高效液相色谱-二极管阵列检测器法测定咖啡、茶叶中咖啡碱、茶碱和可可碱

将高效液相色谱,晶体二极管阵列检测器联用与正交投影分析结合,建立了一种从天然复杂样品中直接定性定量的分析方法。讨论了二维色谱重叠峰中背景的检测与扣除,纯色谱曲线的分辨和组分的定性定量分析。将这一方法用于咖啡和茶叶中咖啡碱,茶碱与可可碱的测定取得满意效果。     

在测定锆中铪时光谱背景的影响及其扣除

在锆中铪光谱分析中,背景严重地影响分析结果,特别是在低含量部分引起极大的误差,通常要进行扣除。本文以锆中铪分析为例,讨论背景的影响及其扣除方法。背景的影响由定量分析基本公式可知,lgR=lgI_L/(I_(L′))=blgc+lga…(1)。式中I_L与I_(L′)分别为分析线(铪)和内标线(锆)强度,c为分析元素(铪)含量,a,b为与试验对象和条件有关的常数。当I_L上有背景(I_B)迭加时,测得迭加有背景的分析线强度I_(L+B)=I_L+I_B;当I_(L′)上有背景(I_(B′)迭加时,测得迭加有背景的内标线强度I_(L+B′)=I_(L′)+I_(B′)。经计算简化得:     

关于谱线扣除背景计算方法的探讨

摄谱法发射光谱定量分析,由于背景的存在,会使标准曲线下部向上弯曲,若不扣除,则会导致分析结果不准。在痕量分析及有色金属分析中,常以背景作内标,对谱线扣除背景,计算公式如下:logI_f/I_b=log(10~(ΔS/γ)-1),并可查阅ΔS/υ与logI_f/I_b换算表。文献[2]介绍为了简化计算过程,在工作中不考虑ν值的变化,将它固定为1,这样logI_f/I-b=log(10~(ΔS)-1),由ΔS值查阅ΔS/υ与logI_f/I_b换算表,使工作更简便。实际     

能量色散X射线荧光光谱背景扣除方法的探讨

能量色散X射线荧光分析使得特征X射线的全能峰叠加在背景之上,针对能量色散X射线荧光谱线背景扣除算法的研究,简述了剥峰法和小波变换法扣除背景的原理,并将这两种方法用于对实际谱线的处理,取得了良好的效果.同时对两种方法的算法和处理效果进行了对比研究,表明剥峰法相对简单,而小波变换法需要考虑小波基和分解层次等的影响,但是对整个谱线的综合处理效果相对要好一些.     

三线性分解方法用于光谱数据中背景漂移的扣除

在光谱测量中, 通常会发生光谱背景漂移现象. 引起光谱背景漂移的因素有很多, 如仪器的背景噪声变化, 测量时环境温度的变化, 光源如氙灯的使用时间等等. 针对三维光谱数阵, 发展了一种基于交替三线性分解(ATLD)算法的化学计量学方法用来处理光谱背景漂移问题. 该方法在进行三线性分解时, 对待光谱背景漂移与感兴趣组分一样, 将其单独当作一个组分或因子来考虑, 并将其从分解得到的相应矩阵中提取出来, 构建一个光谱背景漂移阵, 然后从三维原始响应数阵中将其减掉, 从而达到成功扣除光谱背景漂移的目的. 采用发展的方法处理2组模拟数据和2组实验数据, 都获得了满意的结果. 另外, 对于非线性较严重的背景漂移, 通过再进行一次扣除, 即“二次扣除”, 也达到了理想的效果. 该方法有望发展成为一种很有潜力的光谱预处理技术.     

