溶剂在充电和预先组织的受体之间进行匹配时充当裁判
Nabarupa Bhattacharjee1, Xinfeng Gao1, Akash Nathani2
1Department of Chemistry, Indiana University Bloomington, 800 E. Kirkwood Ave., Bloomington, IN, 47405, USA.
Chemistry (Weinheim an der Bergstrasse, Germany)
|August 24, 2023
概括
离子相互作用是生物分子识别的关键. 这项研究量化了化物与阴离子受体的结合,揭示了充电受体在非极性溶剂中强烈结合阴离子,而无电荷受体在极性溶剂中表现出更大的亲和力.
科学领域:
- 超分子化学 超分子化学
- 主机和客人的化学反应
- 离子识别 离子识别
背景情况:
- 阳离子受体相互作用在生物系统中至关重要,特别是在水性环境中.
- 了解各种溶剂极性的这些相互作用对于设计选择性离子传感器和传送器至关重要.
- 在低极性溶剂中的离子配对使对离子与受体结合的直接研究复杂化.
研究的目的:
- 为了研究溶剂极性对阴离子结合亲和力的影响.
- 量化化物与专门设计的阴离子受体的结合,考虑离子配对效应.
- 为了在不同溶剂中比较阴离子受体与中性宏环受体的结合行为.
主要方法:
- 合成了一种新型的阴离子酸盐受体,其中包含阿里尔-三CH供体和一种烯单元.
- 在各种溶剂中使用定位方法进行化物结合研究:二甲 (低极性),乙二和DMSO (极性).
- 结合常数 (log K) 的热力学分析以确定受体-离子复合体稳定性.
主要成果:
- 阴离子受体与二甲中的化物形成了一个稳定的1:1复合体 (log K ~ 7.3),与中性宏循环 (log K ~ 6.9) 相似.
- 在极性溶剂,乙和DMSO中,阴离子受体的结合稳定性显著下降 (分别为log K ~ 3.7和1.9),显示出比宏循环更大的减少.
- 介电选减少了两种受体的结合,但阴离子受体产生了额外的组织成本,导致极性溶剂的亲和力比中性受体低.
结论:
- 阴离子受体在无极溶剂中表现出更强的离子结合,这是由于有利的静电相互作用.
- 没有电荷的受体在极性溶剂中表现出优异的离子亲和力,这主要是由于减少了组织处罚和对介电选的敏感性.
- 这些发现强调了溶剂极性和受体设计在优化离子识别策略中的关键作用.
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