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1.
Raman spectroscopy, along with discriminant partial least squares (PLS), was successfully used to discriminate among three different groups of cultured pearls (fresh water, Akoya and South seawater). The discrimination between Akoya and South seawater pearls using XRF (X‐ray fluorescence), one of the most frequently adopted analytical methods in pearl analysis, has been especially difficult owing to their similar mineral compositions. The selective Raman features helped in effectively discriminating between these two pearl groups. The difference in the intensities of the CaCO3 bands of Akoya and South seawater pearls provided a valuable clue. Along with the selective Raman feature, a reproducible Raman spectral collection achieved using a wide area illumination (WAI) scheme played an important role in the determination of the pearl groups, although the pearls were hard‐surfaced, round, solid samples of different sizes and surface shapes. Unwanted spectral variation originating from sensitivity to sample placement relative to the focal plane and from unsuccessful sample representation due to the probing of a localized area, factors that could possibly deteriorate Raman reproducibility, were substantially lessened using the WAI scheme. ATR (attenuated total reflection) IR spectroscopy requiring direct contact with the pearl could be inadequate for discrimination or classification where large numbers of repeating and reproducible measurements are required. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

2.
We present a reliable and nondestructive analytical method for the determination of urea concentration in a pharmaceutical cream formulation using Raman spectroscopy. A pharmaceutical cream is a highly viscous emulsion; therefore, its composition and physical mixing could be inhomogeneous on a microscopic scale. The local environment around the urea could vary, which could influence the molecular vibrations of the urea molecule. As expected, when Raman spectra were collected by focusing the laser onto a tiny area (∼2–3 µm), the position of the urea band at 1003 cm−1 varied as a result of the microscopic inhomogeneity within the sample. Therefore, acquisition of Raman spectra representative of the entire sample rather than a localized portion of it is very important for the analysis of pharmaceutical creams. Based on the preliminary Raman mapping results of a urea cream, a sample area of at least 750 × 750 µm should be covered for reliable quantitative analysis. In this study, we used a wide‐area illumination scheme capable of covering a sample area of 28.3 mm2 for Raman spectral collection in order to ensure a reliable representative sample. In addition, to simplify the measurements, Raman spectra of urea creams in plastic bottles were directly collected without further sampling, and partial least squares regression was used for quantitative analysis. The urea concentrations were accurately determined despite the spectral collection being performed through plastic bottles. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

3.
Raman spectroscopy is a common tool for the qualitative and quantitative chemical analysis of molecules. Although the unique identification of molecules is possible via their vibrational lines, high concentrations (mmol/l) are needed for their nonresonant excitation owing to their low scattering cross section. The intensity of the Raman spectra is amplified by the use of the surface‐enhanced Raman scattering (SERS) technique. While the use of silver sols results only in a limited reproducibility of the Raman line intensities, lithographically designed, nanostructured gold surfaces used as SERS‐active substrates should, in principle, combine the high sensitivity with better reproducibility. For this purpose, we have produced gratings of gold dots on Si(001) surfaces by means of electron beam lithography. Qualitative and quantitative investigations of crystal violet (CV) performed using nanostructured surfaces give high reproducibility and enhancement of the Raman lines. The substrates are reusable after cleaning; all results presented could be obtained from a single SERS substrate. For the experiments very low laser powers were used. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

