Exploring enantioselective recognition of dTMP-Co-bpe coordination polymer for natural amino acids using molecular simulations and circular dichroism

The 1D homochiral coordination polymer (CP-1) {[Co(dTMP)(bpe)₂(H₂O)₃]·9H₂O}_n was constructed by using 2′-deoxy thymidine 5′-monophosphate disodium salt (dTMP·2Na), and auxiliary ligand bpe (1,2-bis(4-pyridyl)ethene) and characterized by single-crystal XRD, PXRD, IR, UV-visible, CD and TGA analyses. Molecular simulations revealed the selective chiral behaviour of CP-1 towards phenylalanine and histidine, as indicated by their higher binding free energies compared to other amino acids. Theoretical parameters were also compared with experimental UV-visible verdicts. Notably, the d-enantiomers of phenylalanine and histidine demonstrated strong bonding abilities and optimal configurations for probing and distinguishing them from their l-counterparts. These findings led to propositions suggesting that the dissimilarities between these d and l amino acid forms and their binding orientations with CP-1 may contribute to alterations in the CD signal. CP-1 exhibited a robust inherent circular dichroism (CD) signal in aqueous solutions, modulated by the presence of specific amino acids, namely d/l phenylalanine and d/l histidine. Leveraging the measurement of CD signal intensity, a sensor capable of detecting unmodified amino acids has been developed. Unlike previously reported approaches that relied on complex chemical reactions between initially CD-silent molecules and probed amino acids, this new method offers a more straightforward means of amplifying the CD signal. Consequently, this change facilitates a more accurate differentiation between the enantiomers of these specific amino acids compared to others.