Transient DNA‐Based Nanostructures Controlled by Redox Inputs

Abstract

Synthetic DNA has emerged as a powerful self‐assembled material for the engineering of nanoscale supramolecular devices and materials. Recently dissipative self‐assembly of DNA‐based supramolecular structures has emerged as a novel approach providing access to a new class of kinetically controlled DNA materials with unprecedented life‐like properties. So far, dissipative control has been achieved using DNA‐recognizing enzymes as energy dissipating units. Although highly efficient, enzymes pose limits in terms of long‐term stability and inhibition of enzyme activity by waste products. Herein, we provide the first example of kinetically controlled DNA nanostructures in which energy dissipation is achieved through a non‐enzymatic chemical reaction. More specifically, inspired by redox signalling, we employ redox cycles of disulfide‐bond formation/breakage to kinetically control the assembly and disassembly of tubular DNA nanostructures in a highly controllable and reversible fashion.

Disulfide‐Linked Allosteric Modulators for Multi‐cycle Kinetic Control of DNA‐Based Nanodevices

“…Our design was also facilitated by previous observations obtained with disulfide DNAcontrollers employed for the temporal control of nanotube self-assembly. [40] Thea llosteric inhibitor is composed of two 10-nt portions complementary to the two tails of the nanodevice linked by adisulfide bond (Figure 1b ) so that efficient hybridization of the oxidized inhibitor to the nanodevice could be observed. Ther educed inhibitor portions (i.e.t he 10-nt thiolated halves), in contrast, show am uch poorer affinity for the nanodevice (K D = 1.4 AE 0.3 10 À5 M) so that rapid de-hybridization occurs when the inhibitor is reduced ( Figure S2).…”

Communication and Cross‐Regulation between Chemically Fueled Sender and Receiver Reaction Networks**

“…By taking inspiration from nature, there has been significant progress in the design of relatively simple, chemically fueled self‐assemblies using CRNs and ERNs based on a diversity of fuels, building blocks and approaches [10–23] . However, connecting different fuel‐driven modules and achieving cross‐regulation is challenging.…”

Reorganization of Self‐Assembled DNA‐Based Polymers using Orthogonally Addressable Building Blocks**

“…Similarly to what occurs in natural systems, the reversible non-covalent nature of these interactions leads to supramolecular polymers that can respond to environmental, chemical and biological stimuli. [24][25][26][27][28][29][30][31] It also allows the reconfiguration of the polymer structure by changing the order in which the monomer units self-assemble. 32 Although several examples have appeared in the literature in which different addressable monomers have been used to reconfigure supramolecular polymers using different inputs, [32][33][34][35][36][37][38] the challenge remains to rationally design the monomers in such a way to permit a predictable and versatile reconfiguration of the polymer with a high degree of control.…”