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

{"title":"Comparison of spectroscopic techniques for determination of protein secondary structure","authors":"Andreas Schwaighofer,&nbsp;Heinz Anderle,&nbsp;Martin Lemmerer","doi":"10.1016/j.saa.2025.126345","DOIUrl":"10.1016/j.saa.2025.126345","url":null,"abstract":"<div><div>Determination of the protein secondary structure is a key task in academic and industrial fields related to biotechnology and the pharmaceutical sciences. Spectroscopic techniques offer the potential for rapid estimation of individual shares of secondary structures. In this work, 17 model proteins with known secondary structure were analysed by infrared (IR), Raman, far-UV circular dichroism (CD) spectroscopy and polarimetry. The recorded spectra were evaluated using PLS analysis (IR, Raman) and multiple dedicated algorithms (far-UV CD). Resulting figures of merit were compared and the application parameters of each spectroscopic technique were discussed. The best results were obtained from PLS models of IR and Raman spectra for the estimation of α-helix and β-sheet secondary structures. Far-UV CD spectroscopy combined with the CONTINLL algorithm achieved good figures of merit for α-helix and β-sheet. Polarimetry was shown to give good results for the analysis of α-helix.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126345"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143924805","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":"Rapid detection and identification of plastic waste based on multi-wavelength laser Raman spectroscopy combining machine learning methods","authors":"Zhou Fang ,&nbsp;Dezhi Chen ,&nbsp;Xing Hu ,&nbsp;Zhenghui Deng ,&nbsp;Jun Xu ,&nbsp;Yi Wang ,&nbsp;Yu Qiao ,&nbsp;Song Hu ,&nbsp;Jun Xiang","doi":"10.1016/j.saa.2025.126316","DOIUrl":"10.1016/j.saa.2025.126316","url":null,"abstract":"<div><div>Plastic waste has become a significant environmental concern, necessitating advancements in recycling efficiency.<!--> <!-->Enhancing the purity of recycled plastics facilitates the selection of suitable processing methods for different materials, thereby optimizing the recycling process.<!--> <!-->This study proposed a multi-wavelength laser Raman detection method and system to enable rapid and accurate identification of plastic waste.<!--> <!-->By analyzing the Raman spectra of various plastics under different laser wavelengths and introducing a fluorescence coefficient to quantify wavelength impact,<!--> <!-->the attribution of Raman characteristic peaks for distinct plastics has been elucidated, and the integrated area of Raman spectra across seven bands was identified as the key parameters for identifying plastics. By comparing neural networks, random forests, and k-nearest neighbor algorithms, it was determined that the k-nearest neighbor algorithm achieved the highest accuracy of 97.4 % and fastest identification speed of 1.2 ms/item when using integrated area of 7 characteristic bands as input. A plastic identification model incorporating data augmentation and k-nearest neighbors was finally developed and validated. A 100 % identification rate for actual waste plastic can be achieved by utilising a multi-wavelength laser Raman spectroscopy database. The results demonstrated that the multi-wavelength Raman system was highly effective for online or rapid recycling applications, enabling precise sorting of mixed plastic waste. This system significantly enhances the quality of recycled feedstock, contributing to the sustainability of plastic waste management.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126316"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143929552","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":"Colorimetric detection of fluoroquinolones via MOF inhibition and thiol-response oxidase-mimicking reactions","authors":"Wenzhi Zhang ,&nbsp;Song Liu ,&nbsp;Henggang Wang ,&nbsp;Zhe Wang ,&nbsp;Linfeng Cui ,&nbsp;Nian Fu ,&nbsp;Zhenguang Wang","doi":"10.1016/j.saa.2025.126347","DOIUrl":"10.1016/j.saa.2025.126347","url":null,"abstract":"<div><div>Developing a selective colorimetric assay for fluoroquinolones (FQs) that show visible color response is highly desired, which is challenging because FQs show extremely similarity in structure and inherently absorb light in the UV color range. In this work, a selective colorimetric assay for pefloxacin (PEF) was fabricated through integrating two rection systems: the inhibition effects of PEF on the AChE-like activities of Al³⁺ decorated MOF-808 (MOF-808-Al) and the thiol-response oxidase-mimicking reaction of MnO₂ nanosheets. The MnO₂ nanosheets, due to their oxidase-mimicking properties, can oxidize the colorless 3, 3′, 5, 5′-tetramethylbenzidine (TMB) into its blue-colored oxidized form, TMB⁺. Assisted by the synergistic action of metal–OH and Lewis acid sites, MOF-808-Al exhibits AChE-like activities. These activities catalyze the decomposition of acetylthiocholine into thiocholine. Thiocholine has a stronger reactivity compared to TMB; it can reduce the MnO₂ nanosheets, which in turn prevents the color response. In addition, PEF inhibits the AChE-like activities of MOF-808-Al by blocking its active sites. The quantitative detection of PEF is accomplished by recording the blue color response of the system, both in buffer solutions and in commercial meat samples. This assay demonstrates excellent tolerance and selectivity against various interfering substances, antibiotics, and pesticides.