Optimization of As(Ш) imprinted polymers and dynamic recognition mechanism revelation from perspective of target-monomer interaction.

• Template-monomer binding affinity guide strategy was applied to investigate the optimal self-assembling conditions of H 3 AsO 3 MIPs. • The direct observation of dynamic evolution of targets recognition process was achieved by constructed annular imprinted cavity models with TEOS as cross-linkers. • Optimal self-assembling conditions for H 3 AsO 3 MIPs were proposed. • The critical distance for H 3 AsO 3 recognition away from cavity is 3.0 Å. • The dominant binding interaction was hydrogen bond, and the initial driving force for H 3 AsO 3 recognition was S-H···O formation. Molecular imprinted polymers (MIPs) have been recognized as good adsorbents to detect and remove As(Ш) from environment. 2-mercaptonicoic acid (2-M), having high affinity towards H 3 AsO 3 , is considered as potential functional monomer of H 3 AsO 3 MIPs. In this work, a template-monomer binding affinity guide strategy was applied to investigate self-assembling conditions of H 3 AsO 3 MIPs with 2-M as functional monomer, using quantum chemistry calculation and molecular dynamics simulation. Afterwards, dynamic recognition mechanism of H 3 AsO 3 MIPs was unraveled through imprinted cavity modelling for the first time. Results show that dichloromethane is the most suitable solvent, and 1:4:250 of H 3 AsO 3 , 2-M and dichloromethane is the best ratio. Remarkably, the direct observation of dynamic evolution of targets recognition was achieved by constructed annular imprinted cavity models with optimal 20 TEOS as cross-linkers. It was found that the critical distance for H 3 AsO 3 recognition is 3.0 Å. The dominant binding interaction is clarified to be hydrogen bond, and the initial driving force was S-H···O bond formation. This work provides not only a feasible strategy for computational design of good-performance MIPs, but also a method to perform recognition mechanism study by imprinted cavity modelling, which is significant for MIPs development as adsorbents for contaminants detection and removal from environment. [ABSTRACT FROM AUTHOR]