Analytical Chemistry in Russia - Analytical Chemistry (ACS Publications)

Jul 19, 2016 - *E-mail: [email protected]. Biography. Yuri A. Zolotov is a professor and a head of the Analytical Chemistry Chair, Chemistry ...
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Analytical Chemistry in Russia Research in Russian analytical chemistry (AC) is carried out on a significant scale, and the analytical service solves practical tasks of geological survey, environmental protection, medicine, industry, agriculture, etc. The education system trains highly skilled professionals in AC. The development and especially manufacturing of analytical instruments should be improved; in spite of this, there are several good domestic instruments and other satisfy some requirements. Russian AC has rather good historical roots. Yuri Zolotov*



Department of Chemistry, Division of Analytical Chemistry, Lomonosov Moscow State University, Moscow, Russia 119991 CONTRIBUTIONS THAT ARE STILL VALID



Many more important results were obtained during XXth century and at the beginning of XXIst century. Only most remarkable ones will be noted below. Chromatography was introduced by Russian botanist Mikhail Tswett in 1903 (see Figure 1); and this development is recognized worldwide. Scientific works and the life of Tswett were described in several books, for example,17 and many articles, including the article by L. Ettre.18 Recently, the full collection of Tswett’s works was published.19 The first paper on thin layer chromatography (TLC) was published in 1938 by N. A. Izmailov and M. S. Schreiber, who worked in Khar’kov.20 Several original and interesting approaches to gas chromatography were elaborated by A. A. Zhukhovitskii (in the 1950− 1970s). Significant results on surface interactions in chromatographic systems were obtained by A. V. Kiselev. Ligandexchange chromatography for separation of enantiomers was developed with an active perticipation of V.A. Davankov.21 Multicapillary columns for GC were prepared and used in Novosibirsk in the 1970−1980s.22 L. N. Moskvin and his coworkers developed liquid−gas chromatography23 and the chromato-membrane method.24,25 Probably, the first results in capillary isotachophoresis have been obtained by O. V. Oshurkova in St. Petersburg. B. V. L’vov is the developer of graphite furnace atomic absorption spectroscopy (1959; see Figure 2).26 Besides, L’vov suggested later a special platform for electrothermal atomizers which is widely called the L’vov platform.27 These important achievements are now mentioned in undergraduate textbooks;28 L’vov himself described his work.29 Dual stream plasmatorch as a light source in atomic emission analysis of powders (1976)30,31 can compete with inductively coupled plasma (ICP) from the point of view of the matrix effect. A multicapillary lens by M.A. Kumakhov32 (X-ray optics by Kumakhov) is used in designing of new devices for XRF analysis (see Figure 3). The Shpolskii effect (1952)33 is widely applied in luminescence analysis of PAH and other compounds. Electron spin resonance was discovered by E. K. Zaimovskii in Kazan (1944). Works by V. L. Tal’roze and B. A. Mamyrin34 were of importance for mass spectrometry (ion-molecule

EARLY HISTORY (XVIII−XIX CENTURIES)

Analytical chemistry (AC) as a science started in Russia in the second part of the XVIIIth century.1−3 However, chemical analysis has, of course, a longer history. Perhaps, assay laboratories have appeared in the XVIth century for testing ores and noble metals. Laboratories at the Ural metallurgical plants appeared as early as in the beginning of the XVIIIth century. The first known Russian scientist M. V. Lomonosov (1711− 1765) organized the first research and educational chemical laboratory in Russia (in St. Petersburg) in 1748. T. E. Lowitz (1757−1804), a specialist in pharmacy, discovered the adsorption of substances from solutions (on charcoal),4,5 developed a method for the separation of calcium and barium using absolute alcohol, and used the shape of crystals for salt identification. V. M. Severgin (1765−1826) published the handbook “Art of Assaying or a Guide on the Testing of Metal Ores” in 1801. He widely used the blowpipe, improved the pearl method, refined sedimentation methods, and used the colorimetric technique.6 In the XIXth century, similar to the XVIIIth century, there were no researchers in Russia for whom AC would be the main area of their interest. However, many significant contributions have been done. Some of them are shown in Table 1. © 2016 American Chemical Society