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126347"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143924701","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":"A novel ultrasensitive derivatization-free synchronous fluorescence approach for the simultaneous analysis of propofol and nalbuphine in human plasma and dosage forms: Compliance with greenness and blueness metrics","authors":"Mohamed A. El Hamd ,&nbsp;Galal Magdy ,&nbsp;Mahmoud El-Maghrabey ,&nbsp;Fotouh R. Mansour ,&nbsp;Lateefa A. Al-Khateeb ,&nbsp;Wael A. Mahdi ,&nbsp;Sultan Alshehri ,&nbsp;Bandar R. Alsehli ,&nbsp;Aya Saad Radwan","doi":"10.1016/j.saa.2025.126339","DOIUrl":"10.1016/j.saa.2025.126339","url":null,"abstract":"<div><div>This study presents a very sensitive and eco-friendly synchronous spectrofluorimetric method for the simultaneous quantification of propofol (PRP) and nalbuphine (NAL) for the first time. The technique used the intrinsic fluorescence characteristics of the two drugs, providing enhanced sensitivity and specificity. The two drugs were assessed simultaneously at 217 nm and 281 nm for PRP and NAL, respectively, with a synchronous wavelength difference (Δλ) of 80 nm. The proposed method was validated according to ICH Q2 (R2) requirements, exhibiting satisfactory accuracy, precision, linearity, and selectivity within the designated concentration ranges. The concentrations exhibited linearity within the ranges of 15.0–300.0 ng/mL and 0.5–16.0 µg/mL, with detection limits of 2.67 ng/mL and 0.15 µg/mL for PRP and NAL, respectively. The developed approach, owing to its great sensitivity, was utilized to assess the examined drugs in human plasma samples. The results demonstrated good bioanalytical applicability, exhibiting high recovery percentages (98.40–101.70) and low relative standard deviation (%RSD) values (&lt;1.66). The proposed method was applied to accurately analyze the cited drugs in their ampoule dosage forms with great selectivity. The MoGAPI and AGREE metrics<!--> <!-->demonstrated the method’s exceptional eco-friendliness and sustainability. Additionally, the BAGI tool was employed to assess the method’s economic viability, applicability, and practicality. The three tools demonstrated the sustainability and feasibility of the developed<!--> <!-->approach, as well as its appropriateness for the routine analysis of the examined drugs. The developed method represents the first analytical technique for the concurrent estimation of PRP and NAL without the necessity for toxic reagents, excessive organic solvents, or complicated instruments. The method is derivatization-free and does not require complicated sample treatment or lengthy extraction procedures. The suggested method’s excellent sensitivity, simplicity, speed, environmental friendliness, and cost-effectiveness make it appropriate for therapeutic drug monitoring of the studied drugs.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126339"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143924702","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":"An enzyme-free self-cascade catalytic dual-read biosensor for noninvasive detection of glucose based on oxidase-mimic Fe-MOF","authors":"Xiulin Wang ,&nbsp;Ziyi Guo ,&nbsp;Tao Lian ,&nbsp;Xiaomin Tang ,&nbsp;Ping Qiu","doi":"10.1016/j.saa.2025.126334","DOIUrl":"10.1016/j.saa.2025.126334","url":null,"abstract":"<div><div>Metal-organic framework (MOF) materials have attracted much attention in the glucose detection owing to their high porosity and diverse catalytic sites. In this study, we synthesized Fe-MOF material with both glucose oxidase (GOD) activity and peroxidase (POD)-like activity. Mechanistically, Fe-MOF with GOD activity catalyze decomposition of glucose into H₂O₂ and gluconic acid, which self-cascade catalysis catalyze H₂O₂ decomposition to yield hydroxyl radical (•OH) by means of POD activity. •OH can oxidize the chromogenic substrate o-phenylenediamine (OPD) to yellow product 2,3-diaminophenazine (DAP), which causes strong absorption of the UV visible spectrum at 450 nm. Concurrently, a distinct fluorescence emission peak emerges at 565 nm and the intrinsic fluorescence of Fe-MOF at 465 nm exhibits fluorescence resonance energy transfer (FRET)-mediated quenching. Therefore, a dual-read biosensor for the quantification of glucose was proposed based on Fe-MOF with the aid of colorimetric and ratiometric fluorescence signals of <em>I</em>₅₆₅/<em>I</em>₄₆₅. The LOD was as low as 0.71 μM and 0.69 μM, respectively. Satisfactory recovery and low relative standard deviation were achieved in real human saliva samples.