Energy transfer dynamics and the mechanism of biohybrid photosynthetic antenna complexes chemically linked with artificial chromophores
Energy transfer dynamics and the mechanism of biohybrid photosynthetic antenna complexes chemically linked with artificial chromophores
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与人工发色团化学连接的生物杂化光合天线复合物的能量传递动力学和机制
DOI：
10.1039/d2cp02465a
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发表时间：
2022
影响因子：
3.3
通讯作者：
Dewa Takehisa
中科院分区：
文献类型：
--
作者：
Yoneda Yusuke;Noji Tomoyasu;Mizutani Naoto;Kato Daiji;Kondo Masaharu;Miyasaka Hiroshi;Nagasawa Yutaka;Dewa Takehisa
捕光策略对于太阳能的利用至关重要。在这项研究中，我们解决了扩大光捕获（LH）波长的光合LH复合物2（LH2，从嗜酸性红芽生菌菌株10050）通过共价结合与外部发色团。为了进一步理解激发能量转移（EET）的共轭结构和机制，我们研究了能量供体和受体颜料的发射和吸收光谱之间的连接体长度和光谱重叠积分的影响。在前一种情况下，与基于Förster共振能量转移（FRET）理论的直觉相反，观察到的能量转移速率与连接体长度无关，并且能量转移效率随着连接体长度的增加而增加。在后一种情况下，尽管能量转移速率在更高的光谱重叠增加，它是定量与FRET理论不一致。超越FRET理论的EET机制进行了讨论，在较高的说谎激子状态的B850，介导有效的EET，尽管小的光谱重叠。这一系统的研究为开发高效的人工光合系统提供了参考。
A light-harvesting strategy is crucial for the utilisation of solar energy. In this study, we addressed the expanding light-harvesting (LH) wavelength of photosynthetic LH complex 2 (LH2, from Rhodoblastus acidophilus strain 10050) through covalent conjugation with extrinsic chromophores. To further understand the conjugation architecture and mechanism of excitation energy transfer (EET), we examined the effects of the linker length and spectral overlap integral between the emission and absorption spectra of the energy donor and acceptor pigments. In the former case, contrary to the intuition based on the Förster resonance energy transfer (FRET) theory, the observed energy transfer rate was similar regardless of the linker length, and the energy transfer efficiency increased with longer linkers. In the latter case, despite the energy transfer rate increases at higher spectral overlaps, it was quantitatively inconsistent with the FRET theory. The mechanism of EET beyond the FRET theory was discussed in terms of the higher-lying exciton state of B850, which mediates efficient EET despite the small spectral overlap. This systematic investigation provides insights for the development of efficient artificial photosynthetic systems.