Journal of Raman Spectroscopy最新文献

{"title":"Editorial: Raman Spectroscopy More Topical Than Ever—Insights From ICORS 2024","authors":"Juergen Popp","doi":"10.1002/jrs.70024","DOIUrl":"10.1002/jrs.70024","url":null,"abstract":"<p>It has been nearly a century since the discovery of the Raman effect, and yet its impact on science, technology, and also society continues to grow at an impressive pace. The 28th International Conference on Raman Spectroscopy (ICORS 2024), held in the historic city of Rome, served as a vibrant testament to the continued evolution and interdisciplinary reach of Raman spectroscopy. From fundamental advances in physics and chemistry to innovative applications in biomedicine, materials science, cultural heritage, and even planetary exploration, the field is more topical and relevant than ever.</p><p>The present Special Issue of the <i>Journal of Raman Spectroscopy</i>, entitled “Raman spectroscopy more topical than ever: From physics, chemistry via biomedicine, life science, pharmacy towards mineralogy, arts and even space,” compiles selected contributions from ICORS 2024 participants and reflects the rich diversity and innovation showcased during the conference. With over 19 contributions from leading academic institutions, research centers, and industrial partners worldwide, the issue presents cutting-edge research on experimental and theoretical developments across all major branches of Raman spectroscopy, including resonance Raman, SERS, CARS, SRS, time-domain Raman, and computational approaches.</p><p>To provide clarity and thematic orientation, the contributions in this issue are grouped and briefly introduced below.</p><p>This section includes works applying Raman spectroscopy to complex biological matrices. Plitzko et al. [<span>1</span>] present a hydrolyzation-free characterization method for acetalated dextran using 2D correlated Raman spectroscopy, offering a robust route for analyzing drug delivery materials. Punzalan et al. [<span>2</span>] explore how pulsed electric field-assisted extraction impacts flaxseed protein composition and structure, revealed through Raman spectroscopy and multivariate analysis. Travkina et al. [<span>3</span>] investigate the hair cuticle structure with polarized Raman experiments, focusing on protein secondary and tertiary structures. Warren et al. [<span>4</span>] study the biomimetic cation–<i>π</i> interactions, elucidating weak chemical interactions via vibrational signatures. Demenshin et al. [<span>5</span>] introduce plasmonic tags based on gold nanorods for Raman-based cell imaging. Karnachoriti et al. [<span>6</span>] report the real-time monitoring of nutrient profiles in microalgae cultures using Raman, enabling optimization of biotechnological cultivation. Finally, Rensonnet et al. [<span>7</span>] use the Raman to quantify acidity in ionic liquids through Hammett acidity functions, showcasing applications in chemical process environments.</p><p>Several contributions focus on advanced materials and SERS substrate development. Mercedi et al. [<span>8</span>] propose a robust methodology to determine SERS enhancement factors for colloidal and solid supports. Pavelka et al. [<span>9</span>] fab","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 9","pages":"776-778"},"PeriodicalIF":1.9,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.70024","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013042","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}

{"title":"Correction to “Raman Spectroscopy for Crystallochemical Analysis of Mg-Rich Layered Silicates: Serpentine and Talc”","authors":"","doi":"10.1002/jrs.70015","DOIUrl":"10.1002/jrs.70015","url":null,"abstract":"<p>\u0000 <span>S. Aspiotis</span>, <span>J. Schlüter</span>, <span>F. Hildebrandt</span>, and <span>B. Mihailova</span>, <i>Journal of Raman Spectroscopy</i> <span>2023</span>, <span>54</span>(<span>12</span>), 1502, https://doi.org/10.1002/jrs.6601.</p><p>The corresponding author apologizes for the typos. We would like to thank an anonymous reader for pointing out the errors.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 8","pages":""},"PeriodicalIF":1.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.70015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144767669","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}

