Quantitative Raman spectroscopy: speciation of cesium silicate glasses

The silicate speciation forms an important aspect of the structure of silicate melts, a subject of interest to both the earth‐ and materials science communities. In this study, the Qⁿ speciation of binary cesium silicate glasses was studied by Raman spectroscopy. A method to extract the equilibrium constant from a set of Raman spectra is presented, and the least‐squares optimization algorithm is given (in Supporting Information). Log(K), the equilibrium constant of the speciation reaction, 2Q³ = Q⁴ + Q², equals −2.72 ± 0.11 at the glass transition. This extends the previously established correlation between log(K) and the inverse of the ionic radius of the network modifier to cesium. Copyright © 2009 John Wiley & Sons, Ltd.     

硅酸盐熔体微结构单元的对称伸缩模的拉曼散射系数

通过一种新开发的模拟计算方法，计算了硅酸钠熔体的拉曼谱，及其在高频区代表5种硅氧 四面体(用Qi表示，其中i表示桥氧数)的特征峰的拉曼散射系数Si，发现成分的变化对5 种Qi的特征峰的拉曼散射系数的影响非常小.在此基础上取平均分别得到：S0=1,S1=0 ．514,S2=0242,S3=0090和S4=0015然后将计算得到的散射系数应用于二硅酸 钠熔体的实验谱图的定量分析中，得到了该熔体中硅氧四面体单元的分布.同时从计算与试 验谱图的定量解谱中发现，钠系硅酸盐熔体谱中Q0和Q2的ASS模所产生的散射信号 不容忽视. 关键词： 拉曼散射系数 硅氧四面体 硅酸盐熔体 高温拉曼谱     

Raman spectroscopy of the nickel silicate mineral pecoraite—an analogue of chrysotile (asbestos)

The molecular structure of the mineral pecoraite, the nickel analogue of chrysotile of formula Ni₃Si₂O₅(OH)₄, was analysed by a combination of Raman and infrared spectroscopies. A comparison is made with the spectra of the minerals nepouite and chrysotile and a synthetic pecoraite. Pecoraite is characterised by OH stretching vibrations at 3645 and 3683 cm⁻¹ attributed to the inner and inner surface hydroxyl stretching vibrations. Intense infrared bands at around 3288 and 3425 cm⁻¹ are assigned to the stretching vibrations of water strongly hydrogen‐bonded to the surface of the pecoraite. The asbestos‐like mineral is characterised by SiO stretching vibrations at 979, 1075, 1128 and 1384 cm⁻¹, OSiO chain vibrations at 616 and 761 cm⁻¹ and Ni O(H) vibrations at 397 and 451 cm⁻¹. Copyright © 2008 John Wiley & Sons, Ltd.     

Temperature-induced phase transition in phlogopite revealed by Raman spectroscopy

Raman study of a natural hydrous phlogopite was carried out at temperatures up to 500 °C for the first time. Evolution of four well-resolved Raman modes at wavenumbers 196, 278, 322, and 682 cm⁻¹ was followed in detail with temperature increase. The analysis of data reveals linear decrease of vibrational wavenumbers in the studied temperature range, with small but experimentally significant discontinuities occurring at a temperature of 365±15 °C. Although the overall appearance of Raman spectra remains intact on crossing this temperature, the presence of discontinuities, as well as a marked difference between Gruneisen parameters calculated for high- and low-temperature ranges, signifies the presence of a temperature-induced phase transformation. By combining and correlating the results of the present Raman study with the high-temperature X-ray work performed by Tutti et al. [High-temperature study and thermal expansion of phlogopite, Phys. Chem. Miner. 27 (2000) 599-603] we arrive at the interpretation of a temperature-induced structural phase transformation in phlogopite without a significant symmetry change, with an underlying microscopic mechanism involving deformation of Mg octahedra and rotation of tetrahedral grid from ditrigonal toward hexagonal at the transition temperature.     

Structural study of Mg‐bearing sodosilicate glasses by Raman spectroscopy

The presence of magnesium in glasses of geological, medical, and technological interests influences their physicochemical and durability properties. However, the understanding of the role of magnesium is dependent on the combined knowledge of the structural environment of magnesium in the glass or melt and of the silicate network connectivity of the studied systems. In this article, we present a Raman spectroscopic study of the network connectivity of 10 ternary silicate glasses in the system Na₂O MgO SiO₂ and one Mg‐free binary silicate glass Na₂O SiO₂. Results obtained at constant polymerization suggest the existence of various Qⁿ units according to the nature of the modifying cation. As polymerization decreases for Na₂O MgO αSiO₂ glasses (labeled as NMSα with α decreasing from 10 to 2), the band associated with Si O Si bending in fully polymerized region disappears being gradually replaced by a band attributed to Si O Si bending in region containing mainly Q² and Q³ species. For highly polymerized glasses (NMS10‐NMS4), the coexistence of these two bands suggests the presence of two interconnected networks. Concomitantly, the signal associated with Q³ species first increases. For a further decrease of the polymerization, the high wavenumber part of the signal associated with Q³ species decreases, while the intensity of the high wavenumber part of the band related to Q² species increases. This result strongly suggests that magnesium charge‐balances preferentially Q² species rather than Q³ species. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

