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Flow methods as a general approach to automation of the chemical analysis of aqueous media (review) 流动法作为水介质化学分析自动化的一般方法(综述)
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.001
L. N. Moskvin, N. M. Yakimova, A. L. Moskvin
The article is devoted to the consideration of general approaches to automating the analysis of aqueous media, which are the main objects of chemical analysis including natural and waste waters, as well as technological media in various industries (microelectronics, biochemical industries, nuclear and thermal power engineering), which are the main consumers of high-purity water used for pre-start flushing of inline equipment to the required cleanliness of surfaces, for preparation of coolants that ensure the operation of nuclear and thermal power plants. In all these cases, the content of impurities in used or spent and intended for discharge aqueous media is strictly regulated. Changes in the content of impurities in controlled media often occur spontaneously due to equipment failure on the controlled objects. Prompt response to such changes and their timely elimination can be performed more efficiently if chemical and technological control of the normalized parameters of aqueous media of any named origin and destination is carried out in a continuous automatic, on-line, mode, which guarantees the exclusion of gaps or delays in obtaining information about equipment failure on a controlled facility in case of technological control or about unauthorized discharges of pollutants in case of environmental control. Possible methodological approaches to the development of systems for continuous chemical monitoring of quality or levels of contamination of aqueous media are considered on the basis of the above prerequisites, and applicability of various flow methods for these purposes is discussed in the order of their appearance in the arsenal of analytical chemists.
本文致力于考虑水介质自动化分析的一般方法,水介质是化学分析的主要对象,包括自然和废水,以及各种工业(微电子,生化工业,核能和火力发电工程)中的技术介质,这些技术介质是用于在线设备启动前冲洗所需表面洁净度的高纯水的主要消费者。用于制备冷却剂,保证核电站和火电厂的运行。在所有这些情况下,用过的或用过的和打算用于排放的含水介质中杂质的含量是严格规定的。被控介质中杂质含量的变化往往是由于被控对象上的设备故障而自发发生的。如果以连续的自动在线模式对任何命名的来源和目的地的水介质的归一化参数进行化学和技术控制,则可以更有效地对这些变化作出迅速反应并及时消除它们。这保证了在技术控制的情况下,在获取受控设施的设备故障信息或在环境控制的情况下未经授权排放污染物的信息时,不存在差距或延迟。在上述先决条件的基础上,考虑了开发用于水介质质量或污染水平的连续化学监测系统的可能的方法方法,并按照分析化学家的武器库中出现的顺序讨论了用于这些目的的各种流动方法的适用性。
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引用次数: 0
Comments on the article by I.G. Zenkevich «Calculation of average chronological values – an undeservedly neglected method of statistical data processing» 对I.G. Zenkevich文章的评论«计算平均时间顺序值-统计数据处理的不应被忽视的方法»
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.006
A. L. Pomerantsev
Игорь Георгиевич известный специалист в хроматографии и им опубликовано много превосходных работ в этой области. Моя же область интересов – анализ данных, в том числе и получаемых в аналитической химии. Поэтому я не мог не обратить внимания на публикацию, в которой он предлагает неизвестный мне подход к статистической обработке.
伊戈尔·乔治耶维奇是一位著名的色谱学家,他发表了许多优秀的作品。我感兴趣的领域是分析数据,包括分析化学。因此,我不得不注意到他发表的一篇文章,介绍了一种我不熟悉的统计处理方法。
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引用次数: 0
Supplement to A.L. Pomerantsev's comments on I.G. Zenkevich's article «Calculation of average chronological values – an undeservedly neglected method of statistical data processing» 补充A.L. Pomerantsev对I.G. Zenkevich的文章“计算平均年代值-统计数据处理中不应被忽视的方法”的评论
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.007
Igor G. Zenkevich
Алексей Леонидович – один из известнейших специалистов России в области хемометрики и обработки данных. Это придает особую значимость его коммента­риям [1] относительно воз­можности использования сре­д­них хро­но­логических значе­ний при статистичес­кой обработке данных и тем инте­реснее об­суждение дис­кус­си­онных моментов рассматривае­мой проблемы.
