ISSN 10619348, Journal of Analytical Chemistry, 2010, Vol. 65, No. 4, pp. 434–436. © Pleiades Publishing, Ltd., 2010. Original Russian Text © E.M. Sedykh, B.K. Zuev, and A.S. Grachev, 2010, published in Zhurnal Analiticheskoi Khimii, 2010, Vol. 65, No. 4, pp. 446–448.

IN SCIENTIFIC COUNCIL ON ANALYTICAL CHEMISTRY OF THE RUSSIAN ACADEMY OF SCIENCES

Work of the Moscow Workshop on Analytical Chemistry of the Scientific Council on Analytical Chemistry of the Russian Academy of Sciences in 2008–2009 DOI: 10.1134/S1061934810040167

The workshop on February 26, 2008 was devoted to methods of the processing of spectral information in arc atomic emission spectrochemical analysis of solid natural and technogenic samples. Three reports were made by scientists from Irkutsk (Vinogradov Institute of Geochemistry of the Russian Academy of Sci ences). The transition from the visual processing of spectra to computer processing was considered along with the requirements for the algorithmic and software provision for multielement analysis, based on the developed model and scenarios of the operation of the system of computer interpretation of arc atomic emis sion spectra, recorded by multichannel solidstate detectors, are formulated. An integrated software “Automatic Identification of Arc Atomic Emission Spectra” (IS AIAAES) included into the Register of Computer Software of the Federal Agency of Intellec tual Property, Patents, and Trademarks of the Russian Federation (Certificate no. 2006610490 of 2/1/2006, authors I.E. Vasil’eva, S.M. Pavlov, and E.V. Sha banov) was developed. The use of IS AIAAES in the elaboration of the following procedures is shown: “A Procedure for the Quantitative Atomic Emission Analysis of Geological Samples Using the Insuffla tion–Spilling Method” and “Determination of Impu rities in Natural Quartzites, Enriched Quartz, and Crystalline Silicon.” The use of multidimensional cal ibrations built into IS AIAAES has ensured an improvement of the performance characteristics of the results of analysis. The workshop on March 25, 2008 was devoted to methods for the determination of organic substances. New polycapillary columns for gas chromatography have been introduced. Using these columns allows analysts to reach efficiencies in liquid chromatography of an order of 500–600 theoretical plates at a column length of 20–30 cm. Schemes of gas chromatographs were considered that allow the organization of the cir culation part of the test sample in a closed circuit (B.A. Rudenko and O.O. Naida, Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences). Oxythermography, a new technique for studying substances, was also considered. Oxythermograms are dependences of oxygen demand on the temperature of the sample in the course of its oxidation with a binary

mixture of oxygen with a noble gas. In contrast to ther mogravimetry, the depth of the conversion of chemical processes in a sample, in this case, is the liberation or consumption of oxygen in the course of the pro grammed heating of the sample in a gas atmosphere. The oxythermogram recorded, being a peculiar finger print, bears information on the structure of the organic substance and can be used for the identification of a mixture of organic substances (B.K. Zuev, Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences). On the workshop on April 23, 2008, attention was focused on the analysis of highpurity substances and functional materials (A.I. Saprykin, Institute of Inor ganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk). The basic analyt ical methods are AAS, ICP AES, and ICP MS. The improvement of atomic spectrochemical methods and instruments has allowed speaker to improve perfor mance characteristics and implement direct analysis of nonconducting and lowsoluble materials, to develop procedures of layerbylayer analysis with a resolution of below 1 μm, and to determine the com position of surface pollutants. Vacuum distillation, sublimation, and matrix distillation after chemical transformations allows analysts to save trace impuri ties and use a minimum quantity of reagents. Precon centration methods for a wide range of highpurity materials have been developed, including metals (Cd, Te, Sn, Ga, Bi, Zn, and others), metal oxides and, and semiconductor materials (Si, Ge, compounds АIIIBV and AIIBIV). Limits of detection for impurities reach 10– to 10–10%. A review on the analysis of carbonaceous raw mate rials containing precious metals was presented by V.N. Mit’kin (Institute of Inorganic Chemistry, Sibe rian Branch of the Russian Academy of Sciences, Novosibirsk). The results of the determination of plat inumgroup metals in these objects using different methods differ within 1–2 orders of magnitude. For a reliable determination of the level of platinum con centration, one should (1) determine the chemical nature of the preconcentration of platinumgroup metals on carbonaceous geochemical barriers and reveal the speciation of compounds; (2) conduct inter laboratory tests and certify methods of the analysis of

