摘要
This paper describes the role of tetraalkylammonium counterions [NR4+, R = CH3, -CH2CH3, -(CH2)(2)CH3, or -(CH2)(3)CH3] in gating the electrostatic potential at the interface between the 6-mercaptohexanoate (MHA) ligand shell of a PbS quantum dot (QD) and water. The permeability of this ligand shell to a negatively charged anthraquinone derivative (AQ), measured from the yield of electron transfer (eT) from the QD core to AQ increases as the steric bulk of NR4+ increases (for a given concentration of NR4+). This result indicates that bulkier counterions screen repulsive interactions at the ligand/solvent interface more effectively than smaller counterions. Free energy scaling analysis and molecular dynamics simulations suggest that ion pairing between the ligand shell of the QD and NR4+ results from a combination of electrostatic and van der Waals components, and that the van der Waals interaction promotes ion pairing with longer-chain counterions and more effective screening. This work provides molecular-level details that dictate a nanoparticle's electrostatic potential and demonstrates the sensitivity of the yield of photoinduced charge transfer between a QD and a molecular probe to even low-affinity binding events at the QD/solvent interface.
- 出版日期2017-7-26
- 单位西北大学