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Differentiation of oil samples by isomeric composition of paraffins using cluster analysis methods 用聚类分析方法鉴别石蜡异构体组成的石油样品
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.1.006
Iu. P. Turov, M. I. Guzniaeva
A new method is proposed for controlling the sources of oil samples by chemical composition for their differentiation, identification and establishment of their origin (specific wells of the operating field) using the agglomerative hierarchical data clustering and applying the J. Ward algorithm. The initial information is the data on the composition and relative contents of n-paraffins С17Н36 ÷ С34Н70, isoprenoids of pristane С19Н40 and phytane С20Н42 in oil samples obtained by selected-ion monitoring gas chromatography/mass spectrometry. The solution to the problem was carried out in the absence of the information about the magnitude of the total uncertainty in the data, without using the standard samples for their assessment and without the preliminary assumption of the number of expected clusters. The proposed technique’s possibilities were illustrated by the results of 20 × 27 data matrix processing based on the relative paraffin content in 27 encrypted anonymous samples. As an outcome, three clusters were identified, each of which included objects sampled from the specific well. Differentiating the sources of the samples using the traditional methods by comparing the amounts of n-paraffins and isoprenoids proved to be impossible. Due to the inevitable errors in the analysis results and the possible changes in the composition of the recovered oil, the values of the relative contents of paraffins in the oil samples from all three wells overlap and the sources remain indistinguishable. The newly proposed method made it possible to solve the differentiation problem of oil samples in organic geochemistry and environment control which are complicated by the wide variability of the composition of oil samples, the lability of petroleum system under the influence of natural and technogenic factors and the absence of the estimate of the actual errors in the data.
提出了一种利用聚类分层数据聚类和J. Ward算法,通过化学成分控制油样来源的方法来区分、识别和确定油样来源(作业油田的特定井)。初始信息是通过选择离子监测气相色谱/质谱法获得的油样中正石蜡С17Н36 ÷ С34Н70、异戊二烯С19Н40和植烷С20Н42的组成和相对含量数据。该问题的解决是在没有关于数据中总不确定性的大小的信息的情况下进行的,没有使用标准样本进行评估,也没有对预期群集的数量进行初步假设。基于27个加密匿名样本中相对石蜡含量的20 × 27数据矩阵处理结果说明了该技术的可能性。结果,确定了三个簇,每个簇都包括从特定井中采样的物体。通过比较正石蜡和类异戊二烯含量的传统方法来鉴别样品来源被证明是不可能的。由于分析结果中不可避免的误差和采出油成分可能发生的变化,三口井的油样中石蜡的相对含量值重叠,无法区分来源。该方法解决了油样组成的大变异性、油气系统受自然因素和工艺因素影响的不稳定性以及数据中缺乏实际误差估计等问题,使油样在有机地球化学和环境控制中的分异问题变得复杂。
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引用次数: 0
Book review for “X-Ray Fluorescence in Biological Sciences: Principles, Instrumentation, and Applications”, Eds: V.K. Singh, J. Kawai, D.K. Tripathi. Wiley. 2022, 688 pp. ISBN: 978-1-119-64554-2A 《生物科学中的x射线荧光:原理、仪器和应用》书评,编辑:V.K. Singh, J. Kawai, D.K. Tripathi。Wiley. 2022, 688页。ISBN: 978-1-119-64554-2A
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.2.006
A. G. Revenko
Through the efforts of three editors - V.K. Singh and D.K. Tripathi (India), and J. Kawai (Japan), as well as 79 qualified specialists from 14 countries, “X-ray Fluorescence in Biological Sciences: Principles, Instrumentation and Applications” monograph was prepared and published in March of this year. The book is divided into six parts. Part 1 is a general introduction to RFA (7 chapters). Parts 2 and 3 are relatively new versions of the XRF method using the synchrotron radiation for the excitation of fluorescence (5 chapters) and XRF with total external reflection (4 chapters). Part 4, a beginner's guide, is considered by the editors to be one of the highlights of this book (4 chapters). The main parts of this book are Parts 5 (Application for Biological Samples - 11 chapters) and 6 (Special Topics and Comparison with Other Methods - 8 chapters). The book provides information on advances in the application of X-ray fluorescence analysis that have not been reflected in general monographs published in recent years. Representatives of India prepared 15 chapters, colleagues from Russia – 7, from Mongolia and China – 3 each, Japan, Spain, Turkey and Slovenia – with 2 chapters each, Italy, Argentina, and Bangladesh – 1 each. Representatives of Algeria and Egypt co-authored with colleagues from Turkey, and of South Korea with colleagues from India, respectively. The largest number of participants (authors of chapters) – 29 – was noted for India, 11 – from Russia, and 6 each from China, Turkey, and Slovenia. The monograph will be in demand in the laboratories of universities and research institutes, especially in the laboratories of biological and medical research centers. It will be a useful guide for students of natural and chemical sciences, medical biology, plant physiology, and agriculture.
