The Proton Dissociation of Bio-Protic Ionic Liquids: [AAE]X Amino Acid Ionic Liquids

• Main Authors: Ting He, Cheng-Bin Hong, Peng-Chong Jiao, Heng Xiang, Yan Zhang, Hua-Qiang Cai, Shuang-Long Wang, Guo-Hong Tao
• Format: Article
• Language: English
• Published: MDPI AG 2021-12-01
• Series: Molecules
• Subjects: protic ionic liquids; Brønsted acidity; amino acid ionic liquids; bio-based ionic liquids
• Online Access: https://www.mdpi.com/1420-3049/26/1/62

[AAE]X composed of amino acid ester cations is a sort of typically “bio-based” protic ionic liquids (PILs). They possess potential Brønsted acidity due to the active hydrogens on their cations. The Brønsted acidity of [AAE]X PILs in green solvents (water and ethanol) at room temperature was systematically studied. Various frameworks of amino acid ester cations and four anions were investigated in this work from the viewpoint of structure–property relationship. Four different ways were used to study the acidity. Acid dissociation constants (p<i>K</i>_a) of [AAE]X determined by the OIM (overlapping indicator method) were from 7.10 to 7.73 in water and from 8.54 to 9.05 in ethanol. The p<i>K</i>_a values determined by the PTM (potential titration method) were from 7.12 to 7.82 in water. Their Hammett acidity function (<i>H</i>₀) values (0.05 mol·L⁻¹) were about 4.6 in water. In addition, the p<i>K</i>_a values obtained by the DFT (proton-transfer reactions) were from 7.11 to 7.83 in water and from 8.54 to 9.34 in ethanol, respectively. The data revealed that the cationic structures of [AAE]X had little effect and the anions had no effect on the acidity of [AAE]X. At the same time, the OIM, PTM, Hammett method and DFT method were reliable for determining the acidic strength of [AAE]X in this study.