In recent decades, gold nanorods have been widely used in biomedical fields, such as drug delivery, phototherapy, diagnosis and biosensing, due to their unique properties. And biosafety assessment and therapeutic effect of gold nanorods are very important for their application in biomedicine. In order to evaluate the biological safety and therapeutic effect of gold nanorods, it is necessary to solve the problem of the interaction between cells and gold nanorods. However, the complexity of the gold nanorods properties, cell type and microenvironment will affect the interaction between cells and gold nanorods. In this study, by comparing normal ovarian cancer cells (HOSEpiC) with cancerous ovarian cancer cells (HO-8910), we investigated the toxicity of gold nanorods to the two different kinds of cells, the uptake of gold nanorods by the two different kinds of cells and the intracellular distribution of gold nanorods after they enter the cells. In addition, the effect of protein corona on the interaction of gold nanorods with ovarian cells was also explored. The results showed that the cytotoxicity of gold nanorods and the uptake of gold nanorods by cells were affected by many factors. And the presence of protein corona significantly reduced the internalization ability of gold nanorods. This study will provide a research basis for the future application of gold nanorods in the diagnosis and treatment of ovarian cancer.
A novel polymeric nanoparticle was developed between the negatively charged dendrimer phthalocyanine and positively triblock copolymer for the use as an effective photosensitizer in photodynamic therapy. The intracellular uptake of dendrimer phthalocyanines in HeLa cell was significantly enhanced by encapsulated into nanoparticles. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles located induced efficient cell death.
Gold nanorods have special optical properties, good biological compatibility and easy preparation, making them have broad application prospects in drug carriers and medical imaging. In this paper, the two photon luminescence of silica modified gold nanorods incubated with different subtypes of breast cancer cells was observed. We demonstrate the effects of different subtypes breast cancer cells on cellular uptake of gold nanorods. And The results show that significant decreases internalization of gold nanorods with the presence of fetal bovine serum protein in cell culture. Two-photon imaging revealed that cellular uptake of gold nanorods was affected by serum and subtypes of cells, and movement of gold nanorods in the cells was observed. Our findings can provide useful information for medical imaging of gold nanorods in biomedical application.
Phthalocyanine complexes are promising second-generation photosensitizers. It has many advantages in photodynamic therapy: good photothermal stability, absorption wavelength in the near-infrared region, and low cytotoxicity. However, they also have some disadvantages:easy to aggregate, poor in solubility, and lack tissue-target.Therefore, how to modify the structure of phthalocyanine is becoming a research hotspot. In this paper, a novel polyfluoroalkylyate silicon (IV) phthalocyanine (SiPc-F) was synthesized. The photophysical properties of this novel polyfluoroalkylyate silicon (IV) phthalocyanine complex (SiPc-F) were studied by UV-visible spectroscopy, steady state and time-resolved spectroscopic methods. The effect of the fluorine substituent on the photophysical properties of phthalocyanine complexes and the quantum yield of singlet oxygen was compared. The results show that the maximum absorption wavelength of polyfluoroalkylyate silicon (IV) phthalocyanine is red-shifted and the intensity is enhanced, the fluorescence intensity becomes stronger, fluorescence quantum yields and fluorescence lifetime is higher but singlet oxygen quantum yields was lower than that of non-fluorinated silicon (IV) phthalocyanine at the same concentration. Polyfluoroalkylyate silicon (IV) phthalocyanine complexes are excellent candidate photosensitizers for photodynamic therapy.
A novel polymeric nanoparticle was developed between the negatively charged dendrimer phthalocyanine and positively triblock copolymer for the use as an effective photosensitizer in photodynamic therapy. The intracellular uptake of dendrimer phthalocyanines in HeLa cell was significantly enhanced by encapsulated into nanoparticles. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles located induced efficient cell death.
