Förster共振能量转移（FRET）中频谱重叠建模的启发式方法。,Journal of Chemical Information and Modeling

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Förster共振能量转移（FRET）中频谱重叠建模的启发式方法。
Journal of Chemical Information and Modeling ( IF 5.6 ) Pub Date : 2019-02-04 , DOI: 10.1021/acs.jcim.8b00753
Qi Qi ₁ , Masahiko Taniguchi ₁ , Jonathan S Lindsey ₁

Affiliation

在支持福斯特共振能量转移（FRET）的光物理参数中，可能探索最少的是光谱重叠项（J）。尽管根据定义，J随受体摩尔吸收系数（M-1 cm-1中的ε（A））线性增加，与波长（λ4）成正比，并且取决于供体荧光和受体吸收光谱的重叠程度，对于完全光谱重叠的情况与具有不完全光谱重叠的代表性荧光团的情况，J的值引起了疑问。在此，已经对吸收和荧光光谱的高斯分布进行了建模，该分布涵盖了不同程度的重叠，最大半峰全宽（fwhm）和斯托克斯位移。对于ε（A）= 105 M-1 cm-1和完美重叠，J值（在M-1 cm-1 nm4中）范围为1.15×1014（200 nm）至7。07×1016（1000 nm），几乎与λ4线性（λabs和λflu的平均值），并且几乎与fwhm无关。对于高斯光谱完全重叠的可见区荧光团，J（JG-0）的结果值为〜0.71ε（A）λ4（M-1 cm-1 nm4）。利用从60种代表性化合物（12组，每组5种化合物）的静态数据库中的光谱计算出在光捕获天线中发生的均质转移实验J值，发现其范围为4.2×1010（邻二甲苯）至5.3 ×1016 M-1 cm-1 nm4（萘菁）。对于完全重叠的光谱，重叠度由实验J与模型JG-0的比率定义，范围为〜0.5％（香豆素151）至77％（细菌叶绿素a）。结果提供了各种因素如何影响最终的J值的见解。

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Heuristics from Modeling of Spectral Overlap in Förster Resonance Energy Transfer (FRET).

Among the photophysical parameters that underpin Förster resonance energy transfer (FRET), perhaps the least explored is the spectral overlap term ( J). While by definition J increases linearly with acceptor molar absorption coefficient (ε(A) in M-1 cm-1), is proportional to wavelength (λ4), and depends on the degree of overlap of the donor fluorescence and acceptor absorption spectra, the question arose as to the value of J for the case of perfect spectral overlap versus that for representative fluorophores with incomplete spectral overlap. Here, Gaussian distributions of absorption and fluorescent spectra have been modeled that encompass varying degrees of overlap, full-width-at-half-maximum (fwhm), and Stokes shift. For ε(A) = 105 M-1 cm-1 and perfect overlap, the J value (in M-1 cm-1 nm4) ranges from 1.15 × 1014 (200 nm) to 7.07 × 1016 (1000 nm), is almost linear with λ4 (average of λabs and λflu), and is nearly independent of fwhm. For visible-region fluorophores with perfectly overlapped Gaussian spectra, the resulting value of J ( JG-0) is ∼0.71 ε(A)λ4 (M-1 cm-1 nm4). The experimental J values for homotransfer, as occurs in light-harvesting antennas, were calculated with spectra from a static database of 60 representative compounds (12 groups, 5 compounds each) and found to range from 4.2 × 1010 ( o-xylene) to 5.3 × 1016 M-1 cm-1 nm4 (a naphthalocyanine). The degree of overlap, defined by the ratio of the experimental J to the model JG-0 for perfectly overlapped spectra, ranges from ∼0.5% (coumarin 151) to 77% (bacteriochlorophyll a). The results provide insights into how a variety of factors affect the resulting J values. The high degree of spectral overlap for (bacterio)chlorophylls prompts brief conjecture concerning the relevance of energy transfer to the question "why chlorophyll".

更新日期：2019-02-04

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