Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy最新文献

{"title":"Enhancing soil nitrogen measurement via visible-near infrared spectroscopy: Integrating soil particle size distribution with long short-term memory models","authors":"Xiangchao Fu ,&nbsp;Geng Leng ,&nbsp;Zeyuan Zhang ,&nbsp;Jingyun Huang ,&nbsp;Wenbo Xu ,&nbsp;Zhenwei Xie ,&nbsp;Yuewu Wang","doi":"10.1016/j.saa.2024.125317","DOIUrl":"10.1016/j.saa.2024.125317","url":null,"abstract":"<div><div>Good quality of soil nitrogen data, which is essential for the advancement of both enhanced agricultural management and ecological environment, traditionally depends on labor intensive chemical procedures. Visible near-infrared (Vis-NIR) spectroscopy, acknowledged for its efficiency, environmental compatibility and rapidity, merges as a promising alternative. However, the effectiveness of Vis-NIR measurement models are significantly compromised by soil particle size distribution (PSD), presenting a substantial challenge in improving the measurement accuracy and reliability. Here an innovative deep learning methodology that integrates PSD with Vis-NIR spectroscopy was proposed for the measurement of nitrogen content in soil samples. By leveraging the LUCAS dataset, different strategies for integrating PSD with Vis-NIR spectral data in deep learning models were explored, revealing that our proposed InSGraL framework, which incorporated mixed features of PSD and spectra as LSTM inputs achieves superior performance. Compared to models utilizing solely Vis-NIR data, InSGraL exhibits a 39.47 % reduction in RMSE and a 42.55 % decrease in MAE, and demonstrates robust performance across various land cover types, achieving an R² of 0.94 on grassland samples. Moreover, Shapley Additive exPlanations (SHAP) analysis revealed that incorporating PSD modifies the spectral input importance distribution, effectively mitigating spectral interference from particle size while highlighting critical wavelengths previously obscured. This study provides an innovative modeling strategy to mitigate the influence of PSD by integrating it within deep learning framework using Vis-NIR, contributing a deeper understanding of the relationship between PSD and Vis-NIR spectra for the measurement of nitrogen content and offering an effective means to attain soil nitrogen data.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and mechanistic investigation of BPA fluorescent probes targeting BPA for potential application in Boron Neutron Capture Therapy (BNCT)","authors":"Wenwen Sun ,&nbsp;Yuanfeng Qi ,&nbsp;Le Wang ,&nbsp;Yunpeng Tan ,&nbsp;Xiao Zhang ,&nbsp;Junfeng Wang ,&nbsp;Yingbo Li","doi":"10.1016/j.saa.2024.125318","DOIUrl":"10.1016/j.saa.2024.125318","url":null,"abstract":"<div><div>Boronic acid analogs are crucial in modern organic chemistry and drug development, serving as versatile reagents and intermediates with significant therapeutic applications. This area has gained increased interest with the recent development of the drug 4-boron-L-phenylalanine (L-BPA) for boron neutron capture therapy (BNCT). Fluorescent probe technology offers an essential pathway for imaging drugs in vitro and in vivo, providing high sensitivity with great spatial and temporal resolution for both disease diagnosis and drug development. In this paper, we designed and investigated three fluorescent probes—W-1-NN, W-2-NS and W-3-NO—for sensing 4-boron-L-phenylalanine (L-BPA). Among these, only W-1-NN reacts with L-BPA, resulting in a spectral blue-shift change. This probe can “ratiometrically” and specifically detect L-BPA among various metals, with a limit of detection (LOD) of 7.11 μM. Mechanistic studies revealed that the addition of L-BPA disrupts the inherent ESIPT mechanism of W-1-NN in protonic solutions, resulting in the appearance of a new peak at 372 nm. Additionally, theoretical computational studies have also demonstrated that the complexation of W-1-NN with L-BPA triggers a change in the resonance structure, resulting in a larger energy gap and causing a blue shift in the spectrum. Furthermore, W-1-NN has been successfully applied to the detection of L-BPA in human urine. Therefore, the template probe with N/O as the target and the introduction of N atoms can specifically detect L-BPA. This template probe lays the foundation for the detection of L-BPA, and provides great possibilities for the future realization of the template probe to be connected with different fluorophores to make it emit at long wavelengths to reach the target of the near-infrared.