拉曼光谱技术在爆炸物检测中的应用

随着恐怖活动的蔓延,对爆炸物的检测和溯源变得越来越重要。拉曼光谱能够提供化合物的指纹图谱,是对物质定性分析的有力工具,具有无损、快速、准确度高等优点,近年来在爆炸物检测领域被广泛应用。本文介绍了共聚焦显微拉曼光谱、空间偏移拉曼光谱、表面增强拉曼光谱等拉曼光谱技术在爆炸物检测方面的应用及最新研究进展。     

基于共聚焦显微拉曼的真菌菌丝中几丁质的原位检测研究

几丁质是真菌细胞壁中一种重要的结构多糖,本文首次采用共聚焦显微拉曼技术对山茶刺盘孢菌的气生菌丝进行原位检测研究,首先确定了采集菌丝拉曼光谱的最优实验参数,并获得了菌丝,几丁质标准品和背景三种物质的典型拉曼光谱,对其中的特征峰进行归属分析,发现菌丝光谱中有明显的几丁质特征峰。然后对置于载玻片上菌丝的感兴趣区域进行拉曼光谱面扫描,通过主成分分析法发现面扫描区域中,菌丝和背景两种信号可以明显区分开来,结合主成分的载荷因子图得到了菌丝的两个主要的特征差异峰1 622和1 368 cm-1,1 622 cm-1属于菌丝中几丁质的特征峰,而1 368 cm-1是来源于菌丝中的果胶多糖。最后通过对几丁质在1 622 cm-1特征峰波段附近范围积分,绘制了几丁质在菌丝中二维和三维的化学成像图,直观且无损的再现了几丁质在菌丝中的空间分布。     

姜油细胞原位拉曼光谱研究

提出一种用拉曼光谱原位分析新鲜姜油细胞中姜油主成分的方法。用徒手切片制备新鲜姜样品,该样品置于DXR 激光共焦显微拉曼光谱仪下,用20倍物镜观察到油细胞,将激光聚焦在该油细胞上,获得了姜油细胞中姜油的拉曼光谱,共21条谱峰。不同油细胞上获得的拉曼光谱非常相似。获得了姜精油的拉曼光谱,与姜精油拉曼光谱的37条谱峰比较,油细胞有19条谱峰与之有对应关系。为了解释油细胞精油及姜精油的拉曼光谱,用密度泛函理论计算了姜烯的拉曼光谱。姜精油拉曼光谱有31条谱峰,油细胞中有19条谱峰与计算光谱有对应关系。该研究提供了一种拉曼光谱技术与密度泛函理论计算结合的快速容易的精油质量控制方法。     

共聚焦显微拉曼光谱研究碱处理对稻秸发酵制沼气的影响

碱水解法以其方便高效成为稻秸发酵制沼气中广泛采用的化学预处理方法,但是碱水解对于稻秸细胞壁中高聚物成分及其空间致密交联结构的作用机理有待深入研究。采用共聚焦显微拉曼光谱和透射电镜研究了NaOH碱处理对稻秸厌氧发酵产沼气的影响。首先对未处理稻秸和碱处理稻秸进行微米级空间分辨率的拉曼光谱面扫描,然后对这两类样本进行主成分分析,发现累计贡献率达99%的前两个主成分空间中两类样本分别呈射线状分布,两类样本分界线清楚表明碱处理导致稻叶组织的拉曼光谱响应特性发生了明显变化;进一步分析前两个主成分的载荷图,发现拉曼峰1 739,1 508和1 094 cm-1是影响主成分的重要谱带,而这三个拉曼峰分别归属于半纤维素、木质素和纤维素的拉曼散射效应;结合半纤维素、木质素和纤维素的拉曼特征峰和显微图像信息实现了组织细胞中三种成分的化学成像分析,发现碱处理破坏了稻叶组织中上述三种成分的致密空间结构,并使它们的含量明显减少,尤其是木质素。由此得出结论：共聚焦显微拉曼光谱可实现稻叶组织细胞中半纤维素、木质素和纤维素的无损检测,结合显微空间信息可实现稻秸中三种成分的化学成像分析,该研究有助揭示碱处理促进秸秆厌氧发酵产沼气的作用机理。     