在印度的V.K. Singh、D.K. Tripathi和日本的J. Kawai三位编辑以及来自14个国家的79名合格专家的努力下,《生物科学中的x射线荧光:原理、仪器和应用》专著已于今年3月完成并出版。这本书分为六个部分。第1部分是RFA的总体介绍(共7章)。第二部分和第三部分是使用同步辐射激发荧光的XRF方法(5章)和使用全外反射的XRF方法(4章)的相对较新的版本。第4部分,初学者指南,被编辑认为是本书的亮点之一(4章)。本书的主要部分是第5部分(生物样品的应用- 11章)和第6部分(专题和与其他方法的比较- 8章)。这本书提供了关于x射线荧光分析的应用进展的信息,这些信息没有反映在近年来出版的一般专著中。印度代表编写了15章,俄罗斯代表编写了7章,蒙古和中国代表各编写了3章,日本、西班牙、土耳其和斯洛文尼亚代表各编写了2章,意大利、阿根廷和孟加拉国代表各编写了1章。阿尔及利亚和埃及的代表分别与土耳其的同事和韩国的代表与印度的同事共同撰写了报告。与会者(各章作者)最多的是印度29人,俄罗斯11人,中国、土耳其和斯洛文尼亚各6人。该专著将在大学和研究机构的实验室,特别是在生物和医学研究中心的实验室需求。这将是一个有用的指导学生自然和化学科学,医学生物学,植物生理学和农业。
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引用次数: 0
Electrochemical sensor modified with gold and arenediazonium salts for the determination of copper and mercury in human’s hair 用金和氨基重氮盐修饰的电化学传感器测定头发中的铜和汞
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.2.004
G. Slepchenko, M. S. Ostapenko, Yu. A. Akeneev, E. S. Moiseeva
Current article presents the results of using a solid carbon-containing electrochemical sensor modified with arenediazonium salts (ME-ADT-COOH) for the joint determination of copper and mercury in human hair. The sensitivity of the determination of copper and mercury ions using a graphite electrode modified with gold and arenediazonium salts with a substituent carboxy group is higher compared to the other carbon-containing modified electrodes. The influence of the concentration of arenediazonium tosylates with various substituents on the obtained analytical signal was studied. The conditions for the manufacturing the new carbon-containing modified electrochemical sensor have been developed. The effective surface area of the modified electrode was calculated, which was estimated using a cyclic voltammogram against the background of 0.1 M KCl with the addition of potassium hexacyanoferrate (С=5*10-4mol/l) salts and calculated using the Randles-Ševčík equation for the reversible electrode process. A linear range of determined concentrations in the voltametric determination of microelements on the arendiazonium-modified gold-graphite electrode was established - from 0.1 to 12 µg/g. The error of the determination did not exceed 25 %. The correctness of the results of the determination of copper and mercury in real objects by the “introduced-found” method, which correlates well with the known values, has been verified.