{"title":"Development and Applications of Nonlinear Optical Spectroscopy: 21st ECONOS/41st ECW Meeting in Vienna (Austria)","authors":"Ellen H. G. Backus,&nbsp;Oliver H. Heckl,&nbsp;Johannes Kiefer","doi":"10.1002/jrs.70008","DOIUrl":"10.1002/jrs.70008","url":null,"abstract":"&lt;p&gt;The joint conference of the European Conference on Nonlinear Optical Spectroscopy (ECONOS) and European CARS Workshop (ECW) covers all theoretical and experimental aspects of nonlinear optical spectroscopy and microscopy. Topics include Coherent anti-Stokes Raman scattering (CARS) spectroscopy and microscopy and other forms of coherent Raman scattering, other approaches to the detection of nonlinear optical responses in time and frequency domain, and investigations of the physical and chemical processes defining the spectral signatures in different nonlinear media. Also, emerging analytical techniques and their applications in biomedical research, material science, and engineering are discussed. The 21&lt;sup&gt;st&lt;/sup&gt; ECONOS conference and 41&lt;sup&gt;st&lt;/sup&gt; CARS workshop were held in Vienna, Austria, on April 21–24, 2024, chaired by Ellen Backus and Oliver Heckl (University of Vienna). Altogether, 90 participants shared their research in oral sessions and poster sessions and participated in lively discussions and social activities. The first session already took place on Sunday afternoon starting with an invited talk entitled “Optical-optical double-resonance spectroscopy using a frequency comb probe—broadband precision measurements of molecular hot-band transitions” by Aleksandra Foltynowicz of Umeå University followed by contributed talks and a welcome reception. The main scientific program began on Monday morning in the historic Kardinal König Haus in Vienna. Another four invited talks were given during the course of the conference, embedded in the agenda of contributed oral presentations and a poster session. The main social event was the memorable conference dinner at the historic restaurant Heurigen Zahel.&lt;/p&gt;&lt;p&gt;This special section of the Journal of Raman Spectroscopy constitutes a selection of three papers presented at ECONOS/ECW 2024. Due to the broad scope of the conference, the papers cover a broad range of methods and their applications to a variety of systems.&lt;/p&gt;&lt;p&gt;Vergari et al. [&lt;span&gt;1&lt;/span&gt;] dedicated their contribution to a very fundamental issue, that is, the representation of nonlinear optical interactions in diagrammatic schemes. Such schemes are essential in the understanding and communication of complicated nonlinear optical phenomena. After reviewing the common Feynman diagrams, Liouville pathways, and the Albrecht notation, the authors suggest that the limitations of the conventional approaches can be overcome by a field-type modification of the Albrecht notation that combines the simplicity of the energy-level representation with the more elaborated diagrams.&lt;/p&gt;&lt;p&gt;Raveesh et al. [&lt;span&gt;2&lt;/span&gt;] studied time-domain femtosecond rotational coherent Raman scattering for diagnostic purposes. Experiments in air and pure nitrogen show selectivity and temperature sensitivity in the recorded fs-RCRS temporal scans. A theoretical model is capable of predicting experimental data with good agreement for temporal scans recorded at ","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 8","pages":"655-656"},"PeriodicalIF":1.9,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.70008","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144768022","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}

{"title":"Machine Learning of Raman Spectroscopic Data: Comparison of Different Validation Strategies","authors":"David Lilek,&nbsp;Daniel Zimmermann,&nbsp;Lukas Steininger,&nbsp;Maurizio Musso,&nbsp;Bodo D. Wilts,&nbsp;Sonja Gamsjaeger,&nbsp;Daniel-Ralph Hermann,&nbsp;Christoph Wiesner,&nbsp;Agnes Grünfelder,&nbsp;Birgit Herbinger,&nbsp;Katerina Prohaska","doi":"10.1002/jrs.6842","DOIUrl":"10.1002/jrs.6842","url":null,"abstract":"<div>\u0000 \u0000 <p>Machine learning (ML) techniques are valuable for analyzing complex biological SERS spectra, allowing for the detection of minor differences in cell composition. However, several challenges arise in the data analysis process, such as selecting the appropriate preprocessing methods, machine learning algorithms, and validation strategies to avoid under/overfitting and ensure reliable estimates. This study systematically compared various validation strategies and their impact on multiple ML classifiers using four biological datasets of varying complexities, in terms of class overlap, and sample variability.</p>\u0000 <p>Therefore, a machine learning workflow was established, incorporating more than 10 classifiers and using nested cross-validation (CV) for hyperparameter tuning and performance estimation. Five CV strategies were compared: Leave-One-Group-Out, stratified K-Fold, unstratified K-Fold, Leave-One-Out, and nested CV.</p>\u0000 <p>Our results demonstrate that stratified K-Fold CV yielded performance nearly equivalent to nested CV in terms of accuracy and efficiency but with a reduced computational cost. Leave-One-Group-Out strategy produced lower performance estimates than the other four methods, which may be more representative of real-world performance.</p>\u0000 <p>Conclusively, this work shows that simpler CV strategies can effectively replace computationally expensive nested CV in certain cases, while maintaining comparable performance. Nonetheless, careful consideration of overfitting remains crucial when employing these more efficient methods.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 9","pages":"867-877"},"PeriodicalIF":1.9,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145012020","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}

