Wang Shan, Yue Liang, Wulf Verena, Lilienthal Sivan, Willner Itamar
Institute of Chemistry, The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Department of Biomedical Engineering, Faculty of Engineering, Tel-Aviv University, Tel Aviv 6997801, Israel.
J Am Chem Soc. 2020 Oct 14;142(41):17480-17488. doi: 10.1021/jacs.0c06977. Epub 2020 Oct 5.
Following the significance of dissipative, out-of-equilibrium biological processes controlling living systems, we introduce nucleic acid-based dissipative constitutional dynamic networks (CDNs) that exhibit tunable transient composition changes of the networks dictated by auxiliary fuel strands. CDN "X" composed of four equilibrated nucleic acid constituents, AA', AB', BA', and BB', and the accompanying "dormant" structures TL and TL and nicking enzyme Nt.BbvCI, undergoes dissipative orthogonal transitions to CDN "Y" and back or to CDN "Z" and back. In the presence of the fuel strand L' or L', the displacement of the respective "dormant" structure releases the trigger T or T that activates the reconfiguration of CDN "X" to CDN "Y" or CDN "X" to CDN "Z". The generated duplex LL' or LL' is designed to be nicked by Nt.BbvCI, leading to the regeneration of L or L that rebinds to T or T, resulting in the dissipative cyclic recovery of CDN "X". Kinetic simulations of the dissipative processes allow us to predict the dissipative behavior of the systems under different auxiliary conditions. Subjecting CDN "X" to altering sets of the fuel strands L' and L' yields programmed reconfiguration patterns of dissipative reaction cycles. By engineering functional nucleic acid tethers on the constituents and the triggering strands, orthogonal dissipative emerging catalytic transformations dictated by the dissipative CDNs are demonstrated.
鉴于耗散的、非平衡生物过程对生命系统控制的重要性，我们引入了基于核酸的耗散组成动态网络（CDN），该网络表现出由辅助燃料链决定的网络可调瞬态组成变化。由四种平衡的核酸成分AA'、AB'、BA'和BB'以及伴随的“休眠”结构TL和TL和切口酶Nt.BbvCI组成的CDN“X”经历向CDN“Y”的耗散正交转变并返回，或向CDN“Z”的耗散正交转变并返回。在燃料链L'或L'存在的情况下，相应“休眠”结构的位移释放触发物T或T，从而激活CDN“X”向CDN“Y”或CDN“X”向CDN“Z”的重新配置。生成的双链体LL'或LL'被设计为由Nt.BbvCI切割，导致L或L再生，其重新结合到T或T，从而实现CDN“X”的耗散循环恢复。耗散过程的动力学模拟使我们能够预测系统在不同辅助条件下的耗散行为。使CDN“X”暴露于不同组的燃料链L'和L'会产生耗散反应循环的程序化重新配置模式。通过在成分和触发链上设计功能性核酸连接体，证明了由耗散CDN决定的正交耗散新兴催化转化。
