Komiyama Makoto
a Life Science Center of Tsukuba Advanced Research Alliance; University of Tsukuba ; Tsukuba , Ibaraki , Japan.
Artif DNA PNA XNA. 2014 Dec 15;5(3):e1112457. doi: 10.1080/1949095X.2015.1112457.
Recently, completely chemistry-based tools for site-selective scission of DNA (ARCUT) have been prepared by combining 2 strands of pseudo-complementary PNA (pcPNA: site-selective activator) and a Ce(IV)-EDTA complex (molecular scissors). Its site-specificity is sufficient to cut the whole human genome at one predetermined site. In this first-generation ARCUT, however, there still remain several problems to be solved for wider applications. This review presents recent approaches to solve these problems. They are divided into (i) covalent modification of pcPNA with other functional groups and (ii) new strategies using conventional PNA, in place of pcPNA, as site-selective activator. Among various chemical modifications, conjugation with positively-charged nuclear localization signal peptide is especially effective. Furthermore, unimolecular activators, a single strand of which successfully activates the target site in DNA for site-selective scission, have been also developed. As the result of these modifications, the site-selective scission by Ce(IV)-EDTA was achieved promptly even under high salt conditions which are otherwise unfavourable for double-duplex invasion. Furthermore, it has been shown that "molecular crowding effect," which characterizes the inside of living cells, enormously promotes the invasion, and thus the invasion seems to proceed effectively and spontaneously in the cells. Strong potential of pcPNA for further applications in vivo and in vitro has been confirmed.
最近,通过将两条伪互补肽核酸(pcPNA:位点选择性激活剂)与铈(IV)-乙二胺四乙酸络合物(分子剪刀)相结合,制备出了用于DNA位点选择性切割的完全基于化学的工具(ARCUT)。其位点特异性足以在一个预定位点切割整个人类基因组。然而,在第一代ARCUT中,为了更广泛的应用,仍有几个问题有待解决。本综述介绍了最近解决这些问题的方法。它们分为:(i)用其他官能团对pcPNA进行共价修饰,以及(ii)使用常规肽核酸代替pcPNA作为位点选择性激活剂的新策略。在各种化学修饰中,与带正电荷的核定位信号肽偶联特别有效。此外,还开发了单分子激活剂,其单链成功激活DNA中的靶位点以进行位点选择性切割。这些修饰的结果是,即使在高盐条件下(否则不利于双链双螺旋入侵),也能迅速实现铈(IV)-乙二胺四乙酸介导的位点选择性切割。此外,已经表明,表征活细胞内部的“分子拥挤效应”极大地促进了入侵,因此入侵似乎在细胞中有效且自发地进行。已经证实了pcPNA在体内和体外进一步应用的强大潜力。