanoparticles because the gold nanorods absorb light energy into heat, inducing the release of MLZnPI4 Howeve, the release of MLZnPcI4 also will slow down without laser irradiation.Three different aspect ratio of gold nanorods (2.0,2.8 and 3.2) are produced by using the seed-mediated method through changing the ratio of silver nitrate, respectively. Methylation morpholine zinc(?)/silicon(?) phthalocyanine@polyelectrolyte-coated gold nanorods with different aspect ratio composite nanoparticles were achieved by layer-by-layer assembly. TEM images of different aspect ratio gold nanorods and composite nanoparticles were rod. Their photophysical propertie were studyed by UV/Vis, steady-state and time-resolved fluorescence spectroscopic analyses. In methylated morpholino phthalocyanine loaded with different aspect ratio polyelectrolyte-wrapped gold nanorods system, the aggregation degree of methylation morpholine phthalocyanine were decreased by gold nanorods. It is shown that the methylation morpholino phthalocyanine of maximum absorption red-shift and the absorption intensity increased. The methylation morpholine phthalocyanine@polyelectrolyte-wrapped gold nanorods composite nanoparticles of fluorescence intensity and fluorescence quantum yield decreased, which be attributable to the gold nanorods of surface plasmon resonance enhancement the methylation morpholine phthalocyanine fluorescence competing with gold nanorods quenching methylation morpholine phthalocyanine of fluorescence. The methylation morpholine zinc(?) phthalocyanine@gold nanorods composite nanoparticles of fluorescence lifetime was shorter than methylation morpholino silicon(?) phthalocyanine@gold nanorods composite nanoparticles, which may be related to the degree of aggregation of methylated morpholine zinc(?) phthalocyanine. Because the increasing of the aspect ratio of gold nanorods, their absorption wavelength moved to a longer wavelength, which increased interaction with the morpholino phthalocyanine of excited state dipole and increased the gold nanorods of photonic mode density. Therefore, the methylation morpholine phthalocyanine zinc(?)/silicon(?)@ gold nanorods composite nanoparticles of fluorescence lifetime were increased.