背景吸收强度可调控与扣除干扰组分影响的红外光谱测量方法

多组分混合物的红外光谱由于特征谱带的重叠或部分重叠而给谱峰的归属辨认带来极大的困难。本研究通过扫描两个背景样品(纯KBr压片(1)和KBr+C18TCNQ压片(2))实时合成一系列背景单光束谱。每个背景单光束谱既含有背景样品1的贡献也含有背景样品2的贡献。干扰组分C18TCNQ在系列背景谱中的吸收强度随扫描次数变化而改变。当待测混合物和背景样品中干扰组分的吸收强度相等时,就可以完全扣除干扰组分的影响。本测量方法用于硬脂酸与C18TCNQ混合物中扣除硬脂酸(或者C18TCNQ)的干扰,得到令人满意的结果。合成背景样品中干扰组分的含量在测量时成为与扫描次数有关的变量,为扣除干扰组分的影响提供了直接便利的红外光谱测量方法。     

三线性分解方法用于激发-发射矩阵荧光数据中一阶瑞利散射的扣除

由于荧光分析具有检测灵敏度高、数据容易获得等优点,近年来二阶张量校正方法与激发-发射矩阵荧光光谱技术的联用正受到人们越来越多的关注.但是,在三维荧光分析中,经常出现的一阶瑞利散射干扰往往容易导致建立的三线性模型存在较大的偏离,进而直接影响复杂体系中感兴趣组分的定性、定量分析.针对该问题,我们提出了一种基于对组分数不敏感的三线性分解算法扣除一阶瑞利散射干扰的新思路.该方法的特点是根据一阶瑞利散射分别在水平切片矩阵和侧面切片矩阵所处位置相同,沿I-模和J-模同时构建含一阶瑞利散射的三维数据阵,利用三线性分解算法对此各自建模,将一阶瑞利散射当作一个响应组分或因子拟合后从三维数据阵中扣除掉.通过对模拟和实际三维激发发射矩阵荧光光谱实验数据进行讨论,结果表明该方法能有效地扣除体系中的一阶瑞利散射干扰.改进后的方法不仅操作简单,而且不受组分数选取不当的困扰.另外,由于同时从两个方向进行一阶瑞利散射扣除,因此不会出现因边缘瑞利散射峰形不完整而扣除不完全的情况.该方法为三维荧光光谱的无损分析提供了新思路,为进一步进行三维荧光光谱的定量分析奠定了良好的基础.     

电感耦合等离子体发射光谱法同时测定硅酸盐岩石中九个元素

采用混合酸(硝酸、高氯酸、氢氟酸)溶样,不用内标和缓冲剂,不进行背景扣除及干扰校正,样品溶液直接喷入灯炬,应用岛津ICPQ—100型光量计同时测定硅酸盐岩石中铝、钙、镁、铁、锰、钛、磷、锶、钡九种元素,检出限、精密度符合规范要求。通过对七个管理样、四个国外标样及部份生产样品的测定,证明此方法简单、快速、准确,能满足定量分析的需要。     

标准溶液配制用碳酸锂纯物质中杂质含量的测定

从高纯碳酸锂中杂质含量测定出发,研讨了标准溶液配制用原料的杂质测定方法,首先利用电感耦合等离子体质谱(ICP-MS)法对高纯碳酸锂进行半定量分析,再依据半定量分析结果选择ICP-MS、电感耦合等离子体原子发射光谱(ICP-AES)法、原子吸收光谱(AAS)法等方法对相应元素(杂质含量0.001%)进行定量分析,通过扣除杂质含量得出高纯碳酸锂纯度大于99.991%。从而建立了一个准确、高效,覆盖元素种类多的高纯物质中杂质含量的分析方法     

石墨炉原子吸收光谱测定中碱土金属氯化物的背景吸收

研究了石墨炉原子吸收中碱土金属氯化物在１９０～３６０ｎｍ范围的背景吸收，以及灰化温度和原子化温度对背景吸收的影响，讨论了背景吸收对测量的干扰，以及ＨＮＯ３基体改进剂和氘灯扣除背景测量方式对背景干扰消除情况。     

Quantitative analysis of trace levels of surface contamination by X‐ray photoelectron spectroscopy. Part I: Statistical uncertainty near the detection limit

