Wang Xiaoyuan, Yang Hanhan, Yu Zhenmei, Zhang Zengtao, Chen Yong
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China.
Materials (Basel). 2023 Jul 31;16(15):5393. doi: 10.3390/ma16155393.
Graphene-based laminar membranes exhibit remarkable ion sieving properties, but their monovalent ion selectivity is still low and much less than the natural ion channels. Inspired by the elementary structure/function relationships of biological ion channels embedded in biomembranes, a new strategy is proposed herein to mimic biological K channels by using the graphene laminar membrane (GLM) composed of two-dimensional (2D) angstrom(Å)-scale channels to support a simple model of semi-biomembrane, namely oil/water (O/W) interface. It is found that K is strongly preferred over Na and Li for transferring across the GLM-supported water/1,2-dichloroethane (W/DCE) interface within the same potential window (-0.1-0.6 V), although the monovalent ion selectivity of GLM under the aqueous solution is still low (K/Na1.11 and K/Li1.35). Moreover, the voltammetric responses corresponding to the ion transfer of NH observed at the GLM-supported W/DCE interface also show that NH can often pass through the biological K channels due to their comparable hydration-free energies and cation-π interactions. The underlying mechanism of as-observed K selective voltammetric responses is discussed and found to be consistent with the energy balance of cationic partial-dehydration (energetic costs) and cation-π interaction (energetic gains) as involved in biological K channels.
基于石墨烯的层状膜具有显著的离子筛分特性,但其单价离子选择性仍然较低,远低于天然离子通道。受生物膜中嵌入的生物离子通道基本结构/功能关系的启发,本文提出了一种新策略,即通过使用由二维(2D)埃(Å)尺度通道组成的石墨烯层状膜(GLM)来模拟生物钾通道,以支持一个简单的半生物膜模型,即油/水(O/W)界面。研究发现,在相同的电位窗口(-0.1 - 0.6 V)内,钾在通过GLM支撑的水/1,2 - 二氯乙烷(W/DCE)界面转移时,比钠和锂更受青睐,尽管GLM在水溶液中的单价离子选择性仍然较低(K/Na约为1.11,K/Li约为1.35)。此外,在GLM支撑的W/DCE界面观察到的与铵离子转移相对应的伏安响应也表明,由于铵离子具有可比的无水合能和阳离子 - π相互作用,铵离子通常可以通过生物钾通道。本文讨论了观察到的钾选择性伏安响应的潜在机制,发现其与生物钾通道中涉及的阳离子部分脱水(能量成本)和阳离子 - π相互作用(能量收益)的能量平衡一致。