4.
针对表面增强拉曼光谱信号重复性欠佳的问题,利用实验室自行搭建的拉曼点检测系统,以蜂蜜中硝基呋喃妥因兽药为检测对象,探讨了基于蜂蜜固有内标的硝基呋喃妥因表面增强拉曼峰强校正方法。首先通过含不同浓度硝基呋喃妥因蜂蜜样品及硝基呋喃妥因标准品的拉曼光谱对比分析,确定739 cm-1处蜂蜜拉曼特征位移作为底物蜂蜜的内标峰,用比值法校正硝基呋喃妥因1 353和1 612 cm-1处拉曼特征峰强用于蜂蜜中硝基呋喃妥因定量分析。相同条件下分别采集了浓度为20 mg·kg-1的硝基呋喃妥因蜂蜜样品表面增强拉曼光谱30次,1 353和1 612 cm-1处硝基呋喃妥因特征峰强相对标准偏差(RSD)分别为11.515 6%和11.162 5%,利用739 cm-1处蜂蜜拉曼特征峰强作为内标分别校正1 353和1 612 cm-1处硝基呋喃妥因拉曼特征峰强后相对标准偏差分别降为4.852 6%和4.733 2%,显著提升了表面增强拉曼特征峰强的重复性和稳定性。因为仪器系统误差及表面增强过程中不可控因素引起的人为误差等对样品表面增强光谱中739 cm-1处蜂蜜特征峰强和1 353和1 612 cm-1处硝基呋喃妥因特征峰强的影响是完全相同的,所以通过内标比值法可以有效消除和减少拉曼信号稳定性和重复性差的问题。最后采集硝基呋喃妥因浓度范围为0.4~20 mg·kg-1的69个蜂蜜样品,基于硝基呋喃妥因1 353和1 612 cm-1处拉曼特征峰强和蜂蜜739 cm-1处拉曼特征峰强比值,分别建立了一元线性回归预测模型和多元线性回归模型,其中基于蜂蜜739 cm-1处内标校正硝基呋喃妥因1 612 cm-1处拉曼特征峰强的一元线性回归模型效果最佳,与校正前相比具有更高的精度和预测能力。该模型校正集决定系数(R2C)和验证集决定系数(R2)分别为0.971 2和0.969 6,校正集均方根误差(RMSEC)和验证集均方根误差(RMSEP) 分别为1.115 1和1.242 2,相对分析误差(RPD)为4.306 0。结果表明,被测底物本身持有固有内标的样品可无需加入额外的内标物,简单用内标比值法可以有效消除仪器的系统误差以及表面增强剂与样品的混合时间等对拉曼信号强度的影响,显著提高了拉曼特征信号的重复性和稳定性,为表面增强拉曼光谱定量分析提供了技术参考。  相似文献   

5.
In this study, transmission Raman spectroscopy was explored for the direct measurement of the density of packed polyethylene (PE) pellets. A simple and direct transmission Raman measurement of packed, solid granules or pellet samples without pretreatment is greatly advantageous. Initially, the optimal packing thickness of PE pellets for transmission Raman measurement was determined by investigating the reproducibility of triplicate spectra collected by varying the thickness from 2 to 9 cm. Once determined, transmission Raman spectra were collected for 25 different grades of PE pellets and the partial least squares method was used to determine the sample density. The resulting accuracy was 0.00067 g·cm−3, while that obtained using backscattering measurements was 0.00083 g·cm−3. To investigate possible inhomogeneity within a pellet, Raman line mapping was performed over the face of a sectioned pellet and spectral variations among the mapped spectra were examined using principal component analysis. In addition, differential scanning calorimetry was performed on three samples prepared separately by cutting a pellet into left, middle, and right sections. Based on both studies, internal pellet inhomogeneity was found to be minute, but was clearly present. The correct sample representation of internally inhomogeneous PE pellets by the transmission Raman measurement eventually improved the accuracy for density determination. Finally sample‐to‐sample two‐dimensional correlation analysis was used to further examine the origin of the improved accuracy. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

6.
Raman spectroscopy allows nondestructive analysis of materials using laser illumination. However, most Raman spectrometers can only provide good signal levels and sufficient spectral resolution, by focusing the laser to micrometer-sized spots. This equates to enormous laser intensities, which for samples with even very minor optical absorption either means destroying or damaging it by absorbing even a tiny fraction of the laser power, or it means reducing the laser intensity and hence the signal level. Furthermore, Raman signals generated above or below the focal plane are rejected in traditional Raman spectrometers. As signal levels are already extremely low in Raman spectroscopy, several schemes offer an alternative to focusing down to a diffraction-limited spot, to increase the area by up to 6 orders of magnitude, and increase the sampling depth. This review describes and compares these schemes, and estimates the typical illumination areas.  相似文献   

