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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Photo-physical, theoretical and photo-cytotoxic evaluation of a new class of lanthanide(III)-curcumin/diketone complexes for PDT application
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Photo-physical, theoretical and photo-cytotoxic evaluation of a new class of lanthanide(III)-curcumin/diketone complexes for PDT application

机译：用于PDT施用的新类镧系元素（III） - 氟胺/二酮复合物的照片物理，理论和光学 - 细胞毒性评价

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Herein we report the synthesis, characterization, photophysical and photocytotoxicity studies of a new class of curcumin-based lanthanide(III) complexes of general molecular formula [La(1,10-phen)(2)(L)(NO3)(2)] (1-4), where L = 1-phenylbutane-1,3-dione (L-1, 1), 1-(anthracen-9-yl)butane-1,3-dione (L-2, 2), 1-(3a(1),5a(1)-dihydropyren-1-yl)butane-1,3-dione (L-3, 3) and curcumin (L-4, 4). Complex 1 was characterized by single-crystal X-ray crystallography and it exhibited the N4O6 coordination of La(III). The presence of the low-lying and long-lived triplet excited state enabled the luminescent complexes (2-4) to generate singlet oxygen (O-1(2)) in high yield when the complex was activated with visible light (400-700 nm, 10 J cm(-2)), which could be responsible for the photo-ablation of cancer cells. Complexes (2-4) exhibited remarkable photocytotoxicity in HeLa and MCF-7 cells with photocytotoxicity index 4-50 in the presence of visible light (400-700 nm, 10 J cm(-2)), while they were non-toxic in the dark with an IC50 value of >100 mu M. The significantly lower toxicity (IC50 > 100 mu M in the dark; IC50 in visible light similar to 60 mu M) of the complexes in MCF-10A (normal cells) in the dark and in visible light suggested their potential for targeting anticancer activity. Further studies showed that complex 4 induced caspase-dependent apoptosis through mitochondrial damage, mitochondrial respiration inhibition and reactive oxygen species (ROS) elevation. The cytosolic localization of complex 4 in HeLa cells, having a curcumin moiety as a fluorophore, was proved from the confocal microscopic studies. The photocytotoxicity of the complexes (1-4) was directly correlated to the efficacy of the complexes to generate singlet oxygen, which resulted in the photocytotoxicity order of 4 > 3>2 1. Photo-physical studies revealed that the chelation of curcumin by La(III) facilitated intersystem crossing in curcumin by reducing the energy gap of the singlet to triplet excited state. Therefore, the presence of low-lying and long-lived triplet excited state was responsible for increasing the generation of singlet oxygen and, thereby, photo-cytotoxicity in HeLa and MCF-7 cells. The present study has given an overall (Chemistry to Biology) perspective on the effect of La(III) on the photo-cytotoxicity of selected photo-active curcumin-based beta-diketonate ligands.
机译：本文报告了一般分子式[La（1,10-苯）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2）（2） ]（1-4），其中L = 1-苯基丁烷-1,3-二酮（L-1,1），1-（蒽-9-基）丁烷-1,3-二酮（L-2,2） ，1-（3a（1），5a（1）-dihydyropyren-1-y1）丁烷-1,3-二酮（L-3,3）和姜黄素（L-4,4）。复合体1的特征在于单晶X射线晶体学，它表现出La（III）的N4O6配位。低洼和长寿命的三重态激发状态的存在使发光复合物（2-4）能够在用可见光（400-700）激活复合物时以高产率产生单线氧（O-1（2））（400-700） NM，10 J CM（-2）），其可能负责癌细胞的光烧蚀。复合物（2-4）在可见光（400-700nm，10J厘米（-2））存在下，在Hela和MCF-7细胞中表现出具有光致毒性指数4-50的显着光菌毒性4-50，而它们是无毒的黑暗，IC50值>100μm。在黑暗中，MCF-10A（正常电池）中的复合物中的复合物中的复合物中显着降低的毒性（IC50>100μm，在黑暗中的可见光中的IC50）显着降低在可见光中，表明他们瞄准抗癌活动的可能性。进一步的研究表明，复杂的4诱导的Caspase依赖性凋亡通过线粒体损伤，线粒体呼吸抑制和活性氧（ROS）升高。从共聚焦微观研究证明了将具有姜黄素部分作为荧光团的Hela细胞中复合物4的细胞溶质定位。复合物（1-4）的光致毒性与复合物的功效直接相关，从而产生单向氧的效果，这导致光致毒性阶数为4> 3> 2 1.光学物理研究表明姜黄素的螯合剂通过LA（III）通过降低单态激发状态的单态的能隙，促进了姜黄素中的间隙交叉。因此，低洼和长寿命的三重态激发态的存在负责增加单次氧的产生，从而增加HeLa和MCF-7细胞中的光学 - 细胞毒性。本研究对La（III）对所选择的光活性姜黄素的β-二通酸盐配体的光 - 细胞毒性的影响，本研究已经赋予La（III）的效果。

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