Gold nanorods (GNRs) are promising nanomaterials for applications in biomedicine because of their special optical properties, and tremendous works have reported their potential in imaging, diagnosis and treatment of cancer. Unfortunately, study on gold nanorods and cell interactions is still incomplete, and the interplay between gold nanorods and different subtype of breast cancer cells is rarely reported. In the study, two different type of gold nanorods (GNRs and GNRs@SiO2) was synthesized. And we investigated the interactions of gold nanorods (GNRs and GNRs@SiO2) with ER+ (MCF-7)/ER-(MDA-MB-231) breast cancer cells, including cytotoxicity, cellular uptake. Our results showed that GNRs are more cytotoxic to MCF-7 and MDA-MB-231 cells than GNRs@SiO2. And MCF-7 and MDA-MB-231 cells internalize GNRs in a time dependence, and MCF-7 is far more effective in taking up GNRs. The result suggests different subtype of tumor cells should be considered to fully understand the interactions of gold nanorods and cells.
As an excellent second-generation photosensitizer for photodynamic therapy (PDT), phthalocyanine (Pc) complex has strong absorption peak in the near-infrared region and strong tissue penetrating ability, which endowed them excellent properties for the detection of tumor tissue. In recent years, in order to further ehnaced the penetration depth of the photosensitizer to the tissue, a large number of functional groups have been synthesized . In this work, we designed and synthesized metronidazole-substituted dendrimer silicon phthalocyanine (MT-SiPc) with near-infrared region Q-band of UV absorption, excellent fluorescence properties and photochemical properties.
Phthalocyanines (Pcs) are extensively studied by many scientists because of their interesting optical, electrical properties, and good thermal stability. The unsubstituted Pcs can present solubility and aggregation behaviour problems for their limiting applications. In our study two pyridyl and pyrimidinyloxy silicon (IV) phthalocyanines were synthesized. Their photophysical properties were examined by UV-Vis, steady-state and time-resolved fluorescence spectroscopic methods. The positions of Q band were observed at 670 nm for two phthalocyanines. Compared with silicon phthalocyanine dichloride (SiPcCl2), the fluorescence intensities and lifetimes of pyridyl and pyrimidinyloxy silicon (IV) phthalocyanines increased. In order to improve biocompatibility and tumor-targeted delivery, the hydrophobic dendritic phthalocyanine were encapsulated by diblock amphiphilic copolymer poly (N’-benzyl oxygen carbonyl lysine)-poly (ethylene glycol)-poly (N’-benzyl oxygen carbonyl lysine) (PLL(Z)-PEG-PLL(Z)) to form the polymeric nanoparticles. The morphology of two nanoparticles were investigated by using atomic force microscope. The polymeric nanoparticles were spherical with the diameter at about 35 nm. The polymeric nanoparticle SiPc(OR2)2@PLL(Z)-PEG-PLL(Z) would be the promising third-generation photosensitizer (PS) for photodynamic therapy (PDT).
Phthalocyanines have attracted great attention because of their applications in material science including electro-optical devices, electrochromic display, and photodynamic therapy (PDT) of cancer. In addition, the Pcs exhibit great flexibility of chemical structure modification enabled by either peripheral substituents or metal ions co-ordination to central cavity of highly conjugated tetrapyrrolic macrocycles. However, because of the hydrophobic nature of the phthalocyanine ring, Pcs have strong tendency to aggregate in solution, which limited their applications. To overcome this problem, the introduction of dendritic wedge to peripheral positions of phthalocyanines can prevent the formation of aggregation to some extent. The preparation procedure involved the modification of the zinc (II) and magnesium (II) phthalocyanines with peripherally dendritic substitutions. The photophysical and photochemical properties of dendritic phthalocyanines were studied by UV/Vis and fluorescence spectroscopic methods. Compared with the magnesium (II) phthalocyanine, the intensity of Q band of zinc (II) phthalocyanine was increased but no obviously position changes was observed. Furthermore, the zinc (II) phthalocyanine exhibited relatively higher fluorescence intensity than the magnesium (II) phthalocyanine. The fluorescence quantum yield and lifetimes of magnesium (II) phthalocyanine was clearly longer than that of zinc (II) phthalocyanine. As the better photosensitizer, the zinc (II) phthalocyanine has higher singlet oxygen quantum yield owning superior performance. This results indicated that the singlet oxygen quantum yield would be effected by the nature of metal ions.