7.
Qi J  Shih WC 《Optics letters》2012,37(8):1289-1291
We present a novel parallel Raman microspectroscopy scheme for simultaneously collecting Raman spectra from multiple points. This scheme is realized by projectinga multiple-point laser illumination pattern using a spatial light modulator (SLM) and wide-field Raman imaging collection. We demonstrate the performance of this scheme using uniform samples, trapped polymer microparticles and fixed polymer microparticles with mixed molecular composition within a 50×50 μm(2) field of view. This scheme enables the acquisition of Raman spectra from as many as 40 points simultaneously using a single illumination pattern and detector recording frame without scanning.  相似文献   

8.
It was shown experimentally that the effect of photobleaching in noninvasive measurement of the Raman spectra of light used in determining the carotenoid concentration in human skin can be used to increase measurement accuracy. Increased accuracy occurs as a consequence of a decrease in the measurable Raman spectra of the wideband fluorescent background intensity when a sample is irradiated by laser radiation. Furthermore, it was demonstrated that, for the spectra of skin from nine volunteers, the fluorescent background intensity can be decreased on average by a factor of 1.4, which leads to an increase in the signal-to-noise ratio for Raman lines of skin carotenoids by a factor of 1.2 on average. The kinetics of photobleaching of humans can be described by biexponential decay with a correlation coefficient close to unity, which agrees with the presented theoretical calculations.  相似文献   

9.
We report for the first time on the thorough experimental and theoretical assessment of the noise limit of mechanical stress and temperature measurements with micro‐Raman spectroscopy. A comprehensive study has been performed in which, for different incident laser light intensities and acquisition times, 1000 Raman spectra of mono‐crystalline silicon were acquired per setting. Curve fitting was employed to obtain the peak positions of all the spectra, from which the standard deviations of the measured peak positions were obtained versus the total accumulated amount of laser light incident on the sample during one measurement. It has been found that the noise in the obtained peak position decreases as 1/sqrt(n) over more than three decades of the incident amount of laser light. At very low light conditions, the noise decreases as 1/n. By comparing the experimental results obtained to recent theoretical work, we show that the acquisition is limited by photon shot noise over most of the range and is limited by electronic detector noise at very low light conditions only. Pixelation errors do not play a role. It is concluded that the low electronic noise of typical Raman spectroscope detectors is overkill for the investigation of mechanical stress and temperature in silicon and other materials with comparable peaks, as it has absolutely no influence on the noise level of such an experiment. Maximum Raman signal intensity on the detector and high quantum efficiency detection are more important. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

10.
为实现对有机物混合物的快速、无损检测,提出一种基于激光拉曼光谱技术的二维分析方法。研究结果表明,采用532 nm波长激光作为激发光源,观测到236.2,348.9,449.4,513.6 cm-1四条振动拉曼谱线,且这些谱线的强度比为6.4∶1.7∶9.4∶1.0,可确定四氯乙烯的存在。观测到707.5,1 087.9,1 175.8, 3 078.6 cm-1四条振动拉曼谱线,其强度比为9.6∶6.4∶1.0∶3.9,可确定氯苯的存在。即通过综合分析特征谱线及若干特征谱线的强度比,可快速判断有机混合溶液中某种物质的存在。在定量分析方面,采用多光谱分析结合最小二乘法拟合提高了测量的可靠性,所测样品浓度的准确率为98.4%。本研究为有机物混合物成分识别和浓度探测提供了一套可行的光谱测量方法,有着十分重要的应用前景。  相似文献   

11.
应用激光镊子拉曼光谱技术(LTRS)测定19株芽孢杆菌的单个细菌芽孢吡啶二羧酸(DPA)浓度,并验证了系统的重现性。一束30 mW,785 nm的近红外激光导入倒置显微镜,形成光镊,随机俘获水溶液中的单个芽孢,同时收集其拉曼光谱信号。细菌芽孢的DPA是以与钙离子形成的鳌合物(Ca-DPA)形式存在,收集到的芽孢拉曼光谱信号反映的是Ca-DPA信息,选用信号最强、与Ca-DPA浓度成线性关系的1 017 cm-1作为其定量的谱峰。通过1 017 cm-1的峰强,推算出Ca-DPA的浓度。结果显示,单个芽孢的拉曼光谱能够很好地反映出单个芽孢的特征信息,不同种、同种不同菌株之间的芽孢的DPA浓度有所不同,同一菌株的不同芽孢个体之间DPA浓度也存在差异。该方法不需要复杂的分离、纯化过程,可在水溶液中直接俘获单个芽孢并收集其拉曼光谱信号,便可得到单个芽孢的信息,读出DPA的浓度水平。  相似文献   