We discuss the problem of quantifying common sources of statistical uncertainties for analyses of trace levels of surface contamination by using X‐ray photoelectron spectroscopy. We examine the propagation of error for peak‐area measurements by using common forms of linear and polynomial background subtraction including the correlation of points used to determine both background and peak areas. This correlation has been neglected in previous analyses, but we show that it contributes significantly to the peak‐area uncertainty near the detection limit. We introduce the concept of relative background subtraction variance (RBSV) that quantifies the uncertainty introduced by the method of background determination relative to the uncertainty of the background area itself. The uncertainties of the peak area and atomic concentration and of the detection limit are expressed using the RBSV, which separates the contributions from the acquisition parameters, the background‐determination method, and the properties of the measured spectrum. These results are then combined to find acquisition strategies that minimize the total measurement time needed to achieve a desired detection limit or atomic‐percentage uncertainty for a particular trace element. Minimization of data‐acquisition time is important for samples that are sensitive to X‐ray dose and also for laboratories that need to optimize throughput.     

A microcomputer-based data acquisition and processing system for electrochemical analysis

The system described for electrochemical analysis includes ensemble averaging, boxcar integration and background subtraction. A digital storage oscilloscope interfaced to a microcomputer provides these data-processing techniques for the differential pulse polarographic determination of molybdenum. The system is easily interfaced to the polarograph. An approximately four-fold improvement in the detection limit for molybdenum — to 2.7 × 10^-4 ppm — was achieved by using a combination of ensemble averaging and background subtraction.     

A retention‐time‐shift‐tolerant background subtraction and noise reduction algorithm (BgS‐NoRA) for extraction of drug metabolites in liquid chromatography/mass spectrometry data from biological matrices

A retention‐time‐shift‐tolerant background subtraction and noise reduction algorithm (BgS‐NoRA) is implemented using the statistical programming language R to remove non‐drug‐related ion signals from accurate mass liquid chromatography/mass spectrometry (LC/MS) data. The background‐subtraction part of the algorithm is similar to a previously published procedure (Zhang H and Yang Y. J. Mass Spectrom. 2008, 43: 1181–1190). The noise reduction algorithm (NoRA) is an add‐on feature to help further clean up the residual matrix ion noises after background subtraction. It functions by removing ion signals that are not consistent across many adjacent scans. The effectiveness of BgS‐NoRA was examined in biological matrices by spiking blank plasma extract, bile and urine with diclofenac and ibuprofen that have been pre‐metabolized by microsomal incubation. Efficient removal of background ions permitted the detection of drug‐related ions in in vivo samples (plasma, bile, urine and feces) obtained from rats orally dosed with ¹⁴C‐loratadine with minimal interference. Results from these experiments demonstrate that BgS‐NoRA is more effective in removing analyte‐unrelated ions than background subtraction alone. NoRA is shown to be particularly effective in the early retention region for urine samples and middle retention region for bile samples, where the matrix ion signals still dominate the total ion chromatograms (TICs) after background subtraction. In most cases, the TICs after BgS‐NoRA are in excellent qualitative correlation to the radiochromatograms. BgS‐NoRA will be a very useful tool in metabolite detection and identification work, especially in first‐in‐human (FIH) studies and multiple dose toxicology studies where non‐radio‐labeled drugs are administered. Data from these types of studies are critical to meet the latest FDA guidance on Metabolite in Safety Testing (MIST). Copyright © 2009 John Wiley & Sons, Ltd.     

