Raman spectroscopy of automotive paints: Forensic analysis of variability and spectral quality

Raman spectroscopy was evaluated as a forensic technique for the analysis of automotive paints with the purpose to verify the measurement variability as well as to study the spectral quality by means of parameters and conditions. The objective lens, accumulation number, and laser (power, mode, and wavelength) were observed to significantly affect the spectral quality and thus should be taken into consideration during the development of a forensic database. On the other hand, exposure time, Raman shift range, and baseline correction had less influence on the features of the obtained spectra. Interestingly, samples collected from the bumper coating composed of a plastic substrate in comparison with fragments obtained from other parts of the same vehicle containing metallic substrate showed different absorption band patterns. In addition, less variability of data acquired directly onto the paint chip’s surface has demonstrated that direct analysis should be preferred during spectra library development as opposed to cross-section measurements. Sample homogeneity and distinction power of the technique combined with Principal Components Analysis were also investigated. The preliminary results showed that although Raman spectroscopy is extremely accurate in the identification of vehicles, it is necessary to pay particular attention to the spectral variability in order to avoid false database matching and misleading of forensic investigations. Therefore, we suggest that separated spectra library shall be developed for each laser wavelength as well as for each sample substrate. Further studies with a higher number of paint chips will enable the establishment of prediction models aimed to identify unknown samples involved in hit-and-run cases.     

Experimental and theoretical Raman and surface‐enhanced Raman scattering study of cysteine

Raman spectra in solid and 1 M solution of L ‐cysteine and surface‐enhanced Raman scattering (SERS) spectra of this molecule in the zwitterionic form, by using colloidal silver nanoparticles, have been recorded. Density functional theory with the B3LYP functional was used for the optimizations of the ground state geometries and simulation of the vibrational spectrum of this amino acid. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman and SERS vibrations and the corresponding assignments, as well as a comparison of force constants and geometrical parameters between the free zwitterion cysteine and the one in the presence of the colloidal silver nanoparticles, we can confirm the presence of gauche (P_H) and trans (P_N) rotamers in the solid state, the formation of a S S bond in the solution state, the dissociation of the peptide bond and mixing of rotamers because of the SERS effect, and the relative importance of the interaction of sulphyldryl, NH₃⁺, and carboxylate groups with the metallic surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Anti‐Stokes Raman spectroscopy as a method to identify the metallic and semiconducting configurations of double‐walled carbon nanotubes

Although Raman spectra reveal, as a signature of double‐walled carbon nanotubes (DWCNTs), two radial breathing mode (RBM) lines associated with the inner and outer tubes, the specification of their nature as metallic or semiconducting remains a topic for debate. Investigating the spectral range of the RBM lines, we present a new procedure of the indexing of the semiconducting or metallic nature of the inner and outer shell that forms the DWCNT. The procedure exploits the difference between the intensities of recorded anti‐Stokes Raman spectrum and the anti‐Stokes spectrum calculated by applying the Boltzmann formulae to the recorded Stokes spectrum. The results indicate that the two spectra do not coincide with what should happen in a normal Raman process, namely, that there are RBM lines of the same intensity in both spectra, as well as RBM lines of higher intensity that are observed in the calculated spectrum. This discrepancy results from the surface‐enhanced Raman scattering mechanism that operates differently on metallic or semiconducting nanotubes. In this context, the analysis of the RBM spectrum can reveal pairs of lines associated with the inner/outer shell structure of DWCNT, and when the intensities between the recorded and calculated spectra coincide, the nanotube is metallic; otherwise, the nanotube is semiconducting. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman spectral analysis of renal tissue: a novel application

