Templated Fabrication of DNA-Programmable Vesicles via Amphiphile-Functionalized Nanoparticles

It is a great challenge to prepare vesicles with a specific or predefined size/shape, especially when they also possess targeted properties. Amphiphilic DNA frameworks based on DNA-modified nanoparticles (DNA-NPs) synergize DNA programmability with stimuli responsiveness of polymers, providing enhanced control over dynamic assembly, especially for constructing smart vesicles. Herein, inspired by the amphiphilic frame-guided assembly (AFGA) strategy, we combined molecular dynamics simulation with the geometrical models to study the construction of size-/shape-controllable DNA-programmable vesicles (DNA-PVs) based on amphiphile-functionalized nanoparticle templates. We proposed a predictive paradigm for the rational design of DNA-PVs and identified the density of leading hydrophobic groups and the packing volume fraction of hydrophobic groups as key assessment indexes to design DNA-PVs. The critical thresholds of two indexes at morphological boundaries based on simulation results align well with experimental data and theoretical analysis. The shape-/size-controllable characteristics and DNA-directed surface addressability of DNA-PVs were verified. Our findings can not only gain new insights into the AFGA to fabricate DNA-PVs but also offer opportunities for constructing sophisticated nanomaterials with desirable geometries and versatility.