Small-angle neutron scattering and Molecular Dynamics structural study of gelling DNA nanostars

DNA oligomers with properly designed sequences self-assemble into well defined constructs. Here, we exploit this methodology to produce bulk quantities of tetravalent DNA nanostars (each one composed by 196 nucleotides) and to explore the structural signatures of their aggregation process. We report small-angle neutron scattering experiments focused on the evaluation of both the form factor and the temperature evolution of the scattered intensity at a nano star concentration where the system forms a tetravalent equilibrium gel. We also perform molecular dynamics simulations of one isolated tetramer to evaluate the form factor theoretically, without resorting to any approximate shape. The numerical form factor is found to be in very good agreement with the experimental one. Simulations predict an essentially temperature independent form factor, offering the possibility to extract the effective structure factor and its evolution during the equilibrium gelation.Comment: 9 pages, 5 figure

Cold-swappable DNA gels

We report an experimental investigation of an all-DNA gel composed by tetra-functional DNA nanoparticles acting as network nodes and bi-functional ones acting as links. The DNA binding sequence is designed to generate at room and lower temperatures a persistent long-lived network. Exploiting ideas from DNA-nanotechnology, we implement in the binding base sequences an appropriate exchange reaction which allows links to swap, constantly retaining the total number of network links. The DNA gel is thus able to rearrange its topology at low temperature while preserving its fully-bonded configuration

Microrheology of DNA hydrogel gelling and melting on cooling

We present systematic characterisation by means of dynamic light scattering and particle tracking techniques of the viscosity and of the linear viscoelastic moduli, G′(ω) and G′′(ω), for two different DNA hydrogels. These thermoreversible systems are composed of tetravalent DNA-made nanostars whose sticky sequence is designed to provide controlled interparticle bonding. While the first system forms a gel on cooling, the second one has been programmed to behave as a re-entrant gel, turning again to a fluid solution at low temperature. The frequency-dependent viscous and storage moduli and the viscosity reveal the different viscoelastic behavior of the two DNA hydrogels. Our results show how little variations in the design of the DNA sequences allow tuning of the mechanical response of these biocompatible all-DNA materials