Chromatography in Ukraine: History
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The development of chromatographic science in Ukraine is due to the widespread use of chromatography to solve practical problems. The centers of chromatographic research in Ukraine are in large cities: Kyiv, Kharkiv, Lviv, Odessa, and others. Along with the development of chromatographic research methods, analysis methods for control of food and agricultural raw materials, medicinal products, petroleum products, and determination of the environmental pollution state are created. Chromatography is used in medicine, pharmacology, biology, and other sciences.

  • history of chromatography
  • chromatographic method development
  • methods of analysis

1. History

Chromatographic research in Ukraine is developing quite rapidly due to the wide range of its practical use. The history of chromatography in Ukraine is closely related to Mykhailo Tsvet, whose father was Ukrainian (born in Chernihiv), and his mother Italian [1]. Tsvet performed his chromatographic research at the University of Warsaw from 1902 to 1903. He first reported the method of chromatography in March 1903 at a meeting of the botanical branch of the Warsaw Society of Naturalists in a report on “On a new category of adsorption phenomena and their application to biochemical analysis”.
In 1938, Kharkov Izmailov N.A. and Schreiber M.S., for the first time, published work on circular thin layer chromatography and subsequently developed other variants of the method of thin-layer chromatography [2][3].

2. Research Centers

Research centers in the field of chromatography in Ukraine are located in Kyiv, Kharkiv, Lviv, Odessa, Dnipro, and other cities. At the Institute of Colloid Chemistry and Water Chemistry of the National Academy of Sciences of Ukraine in Kyiv, research and development of the method of ion chromatography are carried out. This method effectively determines ionic compounds and, in many cases, is normative for ecological research of natural waters and water quality control (particularly in energy) [4][5][6][7][8][9][10].
The works were carried out under the guidance of professors L. Loginova and A. Kulikov at the V. N. Karazin Kharkiv National University, the “Ukrainian Scientific Pharmacopoeial Center for Drug Quality” which is dedicated to studying high-performance liquid micellar chromatography [11]. L. Loginova and A. Kulikov proposed models for determining the retention time of compounds in micellar liquid chromatography, which allow optimization of the composition of the micellar mobile phase for better separation of anions [12][13][14]. The influence of reversed-phase sorbents on the separation efficiency [15][16][17] and organic phase modifiers—organic alcohols, acetonitrile, tetrahydrofuran, organic acids—were studied for separation efficiency [18]. Methods of quality control for medicines and substances have also been developed. Studies using micellar thin layer chromatography to analyze biologically active compounds, in particular, coumarin, licurazil, and glycyrrhizinic acid in plant medicinal raw materials, were carried out [19][20].
Methods of pharmaceutical analysis of drugs, medicinal raw materials, and food products are being developed in the O.B. Bogatsky Physical-Chemical Institute of National Academy of Sciences of Ukraine in Odessa. The studies use high-performance liquid and high-performance thin-layer chromatography [21][22].
Investigations of the content of biologically active substances and impurities in drugs and medicinal plant raw materials are carried out in the laboratories of liquid chromatography-mass spectrometry of Zaporizhia State Medical University [23]. This laboratory develops methods for determining compounds that are markers of various diseases [24]. Studies of drug metabolism in living organisms are also conducted [25].
Chromatographic studies at the Department of Toxicological and Analytical Chemistry of Danylo Halytskyi Lviv National Medical University concerning the determination of toxins and residual amounts of drug substances and their metabolites in biological samples were performed by thin-layer chromatography (TLC) and gas chromatography (GC). In particular, Ph.D. Docent Bidnichenko Yuriy Ivanovych deals with the problem of toxins analysis from poisonous fungi [26]. The determination of fungal toxins was performed by TLC [27], disk electrophoresis [28], capillary electrophoresis [29], gel chromatography [30], and high-performance liquid chromatography (HPLC) [31].
Attention in scientific research of the Department of Analytical Chemistry of Kyiv National University is paid to studying sample preparation methods by solid-phase extraction. These studies were developed under the guidance of Prof. V.M. Zaitsev. The method of solid-phase extraction concentration of 2,4-dichlorophenoxyacetic acid, phenol, 1-naphthol, 2,4,6-trinitrophenol using silicon oxide from water and biological fluids is described in [32][33][34]. The topic of associate professor M.G. Zui was related to the determination of oxygen-containing organic compounds: phthalates, parabens, benzophenols, and oxygen-containing compounds [35][36].
Chromatographic studies of the purification of polyacrylamide gels for medical purposes, which were synthesized at the F.D, Ovcharenko Institute of Biocolloid Chemistry of the National Academy of Sciences of Ukraine, were conducted at the Institute of Environmental Geochemistry [37].
Gas and liquid chromatography were used at Lviv Polytechnic National University to study the kinetics of reactions at the departments of basic organic and petrochemical synthesis technology (now the Department of Organic Products), chemical technology of oil and gas refining, at the Department of Analytical Chemistry (analytical and general chemistry, organic chemistry) [38][39].
The scientific work of the zeolite-chromatographic group headed by Professor Onufriy Banach of the Danylo Halytskyi Lviv National Medical University was devoted to the study of using zeolites in gas chromatography [1][40]. For stationary zeolite phases for gas chromatography, the “low substitution effect” was found, which consisted of the fact that in zeolites, when sodium cations were replaced by other alkali metals, the parameters of gas retention in gas chromatography conditions changed sharply. In particular, for ethane, methane, and oxygen with a low degree of substitution (9.8%) of Na + cations on K + in zeolites, the retention time of these gases increased rapidly, which was also observed in cases of substitution of 6% Na + on Rb + and 5% Na + on Cs + [40][41]. The phenomenon of inversion of the chromatographic retention was also observed, which consisted in changing the sequence of the components of the mixtures from straight to inverted. For the phenomenon of chromatographic inversion, two types were identified: (1) inversion caused by exposure to one of the components in the studied gas sample; (2) inversion depending on the degree of substitution of cations in the zeolite [40][42]. Studies of the chromatographic properties of zeolites revealed the specific selectivity of silver-containing zeolites of type Y to carbon monoxide [40]. The study of the properties of modified zeolites made it possible to create effective methods for analyzing the content of oxides of carbon, nitrogen, and sulfur and hydrocarbon gases C1–C4 in atmospheric air. Zeolite stationary phases were used for gas adsorption (solid-phase) chromatography and extraction, concentration, and desorption for the quantitative chromatographic determination of these air pollutants [43][44][45][46][47][48][49].