基于共聚焦显微拉曼光谱揭示炭疽病侵染下茶叶细胞壁变化的研究

采用共聚焦显微拉曼技术研究了炭疽病感染所致茶叶细胞壁结构和化学成分的变化。对茶叶健康和染病组织细胞进行微米级空间分辨率的显微拉曼光谱扫描,并结合透射电镜观察炭疽病侵染所致的细胞超微结构变化,结果显示染病前后细胞壁的拉曼光谱位移和强度都有明显的差异,表明炭疽病侵染导致细胞壁中化学成分发生了较大的变化。其中由纤维素,果胶,酯类化合物产生的拉曼峰强度都有明显下降,说明细胞壁中这些物质的含量在染病后减少了;而木质素拉曼散射引起的拉曼峰强度有所上升,说明木质素的含量在染病后有所增加。随后基于纤维素的拉曼指纹波数和显微空间结构信息实现了茶叶健康组织和染病组织细胞壁中纤维素的化学成像分析,结果显示炭疽病侵染不仅导致细胞壁中纤维素的含量大大减少,而且纤维素的有序结构被破坏。由此得出结论：在无需对样本进行染色或复杂的化学处理的情况下,共聚焦显微拉曼可以揭示由炭疽病侵染引起的茶叶细胞壁化学成分和结构的变化,本研究是共聚焦显微拉曼技术首次用于植物病理学中寄主-病原物互作机制的研究,将为深入研究寄主-病原物在细胞层面上的互作机制开辟蹊径。     

利用拉曼光谱对毒品的检验及基于R软件的数据分析

本文利用拉曼光谱对不同种类的毒品进行检验,利用拉曼光谱对同分异构体氯胺酮和羟亚胺、同系物合成大麻素JWH-018和JWH-073进行区分,并结合R软件,对成分未知的摇头丸样品中各组分的含量进行分析;并且利用拉曼光谱成像技术,对油汗混合指纹、护手霜油脂指纹、502熏显指纹上的毒品颗粒进行了检验。实验结果表明,拉曼光谱是分析各类毒品的有效手段,以其快速、无损、无需样品前处理的优势,实现对分子结构相似的样品的区分;结合拉曼光谱成像技术,可以获得毒品颗粒在指纹上的分布情况,在物证的现场检验中有良好的应用前景。     

蒜氨酸和甲基蒜氨酸的红外及拉曼光谱研究

利用傅里叶红外光谱和共聚焦显微拉曼光谱技术,比较分析了大蒜主要功能活性成分前体蒜氨酸和甲基蒜氨酸粉末纯品的红外和拉曼谱。在3 200～2 800 cm-1和1 700～200 cm-1波段检测到显著的红外和拉曼吸收峰,其中蒜氨酸在3 080,1 617,1 582,1 496,1 418,1 342,1 301,919 cm-1处有8个较强的红外吸收峰,以及在3 088,1 636,1 404,1 290,1 051,790,745,693,588 cm-1处有9个较强的拉曼振动峰,可作为蒜氨酸的特征峰;甲基蒜氨酸在1 644,1 481,1 395,1 370,1 233,1 068,1 004,892 cm-1处有8个较强的红外吸收峰,以及在1 644,1 310,1 073,1 011,998,893,846,702,676 cm-1处有9个较强的拉曼振动峰,可作为甲基蒜氨酸的特征峰。蒜氨酸和同系物甲基蒜氨酸的红外及拉曼光谱具有明显差异,红外及拉曼光谱技术为蒜氨酸及其同系物的快速、 简便的分析提供了方法。     

一种危险液体混合物的拉曼光谱定性定量识别方法

危险液体混合物的拉曼光谱定性定量分析一直是现场应用难点,为解决该问题,分析了多种物质混合后拉曼光谱的峰位、峰值、峰型变化情况,选取拉曼光谱关键特征峰进行数学简化,构建了从混合物物质成分到混合物拉曼光谱的映射关系,该映射关系描述多种物质成分混合的混合物拉曼特征峰响应只和混合物中各成分本身拉曼特征峰响应以及各物质成分混合比例有关,各物质成分按混合比例贡献拉曼特征谱峰,共同形成最终的混合物拉曼光谱。由该映射关系求逆,可实现从采集到的混合物拉曼光谱计算出各物质成分的混合比例。基于此,设计了危险液体混合物成分定性定量识别方法,主要方法步骤包括,首先进行拉曼光谱数据采集,然后进行拉曼光谱数据处理并获得拉曼特征峰,再进行测试样品与数据谱库标准品的正反向特征峰匹配,如果正反向特征峰匹配系数都比较高,在满足一定阈值条件下,可认定测试样品是某种纯净物,如果不是纯净物,则进入混合物分析,通过拉曼光谱特征峰反向匹配系数筛选,确定混合物成分构成,混合物成分确定后再进行混合物成分比例计算,最终实现危险液体混合物定性定量分析。实验部分,选定丙酮、甲苯、三氯甲烷、乙醇及其混合物进行实验验证,当混合物样品是丙酮、乙醇两种成分按3∶7比例混合时,经拉曼光谱识别方法计算,混合成分计算值是丙酮占比0.245 7,乙醇占比0.706 0;当混合物样品是甲苯、三氯甲烷两种成分按3∶7比例混合时,经拉曼光谱识别方法计算,混合成分计算值是甲苯占比0.323 4,三氯甲烷占比0.763 0;当混合物样品是丙酮、甲苯、乙醇三种成分按4∶3∶3比例混合时,经拉曼光谱识别方法计算,混合成分计算值是丙酮占比0.795 9、甲苯占比0.303 5、乙醇占比0.287 5,实验结果表明,当危险液体混合物成分是两种或三种成分混合时,混合成分计算值基本和实际值吻合,应用危险液体混合物的拉曼光谱定性定量识别方法,可较准确的从拉曼混合光谱中解析出各混合物成分以及各成分在混合物中的比例,可以判断混合物每个拉曼特征谱峰都来自于哪个成分或哪些成分拉曼特征谱峰的混合,谱图解析结果良好,对危险液体混合物现场分析鉴别有较大应用价值。     

