Photochemical Property and Photodynamic Activity of Tetrakis(2-naphthyl) Porphyrin Phosphorus(V) Complex

摘要: To examine the photosensitized biomolecules damaging activity, dimethoxyP(V)tetrakis(2-naphthyl)porphyrin (NP) and dimethoxyP(V)tetraphenylporphyrin (PP) were synthesized. The naphthyl moiety of NP hardly deactivated photoexcited P(V)porphyrin ring in ethanol. In aqueous solution, showed quenching effect on porphyrin ring, possibly through electron transfer self-quenching by a molecular association. Binding interaction between human serum albumin (HSA), water soluble protein, these porphyrins could be confirmed absorption spectral change. apparent association constant was larger than that PP. It is explained more hydrophobic can easily bind into pockets HSA. PP effectively induced damage tryptophan residue HSA, transfer-mediated oxidation singlet oxygen generation. also HSA during photo-irradiation contributions mechanisms speculated. mechanism to protein should advantageous for photodynamic therapy hypoxic condition. quantum yield photodamage significantly NP. considered suppress damage. conclusion, naphthalene substitution P(V)porphyrins enhance binding with biomacromolecules such as however, this may reduce media. Photosensitized an important process medicinal applications photochemical reaction, (PDT) cancer. PDT less-invasive treatment cancer some non-malignant conditions. general, are (1O2) generation photo-induced from proteins. Because concentration cells low, PDT. For purpose, we have examined derivatives, which induce under visible-light irradiation. Ligand-substituted derivatives tetraphenylporphyrin P(V) complexes been synthesized their photodamaging activity investigated. study, tetranaphthylporphyrin complex its reference compound (Figure 1) A redshift band enhancement expected case naphthylP(V)porphyrin. DimethoxyP(V)tetrakis(2-naphthyl)porphyrin according previous reports (Supporting information). We tried synthesize tetrakis(1-naphtyl)porphyrin (1-TNP). However, incorporation phosphorus atom free base 1-TNP not established, whereas reaction proceed relatively tetrakis(2-naphtyl)porphyrin (2-TNP). sterically hindered molecules. Steric hindrance around central due axial ligand connecting hydrogen 1-naphthyl inhibit 2). calculated enthalpy change (191 kJ mol) 2-TNP (110 mol), supporting steric inhibits 1-TNP. Figure 1. Structures (left) (right). *To whom correspondence addressed. E-mail: hirakawa.kazutaka@shizuoka.ac.jp Communication Kazutaka Hirakawa et al Shigetoshi Okazaki journal c Korean Society Photoscience 38 RCP 2015 . 4(2) 37-40 2. Optimized structures These obtained semiempirical orbital calculation at PM3 level utilizing Spartan’10 (Wavefunction Inc., CA, USA). properties Absorption fluorescence spectra slightly redshifted compared those 3 Table 1). photosensitizer Naphthyl contributed redshift, however large. (Φf) NP, determined relative bis(ethyleneglycoxy)P(V) (Фf =0.048 water), time profile intensity ethanol fitted single exponential function, analyzed double suggesting two different conformations solution. lifetime (τf) shown state observed following experiments performed. Human used target biomolecule. Sample solutions containing 5 M 10 mM phosphate buffer (pH 7.6) 2.5% (vol/vol) irradiated lightemitting diode (LED) (519 nm, 1 mW cm). Damage evaluated fluorometry residue. excitation wavelength 298 nm.