Journal of Raman Spectroscopy最新文献

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Serum Raman Spectroscopy Explorations in Canine Cancers: A Pilot Study 血清拉曼光谱在犬癌中的探索:一项初步研究
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2025-01-07 DOI: 10.1002/jrs.6760
Panchali Saha, Debosmita Goswami, Arti Hole, Kiran Bendale, Pradip Chaudhari, C. Murali Krishna
{"title":"Serum Raman Spectroscopy Explorations in Canine Cancers: A Pilot Study","authors":"Panchali Saha,&nbsp;Debosmita Goswami,&nbsp;Arti Hole,&nbsp;Kiran Bendale,&nbsp;Pradip Chaudhari,&nbsp;C. Murali Krishna","doi":"10.1002/jrs.6760","DOIUrl":"https://doi.org/10.1002/jrs.6760","url":null,"abstract":"<div>\u0000 \u0000 <p>The examination of canine cancers has garnered substantial attention in recent years. This is primarily because of the parallel between dogs and humans in the development of spontaneous cancers without the need for experimental induction, unlike in laboratory rodents. Numerous studies have explored the utility of canine subjects in the advancement of our understanding of cancers, recognizing their potential as valuable natural models. A particularly noteworthy diagnostic tool in this context is serum Raman spectroscopy (RS), a method known for its minimally invasive, label-free, rapid, and objective nature, with a wide range of applications that extends to various diseases, including cancer. In this study, serum RS was explored for canine cancers, potentially offering a novel approach to the field of veterinary oncology. This investigation included 12 healthy dogs (C) and 38 companion dogs afflicted with an array of malignancies (T), including 18 carcinomas, 9 sarcomas, 3 head and neck tumors, 2 mast cell tumors, and 1 venereal granuloma. Serum was separated from the blood samples collected and subjected to RS, followed by spectral preprocessing and multivariate analyses. Multivariate curve resolution-alternating least squares revealed alterations in nucleic acids, lipids, and proteins among the groups. Principal component-based linear discriminant analysis (PC-LDA) results demonstrated correct identification of 73% of the C and 87% of the T samples. The outcomes of this study highlight the efficacy of serum RS in the detection of canine cancers. Comprehensive large-scale studies involving diverse cancer types are imperative to validate findings.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 4","pages":"301-306"},"PeriodicalIF":2.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143809512","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}
引用次数: 0
Serum Exosome SERS Assay Based on TiN-Ag@Ag Sol Composite Substrate and Its Application in the Diagnosis of Gastric Cancer 基于TiN-Ag@Ag溶胶复合底物的血清外泌体SERS检测及其在胃癌诊断中的应用
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-30 DOI: 10.1002/jrs.6767
Huan Wang, Zhengang Wu, Yingna Wei, Ying Chen, Xiao jie An, Jingwu Li, Zhiwu Wang, Yankun Liu, Hengyong Wei
{"title":"Serum Exosome SERS Assay Based on TiN-Ag@Ag Sol Composite Substrate and Its Application in the Diagnosis of Gastric Cancer","authors":"Huan Wang,&nbsp;Zhengang Wu,&nbsp;Yingna Wei,&nbsp;Ying Chen,&nbsp;Xiao jie An,&nbsp;Jingwu Li,&nbsp;Zhiwu Wang,&nbsp;Yankun Liu,&nbsp;Hengyong Wei","doi":"10.1002/jrs.6767","DOIUrl":"https://doi.org/10.1002/jrs.6767","url":null,"abstract":"<div>\u0000 \u0000 <p>Gastric cancer (GC) is a highly lethal malignancy, seriously threatening people's physical health. Accurate screening of gastric cancer could improve the survival rate of patients. Therefore, exploring noninvasive and efficient cancer screening methods for gastric cancer is of great significance. In the past few years, exosomes have received much attention for their potential in disease diagnosis and treatment. Here, the aim of this study was to explore the detection of serum exosomes via surface-enhanced Raman spectroscopy (SERS) technique based on TiN-Ag@Ag sol composite substrate, and its potential application in gastric cancer diagnosis is evaluated. Exosomes were extracted from the serum of 31 GC patients and 31 healthy controls (HC) using an exosome kit. This study used various machine learning algorithms such as principal component analysis linear discriminant analysis (PCA-LDA), partial least squares discriminant analysis (PLS-DA), support vector machine (SVM), and k-nearest neighbor (KNN) algorithm to analyze SERS spectra, in order to distinguish between HC and GC. The results show that the k-nearest neighbor algorithm performs the best in HC and GC classification. These results indicate that the combination of SERS and machine learning methods provides a new technological approach for gastric cancer screening. This study offers a new proposal for the universal applicability of analysis and identification with SERS of serum exosomes samples in clinical diagnosis.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 4","pages":"307-315"},"PeriodicalIF":2.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143809965","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}
