Solution properties of spherical gold nanoparticles with grafted DNA chains from simulation and theory

There has been a rapidly growing interest in the use of functionalized Au nanoparticles (NPs) as platforms in multiple applications in medicine and manufacturing. The sensing and targeting characteristics of these NPs, and the realization of precisely organized structures in manufacturing applications using such NPs, depend on the control of their surface functionalization. NP functionalization typically takes the form of polymer grafted layers, and a detailed knowledge of the chemical and structural properties of these layers is required to molecularly engineer the particle characteristics for specific applications. However, the prediction and experimental determination of these properties to enable the rational engineering of these particles is a persistent problem in the development of this class of materials. To address this situation, molecular dynamic simulations were performed based on a previously established coarse-grained single-stranded DNA (ssDNA) model to determine basic solution properties of model ssDNA-grafted NP-layers under a wide range of conditions. In particular, we emphasize the calculation of the hydrodynamic radius for ssDNA-grafted Au NPs as a function of structural parameters such as ssDNA length, NP core size, and surface coverage. We also numerically estimate the radius of gyration and the intrinsic viscosity of these NPs, which in combination with hydrodynamic radius estimates, provide valuable information about the fluctuating structure of the grafted polymer layers. We may then understand the origin of the commonly reported variation in effective NP "size" by different measurement methods, and then exploit this information in connection to material design and characterization in connection with the ever-growing number of applications utilizing polymer-grafted NPs.