Dissipative Constitutional Dynamic Networks for Tunable Transient Responses and Catalytic Functions.

Abstract

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 T1L1 and T2L2 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 L1' or L2', the displacement of the respective "dormant" structure releases the trigger T1 or T2 that activates the reconfiguration of CDN "X" to CDN "Y" or CDN "X" to CDN "Z". The generated duplex L1L1' or L2L2' is designed to be nicked by Nt.BbvCI, leading to the regeneration of L1 or L2 that rebinds to T1 or T2, 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 L1' and L2' 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.