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142537793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fourier transform InfraRed spectra analyzed by multivariate and machine learning methods in determination spectroscopy marker of prostate cancer in dried serum","authors":"Przemysław Mitura ,&nbsp;Wiesław Paja ,&nbsp;Bartosz Klebowski ,&nbsp;Paweł Płaza ,&nbsp;Iga Kuliniec ,&nbsp;Krzyszof Bar ,&nbsp;Joanna Depciuch","doi":"10.1016/j.saa.2024.125305","DOIUrl":"10.1016/j.saa.2024.125305","url":null,"abstract":"<div><div>Prostate cancer represents the second most prevalent form of cancer in males globally. In the diagnosis of prostate cancer, the most commonly utilised biomarker is prostate-specific antigen (PSA). It is unfortunate that approximately 25 % of men with elevated PSA levels do not have cancer, and that approximately 20 % of patients with prostate cancer have normal serum PSA levels. Accordingly, a more sensitive methodology must still be identified. It is imperative that new diagnostic methods should be non-invasive, cost-effective, rapid, and highly sensitive. Fourier transform infrared spectroscopy (FTIR) is a technique that fulfils all of the aforementioned criteria. Consequently, the present study used FTIR to assess dried serum samples obtained from a cohort of prostate cancer patients (n = 53) and a control group of healthy individuals (n = 40). Furthermore, this study proposes FTIR markers of prostate cancer obtained from serum. For this purpose, FTIR spectra of dried serum were measured and analysed using statistical, chemometric and machine learning (ML) algorithms including decision trees C5.0, Random Forest (RF), k-Nearest Neighbours (kNN) and Support Vector Machine (SVM). The FTIR spectra of serum collected from patients suffering from prostate cancer exhibited a reduced absorbance values of peaks derived from phospholipids, amides, and lipids. However, these differences were not statistically significant. Furthermore, principal component analysis (PCA) demonstrated that it is challenging to distinguish serum samples from healthy and non-healthy patients. The ML algorithms demonstrated that FTIR was capable of differentiating serum collected from both analysed groups of patients with high accuracy (values between 0.74 and 0.93 for the range from 800 cm⁻¹ to 1800 cm⁻¹ and around 0.70 and 1 for the range from 2800 cm⁻¹ to 3000 cm⁻¹), depending on the ML algorithms used. The results demonstrated that the peaks at 1637 cm⁻¹ and 2851 cm⁻¹ could serve as a FTIR marker for prostate cancer in serum samples. Furthermore, the correlation test indicated a clear correlation between these two wavenumbers and four of the five clinical parameters associated with prostate cancer. However, the relatively small number of samples collected only from patients over the age of 60 indicated that the results should be further investigated using a larger number of serum samples collected from a mean age range. In conclusion, this study demonstrated the potential of FTIR for the detection of prostate cancer in serum samples, highlighting the presence of distinctive spectroscopic markers associated with the analysed cancer type.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142526496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New phenanthridine-based multi-functional chemosensor for selective detection of Th4+ and Hg2+ ions in both aqueous and solid state","authors":"Bharathkumar Thangaraj ,&nbsp;Sambath Baskaran ,&nbsp;Ravichandran Cingaram ,&nbsp;Sathiyanarayanan Kulathu Iyer ,&nbsp;Karthikeyan Natesan Sundaramurthy","doi":"10.1016/j.saa.2024.125312","DOIUrl":"10.1016/j.saa.2024.125312","url":null,"abstract":"<div><div>A new phenanthridine-based multifunctional chemosensor (L), was synthesised via a green synthetic route and characterised using FT-IR, NMR