Multivariate analysis for forensic characterization,discrimination, and classification of marker pen inks

The multivariate analysis methods have recently gained high popularity within the field of forensic sciences because of their high accuracy and precision. The accurate and unbiased results are the preliminary need for a forensic investigation. The aim of the present work is to examine the marker pen inks which are widely used in various places like documentation in parcels, for photograph attestation, and also as a study material in the classroom. This research is focused on the three important aspects; first is to characterize the marker inks, second, to discriminate permanent marker and whiteboard marker inks using destructive (extracting of ink samples from paper substrate) and nondestructive (without ink extraction) techniques of ultraviolet–visible absorbance combined with peak identification examination as well as chemometric methods, and the third is to build a classification model for permanent and whiteboard marker inks. It is concluded that the chemometric method, that is, principal component analysis provides better discrimination power as compared to visual examination. However, destructive and nondestructive approaches give almost similar discriminating power. The classification model developed using linear discriminant analysis provides 87.5% of correct classification of marker ink samples. The method can further be used to formulate a statistical model for the determination of class/group of the other forensic exhibits.     

Improvement of sensitivity using principal component analysis by dual focused ion beam time-of-flight secondary ion mass spectrometry

It is important to develop and to practically use the method to analyze a micro-nanometer order area. Especially, three-dimensional microanalysis for minute structure that consists of the organic compounds and the polymer is difficult. We developed a novel three-dimensional microanalysis method by means of focused ion beam (FIB) for section processing and ToF-SIMS for mapping method. For the purpose of realization of three-dimensional microanalysis and a chemical and structural analysis of the organic matter, the sensitivity improvement of ToF-SIMS in the three-dimensional analysis device and the method of the spectral analysis are examined. To improve the sensitivity of ToF-SIMS, the sample stage was modified to arrange perpendicularly with the ToF optical axis, and the distortion of electric field was corrected. And, by analyzing the fragment ions by using the principal component analysis (PCA) to raise the efficiency of the spectrum analysis, spatial resolution has improved. As a result, the resolution of the device improved to sub micrometer order, and advanced to the achievement of the three-dimensional microanalysis.     

Ga primary ion ToF-SIMS fragment pattern of inorganic compounds and metals

Regularity of Ga⁺ primary ion ToF-SIMS fragment pattern of inorganic compounds is discussed. For an inorganic compound as formulated M–A, where the valence of cation M is +n and that of anion A is −p, the chemical composition of appeared ToF-SIMS fragment are M_xA_y, which satisfy the rule nx≥py+1 for positive ion fragments and nx≤py+1 for negative ones. For example, for oxide fragment of chemical composition, M_xA_y (valence of M is +n), the fragment obeys the rule nx≥2y+1 for positive ions and nx≤2y+1 for negative ones, respectively. The regularity of ToF-SIMS fragment patterns of sulfides, nitrates, sulfates etc. is discussed.     

ToF-SIMS and XPS study of ancient papers

The surface composition of 18th century papers was investigated by means of ToF-SIMS and XPS. The aim of the present study was to explore the possibility of using these surface sensitive methods to obtain information which can help to determine the manufacturing process, provenance and state of conservation of ancient papers. The ToF-SIMS results indicate that the analyzed papers were sized by gelatin and that alum was added as hardening agent. The paper sheets produced in near geographical areas but in different paper mills exhibit a similar surface composition and morphology of the fibers as shown by the ToF-SIMS measurements. The ToF-SIMS and the XPS results indicate that a significant fraction of the cellulose fibers is not covered by the gelatin layer. This was observed for the ancient papers and for a modern handmade paper manufactured according to the old recipes.     

On the examination of raw,pasteurized, powdered,and adulterated milk samples and their multivariate classification: applications in food and forensic science

Abstract

In the present study, we have utilized attenuated total reflectance Fourier transform infrared spectroscopy for the examination of raw, pasteurized and adulterated milk samples. Principal component analysis and discriminant analysis have been applied for discrimination and classification purposes. According to the observations and the model of “goodness of fit”, the obtained results explain 100% of the original classification of the dataset and leave one out cross-validation provides 93.74% of accurate classification.     

