Theoretical investigation into the cooperativity effect of 1,4-dimethoxy-D-glucosamine complex with Na⁺ and H₂O

In order to explore the essence of the hydration process of chitin or chitosan in the presence of cation, the cooperativity effects between the H-bonding and Na⁺···molecule interactions in the 1,4-dimethoxy-D-glucosamine (DMGA) complexes with H₂O and Na⁺ were investigated at the B3LYP/6-311++G(d,p), M06-2X/6-311++G(2df,2p), and ωB97X-D/6-311++G(2df,2p) levels. The result shows that the complexes in which Na⁺ or H₂O is bonded simultaneously to the -NH and -OH groups connected to the C3 atom of DMGA are the most stable. The cooperativity and anti-cooperativity effects occur in DMGA···H₂O···DMGA and DMGA···Na⁺···H₂O, while only the cooperativities are confirmed in DMGA···Na⁺···DMGA. The cooperativity occurs in the DMGA···Na⁺···H₂O complexes without the hydration, while the anti-cooperativity occurs in those with the hydration. Furthermore, the cooperativity and anti-cooperativity in DMGA···Na⁺···H₂O are far stronger than those in DMGA···Na⁺···DMGA or DMGA···H₂O···DMGA. Therefore, a deduction is given that the cooperativity and anti-cooperativity effects play an important role in the hydration of chitin or chitosan in the presence of Na⁺. When only Na⁺ is linked with -OH and -NH groups of chitosan or chitin, due to the cooperativity effect, the hydration does not occur. When both Na⁺ and H₂O are linked with -OH and -NH groups, the anti-cooperativities are dominant in controlling of the aggregation process of Na⁺, H₂O, chitosan, and chitin, leading to the possible hydration. Atoms in molecules (AIM) analysis confirms the cooperativity and anti-cooperativity effects. Graphical abstract.