Renal cell carcinoma (RCC) accounts for 85% of all primary renal cancers. The definitive diagnosis of RCC relies exclusively on the subjective pathological interpretation of the surgical specimen. In this study, we aimed to analyze renal tissue using objective Raman spectroscopy (RS). We obtained 15 pairs of RCC (T) and corresponding normal renal parenchymal tissues (N) from our biobank. There are three subtypes of RCC: clear cell RCC (ccRCC), papillary RCC (pRCC), and chromophobe RCC (cRCC). Five pairs of tissue of each subtype were enrolled. Fresh‐frozen sliced tissues were used for the RS detection. The Raman spectra between T and N were compared and analyzed using partial least squares (PLS) regression. Data for a total of 55 T and 58 N analyzable RS samples were obtained. The spectra were normalized by dividing the intensity of the characteristic peak at 1003 cm⁻¹ using phenylalanine's Raman peak. After further analysis with PLS, the sensitivity and specificity for discriminating T from N were 95% and 93%, respectively. The RCC subtypes can be discriminated at an accuracy of 72% for ccRCC, 88% for cRCC, and 86% for pRCC. This study demonstrates the feasibility of analyzing renal tissue using RS. RS, with its advantages of easy and objective tissue assessment, may be applied to aid intraoperative decision making and pathological tissue assessment. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative Analysis of Simulated Illicit Street-Drug Samples Using Raman Spectroscopy and Partial Least Squares Regression

Modern drug laws require that a seized sample be characterized for both the illegal substances present and the quantity of each of those substances. The goal of this work was to develop a common approach to model development based on Raman spectroscopic analysis followed by partial least squares (PLS) regression that would allow us to obtain quantitative information from simulated street-drug samples. Each drug sample contained one drug surrogate—either isoxsuprine, norephedrine, benzocaine, or lidocaine—and up to 3 different cutting agents. All spectra were acquired on a homebuilt Raman instrument equipped with a rotating sample holder. The same steps were employed for developing separate models for each drug surrogate, including spectral preprocessing by Savitsky-Golay smoothing, differentiation, mean-centering, and autoscaling. PLS models were developed using 2 latent variables that yielded root mean square errors of calibration (RMSEC) values in the 3% range and root mean square error of prediction (RMSEP) values in the 4% range.     

Rayleigh-ritz calculation of the resonant modes of a solid parallelepiped in a pressurizing fluid

Resonant ultrasound spectroscopy relies on comparisons of experimentally determined vibrational spectra to theoretically computed spectra for the extraction of the elastic moduli of the solid samples. To determine the pressure dependence of these moduli, resonant spectra are taken for samples pressurized by a surrounding gas and knowledge of the contribution of the surface loading of the sample by the gas is needed in order to extract the intrinsic pressure dependence of the moduli. To facilitate the required comparisons, a Rayleigh-Ritz variational calculation of the vibrational spectrum is formulated which includes the loading of the solid by the pressurizing fluid. This formalism is used to compute the effect of gas loading on the vibrational spectrum of an isotropic, solid parallelepiped.     

Observation of electronic Raman scattering in metallic carbon nanotubes

We present experimental measurements of the electronic contribution to the Raman spectra of individual metallic single-walled carbon nanotubes (MSWNTs). Photoexcited carriers are inelastically scattered by a continuum of low-energy electron-hole pairs created across the graphenelike linear electronic subbands of the MSWNTs. The optical resonances in MSWNTs give rise to well-defined electronic Raman peaks. This resonant electronic Raman scattering is a unique feature of the electronic structure of these one-dimensional quasimetals.     

Multivariate analysis of combined Raman and fibre‐optic reflectance spectra for the identification of binder materials in simulated medieval paints

The non‐invasive identification of paint materials used in works of art is essential, both for preserving and restoring them, and also for understanding and verifying the history surrounding their creation. As such, the development of suitable non‐invasive techniques has received much interest in recent years. We have investigated the use of Fourier transform (FT)‐Raman spectroscopy and fibre‐optic reflectance spectroscopy (FORS), together with multivariate principal‐component analysis (PCA) techniques, in order to identify the pigment and binding materials used in made‐up samples representative of real artwork. We demonstrate that both types of spectroscopy provide complementary information which can be used to identify the pigments and binders in paint samples. We show that PCA with FT‐Raman spectra can be used to assist in the identification of oil‐based binders, and that the additional data provided by FORS spectra enables PCA on combined spectra to identify more complex proteinaceious and polysaccharide‐based binding media. The results presented here demonstrate that multivariate analyses of lead‐based paints, using data measured by FT‐Raman and FORS in conjunction, have much potential for identifying individual pigments and binders in paint samples. This provides a path towards computer‐assisted characterisation of paint materials on artwork. Copyright © 2013 John Wiley & Sons, Ltd.     