引用次数: 0
Avoiding Overestimation and the ‘Black Box’ Problem in Biofluids Multivariate Analysis by Raman Spectroscopy: Interpretation and Transparency With the SP-LIME Algorithm 避免高估和“黑箱”问题在生物流体多变量分析拉曼光谱:解释和透明度与SP-LIME算法
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-29 DOI: 10.1002/jrs.6764
Lyudmila A. Bratchenko, Ivan A. Bratchenko
{"title":"Avoiding Overestimation and the ‘Black Box’ Problem in Biofluids Multivariate Analysis by Raman Spectroscopy: Interpretation and Transparency With the SP-LIME Algorithm","authors":"Lyudmila A. Bratchenko,&nbsp;Ivan A. Bratchenko","doi":"10.1002/jrs.6764","DOIUrl":"https://doi.org/10.1002/jrs.6764","url":null,"abstract":"<div>\u0000 \u0000 <p>Raman spectroscopy, in combination with multivariate analysis, is a powerful analytical tool for solving regression and classification problems in various fields—from materials science to clinical practice. However, in practical applications, experimental studies and the implementation of Raman spectroscopy present numerous challenges, including multicollinearity in spectral data and the ‘black box’ problem of complex analytical models. To avoid these problems, the proposed classification and regression models require proper interpretation. This study makes use of a comparative analysis of explanation methods based on the SP-LIME (local interpretable model-agnostic explanations with submodular pick) algorithm of a bilinear model (projection onto latent structures [PLS]) and a nonlinear model (one-dimensional convolutional neural network [CNN]). The models to be interpreted are trained to solve the regression task of the blood serum Raman characteristics and the urea levels. Effective SP-LIME evaluation of the blood Raman spectra revealed that in urea analysis for both PLS and CNN models, the important band is at 1003 cm<sup>−1</sup>. This approach is based on the value of the root mean square error estimation only when a single Raman band is analyzed. The aim of this paper is to develop an approach to explain the operation of the analytical models and provides the way to reveal the exact Raman bands with the biggest impact on the model performance.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 4","pages":"353-364"},"PeriodicalIF":2.4,"publicationDate":"2024-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143809925","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}
引用次数: 0
On-Site Raman and XRF Study of Complex Metal Patinas and Cloisonné Enamels From 19th-Century Christofle Masterpieces: Technological Study of the Decoration Techniques 19世纪克里斯托弗杰作中复杂金属铜绿和景泰蓝珐琅的现场拉曼和XRF研究:装饰技术的技术研究
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-29 DOI: 10.1002/jrs.6761
Julie Schröter, Philippe Colomban, Michel Bouchard, Ludovic Bellot-Gurlet, Audrey Gay-Mazuel
{"title":"On-Site Raman and XRF Study of Complex Metal Patinas and Cloisonné Enamels From 19th-Century Christofle Masterpieces: Technological Study of the Decoration Techniques","authors":"Julie Schröter,&nbsp;Philippe Colomban,&nbsp;Michel Bouchard,&nbsp;Ludovic Bellot-Gurlet,&nbsp;Audrey Gay-Mazuel","doi":"10.1002/jrs.6761","DOIUrl":"https://doi.org/10.1002/jrs.6761","url":null,"abstract":"<p>A major effort in technological development was conducted during the 19th century. The polychrome surfaces of the metal parts of a corner cabinet, a torch vase, an “elephant” vase, and a candelabra pair designed by Emile Reiber between 1874 and 1878 for the Christofle &amp; Cie Company were investigated on site by means of noninvasive Raman, FTIR, and X-ray fluorescence spectroscopy after examination under white light at different magnifications and under UV illumination. Despite the low thickness of the patinas (a few tens of microns) different (electro)chemically formed phases were identified in these layers (Cu<sub>2</sub>O, Ag<sub>2</sub>S, CuS or Cu<sub>2</sub>S, and sulfates). Residues of organic conservation products are identified by FTIR reflectance. The results are compared with the information available in the patents filed by the company as well as other written sources from that period. The pigments and opacifiers (Naples yellows, lead arsenates, fluorite, spinels, cassiterite, and chromates), and the vitreous matrices of the cloisonné enamels of the objects above are identified and testify to the deliberate combination of European and Asian enameling techniques.