Journal of Raman Spectroscopy最新文献

{"title":"Flashforward: The Current and Future Applications of Vibrational Spectroscopy for Forensic Purposes","authors":"Riley M. Alpuché,&nbsp;Bhavik Vyas,&nbsp;Igor K. Lednev","doi":"10.1002/jrs.6750","DOIUrl":"https://doi.org/10.1002/jrs.6750","url":null,"abstract":"<div>\u0000 \u0000 <p>Vibrational spectroscopy combined with machine learning has a great potential for forensic applications. For example, handheld Raman spectroscopic instruments are already used by law enforcement agencies for precise, confirmatory identification of drugs. Beyond drug identification, several emerging technologies based on vibrational spectroscopy are currently under development for forensic investigative purposes, including the analysis of questioned documents, gunshot residue, fabrics, soil, hair, nails, and nail polish. This article provides a comprehensive overview of the application of vibrational spectroscopy in various areas of forensic analysis, particularly focusing on forensic serology and the analysis of trace evidences. In the case of forensic serology, the methodology allows for determining complex aspects of serological casework, including the time since deposition of a stain, as well as the phenotypic profile of the stain donor—namely, sex, race, and age. Furthermore, gunshot residues can be accurately identified by grain, caliber, and manufacturer when Raman spectroscopy is paired with machine learning. This integration of advanced spectroscopic techniques with machine learning holds great promise for furthering both the accuracy and efficiency of investigations, helping to reduce the total backlog of evidence investigation currently plaguing modern forensic laboratories.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"193-206"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143565451","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":"Resonance Raman Scattering of Topological Insulators Bi2Te3 and Bi2 − xSbxTe3 − ySey Thin Films","authors":"N. Kumar,&nbsp;N. V. Surovtsev,&nbsp;D. V. Ishchenko,&nbsp;P. A. Yunin,&nbsp;I. A. Milekhin,&nbsp;O. E. Tereshchenko,&nbsp;A. G. Milekhin","doi":"10.1002/jrs.6751","DOIUrl":"https://doi.org/10.1002/jrs.6751","url":null,"abstract":"&lt;p&gt;Phonon occupation is temperature (&lt;i&gt;T&lt;/i&gt;) dependent; it may participate in scattering with electronic states of topological insulators (TIs). Longitudinal optical (LO) phonons \u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;A&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;mi&gt;g&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{A}}_{1g}&amp;#x0005E;1 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and \u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;A&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;mi&gt;g&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{A}}_{1g}&amp;#x0005E;2 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; in Bi&lt;sub&gt;2 − x&lt;/sub&gt;Sb&lt;sub&gt;x&lt;/sub&gt;Te&lt;sub&gt;3 − y&lt;/sub&gt;Se&lt;sub&gt;y&lt;/sub&gt; (BSTS) was resonantly excited by a photon energy (E&lt;sub&gt;&lt;i&gt;p&lt;/i&gt;&lt;/sub&gt;) 2.33 eV due to electronic transition of unoccupied conduction band. The intensity of these modes was enhanced in Bi&lt;sub&gt;2&lt;/sub&gt;Te&lt;sub&gt;3&lt;/sub&gt; film at E&lt;sub&gt;&lt;i&gt;p&lt;/i&gt;&lt;/sub&gt; 1.87 eV, which is close to the electronic transition of unoccupied Dirac states. Fröhlich coupling strength was the main mechanism for higher intensity of \u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;A&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;mi&gt;g&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{A}}_{1g}&amp;#x0005E;1 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and \u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;A&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;mi&gt;g&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{A}}_{1g}&amp;#x0005E;2 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; modes. At 300 K, the intensity of the \u0000&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;A&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;mi&gt;g&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{A}}_{1g}&amp;#x0005E;2 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; mode was significantly decayed in both the BSTS and Bi&lt;sub&gt;2&lt;/sub&gt;Te&lt;sub","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 3","pages":"207-217"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143564677","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":"The Characterization of the Lattice Vibrations of Ammonium Nitrate in ANFO Mixture After Authentic Detonations Using Confocal Raman Microscopy and Single Crystal X-Ray Diffraction","authors":"Jared Estevanes,&nbsp;Nicholas Jernigan,&nbsp;Christopher Zall,&nbsp;Geraldine Monjardez","doi":"10.1002/jrs.6752","DOIUrl":"https://doi.org/10.1002/jrs.6752","url":null,"abstract":"<div>\u0000 \u0000 <p>This