Facile synthesis of pegylated zinc(II) phthalocyanines via transesterification and their in vitro photodynamic activities
Facile synthesis of pegylated zinc(II) phthalocyanines via transesterification and their in vitro photodynamic activities
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DOI：
10.1039/c1ob05955f
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发表时间：
2011-01-01
影响因子：
3.2
通讯作者：
Ng, Dennis K. P.
中科院分区：
文献类型：
--
作者：
Bai, Ming;Lo, Pui-Chi;Ng, Dennis K. P.
4，5-二[4-（2-甲基苯基）氨基]-4-甲基苯并[4-（2-甲基苯基）氨基]-2-甲酰胺的处理（甲氧羰基）苯氧基]邻苯二甲腈和4，5-双[3，5-双（甲氧羰基）苯氧基]邻苯二甲腈与过量的1，3-二亚氨基异吲哚啉在Zn（OAc）（2）中心点2 H（2）O和1的存在下，三甘醇单甲醚或聚乙二醇单甲醚中的8-二氮杂双环[5.4.0]十一碳-7-烯（平均分子量为550）进行“3 + 1”混合环化和酯交换反应，得到相应的二-β-取代酞菁锌（II），产率为7-23%。如吸收光谱所示，这些化合物在N，N-二甲基甲酰胺中基本上不聚集，并且可以有效地产生单线态氧。单线态氧量子产率（Phi（Delta）= 0.53-0.57）与未取代的酞菁锌（II）的单线态氧量子产率（Phi（Delta）= 0.56）相当。这些化合物在Cremophor EL乳剂中也表现出对HT 29人结肠直肠腺癌和HepG 2人肝癌细胞的光细胞毒性，IC（50）值在0.25-3.72 μ M范围内。四个三甘醇链的类似物是最有效的光敏剂和本地化优先在HT 29细胞的线粒体。双（聚乙二醇）-对应物可以在水中和培养基中形成无表面活性剂的纳米颗粒。的流体动力学半径，通过动态激光散射测定，范围从6.3至79.8 nm取决于制备方法和条件。这些纳米颗粒的光细胞毒性（IC（50）= 0.43-0.56 μ M）与Cremophor EL配制的系统的光细胞毒性（IC（50）= 0.34 μ M）相当。
Treatment of 4,5-bis[4-(methoxycarbonyl) phenoxy] phthalonitrile and 4,5-bis[3,5-bis(methoxycarbonyl)phenoxy]phthalonitrile with an excess of 1,3-diiminoisoindoline in the presence of Zn(OAc)(2)center dot 2H(2)O and 1,8-diazabicyclo[5.4.0]undec-7-ene in triethylene glycol monomethyl ether or polyethylene glycol monomethyl ether (with an average molecular weight of 550) led to "3 + 1" mixed cyclisation and transesterification in one pot, affording the corresponding di-beta-substituted zinc(II) phthalocyanines in 7-23% yield. As shown by absorption spectroscopy, these compounds were essentially non-aggregated in N,N-dimethylformamide and could generate singlet oxygen effectively. The singlet oxygen quantum yields (Phi(Delta) = 0.53-0.57) were comparable with that of the unsubstituted zinc(II) phthalocyanine (Phi(Delta) = 0.56). These compounds in Cremophor EL emulsions also exhibited photocytotoxicity against HT29 human colorectal adenocarcinoma and HepG2 human hepatocarcinoma cells with IC(50) values in the range of 0.25-3.72 mu M. The analogue with four triethylene glycol chains was the most potent photosensitiser and localised preferentially in the mitochondria of HT29 cells. The bis(polyethylene glycol)-counterpart could form surfactant-free nanoparticles both in water and in the culture medium. The hydrodynamic radii, as determined by dynamic laser light scattering, ranged from 6.3 to 79.8 nm depending on the preparation methods and conditions. The photocytotoxicity of these nanoparticles (IC(50) = 0.43-0.56 mu M) was comparable with that of the Cremophor EL-formulated system (IC(50) = 0.34 mu M).