本文介绍了用含固碳的芳胺重氮盐修饰的电化学传感器(ME-ADT-COOH)联合测定人发中铜和汞的结果。与其他含碳修饰电极相比,用金修饰石墨电极和带有取代基羧基的arennediazonium盐修饰石墨电极测定铜和汞离子的灵敏度更高。研究了含不同取代基的戊二氮鎓甲酸酯浓度对所得分析信号的影响。研究了新型含碳改性电化学传感器的制备条件。在0.1 M KCl的背景下,加入六氰高铁酸钾(С=5*10-4mol/l)盐,使用循环伏安法估算了修饰电极的有效表面积,并使用可逆电极过程的Randles-Ševčík方程计算了修饰电极的有效表面积。建立了在砷二氮修饰金石墨电极上伏安法测定微量元素浓度的线性范围:0.1 ~ 12µg/g。测定误差不超过25%。验证了“引入发现法”测定实物中铜和汞的结果的正确性,与已知值吻合较好。
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引用次数: 0
Spectrophotometric determination of phenylalanine in aqueous solutions with different acidity 不同酸度水溶液中苯丙氨酸的分光光度法测定
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.3.003
V. Vasil'eva, A. Saud
A method for the determination of phenylalanine using the spectrophotometric method without preliminary correction of the solutions pH and the use of auxiliary chemical reagents has been developed. A comparative analysis of the spectrophotometric determination of phenylalanine by varying acidity of the medium was carried out. The errors and the possibility of their minimization were analyzed. It was shown that the analytical signal and the results of amino acid determination in the solutions with different pH differ significantly due to the presence of phenylalanine in various ionic forms that vary in the magnitude of the molar absorption coefficient. It was found that the maximum value of the molar absorption coefficient decreases in the series ε(Phe−)> ε(Phe+)> ε(Phe±) by 20%. The maximum error in determining the phenylalanine concentration without taking into account the dependence of the optical density of the solution on the acidity of the medium was found in strongly alkaline solutions. The correlation dependences of the analytical wavelength and molar absorption coefficient of phenylalanine on the pH of the medium were obtained experimentally. A long-wavelength (bathochromic) shift of the absorption band maximum was established upon the transition from positive to negative charge of the phenylalanine molecule with increasing pH of the solution. Two ranges of pH values have been identified, in which a change in the acidity of the solutions did not cause spectral changes. These were the regions where the amino acid was predominantly found in cationic Phe+ and bipolar Phe± forms (pH < 8) and in the region of anionic Phe− (pH > 10) form. The regression equations that allow choosing the analytical wavelength at any arbitrary pH of the solution were presented. The advantage of the developed approach is the possibility of increasing the detection sensitivity and ensuring that the error in the amino acid determination in the solutions of arbitrary acidity is less than 0.5% with the variation of no more than 0.3%. The detection limit of amino acid, calculated by 3σ – test, is (1.4 − 1.6) × 10-5 M. The range of the determined phenylalanine contents is (0.5 − 5.3) × 10-3 M. The efficiency of the proposed approach for determining the content of phenylalanine in a sample of the "L-Phenylalanine" (Protein Company, Russia) drug by the method of standard addition was shown. The possibility of minimizing the error in determining the amino acid when applying the technique to control the content of components in the process of demineralization of water-salt solutions of phenylalanine by electrodialysis with experimental membranes has been proven.
