自愈水凝胶
反应性(心理学)
接受者
结合属性
材料科学
水溶液
解耦(概率)
化学
有机化学
高分子化学
物理
数学
凝聚态物理
病理
控制工程
工程类
纯数学
替代医学
医学
作者
Vivian Zhang,Joseph V. Accardo,Ilia Kevlishvili,Eliot Woods,Steven J. Chapman,Christopher T. Eckdahl,Charlotte L. Stern,Heather J. Kulik,Julia A. Kalow
出处
期刊:Chem
[Elsevier]
日期:2023-08-01
卷期号:9 (8): 2298-2317
被引量:1
标识
DOI:10.1016/j.chempr.2023.05.018
摘要
Dithioalkylidenes are a newly developed class of conjugate acceptors that undergo thiol exchange via an associative mechanism, enabling decoupling of key material properties for sustainability, biomedical, and sensing applications. Here, we show that the exchange rate is highly sensitive to the structure of the acceptor and tunable over four orders of magnitude in aqueous environments. Cyclic acceptors exchange rapidly, from 0.95 to 15.6 M−1s−1, whereas acyclic acceptors exchange between 3.77 × 10−3 and 2.17 × 10−2 M−1s−1. Computational, spectroscopic, and structural data suggest that cyclic acceptors are more reactive than their acyclic counterparts because of resonance stabilization of the tetrahedral exchange intermediate. We parametrize molecular reactivity with respect to computed descriptors of the electrophilic site and leverage this insight to design a compound with intermediate characteristics. Lastly, we incorporate this dynamic bond into hydrogels and demonstrate that the characteristic stress relaxation time (τ) is directly proportional to molecular kex.
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