{"title":"Time-Domain Raman Spectroscopy: An Emerging Technique in Space Exploration?","authors":"Y. Ha,&nbsp;S. G. Pavlov,&nbsp;M. D. Rabasovic,&nbsp;A. J. Krmpot,&nbsp;J. Petrovic,&nbsp;J. Woeste,&nbsp;D. A. Azih,&nbsp;S. Wall,&nbsp;I. Weber,&nbsp;N. Stojanovic,&nbsp;M. Gensch","doi":"10.1002/jrs.6848","DOIUrl":"10.1002/jrs.6848","url":null,"abstract":"<p>The potential of time-domain Raman spectroscopy in space exploration is discussed. This work is motivated by the emergence of robust, space-qualified femtosecond lasers and by the fact that time-domain detection allows the design of very compact instruments. As is shown, time-domain Raman spectroscopy gives access to the same fingerprint spectrum of minerals as conventional Raman spectroscopy, while avoiding problems such as fluorescence or ambient light backgrounds.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 9","pages":"916-919"},"PeriodicalIF":1.9,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6848","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145012021","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}

{"title":"Raman Spectroscopy as a Tool for Real-Time Nutrient Monitoring in Bioreactor Cultivation of Microalgae","authors":"M. Karnachoriti,&nbsp;M. Chatzipetrou,&nbsp;E. Touloupakis,&nbsp;A. G. Kontos,&nbsp;I. Zergioti","doi":"10.1002/jrs.6841","DOIUrl":"10.1002/jrs.6841","url":null,"abstract":"<p>In this work, aqueous nutrient solutions replicating bioreactor culture media for microalgae were analyzed using spontaneous Raman spectroscopy. Focusing on nitrate, sulfate, glucose, and phosphate, the study evaluated their potential for real-time monitoring in cell cultivations such as <i>Chlorella vulgaris</i>. Univariate analysis, based on Raman intensities of specific nutrient peaks, was conducted and compared to multivariate analysis results. Four multivariate calibration models were developed using partial least squares regression (PLSR), achieving high calibration and validation performance, with R² values above 0.99 and low RMSE_CV, indicating strong calibration accuracy. The study also examined the limit of detection (LOD) for each nutrient, finding that LODs for nitrate, sulfate, and glucose reached levels relevant for algae bioreactors even without the application of enhanced Raman techniques. To further validate the PLS models, independent real bioreactor samples were analyzed, showing strong predictive accuracy (R_P²: 0.9661–0.9892) and low RMSE_P values. Additional testing with five samples collected over a <i>Chlorella vulgaris</i> cultivation run (day 0 to day 9) confirmed the models' robust performance under real bioprocess conditions. Limitations in practical applications, such as phosphate's relatively high LOD, were also identified. The results suggest that Raman spectroscopy, combined with multivariate analysis, could deliver precise and reliable detection of critical nutrients and their concentrations in bioreactor culture media. This potential of the Raman technique, along with insights into nutrient LODs, PLS model accuracy, and practical application challenges, provides a solid foundation for future research and development in industrial bioprocess monitoring.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 9","pages":"817-826"},"PeriodicalIF":1.9,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6841","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013212","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}