青海不同地区枸杞微量元素分析研究

为了对比青海不同地区枸杞的品质,采用ICP-MS和ICP-AES法对青海省12个产地的枸杞果实中11种微量元素含量进行了测定,并选取人体必需的7种微量元素,结合SPSS统计软件进行主成分分析。结果获得了3个主成分方程,并建立了主成分对变量的回归方程,对比较青海不同地区枸杞优劣以及获得高品质枸杞具有重要意义,为青海枸杞的开发和利用提供了科学依据。     

ToF-SIMS and SEM-EDS analysis of the surface of chosen bioindicators

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy with field emission equipped with energy dispersive spectrometer (SEM-EDS) were applied in order to investigate the surface of chosen biological indicators such as bark, needles and hair. All samples were collected from the urban areas of the Lodz city region, recognized as one of the most polluted in Poland. The high resolution of the applied techniques provides good separation of signals from different chemical species. High detection sensitivity enables an analysis of crucial elements and/or molecules. It was found that the surface of the materials studied was in general covered by many exogenous particles, suggesting, from the monitoring purpose point of view, their possible anthropogenic origin. The preliminary results obtained revealed that these techniques can be successfully used in environmental analysis of various biological samples and can provide detailed information about distribution and composition of airborne pollutants within the sample surfaces studied as well as initiate a renewed interest in the exposure study.     

红外光谱法结合化学计量学对可擦笔油墨检验的研究

可擦笔作为一种新型书写工具,具有墨迹可擦除的特点,因此在当前的公安司法工作中,常见不法分子利用可擦笔对文件进行篡改.为保证物证的完整性,亟待建立一种无损,快速的可擦笔油墨检验方法,为寻找书写工具,确定犯罪嫌疑人提供帮助.常见可擦笔油墨可分为成膜油墨类和温变油墨类,本研究利用傅里叶变换红外光谱仪对市场收集的不同品牌、型号...     

Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

ToF-SIMS studies of Bacillus using multivariate analysis with possible identification and taxonomic applications

In this paper we discuss the application of ToF-SIMS with an Au₃⁺ primary ion beam, combined with principal components analysis (PCA) and discriminant function analysis (DFA) for the identification of individual strains of two Bacillus species. The ToF-SIMS PC-DFA methodology is capable of distinguishing bacteria at the strain level based on analysis of surface chemical species. By classifying the data using hierarchical cluster analysis (HCA) we are able to show quantitative separation of species and of these strains. This has taxonomic implications in the areas of rapid identification of pathogenic microbes isolated from the clinic, food and environment.     

Classification of iron‐based inks by means of micro‐Raman spectroscopy and multivariate data analysis

In this work, multivariate data analysis methods were applied to the analysis and interpretation of micro‐Raman spectra, collected from a broad set of historical iron‐based ink samples, previously characterised for the content of organic acids (gallic acid, ellagic acid and protocatechuic acid). The proposed method relies on principal component analysis of the noisy spectra typically obtained on original, degraded, organic samples, where fluorescence could affect the Raman signal. The signal components could be distinguished from the noise components and then used to build a linear discriminant analysis (LDA) model, achieving separation of the spectra into three classes. Selection of pure signal factors also improved effectiveness and performances of partial least square regression (PLS) algorithms, allowing quantification of condensed tannic acid residuals. Application of multivariate methods to discriminate signal from noise removes the need for spectral data manipulation (filtering, smoothing and differentiating). The obtained classification method for discrimination of historic inks and the regression method for determination of condensed tannic acid residuals supports the use of Raman analysis of fluorescing organic materials, and may provide information to scholars on ink composition and potentially on its provenance. Copyright © 2013 John Wiley & Sons, Ltd.     

两类红花和牛黄的太赫兹光谱法真伪鉴别分析

藏红花和天然牛黄是广泛应用于临床实践的中药材，由于产量较低、药用价值和价格高，市场需求量大等因素，掺伪和伪品较多，不仅严重损害患者健康，而且妨碍市场正常运转。传统的“一看、二闻、三泡”等经验鉴别方法已经越来越难以分辨高仿伪品；而通过化学提取和色谱、质谱等理化检测方法往往步骤繁琐、费时，且对检测环境、人员及设备的要求和依赖度较高，不能适应现场、快速、简便等实际需求，亟需探索新的有效检测方法和鉴别技术。太赫兹时域光谱(THz-TDS)不但具有单纯化合物的高度专属性和特异性，又具有混合体系的“宏观指纹特征”，可以鉴别混合物化学成分的多样性和复杂性。另外，主成分分析(PCA)作为一种常用的统计分析手段，主要是用少数几个且能最大解释原始数据方差的综合变量来取代原始变量，可以对不同种类的样本进行模式识别。采用粉末研磨压片技术分别压制了藏红花和草红花样品各18个、天然牛黄和人工牛黄各20个，并利用太赫兹时域光谱测试技术分别测量了两种名贵中药材及其伪品在0.3～2.5 THz范围的吸收光谱，最后利用主成分分析方法对获得的光谱数据进行分类识别。为了提高PCA对测试数据的鉴别能力，一方面将数据集映射到一组基(特征向量)进行简化，选用较大的特征值代替原来的主要光谱信息；另一方面，为了消除无关因素对分类处理的干扰，在进行PCA之前采取了Savitzky-Golay(S-G)平滑处理进行降噪，去除冗余、不相关的光谱特征；然后通过Fisher诊断线进行判别分析。对比未处理和经过S-G平滑处理的主成分得分图，可以看出平滑处理后的分类效果明显优于未做处理的，在未处理的得分图中，两类样品点重叠比较严重，而经过平滑后的得分图却只有相对较少的部分样品点重叠，由此可以看出SG平滑在光谱识别中的重要性；另外，前两个主成分(PC1和PC2)已经基本能反映光谱之间的差异性。分类结果显示，藏红花和草红花具有明显的聚类趋势，分类鉴别准确率均为100%；而人工牛黄和天然牛黄的类内样品基本聚在一起，但是类间略有重叠，分类鉴别准确率分别为100%和90%。除此之外，样本的主成分得分图还可以反映样本的内部特征和聚类信息。其中，藏红花样本由于藏红花素、藏红花酸等化合物成分含量较高，聚合度较好，分布范围相对集中；反之，天然牛黄为胆囊分泌物，成分较为复杂，聚类效果较差，分布范围较广。研究结果表明，太赫兹光谱技术结合主成分分析可以区分藏红花和草红花以及天然牛黄和人工牛黄，结果可靠。该研究结果为丰富中草药的质量标准提供检测手段和理论依据。     

