A novel method for quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy

In this study, direct quantification of ethanol and methanol in distilled alcoholic beverages using Raman spectroscopy was performed. Raman spectra of varying ethanol–methanol mixtures were obtained, baseline corrections were made, and the data were normalized using Raman scattering intensity of an internal standard (acetonitrile, 921 cm^–1). Then, calibration graphs were produced for ethanol and methanol concentrations in the ranges of 0–7 M and 0–10 M, respectively. Accurate R² values of the calibration graphs proved the notable linear correlations (0.998 for ethanol and 0.998 for methanol). The method was validated based on linearity, sensitivity, intraday and interday repeatability, and recovery tests. The limit of detection and limit of quantification values of the validated method were determined for ethanol concentration as 1.2 and 3.7 mM, and for methanol concentration as 3.4 and 10.3 mM, respectively. The ability of the developed method to detect ethanol and methanol concentrations in real samples was also investigated. The results of the developed method were compared with the experimental results from traditional method and high correlation value (R² = 0.926) was obtained. Besides being sensitive and cheap, the developed method is rapid with the analysis time of less than 30 s. Furthermore, it eliminates labor‐consuming operations, chromatographic separation, and measurement error due to the high number of experiment steps in the standard method. Copyright © 2012 John Wiley & Sons, Ltd.     

一种基于拉曼光谱的石油产品快速分类方法

提出了一种基于拉曼光谱的石油产品快速分类方法.首先,利用经过谱图预处理的石油产品训练样本拉曼谱图构建模型知识库,计算各类别的特征拉曼谱图和类内阈值;其次,将石油产品测试样本的拉曼谱图经过相同的预处理,再计算其与各类别特征拉曼谱图的线性相关系数,若最大相关系数大于或等于最大相关系数对应类别的类内阈值,则该样本属于此类别....     

Microbiological identification by surface-enhanced Raman spectroscopy

New methods for pathogens identification are of growing interest in clinical and food sectors. The challenge remains to develop rapid methods that are more simple, reliable, and specific. Surface-enhanced Raman spectroscopy (SERS) appears to be a promising tool to compete with current untargeted identification methods. This article presents the intensive research devoted to the use of SERS for bacterial identification, from the first to the very recent published results. Compared to normal Raman spectroscopy, the introduction of nanoparticles for SERS acquisition introduces a new degree of complexity. Bacterial Raman fingerprints, which are already subject to high spectral variability for a given strain, become then very dependent on numerous experimental parameters. To overcome these limitations, several approaches have been proposed to prepare the sample, from the microbiological culture conditions to the analysis of the spectrum including the coupling of nanoparticles on the bacterial membrane. Main strategies proposed over the last 20 years are examined here and discussed in the perspective of a protocol transfer towards industry.     

Assessment of robustness and transferability of classification models built for cancer diagnostics using Raman spectroscopy

Over recent years, Raman spectroscopy has been demonstrated as a prospective tool for application in cancer diagnostics. The use of Raman spectroscopy for this purpose relies on pattern recognition methods that have been developed to perform well on data achieved under laboratory conditions. However, the application of Raman spectroscopy as a routine clinical tool is likely to result in imperfect data due to instrument‐to‐instrument variation. Such corruption to the pure tissue spectral data is expected to negatively impact the classification performance of the diagnostic model. In this paper, we present a thorough assessment of the robustness of the Raman approach. This was achieved by perturbing a set of spectra in different ways, including various linear shifts, nonlinear shifts and random noise and using previously optimised classification models to predict the class membership of each spectrum in a testing set. The loss of predictive power with increased corruption was used to calculate a score, which allows an easy comparison of the model robustness. For this approach, three different types of classification models, including linear discriminant analysis (LDA), partial least square discriminant analysis (PLS‐DA) and support vector machine (SVM), built for lymph node diagnostics were the subject of the robustness testing. The results showed that a linear perturbation had the highest impact on the performance of all classification models. Among all linear corruption methods, a gradient y‐shift resulted in the highest performance loss. Thus, the factor most likely to affect the predictive outcome of models when using different systems is a gradient y‐shift. Copyright © 2010 John Wiley & Sons, Ltd.     

