Kinetics of DNA-coated sticky particles

DNA-functionalized particles are promising for complex self-assembly due to their specific controllable thermoreversible interactions. However, there has been little work on the kinetics and the aggregation rate, which depend on the rate of particle encounters and the probability that an encounter results in particles sticking. In this study, we investigate theoretically and experimentally the aggregation times of micron-scale particles as a function of DNA coverage and salt concentration. Our 2-μm colloids accommodate up to 70,000 DNA strands. For full coverage and high salt concentration, the aggregation time is 5 min while for 0.1 coverage and low salt it is 4 days. A simple model using reaction-limited kinetics and experimental oligomer hybridization rates describes the data well. A controlling factor is the Coulomb barrier at the nanometer scale retarding DNA hybridization. Our model allows easy measurements of microscopic hybridization rates from macroscopic aggregation and enables the design of complex self-assembly schemes with controlled kinetics.