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126334"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143918070","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":"Innovative application of confocal Raman spectroscopy and Machine learning in cardiovascular diseases identification","authors":"Renxing Song ,&nbsp;Xunyi Yin ,&nbsp;Manlin Zhu ,&nbsp;Xinyu Chen ,&nbsp;Jingqi Zhang ,&nbsp;Dongmei Liu ,&nbsp;Shimei Wang ,&nbsp;Shuang Jiang ,&nbsp;Zhehan Liu ,&nbsp;Lin Wang ,&nbsp;Kun Feng ,&nbsp;Yang Li","doi":"10.1016/j.saa.2025.126343","DOIUrl":"10.1016/j.saa.2025.126343","url":null,"abstract":"<div><div>Myocardial hypertrophy and heart failure are leading causes of mortality in cardiovascular diseases, yet current diagnostic techniques lack the resolution to monitor molecular changes effectively. In this study, we employed confocal Raman spectroscopy combined with machine learning to evaluate myocardial tissue in a transverse aortic constriction (TAC) mouse model. Mice were divided into three groups: control (CON), myocardial hypertrophy (TAC 2 W), and heart failure (TAC 4 W). The model was validated using echocardiography, histopathology, and transmission electron microscopy. Raman spectroscopy revealed significant changes in chemical composition, including decreased peak intensities at 748, 1309, 1584, 1170, 1359, 1222, 1636, 1335, and 1393 cm⁻¹, increased intensity at 2847 cm⁻¹, and a rightward shift of the peak at 2927 cm⁻¹, which correlated with disease progression. Machine learning analysis demonstrated that the random forest model achieved 85 % accuracy in classifying normal, hypertrophic, and failing myocardial tissues. This study highlights the potential of confocal Raman spectroscopy combined with machine learning for the identification and real-time monitoring of cardiovascular diseases, offering a novel approach to understanding disease mechanisms and improving patient outcomes. Although the model achieved high classification accuracy, the small sample size may limit generalizability and requires further validation in larger cohorts.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126343"},"PeriodicalIF":4.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143924750","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":"Binding activated single molecule burst analysis highlights amyloid sensing interaction of dye SYPRO orange","authors":"Vinu Namboodiri ,&nbsp;Aranyak Sarkar ,&nbsp;Manoj Kumbhakar","doi":"10.1016/j.saa.2025.126335","DOIUrl":"10.1016/j.saa.2025.126335","url":null,"abstract":"<div><div>Mode of interaction between fluorescent probe and local binding site on fibril architecture is central to the design of efficient amyloid sensors. SYPRO orange (SO) is reported to have two binding modes with two distinct binding configurations, namely weakly bound inclined and strongly bound surface hugging populations. Though two distinct sites for non-radiative relaxation, i.e. central π-bridge site and the electron donor amino site is evident from the molecular framework, it is unclear which site dictates fluorescence enhancement upon binding. We recommend employing the inherent sensitivity of fluorescence lifetime to alterations in non-radiative pathways for different binding configurations. In this contribution an attempt has been made to segregate binding activated single molecule bursts recorded with pulsed excitation into requisite weak and strong binding events, which were subsequently correlated with their corresponding excited state lifetimes. Comparison of fluorescence decays for these two binding modes suggest minor role of non-radiative relaxation at π-bridge site in deciding excited state decay of bound SO molecules. On the contrary, plausible hydrophobic interaction of aliphatic tails at the electron donor site with the fibril imparts configurational restrain at the amino group site, hindering its non-radiative pathways leading to increased fluorescence intensity and lifetime. This sensing behaviour of SO is consistent for fibrils of amyloidogenic proteins lysozyme and insulin. Present work has the relevance in the rational design of amyloid sensor as well as better super-resolution imaging probes for localization microscopy.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126335"},"PeriodicalIF":4.3,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911929","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":"Machine learning driven trace detection of pesticide mixtures using citrate optimized Au nanoparticles based in-expensive efficient micro-drop SERS with portable spectrometer","authors":"Shweta Verma ,&nbsp;Venkat Suprabath Bitra ,&nbsp;B. Tirumala Rao","doi":"10.1016/j.saa.2025.126333","DOIUrl":"10.1016/j.saa.2025.126333","url":null,"abstract":"<div><div>Machine learning (ML)-based surface-enhanced Raman scattering (SERS) spectra analysis has potential to determine the composition of analyte mixtures. The requirement for this task is to acquire spectral datasets from numerous sample matrices and experimental parameters, highlighting the need for an effective SERS technique. This study focuses on development of a