study aimed to characterize ammonium nitrate lattice vibrations in an ammonium nitrate and fuel oil mixture (ANFO) following authentic explosive events using confocal Raman microscopy and single-crystal X-ray diffraction (XRD). Two simulated IEDs were constructed and detonated, consisting of several different substrate materials, using ANFO as the main charge. Crystalline material was observed to be growing on several of the postblast substrates. Microscopical examination revealed the crystalline material to have isotropic and anisotropic characteristics. Following recrystallization from water, the material was identified as ammonium nitrate. Single-crystal X-ray diffraction enabled the identification of the unit cells and molecular structures of the crystals formed after the blast. The values corresponded to the known Phase IV structure of recrystallized ammonium nitrate; however, there were minor yet statistically significant variations in the distances in the unit cell dimensions and O–N–O angles. Ex situ analysis of isotropic crystalline fragment using confocal Raman microscopy determined that lattice vibrations within the material were different than the ANFO intact reference, with the blue shifting of several bands, the emergence of new bands, and the loss of other characteristic bands. It was determined that the isotropic crystalline material observed in the postblast residue consisted of stressed state Phase IV AN. This suggests that a thermal change of AN can be observed in the microscopical characteristics and Raman spectrum of the crystals, demonstrating the importance of low frequency Raman spectroscopy (10–250 cm⁻¹), which allows the identification of distinct spectral features of crystalline salts.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"146-154"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362998","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":"Raman Spectroscopy Reveals Microparticles in Synovial Fluids of Patients With Suspected Implant-Related Complications","authors":"Tom Niessink,&nbsp;Jorrit W. A. Schoenmakers,&nbsp;Matthijs Janssen,&nbsp;Marjan Wouthuyzen-Bakker,&nbsp;Sjouke Piersma,&nbsp;Marleen van Oosten,&nbsp;Jan Maarten van Dijl,&nbsp;Cees Otto,&nbsp;Tim L. Jansen","doi":"10.1002/jrs.6753","DOIUrl":"https://doi.org/10.1002/jrs.6753","url":null,"abstract":"<p>Prosthetic implant-associated inflammation and failure can be caused by bacterial infections and mechanical wear of the prosthesis. Currently, there is no diagnostic modality that allows simultaneous identification of both causes of implant failure. Here, we present a proof-of-principle study to assess whether Raman spectroscopy can be applied to diagnose implant failure. Synovial fluids from 10 patients with a clinical suspicion of implant-related complications were previously collected and cultured to determine the presence of bacteria. The presence of microparticles in these synovial fluids was assessed by Raman spectroscopy and verified by scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDX). For control, the possibility to detect in vitro<i>-</i>cultured <i>Staphylococcus aureus</i> by Raman spectroscopy was investigated. Raman spectroscopy revealed that all 10 synovial fluid samples contained microparticles: eight contained microplastics (polyethylene, polypropylene, and polystyrene), and nine contained titanium dioxide nanoparticles (anatase and rutile) as verified by SEM-EDX. There was no clear difference in the microparticle content of synovial fluids with or without bacteria. Raman signals relating to individual bacteria and clusters of bacteria were detectable in in vitro cultures of <i>S. aureus</i>, but it was not possible to demonstrate the presence of bacteria in synovial fluids by Raman spectroscopy. Raman spectroscopy is a potential tool for characterizing microparticles in synovial fluids from patients with implant-related complications. This is of clinical relevance as these microparticles can cause joint inflammation. The identification of bacteria by Raman spectroscopy is feasible, but further research is needed before clinical implementation.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"127-134"},"PeriodicalIF":2.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6753","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362388","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":"Determination of Size, Size Distribution, and Concentration of Nanoparticles Using ICP-MS in the Context of SERS Substrates","authors":"Julie Horne,&nbsp;Pierre Beckers,&nbsp;Kevser Kemik,&nbsp;Charlotte De Bleye,&nbsp;Pierre-Yves Sacré,&nbsp;Nicolas Thelen,&nbsp;Philippe Hubert,&nbsp;Eric Ziemons,&nbsp;Cédric Hubert","doi":"10.1002/jrs.6746","DOIUrl":"https://doi.org/10.1002/jrs.6746","url":null,"abstract":"<div>\u0000 \u0000 <p>Surface enhanced Raman scattering (SERS) is a widely used vibrational spectroscopic technique employing metallic nanostructures to enhance an inherent Raman signal. This study aimed to develop