3. Application

Considerable attention in chromatographic research in Ukraine is paid to the state of environmental pollution by toxic substances. To this end, methods are being developed for environmental monitoring and detecting toxic substances, such as pesticides. This activity is the subject of attention of state bodies and is defined by law.
Chromatography plays a notable role in the chemical and analytical support of toxicology and hygiene of pesticides, occupational health, and the environment. In Ukraine and the former Soviet Union, it was introduced in the early 1960s in the physicochemical laboratory of Kyiv Research Institute of Hygiene Labor and Occupational Diseases. It was headed in 1960–1964 by Marta Arkhipovna Klysenko, who, with the participation of specialists from the same laboratory, had previously developed the country’s first methods for determining pesticides in the air of the working area (arsenic-containing insecticides—1954; phosphorus and organochlorine insecticides—1955–1956); in soil, food and biological environments (1962) [50]. The implementation of such developments was of great importance for the hygienic regulation of pesticides, addressing their use in agriculture, safety for the health of workers and the general population, and the environment. This laid the foundations of a new scientific field—analytical chemistry, namely “analytical chemistry of pesticides”.
In the All-Union Research Institute of Hygiene and Toxicology of Pesticides, Polymers, and Plastics of the Ministry of Health of the USSR 1965–1989, under the guidance of Doctor of Biological Sciences, Professor M.A. Klysenko, special attention was paid to theoretical issues (study of the relationship between chromatographic behavior of pesticides of different chemical nature and their molecular structure, behavior in the environment and the body), application of chromatographic methods in basic research in toxicology, and biological exposure monitoring [51][52][53][54][55].
The organization and coordination of development, testing, and implementation of methods for chromatographic determination of pesticides in all union republics was carried out by the Group of Experts on Review and Recommendation of Methods for Determination of Pesticides and Biologicals in Food, Feed, and Environment at the State Chemical Commission for almost 30 years. During this time, the Ministry of Health of the USSR developed and approved more than 6000 guidelines for the determination of micro quantities of pesticides, which were issued as official guidelines in more than 20 collections of guidelines and 8 reference publications on the determination of pesticides’ micro quantities in food, feed, and environment. Today, these recommendations are relevant in the field of pesticide safety control not only in Ukraine [56][57][58][59][60][61][62][63].

This entry is adapted from the peer-reviewed paper 10.3390/separations9050114


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