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carbonaceous materials for platinumgroup metals; and (3) develop standard samples of composition. A hybrid method of the lowtemperature direc tional crystallization (LTDC) of water or aqueous solutions was presented by L.P. Eksperiandova, Insti tute of Single Crystals of the National Academy of Sciences of Ukraine. This process is accompanied by the simultaneous separation (preconcentration) and determination of components. In the LTDC of an aqueous solution (from bottom to top), the obtained ice ingot possesses a transparent bottom and a non transparent top portion, whose length increases with an increase of the concentration of the dissolved salts. The total mineralization of natural water is estimated by the length of the nontransparent portion. The participants of the workshop on May 27, 2008 considered the new trend in capillary electrophoresis, searching for pseudostationary phases for electroki netic chromatography (E.P. Svidritskii, Biasep Scien tific and Technological Center). The interaction of a polyelectrolyte complex of acrylic acid with a cationic surfactant gives a complex “supermicella.” The “supermicella” contains hydrophobic oil, heptanes, in the interior. Another type of pseudostationary phases is provided by bicontinual microemulsions, used for the first time in capillary electrophoresis. The phases are based on an aqueous buffer solution and heptane. Research is conducted into the use of πdonor aro matic “oils” as pseudostationary phases for the separa tion of compounds with similar structures. Research into the development of new modified capillaries– monoliths has been reported. The results of investigat ing new anticarcinogenic drugs based on metal com plexes have been presented. The possibility of deter mining the main pharmaceutical properties of the developed drugs, using different versions of capillary electrophoresis, have been shown (L.S. Foteeva, Ver nadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences). The data on the saturation of analytical and research labo ratories of the Russian Federation with instruments for capillary electrophoresis were presented (A.I. Gre myakov, Lumex, Moscow). The workshop, which took place on October 23, 2008, was devoted to chemical test methods. To develop efficient test means, the features of various chromogenic reactions in silicic acid xerogels and micellar media were studied. A new method was pro posed for the preparation of modified xerogels with the desired physicochemical properties, and more than 50 new materials, has been synthesized and studied. The kinetics and thermodynamics of heterogeneous complexation, redox, and synthesis reactions have been studied. The possibility of immobilizing not only various analytical reagents but also their mixtures allows the analyst to conduct different chromogenic analytical reactions (complex formations, oxidation reduction, and synthesis) and, therefore, lays a basis for the determination of various inorganic and organic JOURNAL OF ANALYTICAL CHEMISTRY

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substances. Test systems and procedures for perform ing spectrophotometric measurements have passed governmental metrological certification and been allowed for use. Rapid procedures for determining polyphenols in plant raw materials and drinks have been presented. Two approaches have been imple mented: test determination and flowinjection deter mination. A procedure for the extraction of polyphe nol oxidase from plant raw materials has been devel oped. The possibilities of various versions of consecutive injection analysis have been shown: tradi tional, miniature (labonavalve), and with particle injection (E.I. Morosanova and T.A. Matyushina, Moscow State University). M.A. Bol’shov (Institute of Spectroscopy, Russian Academy of Sciences and Moscow State University) presented a survey lecture entitled “ICPMS: Current Status and Prospects” (November 11, 2008). A signif icant part of the lecture was devoted to the problems of interferences and methods for the accounting or elim ination of these interferences. The most efficient method is the application of dynamic reaction cells. Interfering molecular complexes are removed from the ion flow because of the inhibition due to collisions with Не2 or Н2 or because of the decomposition of complexes in gasphase reactions with molecules of reactive gases (CH4, NH3, etc.). Considerable progress was achieved in the development of methods for the direct analysis of solid samples, a combination of laser vaporization with ICP MS. The lectures summarized the results of studies aimed at the sophistication of specific units of spectrometers. A new registration sys tem, similar to solidstate panoramic receivers of opti cal radiation, was demonstrated. The possibilities of ICP MS in the analysis of various highpurity metals (Al, Cu, Sc, etc.) and semiconductors (Si, Ge with natural and shifted isotope distribution), and also of environmental objects were presented by V.K. Karan dashev (Institute of Microelectronic Technology and HighPurity Materials, Russian Academy of Sci ences). He considered the advantages of using ICP MS combined with method ICP AES. A talk on the applications of laser ablation ICP MS for U–Pb dat ings of minerals was made by Yu.A. Kostitsyn (Vernad sky Institute of Geochemistry and Analytical Chemis try, Russian Academy of Sciences). The instrumenta tion is ElementXR spectrometer with a UP213 system of laser ablation (New Wave). The method is used in the analysis of zircon as an uraniferous mineral with a low initial concentration of nonradiogenic lead. The laser cell was modernized to reduce the back ground from lead: the metal cell was replaced by a Plexiglas cell. The possibilities and limitations of the method were surveyed. The results of dating both very young zircons (from rocks of midoceanic ridges) and ancient ones were presented. The meeting on February 17, 2009 was devoted to Xray spectrochemical analysis. N.V. Alov (Moscow State University) spoke about the VI AllRussia Con No. 4