建立了一种不用预先校正溶液pH值和使用辅助化学试剂的分光光度法测定苯丙氨酸的方法。对不同酸度介质分光光度法测定苯丙氨酸进行了比较分析。分析了误差及其最小化的可能性。结果表明,由于苯丙氨酸以不同的离子形式存在,其摩尔吸收系数的大小不同,在不同pH溶液中,分析信号和氨基酸测定结果有显著差异。在ε(Phe−)> ε(Phe+)> ε(Phe±)系列中,摩尔吸收系数的最大值降低了20%。在强碱性溶液中,测定苯丙氨酸浓度时,不考虑溶液的光密度对介质酸度的依赖,误差最大。实验得到了苯丙氨酸的分析波长和摩尔吸收系数与介质pH的相关关系。随着溶液pH值的增加,苯丙氨酸分子的正电荷向负电荷的转变产生了吸收带最大值的长波移(色移)。已经确定了两个pH值范围,其中溶液酸度的变化不会引起光谱变化。这些区域氨基酸主要以阳离子Phe+和双极Phe±形式(pH < 8)和阴离子Phe - (pH bbb10)形式存在。给出了在溶液的任意pH值下选择分析波长的回归方程。该方法的优点是可以提高检测灵敏度,保证在任意酸度溶液中测定氨基酸的误差小于0.5%,变化不大于0.3%。氨基酸的检出限为(1.4 ~ 1.6)× 10-5 m,苯丙氨酸的测定范围为(0.5 ~ 5.3)× 10-3 m,用标准加入法测定“l -苯丙氨酸”(俄罗斯蛋白质公司)药品样品中苯丙氨酸的含量是有效的。应用该技术控制实验膜电渗析苯丙氨酸水盐溶液脱矿过程中各组分含量,可以最大限度地减少测定氨基酸的误差。
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引用次数: 1
Fluorescence of anisotropic primary X-ray radiation 各向异性初级x射线辐射的荧光
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.1.002
B. I. Kitov
In the X-ray spectral fluorescence analysis, the anisotropy of primary radiation results in an uneven radiation of a sample’s surface, strengthening the role of some sections and weakening the role of others. The goal of the current work was to determine the minimal distance from the window of the X-ray tube with a cone-shaped anode at which the intensity of the sample’s radiation becomes homogeneous. The research method was the computer modeling of the X-ray fluorescence experiment. The working model was built on the basis of two equations for the densities of the fluxes of braking and characteristic radiations of the massive anode, which took into account the absorption of primary radiation by the anode’s material and the back-scattering of electrons. The ring source was represented in the model as the sum of infinitely small linear elements of equal power, and the sample was disc-shaped and coaxial with the source. The calculation diagram was very well consistent with the experimental diagram of radiation’s direction described in the research literature. Two spatial distributions were calculated. The first one described the distribution of primary radiation’s intensity on the surface of the sample, while the second one described the distribution of the fluorescent radiation, which was more valuable for the X-ray spectrometry. The calculations showed that although the second distribution, unlike the first one, considered the absorption of the primary radiation and secondary radiation in the sample, the shapes of both radiations were close. It was demonstrated that the area of the sample, which carried the most information on the composition of the irradiated material, was ring-shaped, and the width of this ring depended on the distance to the X-ray tube’s window. As the distance increased, the diagram of the spatial distribution of the radiation’s intensity became smoother, and, when the distance exceeded two diameters of the anode, the radiation became homogeneous. The constructed model, which considered the anisotropy of the primary analysis, could be applied in the method of fundamental parameters of X-ray fluorescence analysis for a spectrometer with compressed geometry.
