School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, PR China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, Shanghai, 200062, PR China.
Anal Chim Acta. 2021 Feb 22;1147:155-164. doi: 10.1016/j.aca.2020.12.058. Epub 2020 Dec 30.
Effective enantioselective recognition with chiral nanomaterials remains a challenge in the field of chemistry and biology. In this paper, a pair of left- and right-handed polyaniline (defined as S-PANI and R-PANI) were synthesized by chemical oxidation of aniline to form a specially twisted nanoribbon, which was induced by enantiomeric camphorsulfonic acid. Both S-PANI and R-PANI were used to construct electrochemical chiral sensors for the discrimination of tryptophan isomers (D- and L-Trp). Owing to the formation of efficient chiral nanospace with special nanoribbon morphology and enormous amounts of oxygen-containing functional groups of S-PANI or R-PANI, the high enantioselectivity was obtained with the recognition efficiency of 4.90 (D-Trp) on S-PANI and 4.20 (L-Trp) on R-PANI, respectively. The obtained chiral electrodes were also used for the determination of the enantiomeric excess (ee) for Trp, and a good linear relationship between peak currents and ee% of Trp was obtained. Furthermore, the strategy we proposed has tremendous potential in enantiomer recognition field.
手性纳米材料的有效对映选择性识别仍然是化学和生物学领域的一个挑战。本文通过苯胺的化学氧化合成了一对左旋和右旋聚苯胺（分别定义为 S-PANI 和 R-PANI），形成了一种特殊的扭曲纳米带，这是由对映体樟脑磺酸诱导的。S-PANI 和 R-PANI 都被用于构建电化学手性传感器，以区分色氨酸异构体（D-和 L-Trp）。由于 S-PANI 或 R-PANI 具有特殊的纳米带形态和大量含氧官能团，形成了高效的手性纳米空间，因此分别在 S-PANI 上获得了 4.90（D-Trp）的高对映选择性和在 R-PANI 上获得了 4.20（L-Trp）的对映选择性。所得手性电极还用于测定 Trp 的对映体过量（ee），并获得了 Trp 的峰电流与 ee%之间的良好线性关系。此外，我们提出的策略在手性识别领域具有巨大的潜力。