{"title":"Conformational Equilibrium of Cysteamine on Silver Metal Surface Studied by Surface-Enhanced Raman Scattering","authors":"Sungjun Kwak,&nbsp;Daeun Lee,&nbsp;Sung Gun Lee,&nbsp;Dae Hong Jeong","doi":"10.1002/jrs.6843","DOIUrl":"https://doi.org/10.1002/jrs.6843","url":null,"abstract":"<p>In this study, we utilized surface-enhanced Raman scattering (SERS) to examine the conformational changes of cysteamine on silver bumpy nanoshell (AgNS) in various solvents, including water, ethanol (EtOH), isopropyl alcohol (IPA), and acetonitrile (ACN). It was found that the interaction between cysteamine and solvent molecules could affect the conformational equilibrium of cysteamine on the AgNS surface, particularly the ratio between its trans and gauche conformations. Using the SERS bands at 630 and 720 cm⁻¹ assigned to S–C stretching modes of the gauche and trans conformations, respectively, and calculating the SERS intensity ratio of these bands (I_trans/I_gauche), we found that water stabilized the gauche conformation because of the strong hydrogen-bonding interactions with cysteamine, while solvents such as ACN favored the trans conformation. SERS measurements over time further indicated that cysteamine reached conformational equilibrium on AgNS slowly within hours in a single solvent environment. In mixed water/ACN solvents, the gauche conformation became increasingly dominant with higher water fractions. Conversely, introducing ACN into water-stabilized AgNS dispersion did not reverse the conformational shift, suggesting that the gauche to trans transition was limited by higher activation barrier due to irreversible stabilization of Ag–N bond in the gauche form and local solvent environment around surface-bound cysteamine. Conformational equilibrium of cysteamine on AgNS could be quantified using the degree of mixing (γ), a parameter reflecting the distribution and interaction of cysteamine in mixed solvent. This study shows that SERS is effective for monitoring solvent-mediated conformational changes in surface-bound cysteamine. This approach might help us optimize solvent selection for applications that leverage the reactive amine group of cysteamine on metal surfaces.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 10","pages":"1010-1017"},"PeriodicalIF":1.9,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6843","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243043","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}

{"title":"Investigating Water Sensing Capabilities of Ca- and Sr-Containing (BaTiO3)3 Clusters: A Computational Study of Electronic Properties and Chemical Effects in Surface-Enhanced Raman Spectroscopy","authors":"N. V. Suresh Kumar,&nbsp;Sitansh Sharma,&nbsp;Abdul Rajjak Shaikh,&nbsp;C. Thirmal","doi":"10.1002/jrs.6845","DOIUrl":"https://doi.org/10.1002/jrs.6845","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;Nanomaterials capable of detecting water or water vapor have significant industrial and environmental applications. Barium titanate (BaTiO\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt;) exhibits spontaneous electric polarization, making it suitable for water vapor sensing. By adjusting the polarization of small BaTiO\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt; clusters, researchers can develop new nanostructures with enhanced sensing capabilities. The present computational study investigates the water-sensing ability of the (BaTiO\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt;)\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt; cluster and its strontium (Sr)- and calcium (Ca)-containing counterparts, focusing on their electronic characteristics and the chemical effects observed in surface-enhanced Raman scattering (SERS) spectra. The geometries of the (BaTiO\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt;)\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt; clusters, along with their Sr and Ca doped configurations and water adsorbed states, are optimized using the M06/6-31G(d,p) level of theory (with LANL2DZ for Ca, Sr, and Ba). The findings indicate a notable increase in binding energy per atom of the clusters with Sr and Ca at interstitial sites. The adsorption of water molecule on Sr(BTO)\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt; and Ca(BTO)\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt; clusters significantly alters the electronic polarizability and enhances Raman activity for vibrational modes of water. The observed trends are supported by vibrational energy-dependent electronic polarizability values. Additionally, calculations of excitation wavelength-dependent electronic polarizability and electron transfer from the cluster to the water molecule further demonstrate that the (BaTiO\u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;&lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;&lt;/math&gt;)\u0000&lt;span&gt;&lt;/","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 10","pages":"1049-1058"},"PeriodicalIF":1.9,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243185","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}

