A hydrogen bond-triggered excimer probe for dynamic monitoring of aspartic acid and glutamic acid

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Pub Date : 2025-07-10 DOI:10.1016/j.saa.2025.126659

Xudong Xie, Xing Wang, Yuanhang Li, Li Yang, Zhengjian Qi

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引用次数: 0

Abstract

Aspartic acid (Asp) and glutamic acid (Glu), as critical neurotransmitters, exhibit concentration abnormalities closely associated with epilepsy, Alzheimer's disease, and other neurological disorders. However, current detection methods face limitations in selectivity, sensitivity, and practicality. In this study, we developed a series of novel D-π-A structured fluorescent probes (PM-1, PM-2, PM-3, and PM-4), Among which PM-4 demonstrates weak monomer emission (540 nm) in aqueous solution. The pyridine side chain of PM-4 forms hydrogen bonds with the dual carboxylate groups of Asp/Glu, triggering the formation of emissive excimers. This process generates a new, enhanced red-shifted emission peak at 630 nm, enabling specific detection. The detection limits reached 1.26 μM (Asp) and 1.29 μM (Glu), with high selectivity. The formation mechanism of the probe-analyte complex was confirmed by NMR titration experiments. PM-4 successfully monitored diurnal fluctuations of Asp/Glu in saliva samples from healthy volunteers and concentration variations after smoking, revealing a correlation with emotional states (e.g., peak concentrations observed 10 min after smoking). The developed PM-4 probe integrates high sensitivity, selectivity, providing a powerful analytical tool for neurometabolic studies and disease biomarker detection. Its demonstrated performance highlights promising potential for both fundamental research and diagnostic product development.

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用于动态监测天冬氨酸和谷氨酸的氢键触发准分子探针

天冬氨酸（Asp）和谷氨酸（Glu）作为重要的神经递质，其浓度异常与癫痫、阿尔茨海默病和其他神经系统疾病密切相关。然而，目前的检测方法在选择性、灵敏度和实用性方面存在局限性。在本研究中，我们开发了一系列新型的D-π-A结构荧光探针（PM-1, PM-2， PM-3和PM-4），其中PM-4在水溶液中表现出弱单体发射（540 nm）。PM-4的吡啶侧链与Asp/Glu的双羧酸基团形成氢键，引发发射准分子的形成。这个过程产生一个新的，增强的红移发射峰在630纳米，使特定的检测。检测限分别为1.26 μM （Asp）和1.29 μM (Glu)，选择性高。通过核磁共振滴定实验证实了探针-分析物络合物的形成机理。PM-4成功地监测了健康志愿者唾液样本中Asp/Glu的每日波动和吸烟后的浓度变化，揭示了与情绪状态的相关性（例如，吸烟后10分钟观察到峰值浓度）。所开发的PM-4探针具有高灵敏度，高选择性，为神经代谢研究和疾病生物标志物检测提供了强大的分析工具。它所展示的性能突出了基础研究和诊断产品开发的巨大潜力。

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来源期刊

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 物理-光谱学

CiteScore

8.40

自引率

11.40%

发文量

1364

审稿时长

40 days

期刊介绍： Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (SAA) is an interdisciplinary journal which spans from basic to applied aspects of optical spectroscopy in chemistry, medicine, biology, and materials science. The journal publishes original scientific papers that feature high-quality spectroscopic data and analysis. From the broad range of optical spectroscopies, the emphasis is on electronic, vibrational or rotational spectra of molecules, rather than on spectroscopy based on magnetic moments. Criteria for publication in SAA are novelty, uniqueness, and outstanding quality. Routine applications of spectroscopic techniques and computational methods are not appropriate. Topics of particular interest of Spectrochimica Acta Part A include, but are not limited to: Spectroscopy and dynamics of bioanalytical, biomedical, environmental, and atmospheric sciences, Novel experimental techniques or instrumentation for molecular spectroscopy, Novel theoretical and computational methods, Novel applications in photochemistry and photobiology, Novel interpretational approaches as well as advances in data analysis based on electronic or vibrational spectroscopy.