基于表面增强拉曼的饮料中山梨酸钾快速定量检测方法

基于实验室自行搭建的拉曼光谱点扫描系统,利用表面增强拉曼技术对橙味饮料中山梨酸钾的含量进行了定量快速检测研究。通过与山梨酸钾标准品拉曼光谱及其水溶液表面增强拉曼光谱等比较分析,确定了山梨酸钾1 648.4,1 389.3和1 161.8 cm-1处的表面增强特征拉曼位移。通过山梨酸钾橙味饮料平行样品的拉曼位移峰强重现性实验并计算其峰强的相对标准偏差证实了该表面增强拉曼方法具有较好的重复性。采集了山梨酸钾浓度范围为1.706～0.180 7 g·kg-1的33个橙味饮料样品的表面增强拉曼光谱,所有原始光谱经S-G 5点平滑及Baseline基线去除荧光背景预处理后分别用一元线性回归分析、多元线性回归分析和偏最小二乘回归分析方法,建立了山梨酸钾的定量预测模型。经比较,选取三个山梨酸钾拉曼特征位移1 161.8,1 389.3和1 648.4 cm-1所建立的多元线性回归模型校正集的相关系数(R2_C)和均方根误差(RMSEC)分别为0.983 7和0.051 7 g·kg-1,验证集的相关系数(R2_P)和均方根误差(RMSEP)分别为和0.969 9和0.052 8 g·kg-1,比一元线性回归模型和偏最小二乘回归模型误差小、精度高。基于表面增强拉曼完全可以实现橙味饮料中山梨酸钾的定量快速预测,为各类食品中山梨酸钾含量的快速监测奠定了技术基础。     

Raman spectroscopy at different excitation wavelengths (1064, 785 and 532 nm) as a tool for diagnosis of colon cancer

Raman spectroscopy is structure sensitive non‐destructive method that allows observing the status of biological tissues with minimal impact. This method has a great potential in the diagnosis of various types of degenerative diseases including cancer damages. Near‐infrared Fourier transform (NIR‐FT)‐Raman (λ_ex ~1064 nm), NIR‐visible (Vis)‐Raman (λ_ex ~785 nm) and Vis‐Raman (λ_ex ~532 nm) spectra of normal and colorectal carcinoma colon tissue samples were recorded in macroscopic mode at 10–20 randomly chosen independent sites. In the cases of NIR‐Vis‐ and Vis‐Raman spectra, enhanced resonance effects were observed for tissue chromophores absorbing in the visible area. Evident spectral differences were noticed for Raman spectra of normal colon tissue samples in comparison with abnormal samples. The average Raman spectra of colon tissue samples were analysed by principal component analysis (PCA) to discriminate normal and abnormal tissues. PCA of combined dataset containing Raman intensities of chosen NIR‐FT, NIR‐Vis or Vis‐Raman bands led to discrimination of normal and abnormal colon tissue samples. Therefore, combination of these three Raman methods can be helpful for recognizing cancer lesions in colon for diagnostic purposes. Copyright © 2014 John Wiley & Sons, Ltd.     

不同制备方法合成的La0.9Sr0.1Ga0.8Mg0.2O3-δ材料晶体结构研究

分别用低温固相反应、高温固相反应和激光快速凝固技术(LRS)合成了固体氧化物燃料电池电解质材料La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM),用Raman谱和X射线衍射研究了三组样品的晶体结构.三组样品Raman谱的明显差异表明它们分别属于三种不同的晶体结构.实验Raman谱与计算的三种可能晶体结构(立方...     

基于傅里叶红外光谱的汽车车身油漆比对

为了通过事故现场遗留的车辆油漆快速排查及确定肇事逃逸车辆的车型范围,采集了287份汽车车身油漆样本,获得了940份油漆红外光谱,建立了汽车车身油漆红外光谱比对数据库。结合特征波峰法与相关系数法实现了车身油漆光谱的比对,并对不同类型油漆碎片进行了比对实验。实验结果表明：对于层次完整的油漆碎片,比对的重点是面漆层和中涂层光谱;对于不完整的油漆碎片,应层次分离后分层进行光谱检索;对于老化油漆,应以面漆层的光谱匹配为主,扩大搜索范围后综合分析搜寻嫌疑车型。     

Raman spectroscopic characterization of a thiophene‐based active material for resistive organic nonvolatile memories