Metal phthalocyanines (MPcs) have been found to be a promising photosensitizers for photodynamic therapy (PDT) of cancers and non-cancer diseases. Nevertheless, phthalocyanines are substantially limited in clinical applications owing to their poor solubility, aggregation and insufficient selectivity for cancer cells. Catechol is an important pharmaceutical intermediate, playing important in vivo biological activity in medicine. Using catechol (pyrocatechin) as axial ligands, utilizing of the pharmaceutical effect of catechins, could improve the bioavailability, and achieve synergistic therapeutic effect in PDT. To address these issues, a novel catechol axially substituted tetra-α-(pentyloxy) titanium(IV) (TiPc(OC5H11)4-Catechol) was synthesized. The structure of TiPc(OC5H11)4-Catechol was characterized by elemental analysis, IR, 1HNMR and MS methods. The photophysical properties of TiPc(OC5H11)4 and TiPc(OC5H11)4-Catechol have been studied by UV/Vis and steady-state fluorescence spectra. After being axially substituted with catechin groups, no obviously intensity and position of maximum wavelength in Q-band of TiPc(OC5H11)4 and TiPc(OC5H11)4-Catechol were observed. The fluorescence intensity of TiPc(OC5H11)4 was stronger than that of TiPc(OC5H11)4-Catechol, but the fluorescence lifetime of TiPc(OC5H11)4-Catechol was longer than that of TiPc(OC5H11)4. TiPc(OC5H11)4-Catechol may be considered as a promising photosensitizer for PDT.
Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern–Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.
The singlet oxygen (1O2) production abilitity is an important factor to assess their potential as effective of photosensitizers. In this paper, the 1O2 production rate, production rate constant and quantum yield of silicon(IV) phthalocyanine axially bearing 1-3 generation dendritic substituents were evaluated by a high performance liquid chromatographic method. The results show that the 1O2 production rate and production rate constant of these compounds increase gradually with dendritic generations increase. And the 1O2 quantum yield of silicon(IV) phthalocyanine with first generation dendritic ligand was the highest. This may be due to the isolation effect of the dendritic ligands on the phthalocyanine core. The parameters of the observed 1O2 production properties will provide valuable data for these dendrimer phthalocyanines as promising photosensitizer in PDT application.
Photodynamic therapy (PDT) is an emerging alternative treatment for various cancers and age-related macular degeneration. Phthalocyanines (Pcs) and their substituted derivatives are under intensive investigation as the second generation photosensitizers. A big challenge for the application of Pcs is poor solubility and limited accumulation in the tumor tissues, which severely reduced its PDT efficacy. Nano-delivery systems such as polymeric micelles are promising tools for increasing the solubility and improving delivery efficiency of Pcs for PDT application. In this paper, nanoparticles of amphiphilic triblock copolymer poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) were developed to encapsulate 1-2 generation carboxylic poly (benzyl aryl ether) dendrimer. The morphologies and photophysical properties of polymeric nanoparticles loaded with 1-2 generation dendritic phthalocyanines (G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m) were studied by AFM, UV/Vis and fluorescent spectroscopic method. The morphologies of self-assembled PLL-PEG-PLL aggregates exhibited concentration dependence. Its morphologies changed from cocoon-like to spheral. The diameters of G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m were in the range of 33-147 nm, increasing with the increase of the concentration of PLL-PEG-PLL. The morphologies of G2-ZnPc(COOH)16/m also changed from cocoon-like to sphere with the increase of the concentration of PLL-PEG-PLL. It was found that, the no obviously Q change was observed between the free phthalocyanines and nanoparticles. The fluorescence intensity of polymer nanoparticles were higher enhanced compared with free dendritic phthalocyanines. The dendrimer phthalocyanine loaded with poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) presented suitable physical stability, improved photophysical properties suggesting it may be considered as a promising formulation for PDT.
