In the present work, numerous samples of motion picture films from different brands and spanning a wide chronological range were examined with the aim of studying their polymeric support materials using various vibrational spectroscopic techniques. The bases of the films investigated included cellulose nitrate, cellulose acetate, polyethylene terephthalate (PET), and cellophane, the support material of the unique Ozaphan films. Regarding Fourier-transform infrared (FTIR) spectroscopy, the external reflection (ER) technique was employed, both in the mid-infrared (MIR) range and in the longer-wavelength portion of the near-infrared (NIR) region. For Raman spectroscopy, the sequentially shifted excitation (SSE™) technique was used to minimize issues related to potential fluorescence emission. The information provided by each technique was carefully considered, particularly in terms of penetration depth and specificity towards certain molecular structures. Furthermore, diffuse reflectance spectroscopy in the entire NIR range was combined with partial least squares (PLS) regression of the spectral data to estimate the degree of substitution (DS) of the polymer in cellulose acetate bases. This parameter is influenced both by the historical period in which the films were produced and possibly by degradation phenomena.
{"title":"Vibrational spectroscopy as a tool for the investigation of polymer bases in motion picture films: A comparison between mid-infrared, near-infrared and Raman techniques","authors":"Alessia Buttarelli , Margherita Longoni , Valentina Rossetto , Silvia Bruni","doi":"10.1016/j.vibspec.2025.103818","DOIUrl":"10.1016/j.vibspec.2025.103818","url":null,"abstract":"<div><div>In the present work, numerous samples of motion picture films from different brands and spanning a wide chronological range were examined with the aim of studying their polymeric support materials using various vibrational spectroscopic techniques. The bases of the films investigated included cellulose nitrate, cellulose acetate, polyethylene terephthalate (PET), and cellophane, the support material of the unique Ozaphan films. Regarding Fourier-transform infrared (FTIR) spectroscopy, the external reflection (ER) technique was employed, both in the mid-infrared (MIR) range and in the longer-wavelength portion of the near-infrared (NIR) region. For Raman spectroscopy, the sequentially shifted excitation (SSE™) technique was used to minimize issues related to potential fluorescence emission. The information provided by each technique was carefully considered, particularly in terms of penetration depth and specificity towards certain molecular structures. Furthermore, diffuse reflectance spectroscopy in the entire NIR range was combined with partial least squares (PLS) regression of the spectral data to estimate the degree of substitution (DS) of the polymer in cellulose acetate bases. This parameter is influenced both by the historical period in which the films were produced and possibly by degradation phenomena.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103818"},"PeriodicalIF":2.7,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144185095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-30DOI: 10.1016/j.vibspec.2025.103813
Akira Yoshihara , Tomoki Karasawa
We performed a series of Fourier Transform infrared (FT-IR) studies on Late Cretaceous Kuji and Iwaki ambers from the Tohoku region, Late Cretaceous Pombetsu and Manji ambers and Eocene Sunago ambers from Mikasa area in the Hokkaido region, and Eocene ambers from Fushun in China. Based on spectral features and principal component scores, these FT-IR spectra could be successfully classified into three groups: Kuji and Iwaki ambers, Pombetsu and Manji ambers, and Sunago and Fushun ambers, respectively. This grouping reflects the fact that amber-forming forests are the same or closely related species within the group, but different among the groups. Geological surveys on the Upper Cretaceous Yezo Group around the Mikasa area indicate that the Pombetsu ambers were reburied in terrestrial environments about 4 million years earlier than the Manji ambers buried in shallow marine deposits. The Late Cretaceous ambers from the Mikasa Formation frequently contain various concentrations of calcite, and their FT-IR spectra are quite different from the Kuji and Iwaki ambers which are free from calcite. These observations strongly suggest different amber-forming environments between the Tohoku and Hokkaido regions in the Late Cretaceous. In contrast, high similarities of FT-IR spectra between Sunago and Fushun ambers suggest the same or similar amber-forming environments in the Eocene near the eastern end of the Eurasian plate. Although the current geographical distance between Sunago and Fushun is about 1500 km, the distance was much closer in the Eocene before the establishment of the Sea of Japan.