alexey leonidovich是俄罗斯最著名的数据识别和处理专家之一。这使他的评论(1)特别重要,关于在统计数据处理中使用crd值的可能性,以及迪斯-库斯- c - c -问题的更深入的评价。
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引用次数: 0
Calculation of average chronological values – an undeservedly neglected method of statistical data processing 按时间顺序计算平均值——一种不应被忽视的统计数据处理方法
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.005
Igor G. Zenkevich
In real analytical practice involving parallel determinations there are certain objective reasons (limited measurement time, available resources, etc.) that prevent performing sufficient number of measurements required for rigorous statistical data processing. Such parameters as standard deviations are particularly unreliable for small data sets (they are usually too high in comparison with the results obtained for more representative data sets). This problem can be minimized by changing the character of data processing, i.e. calculating so-called chronological averages instead of average arithmetical values. This, however, requires ranking the data not in the order as they were measured, but in the ascending order. The essence of calculating chronological averages is that the minimum and the maximum values of the initial data set are replaced with a single number, namely their arithmetical average, which is then averaged with other data. As a result, the total number of data values decreases by one but the changes of the averages would be negligible. At the same time, the standard deviations of the modified data sets become more characteristic and approaching the standard deviations of extended data sets. Replacing the arithmetical means by chronological average values leads to sufficiently smaller distortions of the initial data sets than, for example, in the case of excluding outliers by using the well-known “3s” criterion.
在涉及平行测定的实际分析实践中,存在某些客观原因(有限的测量时间、可用资源等),妨碍执行严格统计数据处理所需的足够数量的测量。标准偏差等参数对于小数据集尤其不可靠(与更具代表性的数据集获得的结果相比,它们通常过高)。这个问题可以通过改变数据处理的特征来最小化,即计算所谓的时间平均值而不是平均的算术值。然而,这需要将数据按升序排列,而不是按测量的顺序排列。计算时间平均的本质是将初始数据集的最小值和最大值替换为一个数字,即它们的算术平均值,然后将其与其他数据平均。因此,数据值的总数减少了一个,但平均值的变化可以忽略不计。同时,修正后的数据集的标准差变得更有特征,接近扩展数据集的标准差。用按时间顺序排列的平均值代替算术平均值,对初始数据集造成的扭曲比使用众所周知的“3s”标准排除异常值的情况要小得多。
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引用次数: 0
Determination of iron (III) in environmental objects by photometric method with acetylacetone derivatives 乙酰丙酮衍生物光度法测定环境物体中的铁(III)
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.2.003
Kh. D. Nagiyev, A. U. Abiyeva, F. M. Chiragov, U. A. Gullarli
Organic reagents containing three carbonyl groups based on acetylacetone, 2,4-diacetyl-3-phenyl-5-methyl-5-hydroxyhexanone (R1), 2,4-diacetyl-3-(3'-nitrophenyl)-5-hydroxy-5-methylcyclohexanone (R2) and 3-acetyl-4,6-diphenylgensandione-2,6 (R3), were synthesized. Their absorption spectra were studied at various pH values of the medium, and the acidity constants were determined by potentiometric titration. It was found that the reagents are monobasic acids and, depending on the acidity of the medium, can be in the molecular (HR) or anionic (R-) form. Formation of iron (III) complexes with synthesized reagents in the presence of hydrophobic amines, 1,10-phenanthroline (Phen), diantipyrylmethane (DAM) and diantipyrylphenylmethane (DAPM) was studied. It was established that mixed ligand complexes with the components ratio of 1:1:1 were formed in the presence of hydrophobic amines. At the same time bathochromic shifts in the absorption spectra were observed and the maximum yield was noted in a more acidic medium compared to the corresponding single ligand complexes. The influence of the reagents concentration, time and temperature on the formation of mixed ligand complexes was studied, and the stability constants were determined by various methods. It was shown that iron (III) in the form of mixed ligand complexes, Fe(III)-R1-DAM, Fe(III)-R2-Phen and Fe(III)-R3-DAM, can be determined with high selectivity in the presence of large excess of other metal cations. The developed methods were tested on fruits – strawberries, apricots, cherries, white cherries and two varieties of apples (Golden Ahmadi and Simirenko), and natural waters – drinking water taken from a tap in the BSU laboratory and Caspian Sea water taken near the Turkan village of Baku city.
