Improved Recovery and Selectivity of Lanthanide-Ion-Binding Cyclic Peptide Hosts by Changing the Position of Acidic Amino Acids

Abstract

The development of an effective host molecule to separate lanthanide (Ln) ions and a method for predicting its guest recognition/self-assembly behavior based on primary chemical structures are highly sought after in both academia and industry. Herein, we report the improvement of one-pot Ln ion recovery and a performance prediction method for four new cyclic peptide hosts that differ in the position of acidic amino acids. These cyclic peptide hosts could recognize Ln3+ directly through a 1:1 complexation–precipitation process and exhibited high Lu3+ selectivity in spite of similar ion size and electronegativity when the positions of the acidic amino acids were changed. This unpredictable selectivity was explained by considering the dipole moment, lowest unoccupied molecular orbital, and cohesion energy. In addition, a semi-empirical function using these parameters was proposed for screening the sequence and estimating the isolated yields without long-time molecular dynamics calculations. The insights obtained from this study can be employed for the development of high-performance peptides for the selective recovery of Ln and other metal ions, as well as for the construction of diverse supramolecular recognition systems.