Application of commercially available fluorophores as triplet spin probes in EPR spectroscopy
Application of commercially available fluorophores as triplet spin probes in EPR spectroscopy
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DOI：
10.1080/00268976.2019.1608379
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发表时间：
2019-04
影响因子：
1.7
通讯作者：
Kerstin Serrer;Clemens Matt;Monja Sokolov;S. Kacprzak;E. Schleicher;S. Weber
中科院分区：
文献类型：
--
作者：
Kerstin Serrer;Clemens Matt;Monja Sokolov;S. Kacprzak;E. Schleicher;S. Weber
摘要近年来，光激发的分子三重态在磁共振中变得越来越流行，例如作为自旋探针来测量相对于其他电子顺磁物质的距离，或者作为将三重态的光产生的电子自旋极化转移到周围的磁性核的部分。在这项研究中，通过使用瞬态吸收光谱和瞬态电子顺磁共振（EPR），研究了三种市售染料（赤藓红B、虎红和Atto Thio 12）在水溶液中的三重态，这些染料通常在光谱和显微镜中用作荧光团。利用这些方法，得到了反映三重态波函数电子结构的三重态寿命及其零场分裂参数D和E。与虎红和赤藓红B相比，Atto Thio 12显示出小得多的D和E值。在零磁场下三重态能量分裂的密度泛函理论计算的基础上，这些发现被合理化。作为应用的概念证明，阿托硫12绑定到一个适体的三重态的属性也被确定，并讨论了结果。图形摘要
ABSTRACT In recent years, photoexcited molecular triplet states became increasingly popular in magnetic resonance, e.g. as spin probes to measure distances relative to other electron-paramagnetic species or as moieties that transfer light-generated electron–spin polarisation of the triplet state to surrounding magnetic nuclei. In this study, the triplet states of three commercially available dyes, Erythrosin B, Rose Bengal and Atto Thio 12, all typically utilised as fluorophores in optical spectroscopies and microscopies, are investigated in aqueous solutions by using transient absorption spectroscopy and transient electron paramagnetic resonance (EPR). From these methods, the triplet-state lifetimes as well as their zero-field splitting parameters, D and E, which reflect the electronic structures of the triplet state wavefunctions, were obtained. Atto Thio 12 exhibits much smaller D and E values as compared to Rose Bengal and Erythrosin B. On the basis of density functional theory calculations of the triplets’ energy splittings at zero magnetic field, these findings were rationalised. As a proof of concept for applications, the triplet-state properties of Atto Thio 12 bound to an aptamer were also determined and the results are discussed. GRAPHICAL ABSTRACT