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"243-261"},"PeriodicalIF":2.4,"publicationDate":"2024-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6761","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rapid Assessment of Tablet Quality Based on Raman Spectroscopy Analysis: Investigating the Effect of Storage Conditions on the Degradation of Active Pharmaceutical Ingredient (API) of Acetaminophen Tablet 基于拉曼光谱分析的片剂质量快速评估:研究储存条件对对乙酰氨基酚片剂活性药物成分 (API) 降解的影响
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-26 DOI: 10.1002/jrs.6757
M. Keshavarz Mohammadian, S. H. Tavassoli, S. Karimi
{"title":"Rapid Assessment of Tablet Quality Based on Raman Spectroscopy Analysis: Investigating the Effect of Storage Conditions on the Degradation of Active Pharmaceutical Ingredient (API) of Acetaminophen Tablet","authors":"M. Keshavarz Mohammadian,&nbsp;S. H. Tavassoli,&nbsp;S. Karimi","doi":"10.1002/jrs.6757","DOIUrl":"https://doi.org/10.1002/jrs.6757","url":null,"abstract":"<div>\u0000 \u0000 <p>The effectiveness and safety of drugs may be compromised by the degradation of APIs during preparation processes or after they have been released to market. This study has investigated the degradation of 500-mg Acetaminophen tablet (C<sub>8</sub>H<sub>9</sub>NO<sub>2</sub>) when stored under unfavorable conditions such as increased temperature and high levels of humidity. To quantify the amount of API, the Raman intensity variations of characteristic peaks of API and polyvinylpyrrolidone (PVP) (C<sub>6</sub>H<sub>9</sub>NO) are explored. By considering various sources of error in all experiments, the reliability of the extracted data set from Raman spectrums and the quality of results obtained using the utilized technique for predicting API is investigated at standard room temperature. The results demonstrate an acceptable precision in the range of pharmacopeia monograph. Then, the effect of temperature and humidity variations on the amount of API is investigated based on the related Raman spectra. The results show that the API's quantity starts to decrease after about 60 min at the temperature of 45°C ± 2°C and the relative humidity (RH) of 75% ± 2%. According to our results, when tablets are kept under the unfavorable conditions, the degradation pattern of API follows a logarithmic trend.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"278-285"},"PeriodicalIF":2.4,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565374","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}
引用次数: 0
Rapid Identification of Candida auris by Raman Spectroscopy Combined With Deep Learning 结合深度学习的拉曼光谱快速鉴定耳念珠菌
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-26 DOI: 10.1002/jrs.6763
S. Kiran Koya, Michelle A. Brusatori, Sally Yurgelevic, Changhe Huang, Jake DeMeulemeester, Danielle Percefull, Hossein Salimnia, Gregory W. Auner
{"title":"Rapid Identification of Candida auris by Raman Spectroscopy Combined With Deep Learning","authors":"S. Kiran Koya,&nbsp;Michelle A. Brusatori,&nbsp;Sally Yurgelevic,&nbsp;Changhe Huang,&nbsp;Jake DeMeulemeester,&nbsp;Danielle Percefull,&nbsp;Hossein Salimnia,&nbsp;Gregory W. Auner","doi":"10.1002/jrs.6763","DOIUrl":"https://doi.org/10.1002/jrs.6763","url":null,"abstract":"<div>\u0000 \u0000 <p><i>Candida</i> auris is a multidrug-resistant yeast that can lead to outbreaks in healthcare facilities, even with strict infection prevention and control measures. <i>Candida auris</i> detection is challenging using standard laboratory methods. Advancements in identification methods, such as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and polymerase chain reaction, have improved detection, though these methodologies can be costly and impractical in resource-limited settings. This study presents a practical, portable, and reagentless platform known as Counter-Propagating Gaussian Beam Raman Spectroscopy (CPGB-RS), integrated with deep learning spectral analysis for the rapid and accurate identification of <i>C. auris</i>. This method has shown a sensitivity of 96% and a specificity of 99% in