Computational insights into the photophysical processes of an acylhydrazone fluorescent probe based on conical intersection and sensing mechanism for Al3+ detection

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2024-10-23 DOI:10.1016/j.comptc.2024.114934

Pengcheng Zhang , Chunxiang Zhao , Hongyu Chen , Han Zhang , Huijie Ni , Yubing Si

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Abstract

Al³⁺ detection is crucial for food safety, environmental monitoring, and biological assays. This work investigated the fluorescent properties of the probe VN62 and its sensing mechanism for the detection of Al³⁺ ion in detail. The ground- and excited-state properties such as isomerization geometries and absorption spectra, as well as the photophysical processes of transitions in PES have been studied. There are few fluorescent S₁ states (PT*, TICT) of the VN62 molecule, and the conical intersections (CIs) have key importance in the fluorescent process. By comparing the radiative rate (k_r) and the rate of transition to CI, we deduce that these fluorescent states are lack of stability for light emission. Therefore, the fluorescence of probe alone can be quenched by CI pathways. After coordination with Al³⁺, the CI pathways will be suppressed, resulting in enhanced fluorescence. This sensing mechanism is different from the previously proposed mechanisms, such as the dark state of TICT or ESIPT. We anticipate that our research would shed some light on the design of turn-on sensors.

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基于锥形交点的酰基腙荧光探针的光物理过程和 Al3+ 检测传感机制的计算见解

Al3+ 检测对食品安全、环境监测和生物检测至关重要。这项工作详细研究了探针 VN62 的荧光特性及其检测 Al3+ 离子的传感机制。研究了 PES 的基态和激发态特性，如异构化几何形状和吸收光谱，以及跃迁的光物理过程。VN62 分子中存在少数荧光 S1 态（PT*、TICT），而锥形交叉点（CI）在荧光过程中具有关键意义。通过比较辐射率（kr）和向 CI 过渡的速率，我们推断出这些荧光态缺乏光发射的稳定性。因此，探针本身的荧光可以通过 CI 途径被淬灭。与 Al3+ 配位后，CI 途径将被抑制，从而导致荧光增强。这种传感机制不同于之前提出的机制，如 TICT 或 ESIPT 的暗态。我们希望我们的研究能为开启传感器的设计提供一些启示。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.