and HRMS analysis. The sensing application of L towards metal ions in both solution and solid-state was studied using UV–vis and fluorescence spectroscopy, which exhibits dual-sensing behaviour for Th⁴⁺ and Hg²⁺ ions with good recyclability. In aqueous acetonitrile, L showed rapid response for the detection of environmental toxic metal ions and has a very low analytical detection limit of 125.5 pM and 1.94 nM for Th⁴⁺ and Hg²⁺ions respectively, which is remarkably lower than the World Health Organization standard. The cation binding property of the L with Th⁴⁺ and Hg²⁺ions was investigated by Job plot, ¹H NMR titration, HR-MS and DFT calculation. The in-situ formed ensemble L-Hg²⁺ was further applied in the naked-eye detection of Cys (Cystine) and His (Histidine) over other common amino acids. The utility of L for real-time detection of Hg²⁺ and Th⁴⁺ ions was explored in various sources of environmental water samples, test paper strips, fingerprint imaging, fluorescent ink and smartphone-assisted sensing techniques, demonstrating the promising on-site visualization of the probe in controlling the toxicity levels in wastewater sources without resorting to expensive instruments.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of a nanobody-horseradish peroxidase fusion-based competitive ELISA to rapidly and sensitively detect Enrofloxacin residues in animal-derived foods","authors":"Ming Yang ,&nbsp;Qiang Xu ,&nbsp;Kui Gu ,&nbsp;Renqiao Wen ,&nbsp;Changyu Zhou ,&nbsp;Yu Zhao ,&nbsp;Boyan Guo ,&nbsp;Wei Xu ,&nbsp;Yuanyuan Zhang ,&nbsp;Cui Li ,&nbsp;Changwei Lei ,&nbsp;Hongning Wang","doi":"10.1016/j.saa.2024.125309","DOIUrl":"10.1016/j.saa.2024.125309","url":null,"abstract":"<div><div>The ability to reliably detect enrofloxacin in animal-derived food products has important health implications. In the present study, a nanobody-horseradish peroxidase fusion specific for ENR was generated to enable a sensitive and rapid competitive ELISA suitable for detecting enrofloxacin in samples of milk and animal tissue. An enrofloxacin hapten generated via the glutaraldehyde method was initially used to immunize an adult Bactrian camel as a means of constructing a phage library. Enrofloxacin−specific nanobodies were then selected through three rounds of biopanning, and HRP-fused versions of these nanobodies were then expressed. Lastly, these nanobodies were used to develop a sensitive cELISA for enrofloxacin detection in milk and animal tissues, with the resultant assay exhibiting an IC₅₀ of 37.41 ng/mL and a linear detection range (IC₂₀-IC₈₀) of 10.89 to 244.34 ng/mL. The limit of detection for this cELISA was 6.48 ng/mL, with 4.66 % cross-reactivity with ciprofloxacin, and recovery rates that ranged from84.99 % to 107.72 % together with an RSD below 10.70 %.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142526718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The enhancement detection method based on the Fabry–Pérot cavity using terahertz frequency-domain spectroscopy","authors":"Yubo Wu ,&nbsp;Kanglong Chen ,&nbsp;Ayesha Kosar Fahad ,&nbsp;Haorang Wang ,&nbsp;Xiaoping Zheng ,&nbsp;Cunjun Ruan","doi":"10.1016/j.saa.2024.125293","DOIUrl":"10.1016/j.saa.2024.125293","url":null,"abstract":"<div><div>This article demonstrates a simple, efficient, and low-cost gas detection method for gases with absorption peaks in the terahertz range. A modes-adjustable Fabry–Pérot cavity is designed. By adjusting the length of the cavity, the center resonant frequency of the cavity can be coupled to the gas absorption peak. This kind of coupling can greatly enhance gas detection. To detect gas absorption peaks, we choose terahertz frequency domain spectroscopy (THz-FDS), whose frequency resolution can be up to the MHz level. Vapor is selected to verify the coupling phenomenon. The resonant frequency of the cavity is modified to couple to 0.56 THz, the absorption peak of vapor. Experiments are conducted at different humidity levels, the humidity is controlled by the supersaturated salt solution. Results indicate that at a humidity level of 15 %, the coupling effect can enhance the detectability of vapor by approximately 167 %, and this enhancement effect diminishes as humidity increases. We analyze the effect of different modes on the coupling and find that the high modes can make the coupling easier, but have little effect on the enhancement. Furthermore, the method is used to detect biomolecule-α-tyrosine to ensure it has wide applicability. This method can be used to detect substances with absorption peaks in the THz regime, especially for low-concentration gas.