Quantitative Analysis of DNA-Mediated Formation of Metal Nanocrystals.

The predictive synthesis of metal nanocrystals with desired structures relies on the precise control of the crystal formation process. Using a capping ligand is an effective method to affect the reduction of metal ions and the formation of nanocrystals. However, predictively synthesizing nanostructures has been difficult to achieve using conventional capping ligands. DNA, as a class of the promising biomolecular capping ligands, has been used to generate sequence-specific morphologies in various metal nanocrystals. However, mechanistic insight into the DNA-mediated nanocrystal formation remains elusive due to the lack of quantitative experimental evidence. Herein, we quantitatively analyzed the precise control of DNA over Ag(+) reduction and the structures of resulting Au-Ag core-shell nanocrystals. We derived the equilibrium binding constants between DNA and Ag(+), the kinetic rate constants of sequence-specific Ag(+) reduction pathways, and the percentage of active surface sites remaining on the nanocrystals after DNA passivation. These three synergistic factors influence the nucleation and growth process both thermodynamically and kinetically, which contributed to the morphological evolution of Au-Ag nanocrystals synthesized with different DNA sequences. This study demonstrates the potential of using functional DNA sequences as a versatile and tunable capping ligand system for the predictable synthesis of metal nanostructures.