Elucidating the excited-state dynamics behavior in near-infrared Bodipy dye and aggregates toward biophotonics

Elucidating the excited-state dynamics behavior in near-infrared Bodipy dye and aggregates toward biophotonics
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阐明近红外 Bodipy 染料和聚集体在生物光子学中的激发态动力学行为

DOI:
10.1007/s11426-020-9731-0
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发表时间:
2020-05
期刊:
Science China Chemistry
影响因子:
--
通讯作者:
Huang Wei
Huang Wei
中科院分区:
其他
文献类型:
--
作者:
Miao Xiaofei;Tao Haojie;Hu Wenbo;Pan Yonghui;Fan Quli;Huang Wei

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有机材料内部的光致激发态动力学从根本上决定了其各种应用的光物理性质,因此了解主要的激发态动力学行为具有基础和实际意义。迄今为止,人们对有机材料对生物光子学的激发态动力学研究甚少,尽管人们在设计生物光子学的有机材料方面做了大量的努力。在此,包括飞秒瞬态吸收(fs-TA)光谱在内的各种光谱技术清楚地揭示了Bodipy单体(2B-BDP染料)和聚集体(2B-BDP NPs)之间完全不同的激发态动力学行为,表明了强烈的形态依赖特征。2B-BDP染料经历了从S1到分子内电荷转移(ICT)状态的超快转换,随后发生光致发光(PL)和非辐射(NR)衰变,而2B-BDP NPs主要通过S1→S0NR衰变加速激发态失活。并结合实验结果讨论了基于相应激发态动力学行为的潜在生物应用。有趣的是,在2B-BDP NPs中NR的加速衰减并没有产生比2B-BDP染料更强的光声(PA)信号,这违背了传统观点,即更快的NR衰减将有利于光热效应,从而获得更好的光声成像(PAI)。这些对激发态动力学的深刻而基本的观察可能有助于在分子水平上为未来设计具有理想性能的功能性基于bodipy的有机分子提供另一种方法。
Photo-induced excited-state dynamics within organic materials fundamentally determine their photophysical properties for various applications, and thus understanding the primary excited-state dynamics behavior is of fundamental and practical significance. Until recently, the excited-state dynamics of organic materials towards biophotonics have been rarely studied, although numerous endeavors have been devoted to the design of organic materials for biophotonics. Herein, various spectroscopy technologies including femtosecond transient absorption (fs-TA) spectroscopy clearly reveal a totally different excited state dynamics behavior within Bodipy monomer (2B-BDP dye) and aggregates (2B-BDP NPs), indicating strongly morphology dependent character. 2B-BDP dye undergoes an ultrafast conversion from S1to intramolecular charge transfer (ICT) state for subsequent photoluminescence (PL) and nonradiative (NR) decay, while 2B-BDP NPs show an accelerated excited-state deactivation mainly through S1→S0NR decay. The potential bioapplications based on the corresponding excited state dynamics behavior are discussed together with experimental results. Interestingly, the accelerated NR decay in 2B-BDP NPs does not yield a stronger photoacoustic (PA) signal than that in 2B-BDP dye, which violates the conventional wisdom that faster NR decay would benefit the photothermal effects for better photoacoustic imaging (PAI). These insightful and fundamental observations of the excited-state dynamics may contribute an alternative approach at the molecular level towards the future design of functional Bodipy-based organic molecules with desirable performances.
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