在x射线光谱荧光分析中,由于一次辐射的各向异性,导致样品表面的辐射不均匀,使某些部分的作用增强,而另一些部分的作用减弱。当前工作的目标是确定从x射线管窗口与锥形阳极的最小距离,在该距离上样品的辐射强度变得均匀。研究方法为x射线荧光实验的计算机模拟。在考虑阳极材料对一次辐射的吸收和电子的后向散射的基础上,建立了大质量阳极的制动通量密度和特征辐射密度方程。环形源在模型中被表示为无穷小的等功率线性单元的和,样品呈圆盘状,与源同轴。计算图与研究文献中描述的辐射方向实验图吻合较好。计算了两个空间分布。第一个描述了一次辐射强度在样品表面的分布,第二个描述了荧光辐射的分布,这对x射线光谱分析更有价值。计算表明,与第一次分布不同,第二次分布考虑了样品中一次辐射和二次辐射的吸收,但两种辐射的形状很接近。结果表明,样品的区域是环形的,它携带了辐照物质组成的最多信息,而这个环的宽度取决于到x射线管窗口的距离。随着距离的增加,辐射强度的空间分布图变得更加平滑,当距离超过阳极两个直径时,辐射变得均匀。所建立的模型考虑了初级分析的各向异性,可应用于压缩几何光谱仪的x射线荧光分析基本参数的计算。
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引用次数: 0
Selection of the parameters of a multicapillary column for portable gas analyzers by Kovach indices 用科瓦奇指数选择便携式气体分析仪用多毛细管柱的参数
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.1.003
A. P. Efimenko, I. Naumenko, E. V. Kirillova, A. Shorokhov
Short straight multicapillary columns (MCC) allow for fast gas chromatographic separation. However, their limited efficiency makes it difficult to use them for the analysis of multicomponent mixtures. Therefore, it is important to preliminarily evaluate the possibility of separation of target substances, based on the available information about their characteristics, in particular, by retention indices (RI). The paper provides an example of the choice of MCC and chromatographic conditions for the separation of explosives in stationary phases OV-5 and SE-54. To find the correspondence of the retention indices of the target substances with their retention factors k on the studied MCCs, the retention times of C10−C19 n-alkanes were experimentally determined at different column temperatures. Then the dependences of the calculated lnk on the quantity of carbon atoms m in n-alkanes CmH2m+2 were plotted and approximated by linear functions ln k = a + bm and their coefficients a and b were found for each temperature. From where, it was easy to calculate the retention factors of the target substances by their RI, assuming that RI = m·100, as well as to estimate the MCC efficiency required to separate neighboring peaks to obtain the desired level of separation. Based on the obtained equations, the explosives retention factors for MCCs at different temperatures were calculated and their required efficiency for separating adjacent peaks was estimated. The retention factors experimentally determined for some explosives on the MCCs at 140 °C turned out to be quite close to the theoretically calculated ones. In the future, the similar approach can be used to predict the possibility of gas chromatographic separation of mixtures of dangerous substances such as narcotic drugs.
短直多毛细管柱(MCC)允许快速气相色谱分离。然而,它们有限的效率使其难以用于多组分混合物的分析。因此,根据有关目标物质特性的现有信息,特别是通过保留指数(RI),初步评估目标物质分离的可能性是很重要的。本文给出了在OV-5和SE-54固定相中分离炸药时MCC的选择和色谱条件的选择实例。为了找出目标物质的保留指数与所研究的mcc上的保留因子k的对应关系,实验测定了C10−C19正构烷烃在不同柱温下的保留次数。然后用线性函数lnk = a + bm近似地绘制了计算出的链与正构烷烃CmH2m+2中碳原子数量m的关系,并求出了它们在不同温度下的系数a和b。由此,很容易通过目标物质的RI(假设RI = m·100)计算其保留因子,也很容易估计分离相邻峰以获得所需分离水平所需的MCC效率。根据得到的方程,计算了不同温度下mcc的炸药保留系数,并估计了其分离相邻峰所需的效率。实验结果表明,某些炸药在140℃时在mcc上的保留系数与理论计算值相当接近。在未来,类似的方法可用于预测气相色谱分离危险物质混合物(如麻醉药品)的可能性。
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引用次数: 0
AMPEROMETRIC IMMUNOSENSORS BASED ON CARBON NANOMATERIALS AND RHENIUM CLUSTERS FOR THE DETERMINATION OF TRICYCLIC ANTIDEPRESSANTS IN A SEQUENTIAL INJECTION SYSTEM 基于碳纳米材料和铼簇的安培免疫传感器在序贯注射系统中测定三环抗抑郁药
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.4.002
E. P. Medyantseva, E. R. Gazizullina, D. Brusnitsyn, A. Dobrynin, K. Brylev, A. Mustafina, J. Elistratova