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ference on Xray Spectrochemical Analysis, devoted to the 100th anniversary of the birth of M.A. Blokhin. Three reports were devoted to different methods of Xray spectrochemical analysis. The talk entitled “Application of Xray Total Internal Reflection Fluo rescence (TIF XRF) to Studies of the Surface of Sol ids” was delivered by N.V. Alov. He considered physi cal processes on which the method is based, including reflection, diffraction, and the total external reflection of Xrays, and the formation of stationary waves upon the total internal reflection of Xrays. The design and main units of the uptodate energydispersive RIF XFR spectrometer were discussed. The main direc tions in studying the solid surface by this method were considered. Among these are the quality control of the surface and surface layers of silicon and other semi conductor plates, the determination of distribution profiles of ionimplanted impurities, study of the mor phology of solid surfaces, and the determination of the composition, thickness, and density of the supported thin films. I.A. Roshchina (Vernadsky Institute of Geochem istry and Analytical Chemistry of the Russian Acad emy of Sciences) delivered a talk on the method of stepbystep analysis of unknown samples of presum ably extraterrestrial origin by Xray fluorescence with out special sample preparation of the analysis. The method is used to assess the average overall chemical composition of an object and the possibility of its assignment to the class of materials of extraterrestrial origin (mainly using the Fe–Ni test). The type of the meteorite substance is then refined by Xray electron probe microanalysis. The type of the substance type is determined by the composition pyroxene–olivine– plagioclase–glass and their heterogeneity. The basic possibility of determining the age of geo logical objects by the results of Xray electron probe microanalysis of monocytes for the presence of Th, U, and Pb was demonstrated by A.A. Mukhanova (Insti tute of Experimental Mineralogy of the Russian Acad emy of Sciences, Chernogolovka, Moscow oblast). At the workshop devoted to oil and petroleum products (March 24, 2009), a survey lecture entitled “The Main Methods of the Determination of Biomar kers and Their Use for the Reconstruction of the His tory of the Formation of Geological Objects” was delivered by E.A. Ablya (Moscow State University). The notion of biomarkers, fossil biomolecules, present in the organic substances (OS) of sedimentary rocks and fossil fuels, was introduced. More than 1000 hydrocarbons (HC) and heteroatomic com pounds that retained a structural similarity with the molecules of living matter have been revealed in oils. The main methods for the determination of biomark ers in natural objects are chromatography–mass spec

trometry and NMR. Each genetic type of OS parent for oils is characterized by the specific distribution of HC biomarkers. This allows the reconstruction of the history of the formation of OS: the conditions of sedi mentation, diagenesis, geochemical conversion con ditions, including those of thermal conversion, sub stance catagenesis, and biodegradation. Biomarkers were revealed that inherit elements of the biota of par ticular conditions and particular stages of the evolu tion of living organisms in the Earth. The biomarker method allows the precise identification of oils and their derivatives. The elemental composition of mineral oil and petroleum products is determined by AAS, AES, MS, XRF, etc. The limiting stage in the determination of trace elements in oil and petroleum products is sample preparation: ashing, acid digestion, dilution with organic solvents, autoclave digestion, and solvent extraction (T.A. Maryutina, Vernadsky Institute of Geochemistry and Analytical Chemistry of the Rus sian Academy of Sciences). The author proposed an alternative method of sample preparation in the pre concentration of trace elements, countercurrent liq uid chromatography. The known standard documents and methods and approaches to the analysis of oil and petroleum products were surveyed by V.V. Zhuchkin (Petroleum Analysts). A workshop on mass spectrometry was organized within the limits of the ATESTex exhibition. The program of the workshop (April 22, 2009) included seven presentations by scientists from Moscow, St. Petersburg, and Ryazan. The main group of reports was devoted to works on the design of domestic mass spectrometers. It was noted that the isotope spectrom eters for nuclear power engineering should meet the world level. The gas dynamic ionization method for isotope mass spectrometry has proved to be a promis ing alternative to ICP. Studies with organic molecules were started by N.R. Gall’. Mass spectrometry has become a reliable and rapid method for the sequence analysis of peptides (T.Yu. Samgina). The possibilities of tandem mass spectrometry for pharmacokinetic studies and the preliminary diagnosis of diseases were illustrated in the talk by E.S. Chernetsova. Electro spray and MALDI mass spectrometry offer a possibil ity of studying highmolecular compounds. The lec ture by R.N. Borisova was devoted to the applied aspects of the mass spectrometry of synthetic poly mers. A monograph by V.G. Zaikin entitled “Mass spektrometriya sinteticheskikh polimerov” (Mass Spectrometry of Synthetic Polymer) was advertized to the participants of the workshop. E.M. Sedykh, B.K. Zuev, and A.S. Grachev

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