12.
A novel setup, combining two spectroscopic techniques, laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy in a hybrid unit, is described. The work presented herein is part of a broader project that aims to demonstrate the applicability of the hybrid LIBS-Raman unit as an analytical tool for the investigation of samples and objects of cultural heritage. The system utilizes a nanosecond pulsed Nd:YAG laser (532 nm) for both LIBS and Raman analysis. In the Raman mode, a low intensity beam from the laser probes the sample surface and the scattering signal is collected into a grating spectrograph coupled to an intensified charge-coupled device (ICCD) detector, which records the Raman spectrum. In the LIBS mode a single high intensity pulse from the laser irradiates the sample surface and the time- and spectrally-resolved emission from the resulting laser ablation plume yields the LIBS spectrum. The use of a non-gated CCD detector was found to produce similar quality data (in terms of S/N ratio and fluorescence background) in the Raman mode, while in the LIBS mode spectral features were clearly broader but did not prevent identification of prominent atomic emission lines. Several model pigment samples were examined and the data obtained show the ability of the hybrid unit to record both Raman and LIBS spectra from the same point on the sample, a clear advantage over the use of different analytical setups. PACS 39.30.+w; 82.80.Dx; 82.80.Gk; 52.38.Mf  相似文献   

13.
开发了一套基于激光拉曼散射的多通道气体光学检测系统,应用于空气中主要组分的摩尔分数定量测量.针对性的设计了532 nm激光脉冲展宽器,能有效地避免脉冲激光在高能量状态下造成气体裂解、石英玻璃损伤等现象的发生,提高了气体拉曼散射的信噪比.在实验室环境压力和温度下,对气体样池内空气进行了长66 mm×直径1 mm激发区域同步10通道(每通道长约6.6 mm)的拉曼散射实验.得到了各通道下氧气(O2)和氮气(N2)的拉曼光谱和摩尔分数,及O2相对于N2的相对响应因子RO2.完成了26次重复性实验,每次为200个激光脉冲激发自发拉曼光谱的累加.结果表明,各通道间计算的平均的氧摩尔分数x-O2和相对于氮气的相对响应因子-RO2的标准偏差分别为0.015和0.024,但它们的平均值与10通道合并方式下的实验结果完全相同,准确率达98%,完全满足实时地并具有时空分辨力的定量测量混合气体摩尔分数的要求.该系统可满足于各种动态燃烧过程的光谱检测与分析.  相似文献   

14.
激光拉曼光谱法测定不同采收期连翘叶中连翘苷的含量   总被引:1,自引:0,他引:1  
采用激光拉曼光谱内标法对不同采收期连翘叶中连翘苷的含量进行测定。分别选取连翘苷甲醇溶液的拉曼光谱中连翘苷呋喃环上C-H对称伸缩振动(2844 cm-1处强峰)和溶剂甲醇中CH3-O反对称伸缩振动(2975 cm-1)作为定量峰和内标参比峰。以两拉曼峰峰强的比值组成相对强度,绘制标准曲线,并对线性和加样回收率进行考察。在1.1×10-5mol.L-1~3.5×10-4mol.L-1(5.9 mg.mL-1~189.1 mg.mL-1)范围内,连翘苷的浓度与相对峰强的线性关系良好,r=0.9980,检出限为5.2×10-6mol.L-1.通过精密度、重复性和加样回收率测定,结果证明该法具有良好的精密度、重复性和准确性。对不同采收期的连翘叶样品进行了测定,结果表明该法简便快速、高效灵敏,可用于其含量测定。拉曼光谱内标法用于连翘苷的定量分析具有操作简便和无需添加其它试剂等优点,可以用于药物的含量测定。  相似文献   