{"title":"FT-IR study on ambers produced from the Tohoku and Hokkaido regions in Japan","authors":"Akira Yoshihara , Tomoki Karasawa","doi":"10.1016/j.vibspec.2025.103813","DOIUrl":"10.1016/j.vibspec.2025.103813","url":null,"abstract":"<div><div>We performed a series of Fourier Transform infrared (FT-IR) studies on Late Cretaceous Kuji and Iwaki ambers from the Tohoku region, Late Cretaceous Pombetsu and Manji ambers and Eocene Sunago ambers from Mikasa area in the Hokkaido region, and Eocene ambers from Fushun in China. Based on spectral features and principal component scores, these FT-IR spectra could be successfully classified into three groups: Kuji and Iwaki ambers, Pombetsu and Manji ambers, and Sunago and Fushun ambers, respectively. This grouping reflects the fact that amber-forming forests are the same or closely related species within the group, but different among the groups. Geological surveys on the Upper Cretaceous Yezo Group around the Mikasa area indicate that the Pombetsu ambers were reburied in terrestrial environments about 4 million years earlier than the Manji ambers buried in shallow marine deposits. The Late Cretaceous ambers from the Mikasa Formation frequently contain various concentrations of calcite, and their FT-IR spectra are quite different from the Kuji and Iwaki ambers which are free from calcite. These observations strongly suggest different amber-forming environments between the Tohoku and Hokkaido regions in the Late Cretaceous. In contrast, high similarities of FT-IR spectra between Sunago and Fushun ambers suggest the same or similar amber-forming environments in the Eocene near the eastern end of the Eurasian plate. Although the current geographical distance between Sunago and Fushun is about 1500 km, the distance was much closer in the Eocene before the establishment of the Sea of Japan.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103813"},"PeriodicalIF":2.7,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144263009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-29DOI: 10.1016/j.vibspec.2025.103814
M.J. Madito
Graphene-based materials, including composites with metals, metal oxides, or polymers, demonstrate enhanced vibrational, electronic, and mechanical properties, rendering them highly promising for applications in energy, sensing, and catalysis. Vibrational spectroscopy is extensively used to characterize these materials, with primary focus on the G band (first-order in-plane vibrational band), the 2D band (second-order overtone), and the defect-activated D band. Although the D band frequently appears in chemically modified or structurally complex graphene systems, its spectral characteristics, such as peak position, linewidth, and relative intensity, alongside variations in the G and 2D bands, are often underreported or inadequately interpreted. This review underscores the critical importance of the D band in assessing disorder, edge structure, doping, and matrix interactions within graphene-based materials. Revisiting the role of the D band in conjunction with the G and 2D bands highlights the necessity for a more comprehensive vibrational analysis framework to accurately evaluate structural perturbations and interfacial effects in graphene-based materials.
{"title":"Revisiting the Raman disorder band in graphene-based materials: A critical review","authors":"M.J. Madito","doi":"10.1016/j.vibspec.2025.103814","DOIUrl":"10.1016/j.vibspec.2025.103814","url":null,"abstract":"<div><div>Graphene-based materials, including composites with metals, metal oxides, or polymers, demonstrate enhanced vibrational, electronic, and mechanical properties, rendering them highly promising for applications in energy, sensing, and catalysis. Vibrational spectroscopy is extensively used to characterize these materials, with primary focus on the G band (first-order in-plane vibrational band), the 2D band (second-order overtone), and the defect-activated D band. Although the D band frequently appears in chemically modified or structurally complex graphene systems, its spectral characteristics, such as peak position, linewidth, and relative intensity, alongside variations in the G and 2D bands, are often underreported or inadequately interpreted. This review underscores the critical importance of the D band in assessing disorder, edge structure, doping, and matrix interactions within graphene-based materials. Revisiting the role of the D band in conjunction with the G and 2D bands highlights the necessity for a more comprehensive vibrational analysis framework to accurately evaluate structural perturbations and interfacial effects in graphene-based materials.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103814"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144205596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-28DOI: 10.1016/j.vibspec.2025.103815
Larissa F. Torres , Marilia R. Oliveira , Thales C.S. Barbalho , Cláudio Dariva , Gustavo R. Borges , Papa M. Ndiaye , Frederico W. Tavares