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142526488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Miniaturized dual-wavelength β-correction spectrophotometric probe for sensitive detection of cyanide in water via formation of cyano dithizone adduct","authors":"E.A. Bahaidarah ,&nbsp;H. Alwael ,&nbsp;M.M. Dabi ,&nbsp;T.N. Abduljabbar ,&nbsp;F.M. Alshareef ,&nbsp;K.A. Alzahrani ,&nbsp;N.A. Asiri ,&nbsp;N.O. Maslamani ,&nbsp;S.O. Bahaffi ,&nbsp;M.S. El-Shahawi","doi":"10.1016/j.saa.2024.125314","DOIUrl":"10.1016/j.saa.2024.125314","url":null,"abstract":"<div><div>Cyanide toxicity in water significantly threatens public health and the environment. To address this, a miniaturized simple, low-cost, selective and sensitive direct dual wave β-correction spectrophotometric probe has been established for cyanide detection in water. The dual-wavelength β-correction spectrophotometry enhances the selectivity and sensitivity of the probe in the presence of interfering species. The assay relies a highly selective nucleophilic addition of cyanide ions to dithizone (H₂Dz) as chromogenic reagent in aqueous media of pH 6.8–7.2, forming a red-colored cyano H₂Dz adduct. The electronic spectrum of the formed adduct displays a sharp absorption peak at λ_max = 480 nm, enabling precise colorimetric detection. The molar absorptivity and Sandell’s sensitivity index for the cyano H₂Dz adduct with and without <em>β</em>-correction spectrophotometry were 5.62 × 10³, and 1.79 × 10³ L mol⁻¹ cm⁻¹, and 0.002 and 0.0033 µg cm⁻², respectively. Beer’s law and Ringbom’s plots are valid in the range 0.01–5.0 and 0.06–2.0 µg mL⁻¹ CN^– concentration, respectively. The limits of detection (LOD) and quantification (LOQ) improved from 1.03 × 10⁻¹ and 3.13 × 10⁻¹ μg/mL using ordinary spectrophotometry to 2.8 × 10⁻² and 8.7 × 10⁻² μg mL⁻¹ employing β-correction spectrophotometry. The probe offers rapid response, good anti-interference ability, reproducibility, and cost-effectiveness. The probe was successfully applied for detection of trace levels of cyanide ions in water with good repeatability. It has been also validated in water samples with good recoveries (99.2 ± 5.02 %). The experimental <em>Student t</em> test (<em>t_exp</em> = 1.2–1.5) was lower than the critical (<em>t_exp =</em> 2.78) at 95 % probability <em>(</em>n = 5). The stoichiometry and mechanism of formation of the cyano adduct were assigned and addressed.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142537795","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ATR-FTIR spectroscopic imaging with variable angles of incidence of crude oil deposits formed by flocculant flow","authors":"Anton S. Shalygin","doi":"10.1016/j.saa.2024.125310","DOIUrl":"10.1016/j.saa.2024.125310","url":null,"abstract":"<div><div>Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic imaging is a method for spatially resolved analysis of materials that combines the capabilities of ATR-FTIR spectroscopy with the use of a focal plane array detector. This paper presents the methodological aspects of adapting the ATR accessory with variable single reflection angle to the FTIR spectroscopic imaging method. The use of a variable reflection angle allows the image to be studied at different sample depths. Using examples of BMIMPF₆ ionic liquid and crude oil droplets placed on the working surface of an internal reflection element, the characteristics of image acquisition as the angle of reflection is varied are discussed. The possibility of obtaining crude oil deposits directly on the working surface of the internal reflection element under the influence of a flocculant flow (n-heptane, acetone) and their study by ATR-FTIR spectroscopic image was demonstrated. Crude oil deposits were obtained under different formation conditions (flow rates of flocculant) and their spectroscopic images were also obtained at different single reflection angles. This information gives an indication of the composition of the deposit’s functional groups not only at spatial resolution but also at depth.