15.
拉曼光谱由于重现性差,在进行定量分析时往往需要内标。在水溶液中,水在2 700~3 900 cm-1范围伸缩振动拉曼峰很强,有作为内标的可能性,但水与溶质的相互作用会导致水伸缩振动拉曼峰形状发生变化,此外水的占比也会随着溶质浓度的变化而变化,当溶质浓度较高时需要对水的含量进行校正。将这两点因素考虑在内,研究了以水为内标,采用拉曼光谱法测量水溶液中NO-3,SO2-4和ClO-4浓度的适用性。不同浓度NaNO3,Na2SO4和NaClO4溶液的拉曼光谱显示随着盐浓度的升高水在2 700~3 900 cm-1范围内的拉曼峰呈现出左肩下降右肩上升的变化趋势。将三种盐溶液拉曼光谱中酸根离子拉曼峰面积(A)和水的拉曼峰面积(AH2O)的比值(S=A/AH2O)与溶液中酸根离子和水的含量的比值(c/cH2O)作图,均呈现出良好的线性关系,拟合得到三条相关曲线的R2分别为0.999 1,0.999 1和0.999 4,说明酸根离子和水的拉曼散射系数均未发生变化或者在同比例变化。虽然水拉曼峰的形状发生了改变,但并不会影响水作为内标的可行性。在引入水的含量修正后,经理论推导cRS符合关系式:c=ARS/(1+BRS)。在0.1 mol·L-1到近饱和的宽浓度范围内,将RSc作图,通过数据拟合获得的NaNO3,Na2SO4和NaClO4的工作曲线分别为cNaNO3=18.8RS/(1+0.6RS) (R2=0.999 1),cNa2SO4=20.2RS/(1+1.0RS) (R2=0.998 8),cNaClO4=15.0RS/(1+0.7RS) (R2=0.999 8)。NaNO3,Na2SO4和NaClO4的检出限分别为0.008 0,0.005 2和0.007 3 mol·L-1。在水拉曼峰形状变化不影响其作内标可行性的基础上,当溶液中同时存在两种阴离子时,通过在水含量修正部分加入干扰离子对水含量的影响,可以在单盐溶液定量工作曲线中加入校正项来消除溶液中干扰离子对待测离子分析结果的干扰,但当干扰离子浓度较大而待测离子浓度较小时,干扰离子拉曼峰强度过大会影响到待测离子拉曼峰面积的准确性,从而使得校正的效果下降。  相似文献   

16.
激光等离子体光谱测量影响因素分析   总被引:4,自引:0,他引:4  
建立了一套激光等离子体光谱测量实验装置,以Nd:YAG调Q固体激光器(单脉冲平均能量38 mJ)为激发光源,铜合金为样品,得到了Cu原子辐射谱线随时间的变化情况,分析了系统中软、硬件因素对测量的谱线影响。实验证明激光器输出能量波动、每个数据点的平均次数、靶面相对于透镜焦点的位置、接受辐射的光纤束相对靶面法线的位置以及接受光纤束的有效通光口径都影响测量谱线的强度和重复精度。  相似文献   

17.
拉曼光谱是研究水中生物分子重要的有效方法之一,然而由于拉曼散射截面小,特别是水分子的电子激发态能级高,因此水中生物分子的拉曼光谱测量甚为困难。将液芯光纤技术和共振拉曼技术结合起来,可大幅度提高拉曼光谱强度。实验中用可以获得最大的共振拉曼光谱强度的514.5 nm Ar+离子激光激发,分别用石英和Teflon液芯光纤对水中β-胡萝卜素生物分子进行了痕量检测研究。结果表明应用石英液芯光纤和Teflon液芯光纤可分别检测浓度为10-7~10-9mol·L-1和10-9~10-10mol·L-1的β-胡萝卜素。  相似文献   