Quantitative and multicomponent analysis of prevalent urinary calculi using Raman spectroscopy

This study established a quantitative micro‐Raman spectroscopic (MRS) method for measuring multicomponents (binary and ternary compositions) of prevalent urine calculi extracted from the ureter after the ureteroscopic lithotripsy (URSL) procedure. The analysis used calibration curves of known mixtures of synthetically prepared calcium oxalate monohydrate (COM), hydroxyapatite (HAP), calcium oxalate dehydrate (COD), dicalcium phosphate dehydrate (DCPD), and uric acid. A variety of samples of binary and ternary mixtures including COM/HAP, COM/COD, COD/HAP, COM/uric acid, COD/uric acid, HAP/uric acid, HAP/DCPD, and COM/COD/HAP were prepared in various concentration ratios for use as the basis of the quantitative analysis. Intensities of the characteristic bands at 961 cm⁻¹ (I_HAP), 986 cm⁻¹ (I_DCPD), 1402 cm⁻¹ (I_UricAcid), 1462 cm⁻¹ (I_COM), and 1477 cm⁻¹ (I_COD) were used for the calculation. We derived a set of quantitative analysis equations for the ternary composition COD/COM/HAP group by combining two binary equations from the groups COM/COD and the HAP/COM. This study quantitatively measured 18 urine samples extracted from the 18 patients' ureters after the URSL procedure. Fifteen samples were binary mixtures, whereas three samples were ternary mixtures. This research successfully applied the quantitative MRS‐based analysis technique from bench to bedside. Copyright © 2012 John Wiley & Sons, Ltd.     

Near-infrared Raman spectroscopy using hollow-core photonic bandgap fibers

We report a NIR Raman spectroscopy system incorporating hollow-core photonic bandgap fibers (HC-PBFs) in both the excitation and collection paths. Raman excitation was achieved at NIR laser wavelength of 785 nm. We demonstrate that using HC-PBFs, Raman spectroscopy can be performed without the use of an additional longpass filter on the collection side. A narrow bandpass filter on the excitation side is also not required. These results provide a framework where HC-PBF based Raman probes can be developed and used in space restricted biomedical and sensing applications.     

An analysis of bivalve larval shell pigments using micro‐Raman spectroscopy

Micro‐Raman spectroscopy has been used on adult bivalve shells to investigate organic and inorganic shell components but has not yet been applied to bivalve larvae. It is known that the organic matrix of larval shells contains pigments, but less is known about the presence or source of these molecules in larvae. We investigated Raman spectra of seven species of bivalve larvae to assess the types of pigments present in shells of each species and how the ratio of inorganic : organic material changes in a dorso‐ventral direction. In laboratory experiments, we reared larvae of three clam species in waters containing different organic signatures to determine if larvae incorporated compounds from source waters into their shells. We found differences in spectra and pigments between most species but found less intraspecific differences. A neural network classifier for Raman spectra classified five out of seven species with greater than 85% accuracy. There were slight differences between the amount and type of pigment present along the shell, with the prodissoconch I and shell margin areas being the most variable. Raman spectra of 1‐day‐old larvae were found to be differentiable when larvae were reared in waters with different organic signatures. With micro‐Raman spectroscopy, it may be possible to identify some unknown species in the wild and trace their natal origins, which could enhance identification accuracy of bivalve larvae and ultimately aid management and restoration efforts. Copyright © 2014 John Wiley & Sons, Ltd.     

A rapid,non‐destructive method of detecting diagenetic alteration in fossil bone using Raman spectroscopy

Biogenic isotopes of analytical interest may be stripped from bone during burial, reducing the utility of fossil specimens for paleobiological and paleoenvironmental reconstruction. Denudation of the bone lattice coupled with the addition of exotic ions can influence the Raman spectra of fossil bone. Modern bone samples (n = 43) were used to establish an unaltered bone standard, and a suite of synthetic apatite samples were produced to simulate the addition of various ions into the bone mineral lattice. Diagenetic alteration produces distinct spectral characters, providing qualifications for major ionic substitution, ionic heterogeneity, the abundance of structural carbonate, the presence of calcium carbonate and the presence of luminescent ions. Spectral indicators (proxies) provide the means of rapidly and nondestructively evaluating the degree of alteration and thus the analytical utility of fossil bones, potentially avoiding exhaustive and destructive analysis on finite material. Copyright © 2007 John Wiley & Sons, Ltd.     

喇曼感生克尔效应光谱的琼斯矩阵分析

介绍喇曼感生克尔效应光谱(RIKES)的琼斯(Jones)矩阵分析方法.探测光束的传输强度不仅由所经过的每一个光学器件的琼斯矩阵所决定,而且还受到强的泵波在非线性介质样品中感生依赖于强度的二向色性和双折射(克尔效应)对琼斯矩阵的影响.同时计及样品和光学器件由强泵波作用下感生应力和其他外部产生的线双折射对喇曼感生克尔效应光谱观察的不利影响,导出测量系统的功率传输函数的完整表达式和喇曼感生克尔效应光谱的实现观察条件,最后简述以甲笨(C_7H_8)液体为试样的喇曼感生克尔效应光谱实验结果分析.     