共焦显微拉曼光谱在界面研究中的应用

本研究的重点是拓宽共焦显微拉曼光谱技术在液／气、液／固界面研究中的应用。通过合理地设计实验,利用共焦显微拉曼光谱技术高的纵向分辨率研究了液／气界面水溶性的卟啉（ＴＳＰＰ）的聚集行为,发现ＴＳＰＰ在本体中和在界面上的行为有着显著的区别。同时,对甲醇电化学氧化过程中电极表面附近的溶液成分进行了剖层分析。利用其高的横向分辨率,借助表面增强效应对沉积在玻碳上的金薄层进行拉曼成像研究,发现光学成像和拉曼成像     

中国文物彩绘常用胶料的显微共聚焦拉曼光谱特征研究

为了鉴定文物彩绘中常用胶料的种类,文章采用显微共聚焦拉曼光谱技术分析了猪皮胶、猪骨胶、蛋清、蛋黄、桃胶等中国古代文物彩绘常用胶料.通过对五种标准胶料的拉曼光谱分析,发现蛋白类胶料和桃胶的拉曼光谱存在明显差别,桃胶在1 463及1 088 cm-1 处存在两个糖类化合物的特征振动峰.虽然蛋白类胶料间的拉曼光谱具有一定的相...     

多波长消荧光拉曼光谱仪的研制及应用研究

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。     

Two‐dimensional standoff Raman measurements of distant samples

A scanning standoff Raman spectroscopy system has been developed to measure the molecular species of distant samples in two dimensions. Computer software is used to control the scanner pan and tilt angles, and Raman measurements are collected of the distant sample area in an x–y grid pattern. The Raman spectra at each grid point are measured and processed to obtain an image of the distant surface composition. The ability to provide interpolated images of distant molecular species is illustrated. Copyright © 2011 John Wiley & Sons, Ltd.     

拉曼光谱技术的应用及研究进展

本文简述了拉曼光谱产生的机理以及与红外光谱的区别,讨论了拉曼光谱在聚合物、生物分子、蛋白质和无机物等方面研究及应用,介绍了傅立叶变换拉曼、共焦显微拉曼、表面增强激光拉曼、固体光声拉曼光谱的原理及其应用以及拉曼光谱和其他检测手段的联用技术。     

复合输出镜（Nd,Ce）：YAG拉曼频移激光器研究

报道了由部分反射凹面镜和辅助平面镜构成的复合输出镜高压ＣＨ４气体（Ｎｄ，Ｃｅ）：ＹＡＧ拉曼频移激光器的理论和实验研究结果，在１０Ｊ的输入下，获得１２ｍＪ的拉曼激光输出，并计算的基频场基模光束参数。     

A novel Raman optical activity instrument operating in the deep ultraviolet spectral region

Raman optical activity (ROA) has been exclusively observed in the visible (VIS) and near‐infrared (NIR) spectral regions to date. During the last few years, we have designed, constructed and tested the first ROA instrument, operating in the deep‐ultraviolet (DUV) spectral region employing 244‐nm excitation. This novel DUV ROA instrument is based on a backscattering geometry and incident circular polarization modulation (ICP); it makes use of a fast DUV imaging lens‐based spectrograph and specially designed DUV grade polarization optics. The performance of this instrument has been evaluated by analysing measured non‐resonant DUV ROA spectra of non‐absorbing enantiomeric liquid samples and by comparing these with corresponding ROA spectra recorded in the visible spectral region. Copyright © 2015 John Wiley & Sons, Ltd.     