Application of multivariate analysis of TOF-SIMS spectra for studying the effect of high glucose intake on aortic lipid profile

Aim

To study the effect of long-term glucose feeding on aortic lipid composition by using the time of flight-secondary ion mass spectrometry (TOF-SIMS).

Method

Rats were divided into two groups, drinking water with or without 10% glucose from birth to 6 months of age. The aortic wall was dissected out, high-pressure frozen, freeze-fractured, freeze-dried and analyzed by TOF-SIMS using a Bismuth cluster ion source. Surface spectra were taken from standardized regions of the vessel wall.

Results

Different peaks, such as cholesterol, fatty acids (FAs) and diacylglycerols (DAGs), were identified by the principal component analysis as carries of variance between two groups. These peaks were then compared by conventional t-test. Our data showed that the intensity of cholesterol, but not FAs and DAGs, was significantly decreased in the glucose-drinking rat. Moreover, the long-term glucose intake changed ratios between different FAs in the aorta.

Conclusion

The long-term glucose intake led to decreased cholesterol intensity in the aortic wall and this effect was revealed through a global analytical approach with objective selection of significant variables.     

自动化学间断分析仪和原子吸收光谱法测定锥栗不同授粉组合果实的元素含量

为探讨锥栗不同授粉组合果实中矿质元素是否也存在花粉直感效应，应用全自动间断化学分析仪和原子吸收光谱法测定了“华栗1号”、“华栗2号”、“华栗3号”和“黄榛”四个锥栗主栽品种自交、异交以及自然授粉的子代坚果中主要矿质元素的含量。结果表明，锥栗不同授粉组合坚果的N，P，K，Ca，Mg，Fe，Zn和Mn八种矿质元素含量差异较为显著，其矿质元素具有明显的花粉直感效应，尤其是铁、锌元素受花粉直感作用的影响较大，“华栗2号”ד黄榛”授粉组合果实铁、锌元素含量最高，分别为162.13和41.79 μg·g-1；“黄榛”ד华栗1号”授粉组合果实中Mn元素含量最高为165.67 μg·g-1，为锰微肥的利用提供了参考；通过主成分分析，评价出19个组合中在矿质元素方面表现最优的授粉组合为“华栗2号”ד黄榛”。该研究结果可为锥栗生产上合理配置授粉树和改善果实品质提供科学的依据。     

红外光谱在纤维质文物材料鉴别中的应用研究

纺织纤维和纸张纤维是常见纤维质文物材料,是构成博物馆精美文物如服饰手稿书画的基本材料,近年来寻求通过无损或微损方法对这一类材料的鉴别以及劣化状况评价备受文物鉴赏家和文物保护工作者的关注。借助傅里叶变换红外光谱,研究博物馆常见纺织纤维材料棉、麻、桑蚕丝、柞蚕丝、羊毛的红外光谱特征和它们的分子结构组成异同,研究传统纸纤维稻草、麦草、龙须草、龙旗松、桑皮红外光谱特征。结果表明：衰减全反射傅里叶变换红外光谱无损分析技术可通过比较3 300～2 800 cm-1 CH,NH,OH振动区间光谱形状以及指纹区峰位以区别不同种类纺织品纤维;碳氧振动纸张纤维最明显光谱差异位置出现在与纤维素OH伸缩振动相关波数3 300 cm-1和与C—O—C相关波数1 332,1 203,1 050 cm-1。文章探索研究红外光谱技术结合主成分分析法在快速鉴别纤维材料中的应用。通过对全光谱数据多元散射校正(MSC)预处理后进行主成分分析,可以把红外光谱十分相似的纺织纤维棉和亚麻、桑蚕丝和柞蚕丝明显分类;对光谱相似的纸纤维,可采用选择不同光谱波数段进行主成分分析,比较发现能够把五种纸纤维明显区分的光谱区间为3 800～2 800 cm-1。本研究为分子光谱无损分析技术应用于文物材料鉴别、科学评估纤维材料保存状况提供基础研究。     