以乙酰丙酮为基料,合成了2,4-二乙酰-3-苯基-5-甲基-5-羟基己酮(R1)、2,4-二乙酰-3-(3′-硝基苯基)-5-羟基-5-甲基环己酮(R2)和3-乙酰-4,6-二苯根二酮-2,6 (R3)三个含三个羰基的有机试剂。研究了它们在不同pH介质下的吸收光谱,并用电位滴定法测定了酸度常数。结果发现,这些试剂是单基酸,根据介质的酸度,可以是分子(HR)或阴离子(R-)形式。研究了在疏水胺、1,10-菲罗啉(Phen)、二安替比基甲烷(DAM)和二安替比基苯基甲烷(DAPM)存在下,铁(III)与合成试剂形成配合物。在疏水胺的存在下,可以形成组分比为1:1:1的混合配体配合物。同时观察到吸收光谱的色移,并且与相应的单配体配合物相比,在酸性更强的介质中发现了最大产率。研究了试剂浓度、时间和温度对混合配体配合物形成的影响,并用各种方法测定了其稳定性常数。结果表明,铁(III)以混合配体配合物Fe(III)-R1-DAM, Fe(III)-R2-Phen和Fe(III)-R3-DAM的形式,在大量过量的其他金属阳离子存在下可以高选择性地测定。研究人员对水果——草莓、杏子、樱桃、白樱桃和两种苹果(Golden Ahmadi和Simirenko)——以及天然水进行了测试,天然水取自俄罗斯国家科学大学实验室的自来水和取自巴库市突厥村附近的里海水。
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引用次数: 0
Novel approaches to the formation of coatings based on gold nanoparticles and albumin for chiral separation in capillary electrophoresis 基于金纳米颗粒和白蛋白的毛细管电泳手性分离涂层的新方法
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.002
V. P. Morgacheva, D. V. Makeeva, E. V. Solovyeva, E. A. Kolobova, L. A. Kartsova
Combination of properties of gold nanoparticles and bovine serum albumin is promising for the formation of chiral stationary phases enabling high enantioselectivity due to developed surface of coatings and increased chiral selector concentration on the capillary walls. In this work we proposed and compared two approaches to the formation of physically adsorbed multilayer coatings based on citrate-stabilized gold nanoparticles (cGNP) and bovine serum albumin (BSA) for the chiral separation in capillary electrophoresis. In the first approach pre-synthesized cGNP modified with BSA were immobilized on the capillary coated by poly(diallyldimethylammonium chloride) (PDADMAC). PDADMAC polymer was used as a binding layer promoting sorption of the nanoparticles on the capillary surface. It was shown that cGNP-BSA was poorly adsorbed on the capillary surface due to low zeta potential and could not be used for the formation of dense coatings. The second approach included sequential layer-by-layer deposition of PDAMAC and cGNP, resulting in the formation of a dense layer of nanoparticles. The main stage included in-capillary functionalization of cGNP with BSA. Scanning electron microscopy confirmed that the layer-by-layer deposition of modifiers ensured the formation of dense layer of nanoparticles on the capillary surface. The coating was stable in the entire range of pH studied (2–10). The application of such coating allowed reduction of BSA concentration (to 5 μM) in the background electrolyte required for the tryptophan enantiomers separation. It confirms the prospectiveness of combining nanoparticles and chiral selectors for the increase of specific surface area of the capillary inner walls.