A method of sequential injection determination of tricyclic antidepressants (amitriptyline, desipramine, imipramine) using amperometric immunosensors based on screen-printed graphite electrodes modified by carbon nanomaterials (carbon nanotubes, graphene oxide or fullerene) in combination with hexarhenium chalcogenide clusters is proposed. Sequential injection analysis was performed at a sweep rate of 10 mV/s; the flow rate (supporting electrolyte – phosphate buffer solution with pH 7.0) was also varied from 20 to 40 µl/s. Composition of the modifier affects the analytical capability of immunosensors. Screening of various types of modifiers showed that the immunosensor based on graphene oxide and cyanide complexes of rhenium chalcogenide clusters exhibited the highest sensitivity of 23.9±0.9 with a range of working concentrations of 1·10–10–1·10–5 M, and even wider range of detectable concentrations, 1·10–10–1·10–4 M was observed for the immunosensor based on fullerene and cyanide complexes of rhenium chalcogenide clusters. The lowest limit of the determined contents was (4–7)·10–11 M. Relative standard deviation of repeatability (Sr) did not exceed 0.046. The results obtained show that the proposed immunosensors can be used in sequential injection determination of trace amounts of medicinal compounds (antidepressants) in biomedical objects.
提出了一种基于碳纳米材料(碳纳米管、氧化石墨烯或富勒烯)修饰的丝网印刷石墨电极与硫属六烯醚簇结合的电流免疫传感器,用于顺序注射检测三环类抗抑郁药(阿米替林、地西帕明、丙咪嗪)的方法。扫描速率为10 mV/s,进行序贯注射分析;流速(支持pH 7.0的电解质-磷酸盐缓冲溶液)也在20至40µl/s之间变化。修饰剂的组成影响免疫传感器的分析能力。对不同类型改性剂的筛选表明,基于氧化石墨烯和硫代铼氰化物配合物的免疫传感器灵敏度最高,灵敏度为23.9±0.9,工作浓度范围为1·10-10-1·10-5 M,基于富勒烯和硫代铼氰化物配合物的免疫传感器检测浓度范围更广,为1·10-10-1·10-4 M。测定含量的最低限为(4-7)·10-11 m,重复性相对标准偏差(Sr)不超过0.046。结果表明,该免疫传感器可用于生物医学对象中微量药物化合物(抗抑郁药)的序次注射测定。
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引用次数: 0
Book review for a book by M. Haschke, J. Flock, M. Haller “Laboratory Applications of X-ray Fluorescence”, Wiley. 2021, 464 pp., 263 illustrations. M.Haschke,J.Flock,M.Haller的一本书的书评“X射线荧光的实验室应用”,Wiley。2021,464页,263幅插图。
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.1.008
A. G. Revenko
The use of X-ray fluorescence analysis (XRF) has been constantly expanding in recent years. The number of users without special training is increasing. This paper provides information on the monograph by M. Haschke, J. Flock, and M. Haller “Laboratory Applications of X-ray Fluorescence”. The book was published by Wiley-VCH. The book under review was written by experts with extensive experience in XRF. The authors made a significant contribution to the development of X-ray fluorescence analysis. The book consists of a Preface, a List of abbreviations and symbols, Information about authors, an Introduction, 18 Chapters, two Appendixs (A - Tables, B - Important information), a References and an Index. The material of the book in the review is discussed chapter by chapter. The book presents various sample preparation procedures that are typical for XRF and discusses their impact on the precision and accuracy of the analysis. The main types of X-ray spectrometers, as well as the design, construction and features of the operation of individual components of the devices are considered. The main techniques for measuring and evaluating X-ray spectra are discussed, and the metrological characteristics of XRF are compared with other analytical methods. In full accordance with the title of the book, the authors paid the main attention to the discussion of options for solving various analytical problems using XRF. Homogeneous and heterogeneous, solid and liquid materials, application in geology, ecology, biology, industrial enterprises, research laboratories in the study of objects of heritage are considered. It should be noted the presence in the book of the Appendix “Important information”. Prepared by the authors, a modern high quality reference guide will be useful for both beginners and qualified professionals. A clear presentation of the material allows us to recommend it as a teaching aid for students and undergraduates. It seems that the book will be in demand in the laboratories of research institutes and universities, as well as in the laboratories of industrial enterprises.