a method for the characterization of SERS substrates in a single analysis by inductively coupled plasma mass spectrometry (ICP-MS) equipped with the single particle module (spICP-MS). For this development, the well-known Lee-Meisel protocol was selected as starting point to synthesize gold nanoparticles (AuNps) and silver nanoparticles (AgNps). A spICP-MS method was successfully developed and gave the mean size, size distribution, and concentration of nanoparticles in only one single analysis. Reference techniques were used to confirm these results namely dynamic light scattering, transmission electron microscopy, and UV–Visible spectroscopy. Thanks to the ICP-MS characterization, it was observed that AgNps synthesized by chemical reduction presented more variability than the AuNps. The dissolved elements concentration in the suspension was investigated. It appeared that reaction yields were close to 100% for the six syntheses. This analysis may be repeated over time to evaluate the suspension stability and monitor any potential degradation of Nps. To conclude, ICP-MS is a powerful technique to characterize SERS substrates and could be an interesting alternative to other characterization techniques.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"117-126"},"PeriodicalIF":2.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363030","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":"The Raman Spectra of \u0000\u0000 \u0000 \u0000 α\u0000 \u0000 $$ alpha $$\u0000 - and \u0000\u0000 \u0000 \u0000 β\u0000 \u0000 $$ beta $$\u0000 -Si3N4 and Si2N2O Determined Experimentally and by Density Functional Theory","authors":"Johannes T. Kehren,&nbsp;Michael Fischer,&nbsp;Olaf Krause","doi":"10.1002/jrs.6749","DOIUrl":"https://doi.org/10.1002/jrs.6749","url":null,"abstract":"<p>High-quality Raman spectra of the two silicon nitride polymorphs \u0000<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>α</mi>\u0000 </mrow>\u0000 <annotation>$$ alpha $$</annotation>\u0000 </semantics></math>- and \u0000<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>β</mi>\u0000 </mrow>\u0000 <annotation>$$ beta $$</annotation>\u0000 </semantics></math>-Si₃N₄ as well as of Si₂N₂O are presented here. This work significantly extends the previously available data on the Raman spectra of all three phases. For \u0000<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>α</mi>\u0000 </mrow>\u0000 <annotation>$$ alpha $$</annotation>\u0000 </semantics></math>-Si₃N₄, a total of 34 Raman bands were confirmed, and for Si₂N₂O, a total of 19 Raman bands were observed for the first time. In the case of \u0000<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>β</mi>\u0000 </mrow>\u0000 <annotation>$$ beta $$</annotation>\u0000 </semantics></math>-Si₃N₄, all 11 known Raman modes were confirmed. For further accuracy and comparison, the spectra of the three phases were also calculated with different density functional theory functionals. Good agreement between the experimental data and the calculated vibrational modes is shown. Between the different DFT functionals, the rSCAN functional had the best agreement with the experimental data, clearly outperforming the PBEsol functional.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"155-164"},"PeriodicalIF":2.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6749","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362991","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":"Assessment of Time-Gated Raman Spectroscopy for Online Mineralogy of a Spodumene Ore","authors":"Teemu Laitinen,&nbsp;Marc Legault,&nbsp;Satu Ojala,&nbsp;Jean-François Boulanger","doi":"10.1002/jrs.6748","DOIUrl":"https://doi.org/10.1002/jrs.6748","url":null,"abstract":"<p>This paper investigates the applicability of time-gated Raman spectroscopy (TRS) for online mineralogy identification, focusing on a Li-bearing spodumene ore. The study provides an overview of existing online mineralogy tools and points out some limitations of elemental analysis techniques. Dense media separation concentrate and tailing samples used originated from a deposit in Quebec, Canada. Various techniques, including ICP-AES, XRD, laser diffraction, and specific gravity determination, were used for detailed sample characterization. Samples and their mixtures at known ratios were prepared as powder and slurries, before being analyzed using TRS, followed by spectrum quantitative analysis. Results show a linear correlation between spodumene percentage by weight and the main Raman peak height or area, in both dry and slurry form, with a higher determination coefficient in slurry form. TRS also provided indications as to the gangue minerals present in the samples. This study shows the potential for TRS as a tool for online mineralogical assessment of spodumene ores, and further work should target the determination of detection limits and quantification of both valuable and gangue minerals.</p>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"135-145"},"PeriodicalIF":2.