A novel series of poly (aryl benzyl ether) dendrimer silicon phthalocyanines loaded block copolymers
ethoxypoly(ethylene glycol)-poly (lactic-co-glycolic acid) (MPEG-PLGA)were formed. The time-dependent intracellular
uptake of nanoparticles in HUVECs cells increased as they were incorporated into nanoparticles. With its highly
effective selective accumulation on choroidal neovascularization(CNV). This treatment resulted in a efficacious
choroidal neovascularization (CNV) occlusion with minimal unfavorable phototoxicity.
KEYWORDS: Luminescence, Zinc, Dendrimers, Energy transfer, Polymers, Absorption, Absorption spectroscopy, Fluorescence spectroscopy, Spectroscopy, Solar energy
The intermolecular electron transfer between the novel dendritic zinc (II) phthalocyanines (G1-DPcB and G2-DPcB) and anthraquinone (AQ) was studied by steady-state fluorescence and UV/Vis absorption spectroscopic methods. The effect of dendron generation on intermolecular electron transfer was investigated. The results showed that the fluorescence emission of these dendritic phthalocyanines could be greatly quenched by AQ upon excitation at 610 nm. The Stern- Volmer constant (KSV) of electron transfer was decreased with increasing the dendron generations. Our study suggested that these novel dendritic phthalocyanines were effective new electron donors and transmission complexes and could be used as a potential artifical photosysthesis system.
Serum albumin, the most abundant plasma protein in mammalian blood, shows significant effects on delivery and therapeutic efficacy of drugs, therefore, the investigation of binding interaction between serum albumin and drugs is vital and necessary. In the present study, the binding interaction of two aluminum (III) phthalocyanine (AlPc) derivatives, tetrasulfonate- and tetra-(p-sulfoazophenyl-4-aminosulfonyl)-substituted AlPc (complexes 1 and 2), with bovine serum albumin (BSA) was investigated by UV-Vis and fluorescence spectroscopy. Adding BSA to the Pc complexes in water caused remarkable changes in the Q-band of the Pc complexes, indicating an altered aggregation behavior. When titrating these AlPcs with BSA in PBS, the intrinsic fluorescence of BSA was significantly quenched through a static quenching process. The binding of Pc complexes to BSA might change its conformation, evidenced by the red shift of maximum emission wavelength. Furthermore, binding constants and binding sites were obtained and binding ability between the Pc complexes and BSA was assessed. Our results suggest that complexes 1 and 2 readily interact with BSA whereas the latter shows more affinity (with higher binding constant value) to BSA, implying the stretched amphiphilic substituents of complex 2 may contribute to their transportation in the blood.
The photophysical properties of a novel dendritic phthalocyanine di-{3,5-di-(4-methoxycarbonyl group benzyloxy)
benzyloxy) benzyloxy} axially substituted silicon (IV) phthalocyanine (DSiPc) were studied by UV/Vis, steady state and
time-resolved spectroscopic methods. The effect of dendritic structure on the photophysical properties and photoinduced
intermolecular electron transfer were investigated. The maximum absorption, fluorescence intensity, lifetime and
fluorescence quantum yield of DSiPc were greatly sensitized by the dendritic structure on the axially position of silicon
(IV) phthalocyanine. The photoinduced intermolecular electron transfer between this novel macromolecule and
benzoquinone (BQ) was studied. The results showed that the fluorescence emission of this dendritic phthalocyanine
could be quenched by BQ with KSV value of DSiPc is 52.84 dm3 mol-1. The cyclic voltammogram and square wave
voltammogram of DSiPc in DMF further evidenced the electron was transfer from DSiPc to BQ from thermodynamics.
Therefore, this novel dendritic phthalocyanine was an effective new electron donor and transmission complex could be
used as a potential artificial photosynthesis system.
