Synthesis,Spectroscopic Properties,and Photodynamic Anticancer Activities of Novel Arginine-modified Silicon(Ⅳ) Phthalocyanines

We design and synthesize a series of novel silicon(IV)phthalocyanines(SiPcs,1a,2a,1b,and 2b)axially conjugated with arginine or arginine-containing oligopeptides(Arg-Arg,Cys-Arg,Cys-Arg-Arg)through ester or ether linkers to demonstrate the effects of substituents and coupling ways on the spectral behaviors and photodynamic activities.The ester-linked SiPcs(1a and 2a)show slight red-shift,higher fluorescence emission and singlet oxygen generation compared to the ether-linked analogues(1b and 2b)due to the stronger electron-withdrawing ability of the ester group,suggesting that electronic effect of the linkers plays an important role in their spectral properties.The introduction of arginine could effectively reduce the aggregation of phthalocyanine in aqueous solutions.With higher cellular uptake and plasma membrane localization ability,1b and 2b exhibit significantly higher photocytotoxicity against both HepG2 and Hela cells.Moreover,the in vivo fluorescence imaging suggests that 2b is the most specific toward H22 tumor-bearing ICR mice,and it shows efficient tumor growth inhibition with the tumor inhibition rate up to 93%.Thus,this work would provide a new reference for the development of phthalocyanine-based photosensitizers.     

四取代羧基酞菁锌与白蛋白共价结合物的制备与光谱性质

通过成酰胺键的方式制备了一系列含羧基酞菁和白蛋白(牛血清白蛋白(BSA),人血清白蛋白(HSA))之间的共价结合物,所涉及到的酞菁分别是α-四(4-羧基苯氧基)酞菁锌(1)和α-四[4-(2-羧基乙基)苯氧基]酞菁锌(3),以及它们相应的β位四取代酞菁锌(化合物2和4).比较了游离酞菁以及它们的白蛋白结合物在磷酸盐缓冲溶液(PBS)中的光谱性质.结果表明,当酞菁被共价固定于白蛋白大分子上之后,展现出比游离酞菁更明显的单体特征吸收,而且结合物中的酞菁光谱特征不受体系pH值变化的影响.羧基在酞菁环上的取代位置,对酞菁与白蛋白结合前后的光谱转变幅度有影响,α位取代比β位取代更有利于光谱的变化.化合物1和3的白蛋白共价结合物在PBS溶液中甚至呈现出单体形式为主的光谱特征,Q带最大吸收波长分别位于697和706nm附近.     

可激活抗癌光敏剂

光动力治疗（Photodynamic therapy,PDT）是利用光敏剂在光照下促使分子氧转为具有细胞毒性的活性氧,从而达到破坏靶细胞和靶组织效应的一种治疗手段。可激活光敏剂（Activatable photosensitizers,aPSs）是指事先屏蔽了光敏效应的光敏剂,只在特定因素下,如与肿瘤相关的特异性酶、酸性pH、核酸等的激活下,光敏剂转为激活状态,从而发挥诊断或者治疗的作用。可激活光敏剂由于具有更高的选择性而备受瞩目,成为医用光敏剂领域的研究前沿热点。本文将总结和分析近年来可激活抗癌光敏剂的研究现状和构效关系,以期为后续的相关研究提供参考。