The use of Near Infrared Spectroscopy (NIRS) has a significant potential to enable the detection and quantification of natural gas components (e.g., CH4, CO2, moisture). It offers a quick, non-invasive, and non-destructive approach, eliminating the challenges associated with traditional sampling methods. Here, we investigated the applicability of the NIR technique to perform accurate quantification of water content and compositional analysis regarding CH4 and CO2 in compressed systems. The system’s pressure is also considered a response variable. The spectra collection was made at room temperature (298.15 K), with pressures up to 120 bar and CO2 concentrations varying from 0 % to 50 % of the total composition. The Partial Least Squares (PLS) was used as the regression method, and the Quartz Crystal Microbalance (QCM) as the reference technique for water content. The PLS models yielded high accuracy, with R² values of 0.990 for CH₄, 0.993 for CO₂, and 0.947 for H₂O, with RMSEP values of 4.43 %, 3.55 %, and 8.35 %, respectively. Although water estimation showed slightly higher deviation, it remained within the experimental uncertainty range of the QCM reference. These results confirm the feasibility of applying NIRS for real-time, multi-component gas analysis in industrial settings
{"title":"The use of NIR spectroscopy for the quantification of water content and compositional analysis in compressed gas-systems","authors":"Larissa F. Torres , Marilia R. Oliveira , Thales C.S. Barbalho , Cláudio Dariva , Gustavo R. Borges , Papa M. Ndiaye , Frederico W. Tavares","doi":"10.1016/j.vibspec.2025.103815","DOIUrl":"10.1016/j.vibspec.2025.103815","url":null,"abstract":"<div><div>The use of Near Infrared Spectroscopy (NIRS) has a significant potential to enable the detection and quantification of natural gas components (e.g., CH<sub>4</sub>, CO<sub>2</sub>, moisture). It offers a quick, non-invasive, and non-destructive approach, eliminating the challenges associated with traditional sampling methods. Here, we investigated the applicability of the NIR technique to perform accurate quantification of water content and compositional analysis regarding CH<sub>4</sub> and CO<sub>2</sub> in compressed systems. The system’s pressure is also considered a response variable. The spectra collection was made at room temperature (298.15 K), with pressures up to 120 bar and CO<sub>2</sub> concentrations varying from 0 % to 50 % of the total composition. The Partial Least Squares (PLS) was used as the regression method, and the Quartz Crystal Microbalance (QCM) as the reference technique for water content. The PLS models yielded high accuracy, with R² values of 0.990 for CH₄, 0.993 for CO₂, and 0.947 for H₂O, with RMSEP values of 4.43 %, 3.55 %, and 8.35 %, respectively. Although water estimation showed slightly higher deviation, it remained within the experimental uncertainty range of the QCM reference. These results confirm the feasibility of applying NIRS for real-time, multi-component gas analysis in industrial settings</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103815"},"PeriodicalIF":2.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144169254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-28DOI: 10.1016/j.vibspec.2025.103816
Seung-Hyun Im , Mohammad Akbar Faqeerzada , Byoung-Kwan Cho , Geonwoo Kim , Hoonsoo Lee
Soil volumetric water content (SVWC) is a critical factor in plant health, influencing water uptake, nutrient transport, and overall physiological performance. Adverse environmental conditions like drought and high temperatures challenge crop growth and reduce yields. Accurate monitoring of SVWC is essential for optimizing growing conditions, preventing water stress, and promoting sustainable agriculture. This study explores a non-destructive method for predicting SVWC in Chinese cabbage seedlings using short-wave infrared (SWIR, 894–2504 nm) hyperspectral imaging coupled with machine learning. Daily hyperspectral images and corresponding SVWC measurements were collected over three days following irrigation cessation, resulting in a dataset of 2700 spectra. Gaussian process regression (GPR) and support vector regression (SVR) models were applied, with Lasso and Ridge regression used for feature selection. The models were evaluated using all spectral bands (E164) and 30 selected bands (L30 and R30). The GPR model with Lasso-selected bands and smoothing preprocessing achieved the highest accuracy (R² = 0.87, RMSE = 1.33). The SVR model with smoothing preprocessing and the entire spectral range demonstrated R² = 0.82 and RMSE = 1.52. Multivariate regression models using 14 shared bands selected by Lasso and Ridge regression yielded moderate performance (R² = 0.67, RMSE = 2.07). These findings highlight the potential of hyperspectral imaging combined with machine learning for non-destructive SVWC prediction, enabling early crop detection of water stress.
