Departamento de Química, Facultad de Ciencias Exactas Físico-Químicas y Naturales, Universidad Nacional de Río Cuarto, Agencia Postal Nro. 3, X5804BYA Río Cuarto, Córdoba, Argentina.
Bioorg Med Chem. 2012 Jul 1;20(13):4032-9. doi: 10.1016/j.bmc.2012.05.012. Epub 2012 May 15.
Novel photoactive bridged polysilsesquioxane films were prepared by doped with a porphyrin derivative. The films were formed by acid-catalyzed polycondensation reaction of a precursor of a bridged silsesquioxane, based on the reaction product of (glycidoxypropyl)trimethoxysilane with n-dodecylamine in the presence of 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin, followed by solvent evaporation. This procedure allowed obtaining flexible thin films. Absorption and fluorescence spectroscopic analysis showed the characteristic bands of the porphyrin in the visible region indicating that the photosensitizer is mainly embedded as monomer in the films. Photodynamic properties of the polymeric films were studied in solution containing photooxidizable substrates. Singlet molecular oxygen, O(2)((1)Δ(g)), production was observed by the reaction with 9,10-dimethylanthracene and 9,10-anthracenediyl-bis(methylene)dimalonic acid in different media. Also, these films photosensitized the decomposition of l-tryptophan. In vitro investigations showed that these films produce photodynamic inactivation of Candida albicans cells in aqueous suspensions and on their surfaces. These films exhibit a photosensitizing activity causing a ∼2.5 log (99.7%) decrease of cellular survival after 60 min of irradiation with visible light. Also, the photocytotoxicity of the surfaces was tested under condition of microbial growth. Yeast cells exposed to the film and illuminated showed growth delay compared with controls. Studies of photodynamic action mechanism showed that the photoinactivation increased in D(2)O, while cells were protected in the presence of azide ion. In contrast, the addition of mannitol produced a negligible effect on the cellular phototoxicity. These results provide evidence that O(2)((1)Δ(g)) produced by the polymeric film doped with porphyrin can successfully inactivate C. albicans in cell suspensions and deposited on the film surface.
新型光活性桥联聚硅氧烷薄膜是通过掺杂卟啉衍生物制备的。薄膜是通过酸催化缩聚反应形成的,前驱体是 bridged silsesquioxane,基于(缩水甘油丙基)三甲氧基硅烷与 n-十二胺的反应产物,在 5-(4-羧苯基)-10,15,20-三(4-甲基苯基)卟啉存在下,然后蒸发溶剂。该方法允许获得柔性薄膜。吸收和荧光光谱分析表明,可见区域的卟啉特征带表明,光敏剂主要以单体形式嵌入到薄膜中。在含有可光氧化底物的溶液中研究了聚合物薄膜的光动力性质。通过与 9,10-二甲基蒽和 9,10-蒽二亚基-双(亚甲基)丙二酸在不同介质中的反应观察到单重态分子氧,O(2)((1)Δ(g))的产生。此外,这些薄膜还敏化了 l-色氨酸的分解。体外研究表明,这些薄膜在水悬浮液中和表面上对白色念珠菌细胞产生光动力失活。这些薄膜表现出光敏化活性,在可见光照射 60 分钟后,细胞存活率降低约 2.5 对数(99.7%)。此外,还在微生物生长条件下测试了光毒性。与对照相比,暴露于薄膜并照射的酵母细胞显示出生长延迟。光动力作用机制的研究表明,在 D(2)O 中,光失活增加,而在叠氮化物离子存在下,细胞受到保护。相比之下,添加甘露醇对细胞光毒性几乎没有影响。这些结果表明,掺杂卟啉的聚合物膜产生的 O(2)((1)Δ(g))可以成功地失活细胞悬浮液中的白色念珠菌和沉积在膜表面上的白色念珠菌。