The structure of solvated halide ions in dimethyl sulfoxide studied by Raman spectroscopy and X-ray diffraction

The solvation structure of chloride, bromide, and iodide ions, X⁻, in dimethyl sulfoxide (DMSO) has been investigated by using Raman spectroscopy and large angle X-ray diffraction under ambient conditions. The positively charged sulfur atom in DMSO interacts with X⁻ and slightly positively charged methyl groups in the coordinating molecules also interact with X⁻. The X⁻---S, X⁻···C, and X⁻···O distances are determined as follows: Cl⁻---S: 416, Cl⁻···C: 363, Cl⁻···O: 543, Br⁻---S: 433, Br⁻···C: 372, Br⁻···O: 544, I⁻---S: 437, I⁻···C: 374 and I⁻···O: 520 pm. The coordination numbers of DMSO molecules around the anions are six, seven and eight for Cl⁻, Br⁻ and I⁻ ions, respectively, with the uncertainty of ±1. Rather large uncertainties in the measured solvation numbers suggest large fluctuations in the solvation structure of the anions.     

Raman spectroscopy of the joaquinite minerals

Selected joaquinite minerals have been studied by Raman spectroscopy. The minerals are categorised into two groups depending upon whether bands occur in the 3250 to 3450 cm⁻¹ region and in the 3450 to 3600 cm⁻¹ region, or in the latter region only. The first set of bands is attributed to water stretching vibrations and the second set to OH stretching bands. In the literature, X‐ray diffraction could not identify the presence of OH units in the structure of joaquinite. Raman spectroscopy proves that the joaquinite mineral group contains OH units in their structure, and in some cases both water and OH units. A series of bands at 1123, 1062, 1031, 971, 912 and 892 cm⁻¹ are assigned to SiO stretching vibrations. Bands above 1000 cm⁻¹ are attributable to the ν_as modes of the (SiO₄)⁴⁻ and (Si₂O₇)⁶⁻ units. Bands that are observed at 738, around 700, 682 and around 668, 621 and 602 cm⁻¹ are attributed to O Si O bending modes. The patterns do not appear to match the published infrared spectral patterns of either (SiO₄)⁴⁻ or (Si₂O₇)⁶⁻ units. The reason is attributed to the actual formulation of the joaquinite mineral, in which significant amounts of Ti or Nb and Fe are found. Copyright © 2007 John Wiley & Sons, Ltd.     

Breast cancer diagnostics by Raman spectroscopy

This paper presents new results for the normal, malignant and benign tissues by Raman spectroscopy. To the best of our knowledge, this is one of the most statistically reliable research (321 spectra from 44 patients) on Raman spectroscopy-based diagnosis of breast cancers among the world's women population. The paper demonstrates that Raman spectroscopy is a powerful medical diagnostic tool with the key advantage in breast cancer research.     

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.     

Quantitative analysis of solid-phase mixtures by Raman spectroscopy

We propose a method for using Raman spectroscopy to determine the phase compositions and concentrations in solid-phase equilibrium mixtures. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 416–418, May–June, 2008.     

Phase Transition and vibration properties of MnCO3 at high pressure and high-temperature by Raman spectroscopy

The high pressure and high-temperature behavior of MnCO₃ was investigated up to 55?GPa at ambient temperature and up to 573?K at ambient pressure by Raman spectroscopy, respectively. Some new modes were detected at ～16 and ～32?GPa, which were assigned to MnCO₃-I below 16?GPa and to MnCO₃-II above 32?GPa, and to a coexisting phase of them in between. The high pressure vibration properties of all Raman modes, especially high frequency modes, were systematically reported. The coexisting phase of MnCO₃-I and MnCO₃-II had much easier compressibility than the MnCO₃-II phase. The thermal stability of MnCO₃ was at least to 573?K and its thermal expansion along the c axis was easier than a and b axes.     