A combined theoretical and experimental Raman study is presented on a diphenyl bithiophene molecule known as a good candidate for the development of organic nonvolatile memory devices. Spectroscopic markers suitable to distinguish the different stable conformers of the molecule have been predicted and detected. The combined analysis of theoretical and experimental Raman spectra recorded in solution indicates that at room temperature a dynamical equilibrium, characterized by interconversion between the two more stable conformers (namely trans and cis), takes place and that the more populated species is the cis form. Referring to the solid phase instead, Raman spectra of single‐crystal samples show the presence of the only trans conformer, as confirmed by X‐ray measurements. Finally, Raman spectra of thin films, as those used for the memory device, were collected; samples just deposited from solution and after few hours from the deposition were analyzed. Following the evolution of selective spectroscopic Raman markers, an isomerization process from the abundant cis (as‐deposited) to the totally trans (after few hours) conformer in the solid phase was detected. These results open the way to the identification of the molecular isomers present in the thin film of the memory cell and finally of the active molecular species involved in the switching mechanism of the operating device. Copyright © 2009 John Wiley & Sons, Ltd.     

苹果可溶性固形物和糖酸比可见/近红外漫反射与漫透射在线检测对比研究

可溶性固形物和糖酸比是苹果内部品质主要评价指标之一。为此进行苹果糖酸比和可溶性固形物可见/近红外漫反射和漫透射对比检测研究。180个冰糖心和红富士样品被分成建模集和预测集(136∶44),分别用于建立偏最小二乘模型和验证模型的预测能力。在运动速度5个/秒时,采集了冰糖心和红富士两种样品的可见近红外光谱。漫反射和漫透射可见近红外光谱经多元散射校正、标准正态变量变换、基线校正等预处理后,建立了偏最小二乘回归模型。未参与建模的44个样品用于评价模型的预测能力,经比较,漫透射检测方式优于漫反射检测方式,主要因为漫透射检测方式能更有效地克服杂散光。可溶性固形物模型预测相关系数达到0.936,预测均方根误差为0.476°Brix;糖酸比模型预测相关系数达到0.785,预测均方根误差为10.94。研究结果表明： 应用可见/近红外漫透射光谱技术,可实现苹果可溶性固形物和糖酸比在线检测。为大宗水果内部品质分选提供了技术支持和参考依据。     

A volume‐exclusion normalization procedure for quantitative Raman confocal microspectroscopy of immersed samples applied to human embryonic stem cells

Raman microspectroscopy is a quantitative instrumental method with considerable promise for the nondestructive analysis of living biological samples. Amongst samples of particular interest are human embryonic stem cells because of their therapeutic potential and because examination using Raman microspectroscopy does not appear to adversely affect this potential. However, it can be difficult to compare different spectra obtained with this technique and to quantify the native cellular constituents of such samples because their characteristic dimensions are difficult to establish or may vary from point to point. We present here a method to normalize spectra and estimate sample thicknesses based on a reference component present in the basal cell culture medium when we perform spectroscopy on colonies of living cells. Because more basal medium is displaced from the sampling volume as the cell layer increases in thickness, and because this component is present in the medium but excluded from cells, a concomitant decline therefore occurs in the intensity of the Raman scattering from the reference component. This permits comparisons between samples because their spectra can be scaled in inverse relation to their excluded volumes. Furthermore, estimations of sample thicknesses can also be obtained based on the same concept. Thus, the absolute quantification of cellular components becomes possible because cell sample volumes can be determined. Although applied to human embryonic stem cells, the approach is sufficiently general to be adapted for use with other samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Teaching Raman Spectroscopy in Both the Undergraduate Classroom and the Laboratory with a Portable Raman Instrument

We have evaluated a small portable Raman instrument on loan from B&W Tek, Inc., and have determined that it can successfully be used in the classroom both as a visual aid for teaching the fundamentals of Raman spectroscopy and for a variety of undergraduate experiments as a normal component of an instrumental analysis class. Having portable Raman instrumentation would allow the instructor to demonstrate the principles of Raman spectroscopy, as well as the concepts of calibration curves, blank subtraction, detection limits, and regression analysis. Both qualitative and quantitative types of experiments were done for solid Tylenol tablets, aqueous solutions of isopropyl alcohol, dimethyl sulfoxide, methanol, and ethanol, and gaseous CO₂ and N₂O₄. Additionally, surface‐enhanced resonance Raman spectra of Rhodamine 6G were obtained using a chloride ion–activated silver colloid. Spectra from the B&W Tek, Inc., instrument were comparable to literature Raman spectra.     

