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首页> 外文期刊>Proceedings of the National Academy of Sciences of the United States of America >Conformation of self-assembled porphyrin dimers in liposome vesicles by phase-modulation 2D fluorescence spectroscopy
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Conformation of self-assembled porphyrin dimers in liposome vesicles by phase-modulation 2D fluorescence spectroscopy

机译:相位调制二维荧光光谱法研究脂质体囊泡中自组装卟啉二聚体的构象

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摘要

By applying a phase-modulation fluorescence approach to 2D electronic spectroscopy, we studied the confprmation-dependent exciton coupling of a porphyrin dimer embedded in a phospholipid bilayer membrane. Our measurements specify the relative angle and separation between interacting electronic transition dipole moments and thus provide a detailed characterization of dimer conformation. Phase-modulation 2D fluorescence spectroscopy (PM-2D FS) produces 2D spectra with distinct optical features, simi lar to those obtained using 2D photon-echo spectroscopy. Specifi cally, we studied magnesium meso tetraphenylporphyrin dimers, which form in the amphiphilic regions of 1,2-distearoyl-sn-glycero-3-phosphocholine liposomes. Comparison between experimental and simulated spectra show that although a wide range of dimer conformations can be inferred by either the linear absorption spectrum or the 2D spectrum alone, consideration of both types of spectra constrain the possible structures to a "T-shaped" geometry. These experiments establish the PM-2D FS method as an effective approach to elucidate chromophore dimer conformation.
机译:通过将相位调制荧光方法应用于二维电子光谱学,我们研究了嵌入磷脂双层膜中的卟啉二聚体的依赖于激发的激子偶联。我们的测量指定了相互作用的电子跃迁偶极矩之间的相对角度和间隔,从而提供了二聚体构象的详细表征。相位调制2D荧光光谱仪(PM-2D FS)产生具有独特光学特征的2D光谱,类似于使用2D光子回波光谱法获得的光谱。具体来说,我们研究了镁内消旋四苯基卟啉二聚体,其形成于1,2-二硬脂酰基-sn-甘油-3-磷酸胆碱脂质体的两亲区域。实验光谱与模拟光谱之间的比较表明,尽管可以通过线性吸收光谱或仅通过2D光谱推断出大范围的二聚体构象,但考虑到两种光谱类型都将可能的结构约束为“ T形”几何形状。这些实验建立了PM-2D FS方法,作为阐明生色团二聚体构象的有效方法。

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