Synthesis and characterization of a solvatochromic urea-schiff base derivative: Investigating optical properties, hydrogen bonding effect, copper ion sensing, computational analysis, DNA and β-cyclodextrin interactions

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Pub Date : 2025-05-04 DOI:10.1016/j.saa.2025.126337

Ibrahim A. Alhagri , Sadeq M. Al-Hazmy , Sarah S. Alammari , Fahd M. Alminderej , Sabri Messaoudi , Lotfi M. Aroua

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Abstract

This study investigates the fluorescence behavior of the synthesized compound (E)-1-(4-chloro-2-(((2-hydroxynaphthalen-1-yl) methylene) amino) phenyl)-3-(naphthalen-1-yl) urea (3DB) in various solvents. A significant increase in fluorescence intensity was observed when transitioning from ethanol to less polar solvents like CH₂Cl₂, CHCl₃, and CCl₄, indicating enhanced fluorescence due to reduced non-radiative processes. Emission wavelengths remained stable with minor shifts (5–6 nm), while significant blue shifts in absorption occurred in water due to strong hydrogen bonding. Fluorescence spectra showed red shifts (519 nm in water, 508 nm in glycerol, and 486 nm in ethylene glycol), highlighting the impact of hydrogen bonding on electronic transitions. Emission intensity in water was six times higher than in ethylene glycol, suggesting that strong hydrogen bonds stabilize the excited state. The study also revealed that 3DB exhibits a large Stokes shift, avoiding reabsorption of emitted light (inner filter effect). Fluorescence was completely quenched by low concentrations of copper ions, demonstrating 3DB’s potential as a copper sensor. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations indicated that luminescence quenching in the Cu(II) complex is due to intramolecular charge transfer (ICT). Additionally, 3DB formed stable complexes with DNA and β-cyclodextrin (β-CD), with binding constants (K_b) of 1.30 × 103 M⁻¹ and 1.89 × 103 M⁻¹, respectively, and negative Gibbs free energy values, indicating spontaneous interactions. Fluorescence spectroscopy confirmed DNA binding, showing a 49.62 % increase in intensity and a 4 nm blue shift, consistent with groove-binding. Docking studies further supported favorable interactions with DNA. These results underscore 3DB’s potential in sensing, imaging, environmental monitoring, and biological applications.

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溶剂致变色脲-希夫碱衍生物的合成与表征：光学性质、氢键效应、铜离子传感、计算分析、DNA与β-环糊精相互作用的研究

本文研究了合成的化合物（E)-1-（4-氯-2-（（2-萘-1-基）亚甲基）氨基）苯基）-3-（萘-1-基）尿素（3DB）在不同溶剂中的荧光行为。当从乙醇过渡到极性较低的溶剂如CH2Cl2、CHCl3和CCl4时，观察到荧光强度显著增加，表明荧光增强是由于减少了非辐射过程。发射波长保持稳定，有较小的偏移（5-6 nm），而由于氢键强，水的吸收发生了明显的蓝色偏移。荧光光谱显示红移（水中519 nm，甘油508 nm，乙二醇486 nm），突出了氢键对电子跃迁的影响。水的发射强度是乙二醇的六倍，这表明强大的氢键稳定了激发态。研究还表明，3DB表现出很大的斯托克斯位移，避免了发射光的再吸收（内部过滤效应）。荧光被低浓度的铜离子完全淬灭，证明了3DB作为铜传感器的潜力。密度泛函理论（DFT）和时间依赖DFT （TDDFT）计算表明，Cu（II）配合物的发光猝灭是由于分子内电荷转移（ICT）引起的。此外，3DB与DNA和β-环糊精（β-CD）形成稳定的配合物，结合常数（Kb）分别为1.30 × 103 M−1和1.89 × 103 M−1，Gibbs自由能为负，表明相互作用是自发的。荧光光谱证实了DNA结合，显示强度增加49.62%，蓝移4nm，与凹槽结合一致。对接研究进一步支持了与DNA的有利相互作用。这些结果强调了3DB在传感、成像、环境监测和生物应用方面的潜力。

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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.