Energies and physicochemical properties of cation-π interactions in biological structures.
The cation-π interactions occur frequently within or between proteins due to six (Phe, Tyr, Trp, Arg, Lys, and His) of the twenty natural amino acids potentially interacting with metallic cations via these interactions. In this study, quantum chemical calculations and molecular orbital (MO) theory are used to study the energies and properties of cation-π interactions in biological structures. The cation-π interactions of H⁺ and Li⁺ are similar to hydrogen bonds and lithium bonds, respectively, in which the small, naked cations H⁺ and Li⁺ are buried deep within the π-electron density of aromatic molecules, forming stable cation-π bonds that are much stronger than the cation-π interactions of other alkali metal cations. The cation-π interactions of metallic cations with atomic masses greater than that of Li⁺ arise mainly from the coordinate bond comprising empty valence atomic orbitals (AOs) of metallic cations and π-MOs of aromatic molecules, though electrostatic interactions may also contribute to the cation-π interaction. The binding strength of cation-π interactions is determined by the charge and types of AOs in the metallic cations. Cation-π interaction energies are distance- and orientation-dependent; energies decrease with the distance (r) and the orientation angle (θ). In solution, the cation-π energies decrease with the increase of the dielectric constant (ɛ) of the solvent; however, solvation has less influence on the H⁺-π and H₃O⁺-π interactions than on interactions with other cations. The conclusions from this study provide useful theoretical insights into the nature of cation-π interactions and may contribute to the development of better force field parameters for describing the molecular dynamics of cation-π interactions within and between proteins.
State Key Laboratory of Non-food Biomass Energy and Enzyme Technology, National Engineering Research Center for Non-food Biorefinery, Guangxi Academy of Sciences, 98 Daling Road, Nanning, Guangxi 530007, China. qishi_du@yahoo.com.cn
Qi-Shi
QS
Du
Jian-Zong
JZ
Meng
Si-Ming
SM
Liao
Ri-Bo
RB
Huang
D000596:Amino Acids / Q000737:chemistry; D004583:Electrons; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D011487:Protein Conformation; D011522:Protons; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics
D000596:Amino Acids; D011522:Protons; D008094:Lithium