differentiating <i>C. auris</i> from other highly prevalent pathogenic species, such as <i>Candida albicans</i>, <i>Candida glabrata</i>, and <i>Candida tropicalis</i>. The differentiation between species is based on unique variations in their Raman spectra, influenced by differences in cell wall composition (including β-glucan, chitin, and mannoprotein), cell membrane components (like ergosterol), and cellular energy states (mitochondrial cytochromes b and c). This platform allows for automated molecular screening, generating diagnostic results within 2 min, making it highly practical for clinical applications. Furthermore, this technology has the potential to evaluate the effectiveness of antifungal agents, which could significantly improve patient outcomes.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"218-227"},"PeriodicalIF":2.4,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565375","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}
引用次数: 0
Material Profiling of Mesopotamian Cylinder Seals by Raman Spectroscopy 用拉曼光谱分析美索不达米亚圆柱密封件的材料
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-26 DOI: 10.1002/jrs.6765
Stylianos Aspiotis, Albert Dietz, Zsombor Földi, Frank Hildebrandt, Jochen Schlüter, Boriana Mihailova
{"title":"Material Profiling of Mesopotamian Cylinder Seals by Raman Spectroscopy","authors":"Stylianos Aspiotis,&nbsp;Albert Dietz,&nbsp;Zsombor Földi,&nbsp;Frank Hildebrandt,&nbsp;Jochen Schlüter,&nbsp;Boriana Mihailova","doi":"10.1002/jrs.6765","DOIUrl":"https://doi.org/10.1002/jrs.6765","url":null,"abstract":"<p>Raman spectroscopy has been used to non-invasively analyse 30 Mesopotamian cylinder seals dated from the end of the fourth to the last half of the first millennium <span>bce</span>, kept in the collection of Museum für Kunst und Gewerbe (Hamburg, Germany). Besides the identification of the mineral constituents of the seals, the chemical compositions of the corresponding minerals were quantitatively determined from the Raman spectra. Using previously established relationships between the crystal chemistry and Raman-peak positions widths and/or relative intensities for various mineral groups, we demonstrate that (i) the Mg content in calcite-based seals as well as the Mg, Fe<sup>2+</sup> and Ca contents in pyroxene present in one silicate seal can be determined with a relative error of 2%; (ii) the <sup>M</sup>Mg and <sup>M</sup>(Fe + Mn)<sup>2+</sup> contents in talc-based seals as well as the <sup>M</sup>Mg and <sup>M</sup>Fe<sup>2+</sup> contents in antigorite-based seals can be quantified with a relative error of 5%; and (iii) in the case of chlorite-based cylinder seals the content of <sup>M</sup>Mg, <sup>M</sup>Fe<sup>2+</sup>, <sup>M</sup>Al, <sup>T</sup>Si and <sup>T</sup>Al could be estimated with relative errors of 15%–20%. We show that a classical gemological description of cylinder seals is insufficient, particularly when the most abundant mineral phases are oxides, iron sulfides and phyllosilicates, such as talc, antigorite and chlorite-group minerals. We demonstrate that combining classical art historical studies with archaeological evidence and detailed material profiles can advance provenance studies, reveal trade roots, unravel forgeries and distinguish replaced parts.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"228-242"},"PeriodicalIF":2.4,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6765","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Experimental and Theoretical Evidence of Weak Spin–Lattice Coupling in the Double Perovskite Sr2YRuO6 双钙钛矿Sr2YRuO6弱自旋-晶格耦合的实验和理论证据
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-17 DOI: 10.1002/jrs.6758
Hsiang-Lin Liu, Bommareddy Poojitha, Yi-Lin Lin, Hsiao-Wen Chen, Chao-Hung Du, Ting-Hua Lu, Supratik Mukherjee, A. C. Garcia-Castro, Ganapathy Vaitheeswaran