cost-effective, straightforward sample preparation SERS technique using citrate-optimized gold nanoparticles (GNPs) attractive for portable spectrometers. Significance of optimal tri-sodium citrate (TSC) to gold precursor ratio and GNP characteristics, like aggregation and size, for maximum SERS signal enhancement is addressed. Additionally, the concentration dependence of SERS intensity variation was correlated to GNPs number-concentration predicted by Mie theory, and extent of analyte adsorption. Raster-scan measurements showed improvement in signal reproducibility. This approach yielded easy detection of about 250 nM and 1.25 µM for thiram and phosmet in beetroot juice, and 5 and 50 nM in water samples, respectively. Further, the potential benefit of this technique is demonstrated with ML based identification of composition of pesticide mixtures using unsupervised and supervised data dimensional reduction methods. For subtle variation spectral classes, effectiveness of five ML models is analyzed with data augmentation, normalization and different number of features and over 97 % classification accuracy is achieved. The study also addresses the principal component analysis for the identification of concentrations in both single and binary mixtures. This efficient SERS technique leverages 3D hot spots from aggregated GNPs of optimum TSC, provides a user-friendly platform to rapidly generate extensive spectral datasets for a variety of sample matrices and compositions at significantly low-cost. Consequently, it is well-suited for novice users, offering the potential for customized ML-driven application development.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126333"},"PeriodicalIF":4.3,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143918068","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 characterization of a solvatochromic urea-schiff base derivative: Investigating optical properties, hydrogen bonding effect, copper ion sensing, computational analysis, DNA and β-cyclodextrin interactions","authors":"Ibrahim A. Alhagri ,&nbsp;Sadeq M. Al-Hazmy ,&nbsp;Sarah S. Alammari ,&nbsp;Fahd M. Alminderej ,&nbsp;Sabri Messaoudi ,&nbsp;Lotfi M. Aroua","doi":"10.1016/j.saa.2025.126337","DOIUrl":"10.1016/j.saa.2025.126337","url":null,"abstract":"<div><div>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 (<em>β</em>-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.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126337"},"PeriodicalIF":4.3,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143918035","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":"Attenuated total reflection mid-infrared spectroscopy to screen Austrian and French wheat from multiple years for deoxynivalenol","authors":"Stephan Freitag ,&nbsp;Maximilian Anlanger ,&nbsp;Polina Fomina ,&nbsp;Antoni Femenias ,&nbsp;Miriam Aledda ,&nbsp;Boris Mizaikoff ,&nbsp;Achim Kohler ,&nbsp;Michael Sulyok ,&nbsp;Rudolf Krska","doi":"10.1016/j.saa.2025.126340","DOIUrl":"10.1016/j.saa.2025.126340","url":null,"abstract":"<div><div>The high-throughput capability of attenuated total reflection mid-infrared spectroscopy (ATR-MIRS) makes it a promising analytical technique for rapid and green mycotoxin screening. In ATR-MIRS, changes in samples induced by mycotoxigenic fungi are correlated with mycotoxin concentrations obtained through reference analysis. Due to its indirect nature, limited research has explored the applicability of this technique for complex sample sets. We demonstrate that ATR-MIRS can effectively screen for deoxynivalenol (DON) contamination in wheat samples collected across two countries over multiple years. A total of 320 naturally contaminated samples from Austria and France were analyzed to develop screening models. Partial least squares discriminant analysis (PLS-DA) was used to classify samples as compliant or non-compliant with the European Commission (EC) limit of 1000 µg/kg DON in unprocessed wheat. Model performance during repeated nested cross-validation exhibited a true positive rate ranging from 0.32 to 1. This variability was primarily influenced by sample splitting, as well as by dataset balancing and spectral preprocessing approaches. These findings underscore the critical importance of sample selection when developing chemometric models for mycotoxin screening. Analysis of variable importance in projection (VIP) scores revealed that classification into compliant or non-compliant is based on wavenumbers associated with dissolved proteins and carbohydrates in the MIRS spectra. Overall, our results demonstrate the feasibility of using ATR-MIRS to assess DON contamination in complex, multiyear wheat sample sets while adhering to regulatory limits. Additionally, this study highlights the potential of MIRS for investigating the effects of mycotoxigenic fungi on wheat composition during the development of DON screening models.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126340"},"PeriodicalIF":4.3,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143918069","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}