近年来,x射线荧光分析(XRF)的应用不断扩大。没有经过特殊训练的用户越来越多。本文提供了M. Haschke, J. Flock和M. Haller的专著“x射线荧光的实验室应用”的信息。这本书是由Wiley-VCH出版的。这本书是由在XRF方面有丰富经验的专家撰写的。作者对x射线荧光分析的发展作出了重大贡献。本书由前言、缩略语和符号表、作者简介、引言、18章、两个附录(a -表、B -重要信息)、参考文献和索引组成。书评中对这本书的材料是逐章讨论的。这本书提出了各种样品制备程序,是典型的XRF,并讨论了他们对分析的精度和准确性的影响。考虑了x射线光谱仪的主要类型,以及设备各个部件的设计、结构和操作特点。讨论了测量和评价x射线光谱的主要技术,并与其他分析方法进行了比较。与本书的标题完全一致,作者主要关注使用XRF解决各种分析问题的选项的讨论。考虑了均质与非均质、固体与液体材料、在地质学、生态学、生物学、工业企业、研究实验室对文物对象的研究中的应用。应该注意的是,本书的附录中有“重要信息”。由作者准备,现代高质量的参考指南将是有用的初学者和合格的专业人士。材料的清晰展示使我们能够推荐它作为学生和本科生的教学辅助工具。看来,这本书将在研究机构和大学的实验室需求,以及在工业企业的实验室。
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引用次数: 0
The use of NIR Fluorimetry with photographic data acquisition in the fingerprinting method with the addition of fluorophores to the samples: discrimination of apple juices 利用近红外荧光法与摄影数据采集在指纹法中添加荧光团的样品:辨别苹果汁
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.1.005
E. Skorobogatov, I. Stepanova, V. S. Orekhov, M. Beklemishev
The application of dyes, that fluoresce in the near infrared (NIR, 700-800 nm) region, for the recognition of samples using a fingerprinting method with the addition of fluorophores to the samples (“fluorescent eye”) is proposed. The technique has been successfully applied to the classification of samples of various nature. In the current work, this strategy has been tested on the example of discrimination of 17 samples of apple juice from different manufacturers, purchased at different times. An indolenine series heptamethine carbocyanine dye in the presence of surfactants was used as the added fluorophore, red LEDs were used as an excitation source, and the signal was recorded using a digital camera with an additional IR filter installed; a spectrofluorimeter with a 96-well plate accessory was used to record the spectra. Photographic images were processed using Unscrambler X and Excel software. The results were presented using the following coordinates: intensity of NIR fluorescence - intensity of visible light reflection (using the photographic images). It was found that such presentation allowed the samples to be divided into groups associated with the manufacturer. We have also obtained intrinsic fluorescence spectra, including those with the addition of NIR dye, and these results were processed by the principal component analysis. It was possible to distinguish 5–6 groups of samples by their intrinsic emission, not counting the blank, while the spectra with the addition of the dye allowed to isolate the largest number of groups of samples (9). At the same time, the classification using spectra did not allow juices to be grouped by the producer. Also, obtaining photographs using a visualizer was easier and faster than recording the fluorescence spectra. The joint processing of emission spectra and photographs did not improve the quality of discrimination.
