General Design Strategy to Precisely Control the Emission of Fluorophores via a Twisted Intramolecular Charge Transfer (TICT) Process,Journal of the American Chemical Society

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General Design Strategy to Precisely Control the Emission of Fluorophores via a Twisted Intramolecular Charge Transfer (TICT) Process
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-10-03 , DOI: 10.1021/jacs.2c06397
Kenjiro Hanaoka ₁ , Shimpei Iwaki , Kiyoshi Yagi ₂ , Takuya Myochin , Takayuki Ikeno , Hisashi Ohno ₁ , Eita Sasaki ₁ , Toru Komatsu , Tasuku Ueno , Motokazu Uchigashima , Takayasu Mikuni , Kazuki Tainaka , Shinya Tahara , Satoshi Takeuchi , Tahei Tahara , Masanobu Uchiyama , Tetsuo Nagano , Yasuteru Urano

Affiliation

Fluorogenic probes for bioimaging have become essential tools for life science and medicine, and the key to their development is a precise understanding of the mechanisms available for fluorescence off/on control, such as photoinduced electron transfer (PeT) and Förster resonance energy transfer (FRET). Here we establish a new molecular design strategy to rationally develop activatable fluorescent probes, which exhibit a fluorescence off/on change in response to target biomolecules, by controlling the twisted intramolecular charge transfer (TICT) process. This approach was developed on the basis of a thorough investigation of the fluorescence quenching mechanism of N-phenyl rhodamine dyes (commercially available as the QSY series) by means of time-dependent density functional theory (TD-DFT) calculations and photophysical evaluation of their derivatives. To illustrate and validate this TICT-based design strategy, we employed it to develop practical fluorogenic probes for HaloTag and SNAP-tag. We further show that the TICT-controlled fluorescence off/on mechanism is generalizable by synthesizing a Si–rhodamine-based fluorogenic probe for HaloTag, thus providing a palette of chemical dyes that spans the visible and near-infrared range.

中文翻译：

通过扭曲分子内电荷转移 (TICT) 过程精确控制荧光团发射的一般设计策略

用于生物成像的荧光探针已成为生命科学和医学的重要工具，其发展的关键是准确理解荧光开/关控制的机制，例如光诱导电子转移 (PeT) 和 Förster 共振能量转移 (FRET) ). 在这里，我们建立了一种新的分子设计策略，通过控制扭曲的分子内电荷转移 (TICT) 过程，合理开发可激活的荧光探针，这些探针表现出响应目标生物分子的荧光关闭/开启变化。该方法是在对N的荧光猝灭机制进行彻底研究的基础上开发的- 苯基罗丹明染料（市售 QSY 系列）通过时间相关密度泛函理论 (TD-DFT) 计算及其衍生物的光物理评估。为了说明和验证这种基于 TICT 的设计策略，我们使用它来开发用于 HaloTag 和 SNAP-tag 的实用荧光探针。我们进一步表明，TICT 控制的荧光开/关机制可通过为 HaloTag 合成基于 Si-罗丹明的荧光探针来推广，从而提供跨越可见光和近红外范围的化学染料调色板。

更新日期：2022-10-03

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