{"title":"Non-invasive Analyses of an Etruscan Fibula From Vulci (Italy): The Benefits of a Combination of Micro-Raman Spectroscopy, 3D Reconstruction Through X-Ray Microscopy and ED-XRF With Monte Carlo Simulation","authors":"Marta Porcaro,&nbsp;Flavio Cognigni,&nbsp;Martina Bernabale,&nbsp;Giancarlo La Penna,&nbsp;Anacleto Proietti,&nbsp;Carlo Casi,&nbsp;Carlo Regoli,&nbsp;Simona Carosi,&nbsp;Marco Rossi,&nbsp;Antonio Brunetti,&nbsp;Caterina De Vito","doi":"10.1002/jrs.6834","DOIUrl":"https://doi.org/10.1002/jrs.6834","url":null,"abstract":"<p>This work investigates the composition of the patina and state of preservation of an Etruscan bronze fibula from Tomb 129 of Vulci Archaeological Park (VT, Italy), dating back between the late eighth and early seventh centuries BC. Non-destructive analytical techniques, such as micro-Raman spectroscopy and energy-dispersive X-ray fluorescence (ED-XRF) combined with Monte Carlo simulations, were used to analyze the patina's mineralogy and the alloy's chemical composition. Monte Carlo simulation was applied to model the layered structure of the fibula accurately and distinguish between the alloy and the patina, allowing the elemental composition of the fibula to be known and excluding selective depletion phenomena. Innovative 3D reconstruction through X-ray microscopy (XRM) allowed the characterization of the internal structure of the artifact and its state of preservation. Micro-Raman results on the patina identified the occurrence of brochantite and sampleite due to interactions with the burial environment and the decomposition of organic matter. The fibula was a binary bronze alloy (Cu-Sn) with a low tin content and minimal lead concentration. XRM analysis detected fragility points and a small blind hole inside the fibula, probably related to the manufacturing processes. These findings provide insight into the artifact's conservation status and contribute to a better understanding of ancient Etruscan metalworking techniques. By integrating advanced analytical methods and non-invasive imaging, this study highlights the potential of combining scientific techniques to preserve cultural heritage and deepen our knowledge of metallurgical practices in ancient civilizations.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 10","pages":"1018-1030"},"PeriodicalIF":1.9,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6834","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145242984","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}

{"title":"Raman Spectroscopy, Dynamical and Nonlinear Optical Properties of Multicomponent Garnet (Eu, Gd, Dy, Er, Y)3Fe5O12: A Combined Experimental and Computational Study","authors":"Elizaveta A. Pankrushina,&nbsp;Evgenii M. Roginskii,&nbsp;Ivan A. Zhelunitsyn,&nbsp;Sergey L. Votyakov","doi":"10.1002/jrs.6837","DOIUrl":"https://doi.org/10.1002/jrs.6837","url":null,"abstract":"<div>\u0000 \u0000 <p>The article presents the results of a combined experimental and computational study by DFT methods of Raman and Mössbauer spectra, dynamical and nonlinear optical (NLO) properties of single-component and multicomponent garnets Y₃Fe₅O₁₂ (YIG), LnIG (Ln = Eu, Gd, Dy, Er), and (Y_0.2Gd_0.2Er_0.2Eu_0.2Dy_0.2)IG (YLnIG), synthesized by glycine–nitrate pyrolysis. The Raman band assignments to fundamental vibrational modes were held using an analysis of experimental data with the support of phonon spectra ab initio calculations. It was shown that displacements of all atoms except Fe in octahedra are involved in Raman active vibrational modes. The most intensive Raman bands are attributed to phonon modes related to atomic displacements in FeO₄ tetrahedra. Raman spectra measurements performed for YIG and YLnIG garnets in the temperature and pressure ranges of 83–773 K and 0–13 GPa revealed their structural stability with the absence of any phase transition fingerprints. The analysis of temperature and baric behavior of vibrational modes disclose that the value of anharmonicity in multicomponent garnet YLnIG is of the same magnitude as the one in single-component YIG. The values of thermal expansion coefficients were estimated to be equal to 11.07·10⁻⁶ and 10.20·10⁻⁶ K⁻¹ for YLnIG and YIG garnets respectively. The nonlinear properties of YIG and EuIG garnets were studied theoretically using the CPHF approach; the values of nonzero susceptibility tensor components were characterized by high values of diagonal components: the values were equivalent to \u0000<span></span><math>\u0000 <msubsup>\u0000 <mi>χ</mi>\u0000 <mtext>xxxx</mtext>\u0000 <mfenced>\u0000 <mn>3</mn>\u0000 </mfenced>\u0000 </msubsup></math> = 35.8·10⁻²² and 38.4·10⁻²² m²/V² and \u0000<span></span><math>\u0000 <msubsup>\u0000 <mi>χ</mi>\u0000 <mtext>xxyy</mtext>\u0000 <mfenced>\u0000 <mn>3</mn>\u0000 </mfenced>\u0000 </msubsup></math> = 9.04·10⁻²² and 9.10·10⁻²² m²/V², respectively, for YIG and EuIG.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 10","pages":"1031-1048"},"PeriodicalIF":1.9,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145242892","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}