Mazzoli Alessandra, Spalletti Anna, Carlotti Benedetta, Emiliani Carla, Fortuna Cosimo G, Urbanelli Lorena, Tarpani Luigi, Germani Raimondo
Department of Chemistry, Biology, and Biotechnology and Centro di Eccellenza sui Materiali Innovativi Nanostrutturati (CEMIN), University of Perugia , 06100 Perugia, Italy.
J Phys Chem B. 2015 Jan 29;119(4):1483-95. doi: 10.1021/jp510360u. Epub 2015 Jan 15.
Photophysical properties of some azinium iodides in aqueous solution of nanostructured systems as DNA and nonionic micelles were investigated using steady-state and ultrafast time-resolved spectroscopy. Spectrophotometric and fluorimetric titrations of the investigated compounds with salmon testes DNA supplied evidence of a good interaction between the salts and DNA with binding constants of 10(4)-10(6) M(-1), making them interesting for pharmaceutical applications. The interaction with DNA also changes the photobehavior of the compounds, increasing the radiative deactivation pathway to the detriment of internal conversion and slowing down the excited state dynamics. The interaction of the azinium salts with the nonionic surfactant Triton X-100 from premicellar to postmicellar concentration was studied by spectrophotometric and fluorimetric titrations evidencing the ability of the micelles to associate the studied salts in their hydrophobic portion and to release them in the presence of DNA, acting as promising drug carriers. Also transient absorption spectroscopy with femtosecond resolution demonstrated the insertion of the investigated compounds into micellar aggregates. Preliminary measurements by confocal fluorescence microscopy on MCF-7 cells in the presence of the studied azinium salts showed that they are able to cross the cellular membrane and that their cytotoxicity can be expressed through interaction with DNA (RNA). In fact, they showed a significant fluorescence signal in all cell compartments, particularly (for 2 and 3) into punctuate structures within the nuclei compatible with a localization into the nucleoli.
利用稳态和超快时间分辨光谱研究了一些氮鎓碘化物在纳米结构体系(如DNA和非离子胶束)水溶液中的光物理性质。用鲑鱼精巢DNA对所研究化合物进行分光光度滴定和荧光滴定,结果表明盐与DNA之间存在良好的相互作用,结合常数为10⁴ - 10⁶ M⁻¹,这使得它们在药物应用方面具有吸引力。与DNA的相互作用也改变了化合物的光行为,增加了辐射失活途径,不利于内转换,并减缓了激发态动力学。通过分光光度滴定和荧光滴定研究了氮鎓盐与非离子表面活性剂Triton X - 100从前胶束浓度到后胶束浓度的相互作用,结果表明胶束能够将所研究的盐缔合在其疏水部分,并在DNA存在时释放它们,可作为有前景的药物载体。飞秒分辨率的瞬态吸收光谱也证明了所研究化合物插入胶束聚集体中。在存在所研究的氮鎓盐的情况下,通过共聚焦荧光显微镜对MCF - 7细胞进行的初步测量表明,它们能够穿过细胞膜,并且它们的细胞毒性可以通过与DNA(RNA)的相互作用来表达。事实上,它们在所有细胞区室中都显示出显著的荧光信号,特别是(对于2和3)在与核仁定位相容的细胞核内的点状结构中。