电火花诱导击穿光谱技术的发展及研究应用分析

电火花诱导击穿光谱(SIBS)技术是一种基于原子发射光谱学的物质浓度与成分的定性、定量分析技术。与传统的实验室分析技术如电感耦合等离子体原子发射光谱(ICP-AES)、原子吸收光谱(AAS)、质谱(MS)等相比具有实时、实地、在线快速检测、高灵敏度以及低成本、小体积、维护简单等优点。目前对该技术已有的研究集中在气溶胶成分分析、土壤成分分析、金属颗粒物浓度检测、水泥成分分析等方向,在环境监测、工业卫生、食品安全、生物医疗等领域都有广泛且良好的应用前景。从SIBS技术的基本原理入手,综述了其光谱分析的原理,即利用高压脉冲电源产生的电火花激发被测物体表面,使被测物体在电源正负极间产生等离子体,利用光谱仪光纤探头收集等离子体冷却过程中通过跃迁放出的光子与特征辐射谱线,由于不同元素具有独特的特征谱线,进而可以根据特征谱线对被测物质进行成分与浓度的定性和定量分析;接着分析了影响SIBS技术光谱图像和光谱分析的相关因素如脉冲电源参数、电极材料与入射角度和等离子体本身特性等,并定量地指出了部分因素与光谱信号强弱的关系;综述了该技术在发展过程中的一些技术革新和应用创新如激光+电火花诱导(LA-SIBS)...     

一种葡萄糖发酵液中乙醇含量的拉曼光谱分析方法

拉曼光谱法可实现样品的快速定量分析,但发酵液等复杂体系中样品的拉曼强度与被测组分含量之间的良好线性关系难以直接得到。本实验中将待测样品与纯被测组分的拉曼光谱均视为向量,并按照向量点积公式计算向量之间的夹角。在被测组分的拉曼光谱特征峰波段,对多组样品在不同光谱区间的向量夹角矩阵和被测组分含量进行偏最小二乘回归,建立定量分析数学模型,从而以光谱向量之间的夹角作为定量指标实现葡萄糖发酵液中乙醇含量的快速测定。选取的主成分数为6时,所建模型校正集和预测集中预测值与实测值的线性相关系数分别为0.9993和0.9933;校正集均方根误差为0.2171。其建模所用样本数量少、对样品无损坏,方法适用于发酵在线监测和过程分析。     

一种简单的在线拉曼光谱spike剔除方法

拉曼光谱体现了物质中不同分子基团的振动情况,可以精确地进行物质的定性和定量分析.凭借着这样的优势,拉曼光谱技术已经成功应用在化工生产、管道传输、生化反应监测等工业在线分析领域.然而,在线拉曼分析很容易受到宇宙射线的干扰.宇宙射线在拉曼谱图上体现为一系列峰宽较窄的尖锐的峰,也被称为spike.这些spike使待测物质的拉...     

应用激光诱导击穿光谱检测污水溶液中的砷

工业冶炼过程中产生的废水中含有As等重金属元素,对环境造成污染并对人类身体健康形成危害,有必要对其进行实时、在线的监测。激光诱导击穿光谱(LIBS)是一种新型的元素测量技术,具有快速检测等优点。文章作者搭建了一套激光诱导击穿光谱实验装置,采用Nd∶YAG激光器产生的脉冲激光击穿样品产生等离子体,其发射的光谱被中阶梯光栅光谱仪分光,并用ICCD进行光电探测。对从现场采集的含砷工业废水开展了LIBS探测实验,并定性分析出了As元素的特征谱线。根据一系列含As浓度不同的污水样品的LIBS实验结果,获得元素浓度与谱线强度的关系曲线(定标曲线)。采用定标曲线可以对未知含As浓度的工业废水进行定量分析。结果表明,采用LIBS方法能够实现对污水溶液中的As元素的快速检测,具有广泛的应用前景。     

等离激元增强拉曼光谱食用合成色素快速检测系统设计

基于等离激元增强拉曼光谱技术,研制出适合现场分析检测的食用合成色素快速检测系统,适用于饮料、肉制品、蜜饯等食品中合成色素的快速检测。检测系统的硬件部分主要由双CPU(ARM和FPGA)主控板、样品前处理模块(含有增强粒子施加装置)、半导体激光光源、光谱数据采集模块构成;软件部分控制样品前处理模块自动运行,并可读取被测样品的拉曼谱图。利用快速检测系统对三种实际样品(蜜饯、汽水、火腿肠)中的食用合成色素胭脂红、柠檬黄、诱惑红进行检测,以验证该系统在食用合成色素检测中的性能。样品检测结果的相对标准偏差小于±5%,表明此检测系统具有良好的灵敏度和重现性,且检测时间短,能够满足食品中合成色素现场快速检测的要求。     