{"title":"Optimized feature selection and machine learning for non-destructive estimation of soil volumetric water content in Chinese cabbage using hyperspectral imaging","authors":"Seung-Hyun Im , Mohammad Akbar Faqeerzada , Byoung-Kwan Cho , Geonwoo Kim , Hoonsoo Lee","doi":"10.1016/j.vibspec.2025.103816","DOIUrl":"10.1016/j.vibspec.2025.103816","url":null,"abstract":"<div><div>Soil volumetric water content (SVWC) is a critical factor in plant health, influencing water uptake, nutrient transport, and overall physiological performance. Adverse environmental conditions like drought and high temperatures challenge crop growth and reduce yields. Accurate monitoring of SVWC is essential for optimizing growing conditions, preventing water stress, and promoting sustainable agriculture. This study explores a non-destructive method for predicting SVWC in Chinese cabbage seedlings using short-wave infrared (SWIR, 894–2504 nm) hyperspectral imaging coupled with machine learning. Daily hyperspectral images and corresponding SVWC measurements were collected over three days following irrigation cessation, resulting in a dataset of 2700 spectra. Gaussian process regression (GPR) and support vector regression (SVR) models were applied, with Lasso and Ridge regression used for feature selection. The models were evaluated using all spectral bands (E164) and 30 selected bands (L30 and R30). The GPR model with Lasso-selected bands and smoothing preprocessing achieved the highest accuracy (R² = 0.87, RMSE = 1.33). The SVR model with smoothing preprocessing and the entire spectral range demonstrated R² = 0.82 and RMSE = 1.52. Multivariate regression models using 14 shared bands selected by Lasso and Ridge regression yielded moderate performance (R² = 0.67, RMSE = 2.07). These findings highlight the potential of hyperspectral imaging combined with machine learning for non-destructive SVWC prediction, enabling early crop detection of water stress.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103816"},"PeriodicalIF":2.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144190377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-21DOI: 10.1016/j.vibspec.2025.103812
Zhonghai He , Haoxiang Zhang , Yi Zhang , Xiaofang Zhang
Spectroscopy are widely used in routine concentration measurement. However, when spectral measurement is carried out in process industry, the measurement environment often changes thus the prediction accuracy of the regression model is spoiled. Existing studies regard the measurement environment change as noise, but in fact, the measurement environment also contains useful information. In this paper, a modeling method is proposed to augment the measured environmental parameters (physical quantities) into the calibration modeling to improve the prediction accuracy. To solve the problem of physical quantity parameters being overridden caused by direct variable extension method, we use the data fusion method based on sample similarity. Gaussian kernel function is used to calculate the similarity matrix of spectral and physical quantities respectively. Then fusion matrix is obtained by weighting combination. Finally, the regression model of fusion matrix and concentration is established by standard PLS modeling method. A regression model is established for the data collected during the fermentation process. The results showed that the prediction performance of the model could be improved by nearly 10 % by adding physical quantity information.
