Oxidative regulation of the mechanical strength of a C–S bond,Chemical Science

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Oxidative regulation of the mechanical strength of a C–S bond
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-14 , DOI: 10.1039/d0sc04381h
Yangju Lin _{1,

2,

3,

4} , Stephen L. Craig _{1,

2,

3,

4}

Affiliation

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters (PE-S) to the corresponding sulfoxide (PE-SO) and then sulfone (PE-SO₂) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO₂ > PE-SO. The relative mechanical strength as a function of oxidation state is revealed through the use of gem-dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.

中文翻译：

C–S键机械强度的氧化调节

单个聚合物链的机械强度被认为是散装材料中许多性能指标的基础，包括粘附力和断裂韧性。因此，可用于改变给定聚合材料的成分的固有分子强度的方法对于希望触发性质改变的应用以及作为本体行为的分子理论的测试都是潜在有用的。在这里，我们报告说，将含硫化物的聚酯（PE-S）依次氧化为相应的亚砜（PE-SO），然后再将砜（PE-SO ₂）氧化（亚砜），然后增强（砜），有效的机械聚合物主链的完整性；PE-S 〜PE-SO ₂ > PE-SO。通过使用宝石-二氯环丙烷非可断裂机制作为内标，揭示了相对机械强度与氧化态的关系，并且观察到的顺序与每种物种中C–S键的键解离能和结果相吻合。 CoGEF建模。

更新日期：2020-10-07

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