阻尼最小二乘法用于激光诱导击穿光谱重叠特征谱线分离提取

近年来,激光诱导击穿广谱技术发展迅速。作为一种用于物质成分探测的新技术,它具有简单、快速、无需复杂样品制备、多种元素同时检测等优点,可实现待测样品物质成分现场、在线的检测,在很多领域都极具应用前景。激光诱导击穿光谱特征谱线的分离拟合提取是光谱特征识别与后续元素浓度定量反演研究的基础。为实现激光诱导击穿光谱重叠特征谱线的有效分离拟合提取,采用阻尼最小二乘法,分析并确定了迭代前的初始拟合参数值,实现了在重叠特征谱线情况下对某火力发电厂粉煤灰中的铬元素特征谱线的分离提取。阻尼最小二乘法基于高斯-牛顿迭代,在迭代步长中引入阻尼因子,在迭代的过程中根据每一步迭代后所反馈的信息动态的调整迭代步长,从而有效防止了迭代的发散,保证了迭代的快速收敛,最终使得元素特征谱线拟合提取的效果更佳、所得到的特征谱线强度值更准确。分别采用阻尼最小二乘法和最小二乘法对不同浓度的样品中铬元素特征谱线进行分离拟合提取并给出特征谱线的强度值,作出特征谱线强度值关于元素浓度的定标曲线并对比两种方法所得结果的线性相关性。结果表明,阻尼最小二乘法所得结果的线性相关性更高,该方法稳定、可靠,适用于激光诱导击穿光谱重叠特征谱线的分离拟合提取。     

激光诱导击穿光谱定量分析玉石中的Mg,Fe和Ca

基于对样品进行的激光诱导击穿光谱和X射线荧光光谱分析测试建立了天然玉石中主要元素Mg,Ca和微量元素Fe的定标曲线。实验采用纳秒级的Nd∶YAG激光器(波长:1 064nm)为光源,在延迟时间为3μs,激光脉冲累积数量为110,单个脉冲能量为100mJ,脉冲重复频率为10Hz的实验条件下,采用激光诱导击穿光谱技术装置对天然南阳独山玉石样品中的元素进行等离子体激发测试,得到波长在300~1 000nm的等离子光谱图。通过将得到的光谱图中特征峰与美国国家标准与技术研究院数据库进行对比,发现测试样品中含有Mg,Fe和Ca等元素,以X射线荧光光谱分析技术对四种南阳独山玉标准样品中测量出的Mg,Fe和Ca元素氧化物含量作为标准数据,选取含量比较高的Al元素作为内标元素,采用内标法对玉石光谱图中Mg,Fe和Ca元素特征峰值进行线性拟合,从而得出Mg,Fe和Ca三种元素的定标曲线,求出待测样品中这3种元素氧化物的含量,结果表明这三种元素氧化物的含量与中国珠宝宝石收藏鉴赏全集资料中所给出的元素氧化物含量的百分比范围MgO(0.28%~1.73%),Fe2O3(0~0.8%),CaO(18%~20%)相符合,相比于常用的方法,激光诱导击穿光谱技术可以快速地对待测样品进行检测,样品预处理简单且对样品损害较小。进一步验证了激光诱导击穿光谱技术对于玉石应用的可行性。     

基于LIBS技术和主成分分析的快速分类方法研究

将激光诱导击穿光谱（LIBS）技术与主成分分析（PCA）法相结合用于铝合金分类研究,对Al—Cu系、Al—Si系、Al—Mg—Si系、Al—Zn系四类13种铝合金标准样品进行了分类实验,实验结果证明LIBS-PCA方法可以实现铝合金的快速分类。通过使用LIBS技术激发130个铝合金标准样品得到130个光谱样本,再用主成分分析方法进行降维分析,计算出贡献率最大的三个主成分并计算各光谱的主成分得分绘制在三维空间中,发现光谱样本点按照铝合金的种类发生了明显的汇聚现象,由此确定了三个主成分和铝合金类型区域。用20个不同类型的铝合金进行实验对所得铝合金类型区域的准确性进行验证,发现所得20个光谱样本点全部落在其对应的标准样品类型区域内, 在一定程度上证明所得的铝合金标准样品类型区域的正确性,在此基础上可以进行未知类型铝合金的鉴别。实验结果表明基于LIBS光谱的PCA方法分类精度达到97.14%以上,能够有效的完成不同模式的区分,相比于常用的化学方法,LIBS技术可以原位快速地对待测样品进行检测,样品预处理简单,因此将激光诱导击穿光谱（LIBS）技术与主成分分析（PCA）法相结合用于质量检测和在线工业控制等领域,可以节约大量的时间及成本,提高检测效率。     

