水溶性酞菁类光敏剂的合成及其光谱性质研究

以3-硝基邻苯二甲腈与3-巯基-1-丙磺酸钠为原料，在醋酸盐存在下通过四环化合成了三种带四个3-磺基丙基磺酰基的水溶性酞菁。利用紫外-可见吸收光谱，荧光光谱等对其光谱性质进行了测量，并计算了其荧光量子产率和单线态氧量子产率。引入吸电子基团所合成的水溶性酞菁与ZnPc相比，其荧光发射光谱的形状并未改变，但其最大荧光发射波长均发生10 nm以上的红移。三种水溶性酞菁中锌酞菁的荧光量子产率最高，铜酞菁的荧光量子产率最低；它们在水溶液中的荧光呈双指数衰减，这可归结为激发态质子化或去质子化的结果。单线态氧量子产率锌酞菁最大，空心酞菁次之，铜酞菁最小。光谱分析结果表明，合成的锌酞菁和空心酞菁具有高的单线态氧量子产率和高的光稳定性，有望用作光动力治疗和光免疫治疗的光敏剂。

Synthesis and Spectral Properties of Water-Soluble Phthalocyanine-Based Photosensitizers

With 3-nitrobenzonitrile and 3-mercapto-1-propanesulfonate as the starting materials, three kinds of water-soluble phthalocyanines with four 3-sulfopropylsulfonyl groups were synthesized by tetracyclization in the presence of metal acetate. The photophysical properties were measured by UV-Vis absorption spectra, fluorescence spectra and so on. The fluorescence quantum yield and the singlet oxygen yield were calculated. Compared with ZnPc, the shape of the fluorescence emission spectrums of the water-soluble phthalocyanines synthesized by introducing electron-withdrawing groups did not change, but the maximum fluorescence emission wavelengths had more than 10 nm red shifts. Among the three kinds of water-soluble phthalocyanines, zinc phthalocyanine had the highest fluorescence quantum yield and copper phthalocyanine had the lowest fluorescence quantum yield. Their fluorescence in aqueous solution showed a double exponential decay, which could be attributed to the protonation or deprotonation of excited states. The singlet oxygen quantum yield of zinc phthalocyanine was maximum, followed by hollow phthalocyanine, and copper phthalocyanine was minimum. The results of spectral analysis showed that the synthesized zinc phthalocyanine and hollow phthalocyanine have high singlet oxygen quantum yield and high photostability and are expected to be used as photosensitizers for photodynamic therapy and photoimmunotherapy.