Photodynamic Activities of Porphyrin Derivative–Cyclodextrin Complexes by Photoirradiation

Abstract

Water-soluble cyclodextrin (CyD) complexed with porphyrin derivatives with different substituents in the -positions showed different photodynamic activities toward cancer cells under illumination at wavelengths over 600 nm, the most suitable wavelengths for photodynamic therapy (PDT). In particular, aniline- and phenol-substituted derivatives had high photodynamic activity because of the efficient intracellular uptake of the complexes by tumor cells. These complexes showed greater photodynamic activity than photofrin, currently the main drug in clinical use as a photosensitizer. These results represent a significant step toward the optimization of porphyrin derivatives as photosensitizers.

Improved Stability and Photodynamic Activity of Water‐Soluble 5,15‐Diazaporphyrins Incorporated in β‐(1,3‐1,6)‐d‐Glucan with On‐Off Switch

“…[7,13,20] UV-vis absorption spectra of b-1,3-glucan-complexed 1-3 contained aS oret band at around4 00 nm and Q-bands at around5 50 and 620 nm that were broader than those of TMeb-CDx-complexed 1-3 in water and 1-3 in chloroform or methanol ( Figures 2a and S1). [7,13,20] UV-vis absorption spectra of b-1,3-glucan-complexed 1-3 contained aS oret band at around4 00 nm and Q-bands at around5 50 and 620 nm that were broader than those of TMeb-CDx-complexed 1-3 in water and 1-3 in chloroform or methanol ( Figures 2a and S1).…”

“…[7,13,20] UV-vis absorption spectra of b-1,3-glucan-complexed 1-3 contained aS oret band at around4 00 nm and Q-bands at around5 50 and 620 nm that were broader than those of TMeb-CDx-complexed 1-3 in water and 1-3 in chloroform or methanol ( Figures 2a and S1). [7] The 1 HNMR peaks assigned to 1, 2,a nd 3 disappeared completely in the b-1,3-glucan complexes ( Figure S2). The random self-aggregation of 1-3 in b-1,3-glucan was also confirmed by fluorescence quenching compared with TMe-b-CDx-complexed 1-3, which showed strong fluorescenceintensities (Figure 2b).…”

“…Formation of b-1,3-glucan-complexed diazaporphyrins b-1,3-Glucan-complexed diazaporphyrins 1-3 werep repared using am echanochemicalh igh-speed vibration millinga pparatus. [7,13,20] UV-vis absorption spectra of b-1,3-glucan-complexed 1-3 contained aS oret band at around4 00 nm and Q-bands at around5 50 and 620 nm that were broader than those of TMeb-CDx-complexed 1-3 in water and 1-3 in chloroform or methanol( Figures 2a and S1). The broad Soret bands originated not only from the inherent absorption of diazaporphyrins but also self-aggregation of 1-3,a sd etermined from the broadening of these bands over time.…”

“…Porphyrind erivatives and analogues,s uch as phthalocyanines and chlorines, that are sensitive to long-wavelengthl ight (> 600 nm), are ex-pectedt ob ee ffective PSs because deeper tissue penetration is achieved in that wavelength region. [7,8] However, aqueous solutionso fd iazaporphyrin (1 and 2)-TMe-b-CDx complexes are unstable and show decreased absorbance for seven days (Figure 1). [4][5][6] Diazaporphyrins show a large absorption at wavelengths over 600 nm andh ave am ore compacts tructure than phthalocyanines.…”

“…Therefore, diazaporphyrins can form the complexes with two trimethyl-b-cyclodextrins( TMe-b-CDxs) that show higherp hotodynamic activity. [7,8] However, aqueous solutionso fd iazaporphyrin (1 and 2)-TMe-b-CDx complexes are unstable and show decreased absorbance for seven days (Figure 1). To solve these problems, in this study, b-(1,3-1,6)-d-glucan (b-1,3-glucan), which has a sugar chain similart ot hose of cyclodextrins, was applieda s the water-solubilizing agent.…”