[Structural identification and quality study on isomers of a novel anticancer photosensitiser photocyanine].

Our work focuses on the quality control and structural identification of Photocyanine as a cancer therapeutic photosensitizer. Photocyanine is a mixture which contains four ZnPcS2P2 type substituted Phthalocyanine isomers. In order to obtain the single component from Photocyanine, the mixture of four isomers possessing the similar structures and chemical property had been isolated and purified. An HPLC method with a mixture of methanol-acetonitrile-ion-pair buffer as the mobile phase was applied to isolate the four isomers by means of a semi-preparative C18 column. To remove the salts which were mixed in the preparative product, a SPE C18 column was used to separate the salts by elution with water and then the marker component was eluted by methanol. Subsequently, a column of Sephadex LH-20 gel was applied to elute the crudes with methanol to desalination. The purity of the isolated compound was measured by TLC and four different isomers of phthalocyanine were obtained. The chemical structures of them were elucidated by 1H NMR spectra, gCOSY and NOE1D. An HPLC-DAD method was developed for simultaneously determination of four major isomers in Photocyanine with a C18 column (Grace Smart, 150 mm x 4.6 mm ID, 5 microm). The separation was carried out with a gradient program at a flow rate of 1.0 mL x min(-1). The mobile phase was a mixture of acetonitrile and ion-pair buffer (0.01 mol x L(-1) hexadecyl trimethyl ammonium bromide and 0.01 mol x L(-1) potassium dihydrogen phosphate, adjusted the pH value to 6.8 with potassium hydroxide solution). The resolution values of four isomers were 2.5, 1.20, 1.33, and 1.8. Linear regression analysis for four compounds was performed by the external standard method. Four constituents were linear in the concentration range of 0.005 to 10 microg. The values of relative standard deviation (RSD) of intra-day were 0.12%, 0.66%, 0.99%, and 1.21%, respectively. The limits of detection for four compounds were 15 ng, 20 ng, 12 ng, and 25 ng, respectively. This method was simple, accurate and reproducible. The developed method can be successfully applied to analyze isomers in Photocyanine.

[Study on UV-Vis absorption spectra and fluorescence emission spectra of sixteen tetra-substituted metallophthalocyanine complexes].

The UV-Visible absorption spectra and the fluorescence emission spectra of sixteen tetra-substituted metallo-phthalocyanine complexes {R4 PcM, where R = 2-[4-(2-sulfonic ethyl) piperazin-1-] ethoxyl (SPEO--), 2-(piperidin-1-yl) ethoxyl (PEO--); substitution position at alpha-position and beta-position of phthalocyanine ring; M = Zn(II), Ni(II), Co(II) and Cu(II)} were measured. The influence of different central ion, substituted group and its position, as well as different solvent on the Q-band of phthalocyanine complex in its UV-Vis absorption spectra was investigated. The influence of different central ion, substituted group and its position on the fluorescence emission spectra was discussed. Some properties of the UV-Vis absorption spectra such as the maximum absorption wavelength (lamdamax ) of Q-band and its molar extinction coefficient (epsilon), and those of the fluorescence emission spectra such as fluorescence quantum yield (phiF), fluorescence lifetime (r) and excited state energy (Es) were studied. The results showed that the lamdamax of Qband of all complexes were located at 681-718 nm, which had a distinct red shift in contrast with unsubstituted metallophthalocyanines (669-671 nm). All complexes of R4 PcM possessed a very high molar extinction coefficient up to 10(5) L x mol(-1) x cm(-1). And the UV-Vis absorption spectra and the fluorescence emission spectra of all complexes exhibited mirror shape concurrently. Two beta-substituted zinc phthalocyanine complexes with formula beta-(SPEO)4PcZn and beta-(PEO)4PcZn possessed very high molar extinction coefficient, fluorescence quantum yield and fluorescence lifetime specially. Therefore, it is hoped that these two would be developing to be new photosensitizers for photodynamic therapy (PDT)and photodynamic diagnosis (PDD).

2-Benzyl-isoindoline-1,3-dione: a monoclinic polymorph.

In the molecule of the title compound, C(15)H(11)NO(2), the dihedral angle between the ring systems is 81.3 (2)°. In the crystal structure, mol-ecules are held together via C-H⋯O inter-actions.

[Synthesis and UV/Vis spectra of a dialkyloxy substituted phthalocyanine].

A dialkyloxy substituted metal-free phthalocyanine was synthesized by using 3-(2',2',4'-trimethyl-3'-pentoxy)-1,3-diiminoisoindoles and 1,3,3-trichloroisoindolenine as starting materials, and characterized by element analysis, 1H NMR, IR and UV/Vis spectra. The dependences of wavelength of UV/Vis spectra and its split of Q band absorption on the number of substituents and, dielectric constant of solvents are discussed based on the comparison with tetraalkyloxy substituted metal-free phthalocyanine.

[Fluorescence spectra and photo-generating rate of singlet oxygen of phthalocyaninatopalladium].