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jrs.6748","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362990","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":"Effect of Particle Size on Raman Signal Strength of Silicate Minerals","authors":"Laura B. Breitenfeld,&nbsp;M. Darby Dyar,&nbsp;Elizabeth C. Sklute,&nbsp;Carey Legett","doi":"10.1002/jrs.6745","DOIUrl":"https://doi.org/10.1002/jrs.6745","url":null,"abstract":"<div>\u0000 \u0000 <p>Understanding the effects of particle size is necessary for quantifying minerals in mixtures using Raman spectroscopy. Raman signal intensity is evaluated using six common silicate minerals (two olivines, two pyroxenes, and two feldspars) at 10 particle size ranges. For olivines and feldspars, the highest peak intensities are observed in samples with 38–63 and 63–106 μm particle sizes. There is no such consistent trend for the pyroxene samples, although the overall low signal strength complicates those measurements. Raman spectra of samples with varying particle sizes appear to be influenced by two competing effects: scattering from particle boundaries and effective sampling volume.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"184-187"},"PeriodicalIF":2.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362864","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":"Probing the Effect of pH Value and Voltage on the Near-Surface Proton Concentration at the Electrochemical Interface by In Situ Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS)","authors":"Xiujuan Zhang,&nbsp;Yaxin Wang,&nbsp;Yongjun Zhang,&nbsp;Kun Zhang,&nbsp;Ruoning Chu,&nbsp;Fengyi Zhang,&nbsp;Xiaoyu Zhao","doi":"10.1002/jrs.6734","DOIUrl":"https://doi.org/10.1002/jrs.6734","url":null,"abstract":"<div>\u0000 \u0000 <p>Understanding the variation of proton concentration near the surface of the electrochemical interface is of great significance for understanding the mechanism of electrochemical reactions. In this work, 4-Mpy molecules that are protonated and deprotonated depending on the surrounding pH value adsorb on the Au nanoparticle film electrode with high SERS activity, and by virtue of the highly interfacial-sensitive EC-SERS technique, we systematically studied the effects of electrolyte pH value and external voltage on the protonation and deprotonation of 4-Mpy at the interface between Au-NP film electrode and phosphate buffer, to analyze the changes of near-surface proton concentration at the electrochemical interface. It is found that the pH value of the electrolyte plays a decisive role in the protonation process of 4-Mpy at the electrode interface at low reduction voltage (&lt; −0.1 V). In acidic and neutral solution, 4-Mpy exists mainly in protonated form on the electrode surface. However, in alkaline solutions, 4-Mpy exists mainly on the electrode surface in the form of deprotonation. At high reduction voltage (≥ −0.1 V), the protonation and deprotonation of 4-Mpy on the electrode surface are mainly determined by the adsorption structure of 4-Mpy on the electrode surface. At the same time, we conducted a comparative study of 2-Mpy and 4-Mpy molecules and found that the adsorption modes were different depending on the position of the N atom. 2-Mpy is inclined adsorbed on the surface of the Au-NP film electrode, and 4-Mpy is vertically adsorbed on the surface of the Au-NP film electrode.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"165-175"},"PeriodicalIF":2.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362989","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":"Effect of Deuteration on Raman Scattering in Single Crystals of Potassium Alum","authors":"L. P. Avakyants,&nbsp;A. V. Skrabatun,&nbsp;A. Yu. Pyatyshev","doi":"10.1002/jrs.6747","DOIUrl":"https://doi.org/10.1002/jrs.6747","url":null,"abstract":"<div>\u0000 \u0000 <p>Raman spectra of KAl(SO₄)₂·12H₂O and KAl(SO₄)₂·12D₂O crystals in the range of 10–4000 cm⁻¹ were experimentally obtained and studied. An increase in the number of sulfate ions, oriented by oxygen atoms towards the K⁺ ion, was detected upon deuteration of the sample. Low-intensity Stokes components ν = 2485 cm⁻¹ (ν = 1820 cm⁻¹ for the deuterated crystal) were recorded, which indicates the formation of hydrogen bonds O–H•••SO₄²⁻ (O–D•••SO₄²⁻), where the donors are water molecules of the [Al(H₂O)₆]³⁺ complex and the oxygen atoms of the sulfate ion act as acceptors. The decrease in the wavenumbers of internal vibrations of the sulfate ion during deuteration was explained by an increase in the strength of hydrogen bonds. The results obtained indicate the direct influence of deuteration on the degree of initial disordering of sulfate ions and on the stability of the crystal structure of potassium alum.</p>\u0000 </div>","PeriodicalId":16926,"journal":{"name":"Journal of Raman Spectroscopy","volume":"56 2","pages":"176-183"},"PeriodicalIF":2.4,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362780","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}