To investigate the non-covalent interaction between cyclodextrins （CD） and lithium ion, a stoichiometry of α-CD, β-CD, heptakis（2,6-di-O-methyl）-β-CD （DM-β-CD）, or heptakis（2,3,6-tri-O-methyl）-β-CD （TM-β-CD） was mixed with lithium salt, respectively, and then incubated at room temperature for 10 min to reach the equilibrium. In posi- tive mode, the electrospray ionization mass spectrometry （ESI-MS） results demonstrated that lithium ion can conjugate to α-, β-, DM-β- or TM-β-CD and form 1：1 stoichiometric non-covalent complexes. The binding of the complexes was further confirmed by collision- induced dissociation. The dissociation constants Kdl of four complexes （Li＋α-CD, Li＋β- CD, Li＋DM-β-CD, and Li＋TM-β-CD） were determined by mass spectrometric titration. The results showed Kdl were 18.7, 26.7, 33.6, 30.5 μmol/L for the complexes of Li＋ with α-CD, β-CD, DM-β-CD, and TM-β-CD, respectively. Kdl for the Li＋ complexes of/3-CD is smaller than that of DM-β-CD due to its steric effect of the partial substituted -CH3. The Kdl for the Li＋ complexes of DM-β-CD is nearly in agreement with that of TM-β-CD, indicating Li＋ is more likely to locate in the small rim of DM-β-CD＇s hydrophobic cavity. The DFT results showed through electrostatic interaction, one Li＋ can strongly conjugate to four neighboring oxygen atoms. For the （α-CD＋Li）＋ complex, one Li＋ may also situate the small rim of α-CD＇s hydrophobic cavity to form a non-specific host-guest complex.