空间偏移拉曼光谱技术的发展及应用

传统拉曼光谱只能探测样品的表层信息,或者只能穿透透明的表层探测样品内部,对多层不透明或不透明包装的样品检测则不适用了,比如搜索隐蔽的爆炸物、识别有包装的假药、无损检测骨骼疾病等。空间偏移拉曼光谱（SORS）技术是一种新型光谱检测技术,能够非侵入不透明包装或表层直接获得样品内部深层特征信息,这一技术的出现解决了上述的难题。首先详细介绍了SORS技术的工作原理：其根本原理在于光子迁移理论,其系统激光光源的入射焦点与光谱系统中收集透镜的焦点在待测样品表层空间上偏移一定的距离ΔS。当激光入射到待测样品表层时,表层样品被激发或散射出宽带荧光,其中有一部分散射光将到达样品内部,样品内部深层处产生的拉曼散射光子相比于样品表层的光子在散射过程中更易于横向迁移,经多次散射后返回样品表层被光谱仪器接收系统收集。到达样品内部不同深度ΔH的散射光返回表层后的位置距离激光光源入射点在样品表层上有不同的偏移距离ΔS。当空间偏移距离ΔS＝0时,激光光源入射点与拉曼光谱收集点重合,此处激发的光子密度最大,系统收集到的拉曼光谱信号大部分来自样品表层,样品深层拉曼信号被淹没;当空间偏移距离ΔS≠0时,光谱仪器收集到的拉曼光谱信号中来自表层的信号衰减很快,来自样品深层的信号衰减较慢,使得更深层的拉曼散射光子比重变大,从而实现光谱分离,再结合多元数据分析方法可以获得样品内部不同深层次的拉曼光谱,即空间偏移拉曼光谱。该技术具有很好抑制表层物质拉曼光谱和荧光光谱干扰的能力,特别适用于隐蔽在不透明包装材料下的物质拉曼光谱的提取,从而快速、非侵入地对目标物成分进行鉴定。其次介绍了SORS技术的特点。SORS技术是拉曼光谱的衍生技术,具备拉曼光谱技术的制样简单、水分干扰小、样品消耗量小、灵敏度高等全部优点,除此之外,有效抑制荧光、深层检测、非侵入无损检测、远距离检测等特点,这些特点有效提高了拉曼光谱强度,降低用户的检测和生产成本以及提高检测人员的人身安全。同时概述并对比了SORS技术现有的三种工作方式：标准SORS、逆SORS和倾斜SORS。标准SORS技术可进行远距离非接触测量,逆SORS较之标准SORS具有更高的灵敏度和抗光谱扭曲的潜力,而且入射的有效光照面和空间偏移距离ΔS是可控的,避免了样品过热;倾斜SORS具有较高的检测灵敏度,而且实验装置容易实现。然后在大量调研文献的基础上综述了近些年来SORS技术结合其他技术在化工生产、安检、生物医学、考古艺术、食品安全、稽查打假以及国防安全等多个领域的国内外发展和应用。最后指出了SORS技术目前存在的问题并展望了该技术未来的发展前景。     