Analysis of alizarin by surface‐enhanced and FT‐Raman spectroscopy

This paper presents the application of Raman spectroscopy (RS) for the structural study of alizarin adsorbed on a metallic surface. As a biologically active molecule, alizarin has remarkable antigenotoxic activity like other anthraquinone dyes. Alizarin is highly fluorescent and that limits the application of RS as an investigation method; however, the Fourier transform‐RS (FTRS) can be applied since the near‐infrared excitation line lies far away from the absorption region of alizarin. The surface enhanced‐RS (SERS) technique also makes the fluorescence quenching possible. In this work, monolayers of alizarin were deposited on the surface of an electrode by the immersion of silver substrates in methanolic solution of the analyte. From such prepared samples, by using the excitation of 488, 514.5 and 647.1 nm the Raman spectra were registered. Depending on the excitation line, SERS or surface‐enhanced resonance Raman scattering (SERRS) spectra of alizarin were observed. The interpretation of experimental data was supported by theoretical calculations. Copyright © 2008 John Wiley & Sons, Ltd.     

基于共焦显微拉曼的柑橘黄龙病无损检测研究

黄龙病危害柑橘果树日益严重,对柑橘黄龙病进行快速检测研究具有重大意义。采用拉曼光谱技术,结合偏最小二乘判别分析(PLS-DA)方法探讨快速诊断柑橘黄龙病及病情类别的可行性。获取柑橘叶片拉曼光谱并进行普通PCR鉴别分为轻度、中度、重度、缺素和正常5类。在715～1 639.5 cm-1范围内采用一阶导,基线校正(Baseline)和多项式拟合三种方法扣除光谱背景,突显叶片拉曼光谱特征峰。多项式拟合方法分别进行了2次,3次和4次拟合,与一阶导和基线校正两种扣除背景方法进行比较,结合最小二乘支持向量机(LS-SVM)和偏最小二乘判别分析(PLS-DA)建立判别模型。经比较发现,多项式拟合方法扣除光谱背景效果均好于另外两种方法,其中用2次多项式拟合的PLS-DA模型的效果最好,预测相关系数(R_P)为0.98,预测均方根误差(RMSEP)为0.67,总误判率最小为0。基线校正扣除光谱背景的LS-SVM模型效果最差,总误判率最大为40%。研究结果表明,利用拉曼光谱技术对柑橘黄龙病进行快速识别研究具有一定的可行性,为柑橘黄龙病无损检测研究提供一种新途径。     

Vibrational spectra of lead(II) oxalate

The infrared and Raman spectra of anhydrous lead oxalate (PbC₂O₄) were recorded and discussed on the basis of its structural peculiarities. Some comparisons with other previously investigated metallic oxalates were made. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman-in-SEM,a multimodal and multiscale analytical tool: Performance for materials and expertise

The availability of Raman spectroscopy in a powerful analytical scanning electron microscope (SEM) allows morphological, elemental, chemical, physical and electronic analysis without moving the sample between instruments. This paper documents the metrological performance of the SEMSCA commercial Raman interface operated in a low vacuum SEM. It provides multiscale and multimodal analyses as Raman/EDS, Raman/cathodoluminescence or Raman/STEM (STEM: scanning transmission electron microscopy) as well as Raman spectroscopy on nanomaterials. Since Raman spectroscopy in a SEM can be influenced by several SEM-related phenomena, this paper firstly presents a comparison of this new tool with a conventional micro-Raman spectrometer. Then, some possible artefacts are documented, which are due to the impact of electron beam-induced contamination or cathodoluminescence contribution to the Raman spectra, especially with geological samples. These effects are easily overcome by changing or adapting the Raman spectrometer and the SEM settings and methodology. The deletion of the adverse effect of cathodoluminescence is solved by using a SEM beam shutter during Raman acquisition. In contrast, this interface provides the ability to record the cathodoluminescence (CL) spectrum of a phase. In a second part, this study highlights the interest and efficiency of the coupling in characterizing micrometric phases at the same point. This multimodal approach is illustrated with various issues encountered in geosciences.