高压下NaCl水溶液的Raman光谱不连续性的证据

在温度21 ℃和压力50～1 100 MPa范围内利用碳化硅压腔进行了10％的NaCl水溶液的Raman光谱的原位测量和研究。研究发现：溶液的Raman拟合谱峰在50～300 MPa压力范围内,随着压力的增加向低波数方向移动,在约300 MPa时达到最小值;在300～800 MPa压力范围内,压力的升高则导致谱峰向高波数方向移动,在约800 MPa时达到最大值;随着压力的进一步升高(＞800 MPa),谱峰又向低波数方向移动。类似地,拟合谱峰的峰面积比值和半高宽在压力约300和800 MPa时也发现了不连续现象。这表明高压下NaCl水溶液的内部结构是不连续的,溶液中的氢键(O—H…Cl-)发生了相应的变化,意味着溶液中出现了结构的重新排列,产生了较为复杂的结构构型。     

Stimulated Raman scattering and spontaneous Raman solitons in ammonia

In this study we report the first observation of spontaneous Raman solitons in stimulated Raman scattering (SRS) by the gas NH₃. The scattered radiation is called Stokes radiation. Raman solitons are of considerable interest, because their existence can be explained by quantum-mechanical fluctuations of the electromagnetic field in vacuum. We have observed spontaneous Raman solitons in a forward SRS configuration for two different molecular transitions of NH₃, the laser emissions at 58 μm and 72.6 μm wavelength. These are optically pumped by 10 μm CO₂-laser pulses with a duration of 100 ns and an energy of 150 mJ. Spontaneous Raman solitons are short spikes in the pump pulse which occur during its depletion. Their origin is the rapid π phase change of the Stokes seed. In contrast to other laboratories we have used single-pass cells. Thus, we have succeeded in observing multiple spontaneous Raman solitons during one pump pulse. Previous experiments with multi-pass cells never showed multiple solitons. Since multiple spontaneous Raman solitons have already been reported in an earlier experiment with a single-pass cell filled with hydrogen at high pressure, we conclude that such multiple Raman solitons can be observed mainly in this type of gas cell. Subsequently, we have performed statistical measurements on the delay time and the height of the spontaneous Raman solitons in the depleted pump pulse for the 58 μm-NH₃ emission. We have compared these statistics with theory and equivalent experimental results of other laboratories. They are in good agreement with the assumption that quantum-mechanical fluctuations are the origin of spontaneous Raman solitons. The most recent theories postulate that the origin of the formation of spontaneous Raman solitons can be explained by the rapid π phase change of the Stokes seed as well as that of the laser or polarization wave. Therefore, we have determined the phase of the spontaneous Raman solitons relative to the depleted pump pulse. Although, such changes of sign of the relative phase have already been observed in an earlier SRS experiment with hydrogen at high pressure, we did not detect any in our experiment. Therefore, we conclude that in this experiment the π phase change occurs in the Stokes or polarization wave.     

Raman Scattering Intensities of the NO2 Symmetric Stretching Vibration Band of Some Aromatic Nitrocompounds (II)

The Raman scattering intensities of the NO₂ symmetric stretching vibration band were investigated experimentally for some para and meta substituted nitrobenzenes. The excitation profiles obtained with the six excitation wavelengths from 457.9 to 514.5 nm were presented. The results were examined in terms of the Albrecht-Hutley's theory, and the electronic states involved in the preresonance Raman intensity enhancement were suggested.     

Identification of Explosive Substances Through Improved Signals Obtained by a Portable Raman Spectrometer

The development of devices to detect explosive substances in situ with characteristics such as easy portability, simple operation, and quick response is of high interest nowadays. Raman spectroscopy meets most of these requirements, allowing for the identification of volume and trace amounts of an unknown substance. In this paper we report the characterization of explosive substances such as ANFO and pentolite, both in their pure forms as well as mixed with other substances, such as sugar and sodium hydrogen carbonate, using a portable Raman Enwave Optronics EZRaman-model M, whose signal is sent and received by a head coupled to an optical fiber. The obtained spectra have been validated by comparison with those obtained by a conventional Raman spectrometer with high resolution. We discuss the advantage of using miniaturized laptops running with a 785-nm laser, making a correction of the signal response to obtain optimized spectral fingerprints with minimum noise, in order to design an autocalibrated, easily portable device that performs the function of identification of the mentioned substances.