Nitric oxide and singlet oxygen photo-generation by light irradiation in the phototherapeutic window of a nitrosyl ruthenium conjugated with a phthalocyanine rare earth complex
Nitric oxide and singlet oxygen photo-generation by light irradiation in the phototherapeutic window of a nitrosyl ruthenium conjugated with a phthalocyanine rare earth complex
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DOI：
10.1016/j.poly.2009.05.051
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发表时间：
2009-09-02
期刊：
影响因子：
2.6
通讯作者：
da Silva, Roberto Santana
中科院分区：
文献类型：
--
作者：
Cicillini, Simone Aparecida;Lemos Prazias, Ana Carolina;da Silva, Roberto Santana
本文报道了一个含有cis-[Ru（H-dcbpy（-））（2）（Cl）（NO）]（H-2-dcbpy = 4，4 ′-二羧基-2，2 ′-联吡啶）和Na-4[Tb（TsPc）（acac）]（TsPc =四磺化酞菁; acac =乙酰丙酮）的混合体系的光化学、物理和光生物学研究。由cis-[Ru（H-2-dcbpy）（2）Cl-2]中心点2 H（2）O得到cis-[Ru（H-dcbpy（-））（2）（Cl）（NO）]，而由酞菁与乙酰丙酮铽反应得到Na-4[Tb（TsPc）（acac）]。cis-[Ru]的紫外-可见光谱（H-dcbpy（-））（2）（Cl）（NO）]在305 nm区域显示一个谱带Na-4[Tb（TsPc）（acac）]的紫外-可见光谱在342 nm处呈现典型的酞菁谱带（Soret lambda（max）in H2O）和642，682（Q带）。cis-[Ru（H-dcbpy（-））（2）（Cl）（NO）] FTIR光谱在1932 cm（-1）处显示一个带（Ru-NO+）。配合物在水溶液中的循环伏安曲线在E = 0.10 V（NO+/0）和E = -0.50 V（NO 0/-）处出现峰。在λ> 550 nm区域的光照射下测得NO浓度和O-1（2）量子产率分别为[NO] = 1.21 +/- 0.14 μ mol L-1和圆分（OS）= 0.41。NO的释放量似乎取决于氧浓度，当在通气条件下测得的NO浓度为1.51 ± 0.11 μ mol L ~（-1）时。cis-[Ru（H-dcbpy（-））（2）（Cl）（NO）]/Na ~（-4）[Tb（TsPc）（acac）]混合物的光化学途径可归因于光诱导电子转移过程。用B16 F10细胞进行的顺式-[Ru（H-dcbpy（-））（2）（Cl）（NO）]和混合物的细胞毒性测定显示，在黑暗中细胞活力降低至80%，在光照下降低至20%。我们的研究结果表明，同时产生NO和O-1（2）可以改善PDT，并可用于癌症治疗。(C)2009爱思唯尔有限公司保留所有权利。
The photochemical, photophysical and photobiological studies of a mixture containing cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)] (H-2-dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and Na-4[Tb(TsPc)(acac)] (TsPc = tetrasulfonated phthalocyanines; acac = acetylacetone), a system capable of improving photodynamic therapy (PDT), were accomplished. cis-[ Ru(H-dcbpy(-))(2)(Cl)(NO)] was obtained from cis-[ Ru(H-2-dcbpy)(2)Cl-2]center dot 2H(2)O, whereas Na-4[Tb(TsPc)(acac)] was obtained by reacting phthalocyanine with terbium acetylacetonate. The UV-Vis spectrum of cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)] displays a band in the region of 305 nm (lambda(max) in 0.1 mol L-1 HCl)(pi-pi*) and a shoulder at 323 nm (MLCT), while the UV-Vis spectrum of Na-4[Tb(TsPc)(acac)] presents the typical phthalocyanine bands at 342 nm (Soret lambda(max) in H2O) and 642, 682 (Q bands). The cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)] FTIR spectrum displays a band at 1932 cm(-1) (Ru-NO+). The cyclic voltammogram of the cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)] complex in aqueous solution presented peaks at E = 0.10 V (NO+/0) and E = -0.50 V (NO0/-) versus Ag/AgCl. The NO concentration and O-1(2) quantum yield for light irradiation in the lambda > 550 nm region were measured as [NO] = 1.21 +/- 0.14 mu mol L-1 and circle divide(OS) = 0.41, respectively. The amount of released NO seems to be dependent on oxygen concentration, once the NO concentration measured in aerated condition was 1.51 +/- 0.11 mu mol L-1 The photochemical pathway of the cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)]/Na-4[Tb(TsPc)(acac)] mixture could be attributed to a photoinduced electron transfer process. The cytotoxic assays of cis-[Ru(H-dcbpy(-))(2)(Cl)(NO)] and of the mixture carried out with B16F10 cells show a decrease in cell viability to 80% in the dark and to 20% under light irradiation. Our results document that the simultaneous production of NO and O-1(2) could improve PDT and be useful in cancer treatment. (C) 2009 Elsevier Ltd. All rights reserved.