金纳米颗粒与牛血清白蛋白的结合,有望形成手性固定相,由于涂层表面的发展和毛细壁上手性选择剂浓度的增加,具有高的对映体选择性。在这项工作中,我们提出并比较了两种基于柠檬酸稳定金纳米粒子(cGNP)和牛血清白蛋白(BSA)的物理吸附多层涂层的形成方法,用于毛细管电泳的手性分离。第一种方法是将预先合成的经BSA修饰的cGNP固定在聚二烯基二甲基氯化铵(PDADMAC)包被的毛细管上。采用PDADMAC聚合物作为结合层,促进纳米颗粒在毛细管表面的吸附。结果表明,由于zeta电位低,cGNP-BSA在毛细管表面的吸附效果较差,不能用于形成致密涂层。第二种方法包括PDAMAC和cGNP的连续逐层沉积,从而形成致密的纳米颗粒层。主要阶段包括cGNP与BSA在毛细管内的功能化。扫描电镜证实,改性剂的逐层沉积保证了在毛细管表面形成致密的纳米颗粒层。该涂层在研究的整个pH范围内(2-10)是稳定的。这种涂层的应用使色氨酸对映体分离所需的背景电解质中的BSA浓度降低(至5 μM)。这证实了纳米颗粒与手性选择剂相结合在增加毛细管内壁比表面积方面的前景。
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引用次数: 0
A study of silver sorption from aqueous solutions by solid-phase modified poly(n-thiocarbamoyl-3-aminopropyl silsesquioxane) 固相改性聚(n-硫代氨基甲酰基-3-氨基丙基硅氧烷)吸附水溶液中银的研究
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.004
E.A. Melnik, A. A. Sysolyatina, Yu. S. Petrova, A. S. Kholmogorova, L. К. Neudachina, V. A. Osipova, A. V. Pestov
Sorption properties of poly(3-aminopropylsilsesquioxanes) modified with thiourea groups were studied to predict the possibility of using poly(n-thiocarbamoyl-3-aminopropylsilsesquioxanes) (TCPS) in separation and concentration techniques. The sorbents were synthesized by the sol-gel method followed by solid-phase modification using ammonium thiocyanate or thiosemicarbazide as modifiers. It was established that sorbents with the highest content of thiocarbamide functional groups (modified with ammonium thiocyanate) enabled quantitative and selective recovery of Ag (I) from strongly acidic solutions. The degree of Ag (I) recovery slightly decreases at pH>5, which is associated with increasing competitive sorption of Cu (II), Ca (II), Mg (II), Mn (II) and Fe (III). The highest recovery of Ag (I) for TCPS-0.63 and TCPS-0.68 was achieved at pH ranging from 4 to 8 (degree of recovery was 55–68% (TCPS-0.63); 21–26% (TCPS-0.68 )); at the same time, there was a predominance of competitive sorption of Ca (II), Mg (II), Mn (II), and Fe (III). Based on the aforementioned, it can be concluded that the sorbents modified with ammonium thiocyanate are characterized by high concentration of attached thiocarbamide groups that make them suitable for the selective recovery of Ag (I) ions from multicomponent solutions at pH 1–2.