Structure and phase transformation of alkali silicate melts analysed by Raman spectroscopy

Raman spectra of binary alkali silicates were measured at various temperatures from 1300°C to room temperature to investigate the relation between structural change and phase transformation phenomena. Distribution of structural units of Q ⁿ was estimated at each temperature by the deconvolution of spectra based on the equilibrium 2Q³ ? Q² + Q⁴. The Q ⁿ distributions of sodium and potassium silicate systems strongly depend on temperature and the equilibrium shifts to the left-hand side with decreasing temperature, but those of lithium silicate system were less sensitive to the temperature variation. In alkali disilicates (33?mol%?R₂O–67?mol%?SiO₂, where R=Li, Na or K), the Q ⁿ distributions near the melting point were independent of alkali ion species, and they held the relation [Q²]?=?[Q⁴]?≈?[Q³]/4. This means that two of 6Q³ units (six-memberd ring) in crystals are transformed into a pair of Q² and Q⁴ in the melting process. Below the melting point, the Q ⁿ distribution in lithium disilicate melt remained while, in sodium and potassium disilicate melts, [Q³] increased with decreasing temperature. Crystallization of the alkali disilicate melts is discussed considering the configuration entropy of Q ⁿ units. In 25?mol%?Li₂O–75?mol%?SiO₂, which is in the range of the immiscibility dome, the Q ⁿ distribution was maintained even when phase separation occurs in the cooling process.     

Investigation of the Cr:LiSrAlF6 crystal by high-temperature Raman spectroscopy

In this paper, Cr-doped LiSrAlF₆ crystals are investigated using high-temperature Raman spectroscopy and the single-crystal Raman spectra of Cr:LiSrAlF₆ are analysed by factor group theory and comparison with other fluorides. The results indicate that Cr:LiSrAlF₆ is stable below its melting point; Raman peaks located at 561, 322 and 250 cm^-1 are assigned to the A_1g modes of AlF₆, SrF₆ and LiF₆ octachdra, respectively; with temperature increasing, Raman peaks associated with AlF₆ octahedra shift towards low frequencies, while LiF₆ and SrF₆ octahedra are temperature-insensitive; around the crystal melting point, three new Raman peaks occur, which are associated with the AlF₆ octahedral chain structure. Finally, the microstructural evolution of Cr:LiSrAlF₆ from room temperature to its melting point is discussed based on its Raman spectra.     

甲苯的激光拉曼光谱研究

采用激光拉曼光谱技术获得了甲苯的振动拉曼光谱,结合群论方法及退偏度测量,指认了其中16条振动谱线,为有机混合物中对甲苯的识别提供了依据．选择甲苯全对称环呼吸振动（1008.8cm－1）为检测谱线,对不同浓度的甲苯／四氯化碳样品进行了分析．研究结果表明：在200．1～2．61g／L浓度范围内,甲苯／四氯化碳振动拉曼光谱强度比与甲苯浓度呈良好的线性关系,线性相关系数为0.997．为甲苯的定量分析提供了一种有效的研究方法．     

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.     

The investigation of single bacteria by means of fluorescence staining and Raman spectroscopy

The successful combination of Raman spectroscopy and fluorescence labelling of single bacterial cells is presented. The results show that the selected dyes (DAPI, SYTO 9, CFDA, SYTOX blue and PI) in most cases do not influence the Raman spectrum of a labelled bacterium significantly compared to an unstained bacterium spectrum. The labelling of bacteria offers the possibility of live/dead or biotic/abiotic differentiation prior to a Raman identification step. Copyright © 2007 John Wiley & Sons, Ltd.     

Monitoring deprotonation of gallic acid by Raman spectroscopy

Gallic acid (GA) is involved in many biochemical processes and reactions and is of great importance in environment thanks to its antioxidant and pro‐oxidant properties. We present in this paper a comprehensive study of GA deprotonation by means of Raman spectroscopy. In the Raman spectra, we identified the characteristic bands that were sensitive to the five pH‐dependent GA forms. From these results, we extracted the GA pKa values that are consistent with the reference values. These results permit the monitoring of GA forms for applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Non‐invasive depth profiling by space and time‐resolved Raman spectroscopy

Time‐resolved Raman spectroscopy, spatially offset Raman spectroscopy and time‐resolved spatially offset Raman spectroscopy (TR‐SORS) have proven their capability for the non‐invasive profiling of deep layers of a sample. Recent studies have indicated that TR‐SORS exhibits an enhanced selectivity toward the deep layers of a sample. However, the enhanced depth profiling efficiency of TR‐SORS, in comparison with time‐resolved Raman spectroscopy and spatially offset Raman spectroscopy, is yet to be assessed and explained in accordance to the synergistic effects of spatial and temporal resolutions. This study provides a critical investigation of the depth profiling efficiency of the three deep Raman techniques. The study compares the efficiency of the various deep Raman spectroscopy techniques for the stand‐off detection of explosive precursors hidden in highly fluorescing packaging. The study explains for the first time the synergistic effects of spatial and temporal resolutions in the deep Raman techniques and their impact on the acquired spectral data. Copyright © 2013 John Wiley & Sons, Ltd.