{"title":"Experimental and Theoretical Evidence of Weak Spin–Lattice Coupling in the Double Perovskite Sr2YRuO6","authors":"Hsiang-Lin Liu,&nbsp;Bommareddy Poojitha,&nbsp;Yi-Lin Lin,&nbsp;Hsiao-Wen Chen,&nbsp;Chao-Hung Du,&nbsp;Ting-Hua Lu,&nbsp;Supratik Mukherjee,&nbsp;A. C. Garcia-Castro,&nbsp;Ganapathy Vaitheeswaran","doi":"10.1002/jrs.6758","DOIUrl":"https://doi.org/10.1002/jrs.6758","url":null,"abstract":"<div>\u0000 \u0000 <p>Sr<sub>2</sub>YRuO<sub>6</sub> is a material that provides an ideal platform for studying magnetic frustration in three-dimensional geometries. Herein, we combine Raman spectroscopy and density functional theory calculations to establish connections between the lattice dynamics and magnetic states in Sr<sub>2</sub>YRuO<sub>6</sub> single crystals. The x-ray diffraction profiles reveal that Sr<sub>2</sub>YRuO<sub>6</sub> possesses an ordered double-perovskite structure with distorted monoclinic symmetry. Three magnetic phase transitions are observed and linked to the presence of weak ferromagnetism at 135 K and short- and long-range antiferromagnetic orderings at 32 and 26 K. The oxygen-octahedron antistretching and stretching modes, observed at 570 and 766 cm<sup>−1</sup>, exhibit anomalies near the magnetic phase transition temperatures, indicating an intriguing interplay between the lattice and spin degrees of freedom. Their spin–phonon coupling constants of 0.7 cm<sup>−1</sup> reflect the weak spin–lattice interactions in Sr<sub>2</sub>YRuO<sub>6</sub>.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"286-296"},"PeriodicalIF":2.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565394","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}
引用次数: 0
Conformation Dependence of Phenylalanine Characteristic Raman Markers 苯丙氨酸特征拉曼标记的构象依赖性
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-12 DOI: 10.1002/jrs.6759
Belén Hernández, Yves-Marie Coïc, Sergei G. Kruglik, Santiago Sanchez-Cortes, Mahmoud Ghomi
{"title":"Conformation Dependence of Phenylalanine Characteristic Raman Markers","authors":"Belén Hernández,&nbsp;Yves-Marie Coïc,&nbsp;Sergei G. Kruglik,&nbsp;Santiago Sanchez-Cortes,&nbsp;Mahmoud Ghomi","doi":"10.1002/jrs.6759","DOIUrl":"https://doi.org/10.1002/jrs.6759","url":null,"abstract":"<div>\u0000 \u0000 <p>Conformational dependence of six characteristic phenylalanine (Phe) Raman markers (F<sub>i</sub>, i = 1, …, 6) was assessed through a multiconformational approach. Herein, aqueous solution off-resonance Raman spectra of the cationic species of the tripeptide Gly-Phe-Gly, with amine/amide backbone terminal groups, accompanied by the density functional theory calculations, using three different hybrid functionals (B3LYP, wB97XD and M062X), were presented. A set of 15 initial conformers, having five types of backbone secondary structures (β-strand, polyproline-II, helical, classic and inverse γ-turn) and three plausible side chain orientations, were submitted to geometry optimization. The optimized conformers permitted analysing the effect of non-bonded interactions, such as intramolecular hydrogen bonds, as well those occurring through space between aromatic side chain and adjacent peptide bonds. It has been shown that M062X was the only functional capable of maintaining the stability of all conformers, especially those having an inverse γ-turn backbone. In all calculations, extended chains (β-like) and classic γ-turn structures were shown to form the lowest and the highest energy conformers, respectively. Helical and pP-II structures belong to intermediate energy conformers. Raman spectrum was calculated by the thermal (Boltzmann) average of those spectra arising from the whole optimized conformers. An increasing global improvement of the spectral shape is to be noticed in going from the data obtained B3LYP to ωB97XD and M062X. Furthermore, explicit hydration of conformers improves the quality of the calculated spectrum by means of M062X. Wavenumber dispersion of the characteristic Raman markers revealed that F<sub>5</sub> (~1004 cm<sup>−1</sup>) has the lowest dispersion (≤ 1 cm<sup>−1</sup>), remaining unaffected by explicit hydration. In contrast, F<sub>3</sub> (~1207 cm<sup>−1</sup>) shows the largest shift (≤ 6 cm<sup>−1</sup>), whereas a moderate one (≤ 3 cm<sup>−1</sup>) was predicted for F<sub>1</sub> (~1605 cm<sup>−1</sup>), F<sub>2</sub> (~1586 cm<sup>−1</sup>) and F<sub>4</sub> (~1035 cm<sup>−1</sup>). Explicit versus implicit hydration seems to affect the wavenumber dispersion of F<sub>6</sub> (~622 cm<sup>−1</sup>). It can be concluded that the conformational sensitivity of the Phe characteristic markers basically arises from the nature of their vibrational motions.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"262-277"},"PeriodicalIF":2.4,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565429","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}
引用次数: 0
Applications of Raman Spectroscopy in Art and Archaeology 拉曼光谱在艺术和考古中的应用
IF 2.4 3区 化学
Journal of Raman Spectroscopy Pub Date : 2024-12-02 DOI: 10.1002/jrs.6756
Anastasia Rousaki, Juan Manuel Madariaga
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