Combinatorial-Entropy-Driven Aggregation in DNA-Grafted Nanoparticles

We use computer simulations and experiments to study the interactions between nanoparticles (NPs) grafted with self-complementary DNA strands. Each strand ends with a sticky palindromic single-stranded sequence, allowing it to associate equally favorably with strands grafted on the same particle or on different NPs. Surprisingly we find an attractive interaction between a pair of NPs, and we demonstrate that at low temperature it arises purely from a combinatorial-entropy contribution. We evaluate theoretically and verify numerically this entropic contribution originating from the number of distinct bonding patterns associated with intra- and interparticle binding. This entropic attraction becomes more favorable with decreasing inter-NP distance because more sticky ends can participate in making this choice.