18.
拉曼光谱技术作为探究分子、晶体及其结构特征的有力手段,具有快速、无损、样品用量小、无需前处理且适应性强等优点,已被广泛应用于食品安全、石油化工等领域。但在拉曼光谱应用中,常常受到荧光背景干扰,导致拉曼信号降低,严重的情况下拉曼信号甚至会淹没在荧光背景中。为解决拉曼技术在实际应用中荧光背景干扰的问题,从仪器角度出发,采用二色镜对多波长拉曼光谱进行光路耦合设计,研制了近红外拉曼光谱与移频差分拉曼复合一体的多波长消荧光拉曼光谱检测系统,其中近红外拉曼光谱采用1 064 nm激光光源设计,移频差分拉曼光谱选取784.5和785.5 nm两组激光光源进行时分复用,在移频差分拉曼光谱检测的同时,亦可获得两组单波长拉曼光谱数据。通过对比同步测试和分时逐次测试的强度及峰位稳定性,验证了多波长消荧光拉曼光谱仪的同步测试性能;选取了多种荧光背景强弱不同的样品,进行了单波长拉曼、近红外拉曼及移频差分拉曼光谱的对比分析。针对丙酮、乙腈等荧光背景较弱的样品,可采用单波长拉曼光谱对样品进行定量及定性分析;针对食用油、红色塑胶微粒等荧光背景与拉曼信号强度相当的样品,可采用近红外拉曼光谱对样品进行定量及定性分析;针对红酒、棕色塑胶微粒等荧光背景较强的样品,需结合近红外拉曼光谱和差分拉曼光谱对样品进行定性分析。研究表明:通过多波长消荧光拉曼光谱检测系统的研制,在常规单波长拉曼光谱技术的基础上,将两种抑制荧光干扰技术有机结合,有效扩充了应用领域及样品检测范围。  相似文献   

19.
拉曼光谱强度与物质量存在的线性关系会受到许多复杂因素破坏,包括激发光源、聚焦、散射、折射等,导致定量效果不佳。各种因素的干扰效应,总体上分成加性和乘性效应,而消除乘性效应的难度会更大一些。光谱序列信号可视为向量,信号强度对应向量的模量,而体现向量本质的方向属性不会受模量变化的影响。根据这一原理,利用向量的方向确定性,将信号的强度度量转换成空间角度度量,建立了一种消除乘性效应的方法。首先,选择一个与待定量组分相近而与背景空间近似正交的基准向量,并定义移动窗口; 然后,计算移动窗口内的光谱向量与基准向量的夹角,所得值存储为矩阵,完成角度描述转换。角度矩阵消除了乘性效应的干扰,而定量关系仍然近似线性,只要将该矩阵的秩满足多元统计建模要求,就可以用于多元校正,并得到良好结果。研究采用甲醇-乙醇-异丙醇混合体系,验证了消除乘性效应后改进的定量效果,对于积分时间波动的预测值与实际值,直接PLS方法的相关系数r为0.911 9,预测标准偏差(RMSEP)为0.110 2; 采用MSC预处理的r为0.906 0,RMSEP为0.100 8; 而本文提出的VAPLS的r为0.998 7,RMSEP为0.015 2。结果表明向量角转换度量处理后,光谱的乘性干扰得到了有效校正,拉曼定量分析准确性得到了提高。  相似文献   

20.
The intensity calculation is the basis for all quantitative applications of electron spectroscopy. Unfortunately, some misinterpreted terms are used and correctly interpreted terms are misused in the overwhelming majority of publications in XPS, including most textbooks as well as accepted and proposed standards. Due to this mistake the number of the detected electrons is given as having dimension of energy (?) and also the formulas for calculating the peak area and its standard deviation are wrong. Since in all other spectroscopic fields the number of the detected particles is dimensionless, continuing this practice leads to isolating XPS from both other measurement sciences and theory, because the measured total intensity in XPS is simply not comparable to the ones derived with other spectroscopic methods or theoretically. Therefore, the basic measuring processes and terms are critically reviewed and their physically correct interpretation is given. This interpretation reveals that the error is hidden in the incorrect interpretation of both the measurement process and the measured quantity. It is shown that through using the correct interpretation both the dimensions of the intensity calculated from electron spectroscopic measurements as well as the formulas related to the intensity and its standard deviation will agree with all other spectroscopic fields.  相似文献   

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