{"title":"Similarity based spectral data fusion physical parameter regression modeling method","authors":"Zhonghai He , Haoxiang Zhang , Yi Zhang , Xiaofang Zhang","doi":"10.1016/j.vibspec.2025.103812","DOIUrl":"10.1016/j.vibspec.2025.103812","url":null,"abstract":"<div><div>Spectroscopy are widely used in routine concentration measurement. However, when spectral measurement is carried out in process industry, the measurement environment often changes thus the prediction accuracy of the regression model is spoiled. Existing studies regard the measurement environment change as noise, but in fact, the measurement environment also contains useful information. In this paper, a modeling method is proposed to augment the measured environmental parameters (physical quantities) into the calibration modeling to improve the prediction accuracy. To solve the problem of physical quantity parameters being overridden caused by direct variable extension method, we use the data fusion method based on sample similarity. Gaussian kernel function is used to calculate the similarity matrix of spectral and physical quantities respectively. Then fusion matrix is obtained by weighting combination. Finally, the regression model of fusion matrix and concentration is established by standard PLS modeling method. A regression model is established for the data collected during the fermentation process. The results showed that the prediction performance of the model could be improved by nearly 10 % by adding physical quantity information.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103812"},"PeriodicalIF":2.7,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-20DOI: 10.1016/j.vibspec.2025.103811
Jiawei Ma , Shizheng Zhang , Rui Cheng , Chang Zhao , Xiaoli Zhu , Peng Du , Xiaolei Wang , Huinan Yang
Ulcerative colitis (UC) is a type of inflammatory bowel disease (IBD), which can be diagnosed by a combination of invasive endoscopy, clinical examination and histopathology. However, Crohn's disease (CD), as another subtype of IBD, exhibits similar clinical and pathological manifestations to UC. This usually leads to delayed diagnosis of UC and increases the possibility of conversion to colorectal cancer. Moreover, it is difficult to distinguish patients with UC from healthy controls (HC) in early diagnosis. Therefore, it is very important to accurately distinguish IBD subtypes and early identification of UC patients and HC in clinical practice. In this work, surface-enhanced Raman spectroscopy (SERS) was used to measure urine samples from 166 IBD patients (including 83 UC and 83 CD) and 83 HC, totaling 249 samples. It shows that there are significant differences in the intensities at several main Raman peaks between UC and CD, as well as between UC and HC. Then, classification models based on principal component analysis (PCA) were constructed for UC/CD and UC/HC to reduce the dimensionality of the dataset, followed by analysis of the reduced-dimension samples using the constructed support vector machine (SVM) models. After the leave-one-out cross-validation (LOOCV), the UC/CD classification model achieved an accuracy of 72.89 %, sensitivity of 67.47 %, and specificity of 78.31 %, while the UC/HC classification model achieved 82.53 %, 90.36 %, and 74.70 % respectively for these metrics. Therefore, this indicates that SERS, based on urine samples combined with PCA and SVM analysis techniques, can effectively identify IBD subtypes and accurately diagnose UC patients from HC patients, greatly facilitating the clinical diagnosis process. The application of this method has great potential to achieve non-invasive early diagnosis of UC, thereby providing more timely and effective treatment strategies for patients.
{"title":"Early diagnosis of ulcerative colitis based on urine SERS and multivariate analysis","authors":"Jiawei Ma , Shizheng Zhang , Rui Cheng , Chang Zhao , Xiaoli Zhu , Peng Du , Xiaolei Wang , Huinan Yang","doi":"10.1016/j.vibspec.2025.103811","DOIUrl":"10.1016/j.vibspec.2025.103811","url":null,"abstract":"<div><div>Ulcerative colitis (UC) is a type of inflammatory bowel disease (IBD), which can be diagnosed by a combination of invasive endoscopy, clinical examination and histopathology. However, Crohn's disease (CD), as another subtype of IBD, exhibits similar clinical and pathological manifestations to UC. This usually leads to delayed diagnosis of UC and increases the possibility of conversion to colorectal cancer. Moreover, it is difficult to distinguish patients with UC from healthy controls (HC) in early diagnosis. Therefore, it is very important to accurately distinguish IBD subtypes and early identification of UC patients and HC in clinical practice. In this work, surface-enhanced Raman spectroscopy (SERS) was used to measure urine samples from 166 IBD patients (including 83 UC and 83 CD) and 83 HC, totaling 249 samples. It shows that there are significant differences in the intensities at several main Raman peaks between UC and CD, as well as between UC and HC. Then, classification models based on principal component analysis (PCA) were constructed for UC/CD and UC/HC to reduce the dimensionality