The absorption spectral properties, fluorescence spectral properties and the abilities of photo-generating singlet oxygen of four phthalocyanines, namely tetra-alpha-(2,2,4-trimethyl-3-pentoxy) phthalocyaninatopalladium (zinc) and tetra-alpha-(2,4-diterbutylphenoxy) phthalocyaninatopalladium (zinc), were determined. Experimental results show that the ability of photo-generating singlet oxygen of phthalocyaninatopalladium is similar to that of phthalocyaninatozincx, though palladium(II) is an open shell electron structure and zinc( II ) is a closed shell structure. This may be concerned with a weak flourescence intensity and a strong inter-crossing transition of phthalocyaninatopalladium.

[Study on UV-Vis absorption spectra of tetra-azo-aromaticoxy substituted metallophthalocyanines].

UV-Vis absorption spectras of six series (18 kinds) of tetra- azo-aromaticoxy substituted metallophthalocyanines (R4 PcM, R = 4-pyridyloxy, 8-quinolinoxy, 2-methyl-8-quinolinoxy; substitution position: a position and beta position; M = Ni (II), Cu(II), Zn(II)) were measured. The effects of central mentals, the kinds and the positions of substitution groups, and solvents on the metallophthalocyanines' lamdamax in Q-band were discussed. Experimental data show: The lamdamax in Q-band of title complexes is about 680 nm. In contrast with substitution-free metallophthalocyanines(669-671 nm), the lamdamax in Q-band of the title complexes with the same central metal exhibits a different red-shift. The effect of substitution group's kinds on lamdamax in Q-band of the title complexes is more obvious in a position than in beta position, and with the same substitution group and central metal, lamdamax in Q-band of alpha position substituted complexes exhibits more obvious red-shift than beta position substituted complexes. The effects of central metal and solvent on lamda,ax in Q-band of the title complexes aren't obvious.

[Meso-tetraphenylporphyrinatozinc/TiO2 nanocompound synthesized by in-situ method and photocatalysis under visible-light irradiation].

The meso-tetraphenylporphyrinatozinc/titanium dioxide (ZnTPP/TiO2) nanocompounds with different molar ratios were synthesized by sol-gel method at 400 degrees C, 4h. The nanocompounds were characterized by XRD, UV-Vis, FTIR and Fluorescence methods. Anatase for TiO2 in the nanocompounds was defined, and ZnTPP was also obtained during in-situ process. Photocatalystic activities of them influenced by the proportion between ZnTPP and TiO2 were discussed under visible light. The results show that a nanocompound (ZnTPP:TiO2 = 1:100 mol%) has the best photocatalystic activity, and the degradation of Rhodanmine B is up to 92% after 150 minutes under visible light irradiation. The sensitization mechanism is that the photogenerated charge carriers are separated by Zn--O bond between ZnTPP and TiO2.

[A silicon phthalocyanine axially substituted by nipagin: synthesis, molecular spectroscopic properties, and in vitro photodynamic activities].

A new silicon phthalocyanine axially substituted by Nipagin, i.e. bis(4-methoxycarboxyl phenoxy)phthalocyaninatosilicon, has been synthesized and characterized by IR, NMR, HPLC and elemental analysis. Its electronic absorption spectra and fluorescence spectra in different solvents were investigated. It was found that the compound existed in the form of monomer in a saline solution containing 2% (phi) Cremophor EL and 20% (phi) propanediol. The electronic absorption spectra of the compound in the above saline solution were typical for non-aggregated phthalocyanines, showing an intense and sharp Q band at 683 nm with a molar absorption coefficient of 7.47 x 10(4) mol(-1) x L x cm(-1). The compound exhibited a relatively strong fluorescence emission at 690 nm with a quantum yield of 0.34 and with a fluorescence lifetime of 4.7 ns. The primary in vitro assay showed the compound had photodynamic killing activities against B16 melanoma cells with a LD50(half lethal dose) of 1.2 x 10(-4) mol x L(-1).

[Determination and pharmacokinetics of photosensitizer ZnPcS2P2 uptaken by K562 cells].

The di-sulfonated di-phthalimidomethyl phthalocyanine zinc (ZnPcS2P2) was an amphiphilic photosensitizer for photodynamic therapy of cancer. According to fluorescence analytical method, extracting efficiencies of 2.0% SDS (Wt%), 1.5% Triton X-100 (phi) and DMF for ZnPcS2P2 in K562 cells were compared. The results showed that 1.5% Triton X-100 was the most efficient reagent for the first time extracting. Using 1.5% Triton X-100 as extracting reagent, the kinetic curves of cellular uptake of ZnPcS2P2 as well as LDL-ZnPcS2P2 complex by K562 cells were determined. Compared with ZnPcS2P2, the maximum cellular uptake of LDL-ZnPcS2P2 by K562 was doubled, which indicated that LDL was an effective targeting delivery vehicle for ZnPcS2P2.

Syntheses of Metal Phthalocyanines and Their Photoinactivations on Cancer Cells.

This paper reported the syntheses of amphiphilic substituted metal phthalocyanines containig sulfonic acid groups and phthalimidomethyl groups (MPcSP, M=Zn or Al(OH), S=-SO(3)(-), P=phthalimidomethyl). We have selected zinc phthalocyanine (Zn-D) as the one with better cell killing potential by an in vitro cell survival assay. Over 90 % tumor cells were killed with 10 mg/L Zn-D, after they were exposed to 12 J/cm(2) red light.