On the temperature-dependent isomerization of all-trans-1,6-diphenyl-1,3,5-hexatriene in solution: A reappraisal
On the temperature-dependent isomerization of all-trans-1,6-diphenyl-1,3,5-hexatriene in solution: A reappraisal
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DOI：
10.1002/poc.4336
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发表时间：
2022-02-21
影响因子：
1.8
通讯作者：
Catalan, Javier
中科院分区：
文献类型：
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作者：
Catalan, Javier
在这项工作中，我们提出的吸收，发射，并在77和363 K之间的溶液中获得的全反式-DPH的发射光谱的激发。这些光谱的分析允许评估，这种分子探针，广泛用于生物物理学，不异构化在溶液中的s-cis-DPH在探索的温度。这些结果与以前的研究报告相矛盾，以前的研究强调：（a）全反式DPH异构化为s-顺式DPH时，溶解和温度范围从283至373 K和（B）的摩尔分数的s-顺式构象等于，甚至超过，在研究的最高温度下的全反式构象的摩尔分数。在这项工作中，我们展示了如何通过观察吸收和发射光谱上峰值的波数（nu）位移作为温度的函数来推断DPH分子结构中发生的变化。这些谱带位移的分析使我们能够证实Ogawa等人通过X射线衍射确定的变化，该变化发生在结晶相的DPH结构中，通过自行车踏板过程随温度变化。
In this work, we present absorption, emission, and excitation of emission spectra of all-trans-DPH obtained in solution between 77 and 363 K. The analysis of these spectra allows to evaluate that this molecular probe, widely used in biophysics, does not isomerizes in solution to s-cis-DPH at the temperatures explored. These results are in contradiction to those reported by previous studies that emphasize that (a) all-trans-DPH isomerizes to s-cis-DPH when dissolved and the temperature ranges from 283 to 373 K and (b) the molar fraction of s-cis-conformer equals, or even exceeds, the molar fraction of the all-trans-conformer at the highest temperature studied. In this work, we show how we can infer the changes taking place in the molecular structure of DPH looking at the wavenumber (nu) shift of the peaks on the absorption and emission spectra as a function of temperature. The analysis of these band shifts allows us to corroborate the change, determined by Ogawa et al. by X-ray diffraction, that occurs in the structure of DPH in the crystalline phase through a bicycle pedal process with temperature.