染料的应用,荧光在近红外(近红外,700-800纳米)区域,用于识别样品使用指纹法与添加荧光团的样品(“荧光眼”)。该技术已成功地应用于各种性质的样品分类。在目前的工作中,以不同厂家在不同时间购买的17个苹果汁样品为例,对这一策略进行了测试。采用表面活性剂存在下的吲哚胺系列七甲基碳氰染料作为添加的荧光团,红色led作为激发源,使用安装了附加红外滤光片的数码相机记录信号;使用带有96孔板附件的荧光光谱仪记录光谱。摄影图像使用Unscrambler X和Excel软件进行处理。结果用以下坐标表示:近红外荧光强度-可见光反射强度(使用摄影图像)。结果发现,这样的展示方式可以将样品分成与制造商相关的组。我们还得到了本征荧光光谱,包括加入近红外染料后的荧光光谱,并对这些结果进行了主成分分析。不计算空白,可以通过其固有发射来区分5-6组样品,而添加染料的光谱可以分离出最多的样品组(9)。同时,使用光谱的分类不允许生产者对果汁进行分组。此外,使用可视化器获得照片比记录荧光光谱更容易和更快。发射光谱与照片的联合处理并不能提高识别质量。
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引用次数: 0
Decreasing the uncertainty of gas chromatographic quantification using the solvent’s signal in the method of external standard 外标法中利用溶剂信号降低气相色谱定量的不确定度
Q4 Chemistry Pub Date : 2022-01-01 DOI: 10.15826/analitika.2022.26.2.005
I. Zenkevich, S. V. Byvsheva, A. Gerasimov, S. Gladnev, M. V. Grigoriev, N. Gubina, E. Didenko, A. S. Kazantsev, T. D. Kalutskaia, E. V. Katernuk, A. Koblova, D. V. Krutin, K. P. Malkova, S. A. Metliaeva, V. S. Odegova, D. S. Smirnova, V. Spivakovskyi, P. Terno
Uncertainties of the results of quantitative determinations in gas chromatography using the methods based on the absolute peak areas (including the external standard method) are rather “sensitive” to the reproducibility of injections. The effective way to compensate for such errors is to introduce the additional standards into the samples, followed by replacing the absolute peak areas by their ratios to peak areas of the standards. It is important to underline that any constituents of the samples can be used as additional standards, including the solvents. Solvents can be used for these purposes even if the heights of their peaks are restric­ted when the analytical signals exceed the amplifier limits. Using the relative peak areas does not require any extra sample processing besides the registration of peak areas for solvents. Comparing the commonly known and modified methods of external stan­dard demonstrates that using the relative peak areas instead of the absolute ones does not influence the overall precision of determinations (according to the criterion “intro­duced-determined”) but improve the reproducibility by 2-3 times. The problem of increasing the reliability of such statistical evaluations of results is discussed and to solve it, it is proposed to change the “design” of the experiments. Instead of series of successive analyses of similar origin samples, the use of parallel determinations is preferable. This can be realized, for example, during the fulfillment of student’s practical works.
采用绝对峰面积法(包括外标法)的气相色谱定量测定结果的不确定度对注射剂的重现性相当“敏感”。补偿这种误差的有效方法是在样品中引入额外的标准品,然后用它们与标准品的峰面积之比代替绝对峰面积。需要强调的是,样品的任何成分都可以用作附加标准,包括溶剂。溶剂可以用于这些目的,即使当分析信号超过放大器限制时,其峰的高度受到限制。使用相对峰面积不需要任何额外的样品处理,除了登记溶剂的峰面积。比较常用的外标法和改进后的外标法,用相对峰面积代替绝对峰面积不影响测定的整体精密度(按“引入-测定”标准),但可将重现性提高2-3倍。讨论了如何提高这类结果的统计评价的可靠性问题,并提出了改变实验“设计”的建议。而不是一系列的连续分析类似的来源样品,使用平行测定是可取的。例如,在学生实践作业的完成过程中可以实现这一点。
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Analitika i Kontrol
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