时间分辨飞秒激光诱导击穿光谱的设计与研究

激光诱导击穿光谱(LIBS)具有样品无需预处理,操作简单,分析快速等优点,已在多个领域获得应用。实验搭建了飞秒激光诱导击穿光谱(Fs-LIBS)装置,使用波长800 nm,脉宽100 fs的飞秒激光器作为激发光源,门控ICCD作为检测器。LIBS用于检测静态液体时会发生液体波动飞溅等问题,信号较差,该实验以液体射流的方式进样,以NaCl标准溶液为模型体相,Na(Ⅰ) 589.0 nm为分析线进行测试。该实验采用时间分辨LIBS的方法,考察了飞秒激光作用于样品后的LIBS发射光谱随时间的演化,发现在激光脉冲作用于样品表面40 ns后Na原子发射谱线达到最强,信背比也同时达到最大值。表明飞秒脉冲激发的LIBS可以通过时间分辨,有效消除宽带背景发射的影响,更高效地对样品中的待测目标进行检测。研究了激光激发功率、 ICCD门宽、激光焦点到样品表面距离等实验条件对LIBS信号强度和信噪比的影响,并优化了实验参数。在延迟时间40 ns、激发功率100 mW、门宽5μs、焦点位于样品前表面的最佳实验条件下,测试了海水样品的LIBS光谱和Na含量,检测了不同浓度NaCl标准溶液,并绘制了Na(Ⅰ) 5...     

Non-destructive evaluation of elastic material properties in anisotropic circular cylindrical structures

In this paper, non-axisymmetric guided wave propagation in circular cylindrical, anisotropic structures is studied in a frequency range up to 1 MHz. The investigations are carried out with carbon fibre reinforced tubes. The aim is the experimental determination of their effective linear elastic material properties in a non-destructive way. Therefore, an analytical model of the dispersion equation is fitted to the experimentally detected dispersion curves by systematically adjusting the desired material properties. A total least square scheme accompanied by an outlier detection criterion is used for this optimization task. Since the raw data of the measured dispersion curves contain a lot of noise, these outliers have to be detected and excluded, to achieve accurate results. Good agreement is found between the measured curves and the analytically calculated curves based on the estimated parameters. This fact indicates a high accuracy of the determined material properties.     

Non-destructive evaluation of elastic material properties in anisotropic circular cylindrical structures

In this paper, non-axisymmetric guided wave propagation in circular cylindrical, anisotropic structures is studied in a frequency range up to 1 MHz. The investigations are carried out with carbon fibre reinforced tubes. The aim is the experimental determination of their effective linear elastic material properties in a non-destructive way. Therefore, an analytical model of the dispersion equation is fitted to the experimentally detected dispersion curves by systematically adjusting the desired material properties. A total least square scheme accompanied by an outlier detection criterion is used for this optimization task. Since the raw data of the measured dispersion curves contain a lot of noise, these outliers have to be detected and excluded, to achieve accurate results. Good agreement is found between the measured curves and the analytically calculated curves based on the estimated parameters. This fact indicates a high accuracy of the determined material properties.     

Detection of surface changes of materials caused by intense irradiation with laser-plasma EUV source utilizing scattered or luminescent radiation excited with the EUV pulses

Extreme ultraviolet (EUV) radiation is absorbed in a thin surface layer of any material. Irradiation of material samples with intense EUV pulses may cause different surface changes. Some of them, especially connected with material desorption, can be clearly visible using an optical or electron microscope. Other changes concerning crystal structure or chemical composition may not be visible under the microscope. They can however be detected using the EUV radiation itself. In this paper a new method of measurement of surface changes by irradiation with a laser-plasma EUV source is presented. The radiation was collected and focused on a material surface using a specially designed multifoil collector. Radiation scattered or excited in the material was detected with the use of a Wolter-type mirror coupled to a back-illuminated CCD camera. Depending on material samples, images with different intensity distributions were registered. For some samples, the intensity distributions of the images obtained before and after irradiation were slightly different. The intensity differences in such cases allowed us to obtain differential images. The appearance of such images was assumed to be evidence of surface changes. PACS 42.62.-b; 61.80.-x; 52.25.Os     

Handheld device for fast and non-contact optical measurement of protein films on surfaces

Thin films of bacteria, proteins and other biochemical substances are almost always found on surfaces exposed to the environment. Optical methods enable innovative tools for the study of such films. Residua of proteins exhibit fluorescence when excited in the UV. We present a specially designed handheld measuring device that can detect organic contamination levels down to 100 ng/cm² with measurement times shorter than a second. Using time-correlated spectroscopy methods the fluorescence detection of contamination levels on surfaces is possible even if the fluorescence spectra of contamination and base material overlap. The results presented in this paper show that a detection of contamination levels of bovine serum albumine (BSA) down to 100 ng/cm² is possible on non-fluorescent materials. A theoretical analysis shows the possibility to detect BSA levels down to less than 1 ng/cm² with the presented setup. Future development of handheld optical devices suitable for the detection or analysis of various compounds can be based on these results. A compact formalism is suggested that can be used to calculate the minimal concentration of a given organic contamination that can be detected with a certain measurement setup.     

