论文标题
通过与脂质膜结合引起的基于RU的光敏剂的激子定位
Exciton Localization on Ru-based Photosensitizers Induced by Binding to Lipid Membranes
论文作者
论文摘要
嵌入在膜环境中的金属复合物的电子性质的表征对于开发有效的光遗传应用中有效的光敏剂至关重要。分子动力学和QM/MM模拟以及定量波函数分析揭示了激发[RU（BPY）2（BPY）2（BPY-C17）] 2+在脂质双层中嵌入的激发型激元之间的差异，尽管媒体不会影响电荷转移特征和吸收能量的吸收能量和吸收性谱。在水中，激子在两个配体上主要被定位，而非极性取代基的存在诱导电子过渡的方向性。取而代之的是，当光敏剂嵌入脂质膜中时，激子大小会减小，并且由于静电相互作用与双层带正电荷的表面，因此在一个旁吡啶基位点上更加局部。这些差异表明，可以通过与外部物种的结合来控制金属复合物的电子结构，从而强调了环境在激发时指导电子流中的关键作用，从而有助于光遗传剂的合理调整。
The characterization of electronic properties of metal complexes embedded in membrane environments is of paramount importance to develop efficient photosensitizers in optogenetic applications. Molecular dynamics and QM/MM simulations together with quantitative wavefunction analysis reveal an unforeseen difference between the exciton formed upon excitation of [Ru(bpy)2(bpy-C17)]2+ embedded in a lipid bilayer and in water, despite the media does not influence the charge-transfer character and the excitation energy of the absorption spectra. In water the exciton is mainly delocalized over two ligands and the presence of non-polar substituents induces directionality of the electronic transition. Instead, when the photosensitizer is embedded into a lipid membrane, the exciton size diminishes and is more localized at one bypyridyl site due to electrostatic interactions with the positively charged surface of the bilayer. These differences show that the electronic structure of metal complexes can be controlled through the binding to external species, underscoring the crucial role of the environment in directing the electronic flow upon excitation and thus helping rational tuning of optogenetic agents.