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142515647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"From elemental mapping to structural insights: A multi-technique investigation into the nephrite from various provenances","authors":"Dian Chen ,&nbsp;Chengye Xing ,&nbsp;Yu Li","doi":"10.1016/j.saa.2024.125304","DOIUrl":"10.1016/j.saa.2024.125304","url":null,"abstract":"<div><div>Nephrite, a historically significant material in Chinese jade culture, varies in elemental composition and spectroscopic properties based on its geographic origin due to differing mineralization environments. This study aims to address the limitations of traditional methods by employing a multi-technique approach that combines XRF mapping, fiber optic reflectance spectroscopy (FORS), near-infrared spectroscopy (NIR), and synchrotron-based X-ray absorption fine structure (XAFS) analysis, focusing on a comprehensive characterization of Fe to understand the properties of nephrite from various provenances. Our results reveal that while major elements like Si, Mg, and Ca are uniformly distributed, elements such as K, Mn, and Fe show significant variability, with Fe and Mn exhibiting nearly identical distribution patterns. Transparency variations in Qinghai nephrite correlate with Ca distribution. Chromaticity analysis indicates that Fe significantly influences the yellow coloration of nephrite, and NIR spectroscopy shows that Fe content affects spectral characteristics. XAFS analysis provides detailed insights into the valence and coordination environment of Fe, highlighting its role in color variation and spectral shifts. This integrated approach bridges the correlation between elemental composition and distribution, structural properties and visual representation, and its non-destructive advantages could hold great promise for jade research.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142549905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of functional groups on ESIPT and antioxidant activity of apigenin: A non-existent enol* state fluorescein","authors":"Bifa Cao ,&nbsp;Ke Li ,&nbsp;Chuangui Chen ,&nbsp;Ying Shi","doi":"10.1016/j.saa.2024.125287","DOIUrl":"10.1016/j.saa.2024.125287","url":null,"abstract":"<div><div>The development and enhancement of antioxidant drugs, which are aimed at mitigating DNA damage, mutations, and cancer, are of paramount significance in the biomedical sphere. In recent years, antioxidant drug molecules with photoluminescence have sprung up like mushrooms. Apigenin (AP), characterized by its distinctive property of excited state intramolecular proton transfer (ESIPT), plays a pivotal role in mediating antioxidant and anticancer activities. Despite being a representative molecule of the non-existent enol form (E*) state with ESIPT nature, there is a notable lack of theoretical investigations into its antioxidant properties. Herein, density functional theory (DFT) and time-dependent DFT methodologies were utilized to explore the effects of various functional groups on AP molecules in a methanol solvent. Studies have demonstrated that for the non-existent E* state fluorescence molecule AP, the ESIPT process can significantly enhance the antioxidant potency of AP and its derivatives. However, the introduction of electron-withdrawing groups significantly accelerated the ESIPT process while simultaneously suppressing the antioxidant activity of AP-CN. Conversely, the incorporation of electron-donating groups effectively inhibited the ESIPT process, yet markedly enhanced the antioxidant activity of AP-NH₂. This investigation furnishes vital perspectives and sources of reference for the conception and advancement of groundbreaking antioxidant medications that aim to tackle non-existent E* state molecules.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142515639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}