Application of FTIR Spectroscopy for Identification of Blood and Leukemia Biomarkers: A Review over the Past 15 Years

Abstract

Fourier transform infrared (FTIR) spectroscopy is an effective and nondestructive method for monitoring cellular alterations. Combining the advantages of FTIR spectroscopy with the challenge of cellular characterization, the main objective of this review is to collect information related to the spectroscopic identification of blood cells, focusing on specific biochemical features of leukemia cells detected through FTIR spectral analysis. Some interesting results obtained by different authors regarding human promyelocytic leukemia, white blood cells, chronic lymphocytic leukemia, and human peripheral blood mononuclear cells are presented. In addition, the characterization of two types of cells, namely, leukemia T and a healthy human blood cells, is reported and the identification of biochemical markers provides important information that, associated with clinical examination, can assist in the diagnosis of diseases.     

Prediction of interaction between small molecule and enzyme using AdaBoost

The knowledge of whether one enzyme can interact with a small molecule is essential for understanding the molecular and cellular functions of organisms. In this paper, we introduce a classifier to predict the small molecule– enzyme interaction, i.e., whether they can interact with each other. Small molecules are represented by their chemical functional groups, and enzymes are represented by their biochemical and physicochemical properties, resulting in a total of 160 features. These features are input into the AdaBoost classifier, which is known to have good generalization ability to predict interaction. As a result, the overall prediction accuracy, tested by tenfold cross-validation and independent sets, is 81.76% and 83.35%, respectively, suggesting that this strategy is effective. In this research, we typically choose interactions between small molecules and enzymes involved in metabolism to ultimately improve further understanding of metabolic pathways. An online predictor developed by this research is available at . Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Chemistry and morphology of dried‐up pollen suspension residues

Pollen grains are covered with lots of different biochemical compounds, like proteins, saccharides and lipids, which are only loosely attached to the pollen. Therefore, they can be separated from the pollen by suspending them in water. Since these compounds play a key role in many atmospheric processes (e.g. cloud condensation nucleation, ice nucleation, aerial allergen exposure), their separation and analyzing are of interest. The chemical composition of whole pollen grains is compared by both Raman and infrared spectroscopy with material that could be extracted from pollen with water. The dominant signals in the pollen grain Raman spectra are those from sporopollenin and carotenoids. These bands decrease in the washing water spectra, since sporopollenin is high molecular and thus is not extractable. The released material shows in turn a chemical composition that differs significantly between species, what is quite expected, since they differ even in the optical properties of their aqueous suspensions. The FTIR spectra show some additional bands to appear in comparison to the Raman spectra. Furthermore, we investigated the pollen rupturing and material release in the aqueous suspensions by drying them up and picturing the residues with a scanning electron microscope. We saw that corn pollen ejected loads of micrometer‐sized organelles, which are most likely starch granules. The more the pollen disrupted, the more the measured samples were covered with an amorphous film, which consists of the extracted pollen material, like lipids, sugars, and proteins – the same substances we detected by spectroscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

利用激光技术对材料表面缺陷进行自动测量的研究

就激光光热辐射技术测量材料缺陷的原理、实验技术进行了研究，设计了硬件与软件，实现了测量自动化，并对复合材料样品进行了测量．     

介质保护膜在表面等离子体波探测器中的应用研究

基于表面等离子体波共振技术的探测器中金属膜通常与被探测物直接接触,在金属膜和被探测物之间增加一层介质膜,可以对金属膜进行保护.为了优化探测器的设计,通过对四层共振结构中表面等离子体波共振吸收峰随保护层厚度及其介电常数变化的计算,得到了对保护层参量的选择条件.     

Theoretical study on single-molecule spectroscopy

The photon-by-photon approach for single molecule spectroscopy experiments utilizes the information carried by each detected photon and allows the measurements of conformational fluctuation with time resolution on a vast range of time scales, where each photon represents a data point. Here, we theoretically simulate the photon emission dynamics of a single molecule spectroscopy using the kinetic Monte Carlo algorithm to understand the underlying complex photon dynamic process of a single molecule. In addition, by following the molecular process in real time, the mechanism of complex biochemical reactions can be revealed. We hope that this theoretical study will serve as an introduction and a guideline into this exciting new field.