Conservation of ultrafast photoprotective mechanisms with increasing molecular complexity in sinapoyl malate derivatives.
Conservation of ultrafast photoprotective mechanisms with increasing molecular complexity in sinapoyl malate derivatives.
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DOI：
10.1002/cphc.202000429
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发表时间：
2020-09-02
期刊：
影响因子：
--
通讯作者：
Stavros VG
中科院分区：
文献类型：
--
作者：
Baker LA;Staniforth M;Flourat AL;Allais F;Stavros VG
苹果酸Sinapoyl是一种天然的植物防晒分子，可以保护树叶免受有害的紫外线辐射。本文利用瞬态电子吸收光谱技术，研究了三种苹果酸新萘酰基衍生物，苹果酸新萘酰基L -二甲基苹果酸，苹果酸新萘酰基L -二乙基苹果酸和苹果酸新萘酰基L -二- t -丁基苹果酸在二氧六烷和甲醇溶剂环境下的超快动力学，以研究随着分子复杂性的增加，这些动力学是如何被很好地保存下来的。在所有情况下，发现光激发后，在20-30 ps内通过反式-顺式异构化途径发生失活。这种顺式光产物是在光失活过程中形成的，对于两种溶剂中的所有分子来说都是稳定且长寿命的。随着分子复杂性的增加，异构化途径的守恒程度令人难以置信，这证明了这些分子作为紫外线光保护剂的功效，即使在强烈扰动的溶剂中也是如此。因此，我们认为这些分子可能非常适合用于增强，以进一步提高其光防护功效或与防晒霜混合物中其他成分的化学相容性，同时保留其潜在的光动力特性。紫外-可见泵浦-探针光谱研究了一系列苹果酸sinapoyl衍生物的光失活机理。在苹果酸sinapoyl中，这种光失活通过反式-顺式分离途径在20-30 ps内发生。即使在研究最多的增广系统中，该途径也表现出非常好的保守性，即sinapoyl L - di - t -丁基苹果酸盐。因此，这些分子可能非常适合进一步增强，以提高它们在防晒霜混合物中的功效或化学相容性。
Sinapoyl malate is a natural plant sunscreen molecule which protects leaves from harmful ultraviolet radiation. Here, the ultrafast dynamics of three sinapoyl malate derivatives, sinapoyl L‐dimethyl malate, sinapoyl L‐diethyl malate and sinapoyl L‐di‐t‐butyl malate, have been studied using transient electronic absorption spectroscopy, in a dioxane and methanol solvent environment to investigate how well preserved these dynamics remain with increasing molecular complexity. In all cases it was found that, upon photoexcitation, deactivation occurs via a trans‐cis isomerisation pathway within ∼20–30 ps. This cis‐photoproduct, formed during photodeactivation, is stable and longed‐lived for all molecules in both solvents. The incredible levels of conservation of the isomerisation pathway with increased molecular complexity demonstrate the efficacy of these molecules as ultraviolet photoprotectors, even in strongly perturbing solvents. As such, we suggest these molecules might be well‐suited for augmentations to further improve their photoprotective efficacy or chemical compatibility with other components of sunscreen mixtures, whilst conserving their underlying photodynamic properties. UV‐visible pump‐probe spectroscopy is used to understand the photodeactivation mechanism in a series of sinapoyl malate derivatives. In sinapoyl malate, this photodeactivation occurs via a trans‐cis isomeration pathway within ∼20–30 ps. This pathway appears remarkably well‐conserved even in the most augmented system studied, sinapoyl L‐di‐t‐butyl malate. As such, these molecules might be well‐suited for further augmentation to improve their efficacy or chemical compatibility within sunscreen mixtures.
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影响因子：
2.8
作者：
Bauernschmitt, R;Ahlrichs, R
通讯作者：
Ahlrichs, R
影响因子：
4.4
作者：
Hättig, C;Weigend, F
通讯作者：
Weigend, F
影响因子：
3.3
作者：
Hättig, C;Hellweg, A;Köhn, A
通讯作者：
Köhn, A
影响因子：
1.6
作者：
Grubb, Michael P.;Orr-Ewing, Andrew J.;Ashfold, Michael N. R.
通讯作者：
Ashfold, Michael N. R.
DOI：
10.1007/bf00698753
发表时间：
1985-01-01
期刊：
THEORETICA CHIMICA ACTA
影响因子：
--
作者：
HANDY, NC;KNOWLES, PJ;SOMASUNDRAM, K
通讯作者：
SOMASUNDRAM, K