Synthesis,photophysical properties and biological evaluation of β-alkylaminoporphyrin for photodynamic therapy

A series of β-alkylaminoporphyrins conjugated with different amines at β position (D1–D3) or with electron-donating and electron-withdrawing substituents at phenyl position (D4–D6) were synthesized. Their photophysical and photochemical properties, intracellular localization, photocytotoxicities in vitro and vivo were also investigated. All target compounds exhibited no cytotoxicities in the dark and excellent photocytotoxicities against HeLa cells. Among them, D6 showed the highest phototoxicity and the lowest dark toxicity, which was more phototoxic than Hematoporphyrin monomethyl ether (HMME). In addition, D6 exhibited best photodynamic antitumor efficacy on BALB/c nude mice bearing HeLa tumor. Therefore, D6 is a powerful and promising antitumor photosensitizer for photodynamic therapy.     

Synthesis and characterization of tetraphenylporphyrin iron(III) complexes with substituted phenylcyanamide ligands

Several five coordinate complexes of [(TPP)Fe^III(L)] in which TPP is the dianion of tetraphenylporphyrin and L is the monoanion of phenylcyanamide (pcyd) (1), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd) (2), 2,6-dichlorophenylcyanamide (2,6-Cl₂pcyd) (3), and 2,3,4,6-tetrachlorophenylcyanamide (2,3,4,6-Cl₄pcyd) (4) have been prepared by the reaction of [(TPP)Fe^IIICl] with appropriate thallium salt of phenylcyanamide. Each of the complexes has been characterized by IR, UV-Vis and ¹H NMR spectroscopic data. Dark red-brown needles of [(TPP)Fe^III(2,6-Cl₂pcyd)] (C₅₁H₃₁Cl₂FeN₆ · CHCl₃) crystallize in the triclinic system. The crystal structure of Fe(III) compound shows a slight distortion from square pyramidal coordination with the 2,6-dichlorophenylcyanamide anion in the axial position through nitrile nitrogen atom. Iron atom is 0.47(1) Å out of plane of the porphyrin toward phenylcyanamide ligand. In non-coordinating solvents, such as benzene or chloroform, these complexes exhibit ¹H NMR spectra that are characteristic of high-spin (S = 5/2) species. The X-ray crystal structure parameters are also consistent with high-spin iron(III) complexes. The iron(III) phenylcyanamide complexes are not reactive toward molecular oxygen; however, these complexes react with HCl and produce TPPFe^IIICl.     

Synthesis and characterization of monomer and dimer complexes of porphyrin iron(III) with bridging phenylcyanamide ligands

Several new mono and dinuclear complexes of [(P)Fe^III(L)], in which P is the dianion of tetraphenylporphyrin(TPP) and tetramesitylporphyrin(TMP) and L is the monoanion of 4-azo(phenylcyanamido)benzene (apc) (1) and (2) or dianion 1,4-di cyanamidobenzene (dicyd) (3), (4), (7), (8) and 4,4′-azo-diphenylcyanamide (adpc) (5), (6), (9), (10) have been prepared by the reaction of [(P)Fe^IIICl] with appropriate thallium salts of phenylcyanamide derivatives. Each of the complexes has been characterized by FT-IR, UV-Vis, ¹H NMR, MALDI-TOF and EPR spectroscopic data. In non-coordinating solvents (such as toluene or chloroform) these complexes exhibit ¹H NMR spectra that are characteristic of high-spin (S = 5/2) species. The cyanamide group (NCN) of the bridging ligand is coordinated to Fe(III) ions through the nitrile-nitrogen. The iron(III) phenylcyanamide complexes are not reactive toward dioxygen, they convert into [TPPFe^IIICl] when treated with HCl. EPR and NMR have shown that in dinuclear complexes weak magnetic interactions take place between two iron(III) paramagnetic centers.