Zhang Junda, Ramu Vadde, Zhou Xue-Quan, Frias Carolina, Ruiz-Molina Daniel, Bonnet Sylvestre, Roscini Claudio, Novio Fernando
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus UAB, Bellaterra, 08193 Barcelona, Spain.
Leiden Institute of Chemistry, Universiteit Leiden, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
Nanomaterials (Basel). 2021 Nov 16;11(11):3089. doi: 10.3390/nano11113089.
Green light photoactive Ru-based coordination polymer nanoparticles (CPNs), with chemical formula Ru(biqbpy) (biqbpy = 6,6'-bis[N-(isoquinolyl)-1-amino]-2,2'-bipyridine; bis = bis(imidazol-1-yl)-hexane), were obtained through polymerization of the trans-[Ru(biqbpy)(dmso)Cl]Cl complex (Complex ) and bis bridging ligands. The as-synthesized CPNs (50 ± 12 nm diameter) showed high colloidal and chemical stability in physiological solutions. The axial bis(imidazole) ligands coordinated to the ruthenium center were photosubstituted by water upon light irradiation in aqueous medium to generate the aqueous substituted and active ruthenium complexes. The UV-Vis spectral variations observed for the suspension upon irradiation corroborated the photoactivation of the CPNs, while High Performance Liquid Chromatography (HPLC) of irradiated particles in physiological media allowed for the first time precisely quantifying the amount of photoreleased complex from the polymeric material. In vitro studies with A431 and A549 cancer cell lines revealed an 11-fold increased uptake for the nanoparticles compared to the monomeric complex Ru(biqbpy)(N-methylimidazole) (Complex ). After irradiation (520 nm, 39.3 J/cm), the CPNs yielded up to a two-fold increase in cytotoxicity compared to the same CPNs kept in the dark, indicating a selective effect by light irradiation. Meanwhile, the absence of O production from both nanostructured and monomeric prodrugs concluded that light-induced cell death is not caused by a photodynamic effect but rather by photoactivated chemotherapy.
绿光光活性钌基配位聚合物纳米颗粒（CPNs），化学式为Ru(biqbpy)（biqbpy = 6,6'-双[N-(异喹啉基)-1-氨基]-2,2'-联吡啶；bis = 双(咪唑-1-基)-己烷），是通过反式-[Ru(biqbpy)(dmso)Cl]Cl络合物（络合物）与双桥连配体聚合得到的。所合成的CPNs（直径50±12 nm）在生理溶液中表现出高胶体稳定性和化学稳定性。与钌中心配位的轴向双(咪唑)配体在水介质中光照时被水进行光取代，生成水取代的活性钌络合物。照射后悬浮液中观察到的紫外-可见光谱变化证实了CPNs的光活化，而生理介质中照射颗粒的高效液相色谱（HPLC）首次精确地定量了从聚合物材料中光释放的络合物的量。对A431和A549癌细胞系的体外研究表明，与单体络合物Ru(biqbpy)(N-甲基咪唑)（络合物）相比，纳米颗粒的摄取增加了11倍。照射（520 nm，39.3 J/cm）后，与黑暗中保存的相同CPNs相比，CPNs产生的细胞毒性增加了两倍，表明光照射具有选择性作用。同时，纳米结构和单体前药均未产生O，这表明光诱导的细胞死亡不是由光动力效应引起的，而是由光活化化疗引起的。