Because of their excellent near-infrared (NIR) optical properties, phthalocyanines (Pcs) have been regarded as promising therapy agents for fluorescence image-guided drug delivery and noninvasive treatment of tumors by photodynamic therapy (PDT). Nevertheless, phthalocyanines are substantially limited in clinical applications owing to their poor solubility, aggregation and insufficient selectivity for cancer cells. To address these issues, we have developed a novel dendrimer-based theranostic nanoparticle for tumor-targeted delivery of phthalocyanine. The preparation procedure involved the modification of the silicon (IV) phthalocyanine molecule with a dendritic axially substitution, which significantly enhances their photophysical property. In order to improve biocompatibility and tumor-targeted delivery, the hydrophobic dendritic phthalocyanine was encapsulated by diblock amphiphilic copolymer poly (ethylene glycol)-poly (Epsilon-caprolactone) (MPEG-PCL) to form a polymeric nanoparticle. The polymeric nanoparticle is spherical with a diameter at about 90 nm. The photophysical property of the polymeric nanoparticle was studied by UV/Vis and fluorescence spectroscopic methods. Compared with the free dendritic phthalocyanine, the Q band of the polymeric nanoparticle was red-shifted, and the fluorescence intensity decreased. Furthermore, the polymeric nanoparticle has a relatively high loading amount and encapsulation rate. Therefore, the polymeric nanoparticle would be a promising third-generation photosensitizer (PS) for PDT.
The intermolecular electron transfer between the carboxylic dendritic zinc(II) phthalocyanines [G 1 -ZnPc(COOH) 8 and G 2 -ZnPc(COOH) 16 ] and methyl viologen (MV 2+ ) is studied by steady-state fluorescence and UV/Vis absorption spectroscopic method. The effect of dendron generation of this series of dendritic phthalocyanines on intermolecular electron transfer is investigated. The results show that the fluorescence emission of these dendritic phthalocyanines could be greatly quenched by MV 2+ upon excitation at 610 nm. The Stern–Volmer constant (K SV ) of electron transfer is decreased with increasing dendron generations. Our study suggests that these dendritic phthalocyanines are an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.
The intermolecular electron transfer between carboxylic dendritic zinc(II) phthalocyanine bearing carboxylic terminal
groups(G1-ZnPc(COOH)8) and methyl viologens (MV2+) was studied by steady-state fluorescence and UV/Vis
spectroscopy. The effect of different concentrations of MV2+ on intermolecular electron transfer was investigated. The
results show that the fluorescence emission of this dendritic phthalocyanine could be greatly quenched with an increasing
amount of MV2+ upon excitation at 610 nm. Our study suggests that this novel dendritic phthalocyanine is an effective
new electron donor and transmission complex and could be used as a potential biosensor conjugated with suitable
fluorescence quencher.
A novel series of zinc (II) phthalocyanines bearing four poly (aryl benzyl ether) dendritic substituents with carboxylic
acid functionalities (Gn-DPcZn (Gn=n-generation dendrimer, n=1-2)) loaded polymeric micelles (Gn-DPcZn/m) were
formed. The time-dependent intracellular uptake of Gn-DPcZn in RPE cells increased as they were incorporated into
micelles, but inversely correlated with the generation. The photocytoxity of Gn-DPcZn was improved by incorporation
into polymeric micelles and increased with the generation.
The photophysical properties of a novel series dendrimer phthalocyanine-SWNTs nanoconjugates in
which the dendrimer phthalocyanine was tetra-[3,5-di-(4-carboxylic benzyloxy)benzyloxy] zinc(Ⅱ)
phthalocyanine covalently linked with SWNTs using ethylenediamine or hexamethylenediamine as
space linkers were investigated in detailed by the fluorescent spectra and time-resolved spectroscopy.
The photoindued intramolecular electron was transferred from phthalocyanine (donor) to carbon
nanotubes (acceptor). Novel functionalized constituents in this work are fundamentally important due
to the synergy effects of carbon nanotubes and dendritic zinc phthalocyanine, which may find potential
applications in the drug delivery, biological labels and many other related fields.
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