of the dataset, followed by analysis of the reduced-dimension samples using the constructed support vector machine (SVM) models. After the leave-one-out cross-validation (LOOCV), the UC/CD classification model achieved an accuracy of 72.89 %, sensitivity of 67.47 %, and specificity of 78.31 %, while the UC/HC classification model achieved 82.53 %, 90.36 %, and 74.70 % respectively for these metrics. Therefore, this indicates that SERS, based on urine samples combined with PCA and SVM analysis techniques, can effectively identify IBD subtypes and accurately diagnose UC patients from HC patients, greatly facilitating the clinical diagnosis process. The application of this method has great potential to achieve non-invasive early diagnosis of UC, thereby providing more timely and effective treatment strategies for patients.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103811"},"PeriodicalIF":2.7,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144124309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study evaluates the accuracy and convergence of 12 DFT quadrature grid combinations for computing potential energy surfaces (PESs) to address quantum anharmonic vibrational spectra. The grids, ranging from 23 to 300 radial and 170 to 1202 angular points, are tested with widely used six DFT functionals (B3LYP-D, PBE0-D, B3PW91-D, B98-D, ωB97X-D, M06–2X) using def2-type triple-ξ basis sets. The computed anharmonic transitions for fundamentals and overtones along with the intensities are benchmarked using vibrational self-consistent field (VSCF) and its second-order perturbative corrected (VSCF-PT2) algorithms across different molecules, against the reference/largest grid (300,1202). While the smallest grid (23,170) had significant deviations, the largest grid is accurate but computationally expensive. Moderate grids like 75,302 achieved excellent accuracy with lower CPU demands, making them ideal for large molecules, while 75,590 is preferred for flexible systems. Furthermore, the angular grid has a greater impact on the accuracy of computed spectra than the radial grid.
{"title":"Accuracy of DFT quadrature grids for the computation of quantum anharmonic vibrational spectroscopy","authors":"Dhiksha Sharma , Jyoti Devi , Avantika Sharma , Mokshi Sharma , Meenakshi Raina , Akriti Jamwal , Tapta Kanchan Roy","doi":"10.1016/j.vibspec.2025.103810","DOIUrl":"10.1016/j.vibspec.2025.103810","url":null,"abstract":"<div><div>This study evaluates the accuracy and convergence of 12 DFT quadrature grid combinations for computing potential energy surfaces (PESs) to address quantum anharmonic vibrational spectra. The grids, ranging from 23 to 300 radial and 170 to 1202 angular points, are tested with widely used six DFT functionals (B3LYP-D, PBE0-D, B3PW91-D, B98-D, ωB97X-D, M06–2X) using def2-type triple-ξ basis sets. The computed anharmonic transitions for fundamentals and overtones along with the intensities are benchmarked using vibrational self-consistent field (VSCF) and its second-order perturbative corrected (VSCF-PT2) algorithms across different molecules, against the reference/largest grid (300,1202). While the smallest grid (23,170) had significant deviations, the largest grid is accurate but computationally expensive. Moderate grids like 75,302 achieved excellent accuracy with lower CPU demands, making them ideal for large molecules, while 75,590 is preferred for flexible systems. Furthermore, the angular grid has a greater impact on the accuracy of computed spectra than the radial grid.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"139 ","pages":"Article 103810"},"PeriodicalIF":2.7,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144068182","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01DOI: 10.1016/j.vibspec.2025.103807
Chun Li , Yanan Lu , Shengzhu Fu, Yulong Guo, Zhengwei Huang, Lei Wen, Ling Jiang
With the increased awareness of food safety, rapid, accurate, and non-destructive detection of pesticide residues on fruit peels has attracted widespread attention. In this work, we utilize the attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to directly detect multiple pesticide residues (including carbendazim, thiophanate-methyl, and thiabendazole) on the surface of the apple peels. To further improve the efficiency of detection and meet the practical application needs, a multi-task learning (MTL) model based on multi-task neural networks is introduced to perform qualitative and quantitative analysis of three pesticides, simultaneously. The optimal results in the testing set demonstrate an average accuracy of 100 % for the qualitative task, while the average R2 of 0.9415 and root mean square error (RMSE) of 2.567 μg/cm2 can be achieved in the quantitative task. The limit of detection (LOD) of carbendazim, thiophanate-methyl, and thiabendazole were determined as 7.308 μg/cm2, 1.595 μg/cm2 and 0.159 μg/cm2, respectively. Compared with the traditional single-task model, our work greatly simplifies the complexity of pesticide detection while ensuring prediction accuracy, which offers an alternative approach for further deployment and operation of the on-site system.