Software-induced variance in two-dimensional gel electrophoresis image analysis

Experimental variability in 2-DE is well documented, but little attention has been paid to variability arising from postexperimental quantitative analyses using various 2-DE software packages. The performance of two 2-DE analysis software programs, Phoretix 2D Expression v2004 (Expression) and PDQuest 7.2 (PDQuest), was evaluated in this study. All available background subtraction and smoothing algorithms were tested using both data generated from one single 2-DE gel image, thus excluding experimental variance, and with authentic sets of replicate gels (n = 5). A slight shift of the image boundaries (the "cropping area") caused both programs to induce variance in protein spot quantification of otherwise identical gel images. The resulting variance for PDQuest (CV(mean) = 8%) was approximately twice that for Expression (CV(mean) = 4%). In authentic sets of replicate 2-DE gels (n = 5), the experimental variance confounded the software-induced variance to some extent. However, Expression still outperformed PDQuest, which exhibited software-induced variance as high as 25% of the total observed variance. Surprisingly, the complete omission of background subtraction algorithms resulted in the least amount of software-based variance. These data indicate that 2-DE gel analysis software constitutes a significant source of the variance observed in quantitative proteomics, and that the use of background subtraction algorithms can further increase the variance.     

Improved sensitivity using a microcomputer for electrothermal atomic absorption spectrometry with a metal microtube

Data enhancement by signal accumulation, scale expansion after background subtraction, and smoothing with the aid of the microcomputer enables limits of detection to be improved by up to an order of magnitude. Data are reported for 15 elements.     

True ion pick (TIPick): a denoising and peak picking algorithm to extract ion signals from liquid chromatography/mass spectrometry data

Liquid Chromatography ‐ Time of Flight Mass Spectrometry has become an important technique for toxicological screening and metabolomics. We describe TIPick a novel algorithm that accurately and sensitively detects target compounds in biological samples. TIPick comprises two main steps: background subtraction and peak picking. By subtracting a blank chromatogram, TIPick eliminates chemical signals of blank injections and reduces false positive results. TIPick detects peaks by calculating the S(CC_INI) values of extracted ion chromatograms (EICs) without considering peak shapes, and it is able to detect tailing and fronting peaks. TIPick also uses duplicate injections to enhance the signals of the peaks and thus improve the peak detection power. Commonly seen split peaks caused by either saturation of the mass spectrometer detector or a mathematical background subtraction algorithm can be resolved by adjusting the mass error tolerance of the EICs and by comparing the EICs before and after background subtraction. The performance of TIPick was tested in a data set containing 297 standard mixtures; the recall, precision and F‐score were 0.99, 0.97 and 0.98, respectively. TIPick was successfully used to construct and analyze the NTU MetaCore metabolomics chemical standards library, and it was applied for toxicological screening and metabolomics studies. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of impurities in highly pure platinum by inductively coupled plasma-atomic emission spectrometry

In this work, a cyclone spray chamber system is used in conjunction with an inductively coupled plasma-atomic emission spectrometer instead of the conventional Scott-type chamber system to reduce the lower limit of detection achieved by the instrument, and an internal standard element (Y) is introduced to eliminate the effects caused by the drift in the plasma background level. An ICP-AES method for the determination of 13 impurity elements in a highly pure platinum sample has been developed. In this method, it is not necessary either to add a platinum matrix to the calibration standard or to separate and concentrate the elements to be determined in the samples. The effect of the platinum matrix on the elements to be analyzed is corrected for by a background equivalent concentration subtraction method. The determination ranges of the method are as follows: 0.00010-0.0050% for Mg, Mn, Cu, Ag, Fe and Zn; 0.00030-0.015% for Au, Ir, Ni and Pb; 0.00050-0.025% for Rh and Al; and 0.00080-0.040% for Pd. The method is simple, rapid and accurate, and can be applied to the analysis of 99.9–99.995% pure platinum.     

A semi-empirical method for photofraction determination

A semi-empirical method for photofraction determination is proposed: the photopeak efficiency is plotted as a function of the calculated total number of photons which interact at least once with the crystal for different sample to crystal distances. The tangent to this curve gives the photofraction at the point considered. No background subtraction or shielding is necessary.     

Experimental derivation of Auger transition probabilities from X-ray excited Auger electron spectra in XPS

Auger transition probabilities were experimentally derived from dominant XAES and related XPS peaks observed in XPS spectra. Some values of derived probabilities were higher than 1, because of addition or subtraction of background signal from the XAES or/and XPS peak intensity. However, the probabilities obtained are recognized to be useful for practical quantification by XAES and AES.