A novel demonstration of photoacoustic Raman spectroscopy with combined stimulated Raman pumping in H2 molecule

We present the experimental demonstration of a novel, efficient, and vibrational selective technique to prepare population in vibrational level v″ = 1 using the stimulated Raman pumping. Photoacoustic Raman signal has been studied in non-radiative transitions in the molecule H₂ (v″ = 0) and (v″ = 1). The population fraction in the v″ = 1 level can be estimated by using combined photoacoustic Raman spectroscopy with stimulated Raman pumping for the first time.     

激光拉曼光谱对苯的低浓度探测研究

激光拉曼光谱技术是基于拉曼散射理论的检测技术,具有快速、无损、样品无需预处理等优点。运用激光拉曼光谱技术对苯的25种不同浓度的样品进行了研究,结果表明,在184.8g/L~0.264g/L浓度范围内,苯的振动拉曼光谱强度与其浓度呈线性关系,利用最小二乘法拟合得到线性相关系数R=0.99626,检出限为0.223g/L。     

Experimental and statistical analysis methods for peptide detection using surface‐enhanced Raman spectroscopy

Surface‐enhanced Raman spectroscopy (SERS) has the potential to make a significant impact in biology research due to its ability to provide information orthogonal to that obtained by traditional techniques such as mass spectrometry (MS). While SERS has been well studied for its use in chemical applications, detailed investigations with biological molecules are less common. In addition, a clear understanding of how methodology and molecular characteristics impact the intensity, the number of peaks, and the signal‐to‐noise of SERS spectra is largely missing. By varying the concentration and order of addition of the SERS‐enhancer salt (LiCl) with colloidal silver, we were able to evaluate the impact of these variables on peptide spectra using a quantitative measure of spectra quality based on the number of peaks and peak intensity. The LiCl concentration and order of addition that produced the best SERS spectra were applied to a panel of synthetic peptides with a range of charges and isoelectric points (pIs) where the pI was directly correlated with higher spectral quality. Those peptides with moderate to high pIs and spectra quality scores were differentiated from each other using the improved method and a hierarchical clustering algorithm. In addition, the same method and algorithm was applied to a set of highly similar phosphorylated peptides, and it was possible to successfully classify the majority of peptides on the basis of species‐specific peak differences. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and surface-enhanced Raman spectroscopy evidence for oxidation-induced decomposition of graphite

It has been proposed that reduction of exfoliated graphite oxide could be a potential method for producing large quantities of graphene. Raman and surface-enhanced Raman spectroscopy are used to show that oxidation of graphite and exfoliated graphite significantly increases the defect structure of both materials. This would likely lead to a heavily defected graphene structure when oxygen is removed. To insure the observed decomposition is not due to the laser light, the effect of laser intensity on the materials was investigated. It was found that at the highest laser intensity (1.4 × 10⁸ W/M²) there was a significant increase in defects. However, lower laser intensity was found which did not produce defects and was used in the studies of the effect of oxidation on the spectra.     

Application of portable Raman spectroscopy and benchtop spatially offset Raman spectroscopy to interrogate concealed biomaterials

In this paper, we demonstrate the ability of portable Raman spectroscopy and benchtop spatially offset Raman spectroscopy (SORS) techniques to rapidly identify real and fake ivory samples. Both techniques were able to identify exposed genuine from fake ivory samples. In contrast to conventional Raman spectroscopy, SORS was, in addition, able to identify ivory concealed by plastics, paints, varnishes and cloth. Application of the SORS technique allows the interrogation of biomaterial samples through materials in which conventional Raman spectroscopic instrumentation cannot penetrate. Copyright © 2009 John Wiley & Sons, Ltd.     

Applications of Raman spectroscopy in herbal medicine

Raman spectroscopic techniques are a group of chemical fingerprint detection methods based on molecular vibrational spectroscopy. They are compatible with aqueous solutions and are time saving, nondestructive, and highly informative. With complementary and alternative medicine (CAM) becoming increasingly popular, more people are consuming natural herbal medicines. Thus, chemical fingerprints of herbal medicines are investigated to determine the content of these products. In this study, I review the different types of Raman spectroscopic techniques used in fingerprinting herbal medicines, including dispersive Raman spectroscopy, resonance Raman spectroscopy, Fourier transform (FT)–Raman spectroscopy, surface-enhanced Raman scattering (SERS) spectroscopy, and confocal/microscopic Raman spectroscopy. Lab-grade Raman spectroscopy instruments help detect the chemical components of herbal medicines effectively and accurately without the need for complicated separation and extraction procedures. In addition, portable Raman spectroscopy instruments could be used to monitor the health and safety compliance of herbal products in the consumer market.     