{"title":"Simultaneous qualitative and quantitative analyses of pesticide residues on fruit peels with ATR-FTIR spectroscopy and multi-task learning","authors":"Chun Li , Yanan Lu , Shengzhu Fu, Yulong Guo, Zhengwei Huang, Lei Wen, Ling Jiang","doi":"10.1016/j.vibspec.2025.103807","DOIUrl":"10.1016/j.vibspec.2025.103807","url":null,"abstract":"<div><div>With the increased awareness of food safety, rapid, accurate, and non-destructive detection of pesticide residues on fruit peels has attracted widespread attention. In this work, we utilize the attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to directly detect multiple pesticide residues (including carbendazim, thiophanate-methyl, and thiabendazole) on the surface of the apple peels. To further improve the efficiency of detection and meet the practical application needs, a multi-task learning (MTL) model based on multi-task neural networks is introduced to perform qualitative and quantitative analysis of three pesticides, simultaneously. The optimal results in the testing set demonstrate an average accuracy of 100 % for the qualitative task, while the average R<sup>2</sup> of 0.9415 and root mean square error (RMSE) of 2.567 μg/cm<sup>2</sup> can be achieved in the quantitative task. The limit of detection (LOD) of carbendazim, thiophanate-methyl, and thiabendazole were determined as 7.308 μg/cm<sup>2</sup>, 1.595 μg/cm<sup>2</sup> and 0.159 μg/cm<sup>2</sup>, respectively. Compared with the traditional single-task model, our work greatly simplifies the complexity of pesticide detection while ensuring prediction accuracy, which offers an alternative approach for further deployment and operation of the on-site system.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"138 ","pages":"Article 103807"},"PeriodicalIF":2.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01DOI: 10.1016/j.vibspec.2025.103808
Ying Wang , Shouqi Zhang , Xiaowen Kong , Zhengren Xu , Zhiqiang Wang , Ruiting Zhang , Lin Ma , Ke Lin
Isoprenol has important applications in both biological and medical fields, and the measurement of its structure in living organisms is very important to understand the mechanism of its role at the molecular level. We synthesized five kinds of deuterated isoprenols, and optimized structure of the deuterated rotational isomers by quantum chemical calculations, and calculated and record the Raman spectra of all the deuterated isoprenols. These experimental and theoretical results suggest that the stretching vibrational spectra of individual C-D bonds in deuterated methylene and methanediyl group can be used to identify the conformers of isoprenol. This work not only analyzed the correlation between the structure of isoprenol and the spectra of this particular deuterated molecule, but also demonstrates the potential of combining this novel method with other techniques, such as X-ray diffraction, to obtain more precise molecular structures in complex environments.
{"title":"Identification of the isoprenols conformers by the Raman spectra of the deuterated compounds in the C-D stretching region","authors":"Ying Wang , Shouqi Zhang , Xiaowen Kong , Zhengren Xu , Zhiqiang Wang , Ruiting Zhang , Lin Ma , Ke Lin","doi":"10.1016/j.vibspec.2025.103808","DOIUrl":"10.1016/j.vibspec.2025.103808","url":null,"abstract":"<div><div>Isoprenol has important applications in both biological and medical fields, and the measurement of its structure in living organisms is very important to understand the mechanism of its role at the molecular level. We synthesized five kinds of deuterated isoprenols, and optimized structure of the deuterated rotational isomers by quantum chemical calculations, and calculated and record the Raman spectra of all the deuterated isoprenols. These experimental and theoretical results suggest that the stretching vibrational spectra of individual C-D bonds in deuterated methylene and methanediyl group can be used to identify the conformers of isoprenol. This work not only analyzed the correlation between the structure of isoprenol and the spectra of this particular deuterated molecule, but also demonstrates the potential of combining this novel method with other techniques, such as X-ray diffraction, to obtain more precise molecular structures in complex environments.</div></div>","PeriodicalId":23656,"journal":{"name":"Vibrational Spectroscopy","volume":"138 ","pages":"Article 103808"},"PeriodicalIF":2.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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