在脱酸的宏环聚合时的离子化证据
Suzanne M Batiste1, Jeffrey N Johnston1
1Department of Chemistry and Vanderbilt Institute of Chemical Biology , Vanderbilt University , Nashville , Tennessee 37235-1822 , United States.
Journal of the American Chemical Society
|March 23, 2018
概括
离子介导的宏环聚化 (M-MCO) 产生循环分子. 异热定位热量计 (ITC) 揭示了金属离子结合,使得有针对性的循环尺寸的合理模板选择.
科学领域:
- 有机化学
- 超分子化学
- 化学热力学
背景情况:
- 离子介导的三布宏环氧化 (M-MCO) 是合成循环脱的方法.
- 易斯酸金属盐在MCO反应中的作用,特别是关于模板机制,仍然不清楚.
研究的目的:
- 使用异热定位热量计 (ITC) 调查金属离子和循环脱之间的结合相互作用.
- 将热力学结合数据与通过M-MCO产生的脱酸的尺寸分布相关联.
- 建立一个用于选择金属离子模板的分析平台,以控制循环寡合的尺寸.
主要方法:
- 基于Mitsunobu的酸脱酸的宏环聚合 (MCO).
- 异热定位热量计 (ITC) 用于量化金属离子-循环脱结合亲和力 (Ka),结合度 (ΔH) 和静态测量.
- 热力学数据与宏观循环的动力学尺寸分布的相关性.
主要成果:
- 在不同宏观循环系列中确定金属离子-循环脱结合亲和力,和固态度的关键趋势.
- 证明了热力学结合参数与MCO产品的大小分布之间的相关性.
- 已确定金属离子结合会影响M-MCO反应的结果.
结论:
- 在M-MCO反应中,金属离子结合相互作用对于控制周期性的尺寸和形成至关重要.
- ITC为了解和预测金属离子的模板效应提供了有价值的工具.
- 这项工作提供了第一个用于合理选择金属离子模板的分析平台,以实现目标循环寡合体脱酸大小.
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