Raman spectroscopy as a rapid screening method for ancient plain window glass

The aim of this paper is to highlight the potential of Raman spectroscopy as a fast screening method for large amounts of glass samples. Besides the dedicated research of specific glass collections during the last ten years, a broad corpus of archaeological window glass still needs to be investigated. For many sites, the amount of excavated glass artefacts is enormous and a selection of the most appropriate samples for chemical analysis is necessary. A classification can be made on the basis of the typical Raman signatures for the different kinds of glasses (alkali glass, high‐lime low‐alkali (HLLA) glass, Pb‐rich glass). Even in case of strong fluorescence, an uncomplicated treatment (normalisation) of the measured signals makes it possible to distinguish between the different types of glass. The preliminary screening of glass artefacts with Raman spectroscopy is a useful tool in the study of historical glass and can already answer some questions about provenance, period of production and authenticity of the glass samples. Copyright © 2010 John Wiley & Sons, Ltd.     

纳米级润滑膜分子排列取向的拉曼光谱表征技术

利用激光拉曼散射技术,对剪切作用下受限于钢球与石英盘之间的纳米级液晶5 CB的分子排列取向进行研究. 结果表明,在特定的实验条件下,可以得到高信噪比的纳米级润滑膜的拉曼散射信号(20∶1). 同时发现,当激光偏振方向与剪切运动方向平行(垂直)时,所得拉曼信号强度达到最大(小)值,表明纳米级液晶5 CB分子在剪切诱导作用下,沿剪切运动方向趋于定向排列. 另外,当钢球与石英盘之间的剪切速度逐渐增大时,受限的纳米级液晶5 CB的拉曼信号强度也逐渐增大. 最后,利用根据相对光强干涉原理研制的纳米膜厚测量仪对纳米级 关键词： 薄膜润滑 分子排列取向 拉曼散射     

Recent Advances in linear and nonlinear Raman spectroscopy I

Raman spectroscopy has advanced considerably in the last several years due to rapid developments in instrumentation and the availability of theoretical methods for accurate calculation of Raman spectra, thus enormously facilitating the interpretation of Raman data. This review is restricted to cover papers mainly published in the Journal of Raman Spectroscopy, which serve to give a fast overview of recent advances in this research field as well as to provide readers of this journal a quick introduction to the various subfields of Raman spectroscopy. It also reflects the current research interests of the Raman community. Similar reviews of highly active areas of Raman spectroscopy will appear in future issues of this journal. Copyright © 2007 John Wiley & Sons, Ltd.     

A method for measuring bending stresses based on electromagnetic actuation and Raman spectroscopy

Bending stress and fracture strength of micromachined structures are the parameters determining the function and life span of microelectromechanical systems (MEMS) and are also indispensable data for MEMS design. This paper reports the results of a study in which a bending stress measurement method based on electromagnetic actuation and Raman spectroscopy has been examined. In this study, an eight‐cantilever mass structure is chosen as the experimental object. The results have indicated that it can accurately measure the bending stresses and fracture strength. Copyright © 2006 John Wiley & Sons, Ltd.     

Multiclass discrimination of cervical precancers using Raman spectroscopy

Raman spectroscopy has the potential to differentiate among the various stages leading to high‐grade cervical cancer such as normal, squamous metaplasia, and low‐grade cancer. For Raman spectroscopy to successfully differentiate among the stages, an applicable statistical method must be developed. Algorithms like linear discriminant analysis (LDA) are incapable of differentiating among three or more types of tissues. We developed a novel statistical method combining the method of maximum representation and discrimination feature (MRDF) to extract diagnostic information with sparse multinomial logistic regression (SMLR) to classify spectra based on nonlinear features for multiclass analysis of Raman spectra. We found that high‐grade spectra classified correctly 95% of the time; low‐grade data classified correctly 74% of the time, improving sensitivity from 92 to 98% and specificity from 81 to 96% suggesting that MRDF with SMLR is a more appropriate technique for categorizing Raman spectra. SMLR also outputs a posterior probability to evaluate the algorithm's accuracy. This combined method holds promise to diagnose subtle changes leading to cervical cancer. Copyright © 2008 John Wiley & Sons, Ltd.