红外光谱在纤维质文物材料鉴别中的应用研究

纺织纤维和纸张纤维是常见纤维质文物材料, 是构成博物馆精美文物如服饰手稿书画的基本材料, 近年来寻求通过无损或微损方法对这一类材料的鉴别以及劣化状况评价备受文物鉴赏家和文物保护工作者的关注。借助傅里叶变换红外光谱, 研究博物馆常见纺织纤维材料棉、麻、桑蚕丝、柞蚕丝、羊毛的红外光谱特征和它们的分子结构组成异同, 研究传统纸纤维稻草、麦草、龙须草、龙旗松、桑皮红外光谱特征。结果表明: 衰减全反射傅里叶变换红外光谱无损分析技术可通过比较3 300～2 800 cm-1 CH, NH, OH振动区间光谱形状以及指纹区峰位以区别不同种类纺织品纤维;碳氧振动纸张纤维最明显光谱差异位置出现在与纤维素OH伸缩振动相关波数3 300 cm-1和与C—O—C相关波数1 332, 1 203, 1 050 cm-1。文章探索研究红外光谱技术结合主成分分析法在快速鉴别纤维材料中的应用。通过对全光谱数据多元散射校正(MSC)预处理后进行主成分分析, 可以把红外光谱十分相似的纺织纤维棉和亚麻、桑蚕丝和柞蚕丝明显分类;对光谱相似的纸纤维, 可采用选择不同光谱波数段进行主成分分析, 比较发现能够把五种纸纤维明显区分的光谱区间为3 800～2 800 cm-1。本研究为分子光谱无损分析技术应用于文物材料鉴别、科学评估纤维材料保存状况提供基础研究。     

基于无机元素的含量判别食醋的种类和品牌方法研究

化学计量学广泛应用于食品种类和原产地的区分。文章采用原子吸收法测定了32个食醋样品中的Mg, K, Pb, Zn, Fe, Mn, Ca和Cu等八种无机元素含量。采用向量相似法计算了陈醋和白醋以及同一种类不同品牌食醋的相似度;通过聚类分析和主成分分析对来自北京、江西、江苏和山西4个地区品牌的食醋进行了分类,对不同种类的食醋(陈醋和白醋)也进行了分类。聚类分析和主成分分析都将食醋样品分为两大类,每个大类又将食醋样品按不同品牌分开。食醋中无机元素含量差异可作为食醋种类和品牌判别的测量指标之一。     

基于PCA-BP神经网络的EDXRF分析测定地质样品中铁、钛元素含量的应用研究

为实现地质样品中元素含量的准确预测,提出了基于主成分分析(PCA)的改进型BP神经网络模型。采用X荧光光谱法,对新疆西天山地质样品中Fe,Ti,V,Pb和Zn等元素进行测量,将得到的X荧光计数作为输入变量,应用该模型对未知地质样品中Fe和Ti元素进行定量预测。结果表明：主成分分析与改进型BP神经网络模型取得了较好的预测效果,预测结果与化学分析值的相对误差小于3%,为地质样品元素含量预测提供了一种新型有效的方法。     

蛇足石杉及其近缘种表征关系的FTIR主成分分析

蛇足石杉是一种重要药用植物,其种内变异程度高,近缘种多,植株体型小,可供鉴别性状少。运用OMNI采样器-傅里叶变换红外光谱直接测定法,获得了蛇足石杉(Huperzia Serrata)及其5个近缘种：四川石杉(Huperzia Sutchueniana)、闽浙马尾杉(Phlegmariurus Mingchegensis)、石松(Lycopodium Japonicum)、深绿卷柏(Selaginella Doederleinii)和异穗卷柏(Selaginella Heterostachys)16个叶片样品的红外光谱,以666～3 145 cm-1范围内吸收峰吸光度为指标,以红外光谱图为对象,应用主成分分析(Principal Component Analysis),比较了16个样品在红外光谱上的差异程度。发现基于傅里叶变换红外光谱的主成分分析排序图能够在一定程度上表征16个样品的分类关系。应用FTIR直接测定法能够鉴别蛇足石杉及其近缘物种。