研究了巯基修饰的聚(3-氨基丙基硅氧烷)的吸附性能,预测了聚(n-硫氨基氨基甲酰-3-氨基丙基硅氧烷)(TCPS)在分离和浓缩技术中的应用前景。采用溶胶-凝胶法合成吸附剂,然后以硫氰酸铵或氨基硫脲为改性剂进行固相改性。结果表明,硫脲官能团(硫氰酸铵修饰)含量最高的吸附剂能够定量和选择性地从强酸性溶液中回收Ag (I)。pH = 5时,银(I)的回收率略有下降,这与Cu (II)、Ca (II)、Mg (II)、Mn (II)和Fe (III)的竞争性吸附增加有关。在pH = 4 ~ 8时,tps -0.63和tps -0.68的银(I)回收率最高,回收率为55 ~ 68% (tps -0.63);21-26% (tcp -0.68);同时,对Ca (II)、Mg (II)、Mn (II)和Fe (III)的竞争性吸附占优势。综上所述,硫氰酸铵修饰的吸附剂具有高浓度的附着硫脲基团的特点,适合在pH 1-2的多组分溶液中选择性回收Ag (I)离子。
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引用次数: 0
PHOTOMETRIC DETERMINATION OF ERYTHROSIN IN THE PRESENCE OF SYNTHETIC ACIDIC DYES IN FOOD PRODUCTS 食品中合成酸性染料中红血素的光度测定
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.2.004
Y. М. Pliashak, S. M. Leschev, A. I. Palianskikh, L. L. Belysheva
In Republic of Belarus and the countries of the EACU, the synthetic dye E 127 (erythrosine) is prohibited for the use in the production of food products. To control the content of this additive, accurate and rapid methods of determination are required. In order to develop a methodology for determination of erythrosin in the presence of food synthetic dyes (E 102, E 104, E 110, E 122, E 123, E 124, E 128, E 129, E 131, E 132, E 133, E 142, E 143 , E 151, E 155) the extraction of dyes with organic solvents from aqueous solutions was studied and their distribution coefficients were determined. Based on the data obtained in the presence of the above dyes, a method for determining E 127 without the use of expensive chromatographic equipment was proposed. The technique is based on sample preparation, which consists of the selective extraction of E 127 from an aqueous solution of the food matrix (pH=2) using chloroform. Other synthetic dyes were not extracted. Next, the extract was evaporated, dissolved in a buffer solution at pH=9 and photometrically measured at the wavelength of 527 nm. In the presence of hydrophobic organic dyes (carotene, lycopene) in the food matrix, their preliminary extraction was carried out from the aqueous solution at pH=9 with chloroform; under these conditions all dyes, including E 127, were not extracted. The limit of quantitative determination by the proposed method for liquid food products was 0.05 mg/kg, for solid – 0.13 mg/kg, the standard deviation was 2–3 %.
在白俄罗斯共和国和欧亚经济联盟国家,合成染料e127(红素)被禁止用于生产食品。为了控制该添加剂的含量,需要准确、快速的测定方法。为了建立食品合成染料(e102、e104、e110、e122、e123、e124、e128、e129、e131、e132、e133、e142、e143、e151、e155)中红素含量的测定方法,研究了有机溶剂对染料的萃取方法,并测定了染料的分布系数。根据在上述染料存在下获得的数据,提出了一种不使用昂贵的色谱设备测定e127的方法。该技术基于样品制备,包括使用氯仿从食品基质(pH=2)的水溶液中选择性提取e127。其他合成染料未提取。然后,将提取液蒸发,溶解于pH=9的缓冲溶液中,在527 nm波长处进行光度测定。在食品基质中存在疏水有机染料(胡萝卜素、番茄红素)的情况下,用氯仿从pH=9的水溶液中初步提取;在此条件下,包括e127在内的所有染料均未被提取。液体食品的定量限为0.05 mg/kg,固体食品的定量限为- 0.13 mg/kg,标准偏差为2 ~ 3%。
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引用次数: 0
XXXII Annual Meeting of the Analytical Centers Association "Analitica" 第三十二届分析中心协会年会
Pub Date : 2023-01-01 DOI: 10.15826/analitika.2023.27.1.008
V. V. Stepanovskikh
С 24 по 28 апреля 2023 г. в пансионате ФГАУ «ОК «Клязьма» (Москва) состоялось Ежегодное собрание Ассоциации аналитических центров (ААЦ) «Аналитика».
从2023年4月24日到28日,在福高寄宿学校举行了年度分析中心协会会议。
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引用次数: 0
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