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Dissertation “Study of the Chemical Composition and Healing Properties of Russian Mineral Waters” (1825). Improvement of the elemental analysis of organic substances in an oxygen flow. Introduction of systematic practical training students in AC Compounds of platinum group metals as analytical reagents (chloroplatinic acid for K+ and NH4+; Os and Ir compounds for alcaloids, Pd compounds for iodine). Books: “Materials on Chemistry of Platinum Group Metals”, “Simple Methods for Detection of Platinum Group Metals”. The first original Russian text book on chemical analysis in three volumes (1854) Method for the determination of small amounts of hydrogen peroxide using lead dioxide (1869). Publication of “Chemical Tables for the Calculation of Quantitative Decompositions” (1853) Finding free hydrochloric acid in gastric juice. Handbook on microcrystalloscopy (with new reactions of elements) The influence of the current strength and the anode surface area on the rate and completeness of electrolysis. Using solid sorbents in gas analysis (1875) Electroanalysis with rotating anode stirring in the analyzed solution (1888) Simplified method for the determination of carbon in soils (1886) Method for the determination of phosphorus in wines Magnesium diiodoacetylene as a reagent for the carbonic group “Guide on Qualitative Chemical Analysis” (1867) (translated in German, Dutch, English and French). Totally 5 editions. A laboratory of gas analysis (the first one in Russia) Textbook “Analytical Chemistry” (the first edition of 16), 1871. The book has been translated into all main languages Study of the interaction of substances in solid phase and the related method for qualitative analysis; developing a small-scale hand-held laboratory Methods for the determination of ozone in air, aniline dyes in foodstuffs and unsaturated hydrocarbons. Methods and divices for oxygen determination in air (1898) and water (1896) Publication of “Introduction to Chemical Analysis and Table for Qualitative Analysis” (Kiev, 1889)

accomplishments or discoveries

Table 1. Some Accomplishments of Russian Chemists of the XIXth Century in Analytical Chemistry

13 14 15 15 16 16 16

N. P. Klobukov (1860−1899) G. G. Gustavson (1842−1917) A. A. Pavlinov (died in 1893) Zh. I. Iotsich (1870−1914) F. F. Beilstein (1830−1906) N. A. Menshutkin (1842−1907) F. M. Flavitskii (1848−1917)

16

11 12

K. E. Schmidt (1822−1894) N. A. Bunge (1842−1914)

S. N. Reformatskii (1860−1934) and Ya. I. Mikhailenko (1864−1943)

9 10

N. A. Ivanov (1816−1883) G. V. Struve (1822−1908)

15

8

C. C. Claus (1796−1864)

G. V. Khlopin (1863−1929)

7

H. I. Hess (1802−1850)

researchers

ref or other sources

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Analytical Chemistry

reactions in the gas phase, and Mamyrin’s “mass reflectron” is used in time-of-flight (TOF) mass spectrometers). Everybody who deals with ion-selective electrodes (ISE) are familiar with Nikolski equation formulated in the 1930s. The electron (artificial) tonque was developed by Yu. G. Vlasov,35,36 who suggested this term (see Figure 4). The theory of inverse voltammetry and many applications of the technique were developed by A. G. Stromberg and his school in Tomsk in Siberia.37

Figure 1. Mikhail Tswett, the inventor of chromatography.

Figure 2. Boris L’vov, the founder of ETAAS. Courtesy and permission of Prof. L’vov. Figure 4. Yu. G. Vlasov. Courtesy and permission of Prof. Vlasov.

The list of other achievements includes new versions and the first monograph on kinetic methods of analysis (K. B. Yatsimirskii).38 A new approach in phase analysis called stechiography has been elaborated by V. V. Malakhov in Novosibirsk.39,40 N. A. Tananaev developed, simultaneously with F. Feigl in Austria, the spot test method in the 1920s. Many analytical reagents were proposed in 1940−1980s, mostly for UV−vis spectrophotometry. Some reagents of this series are well-known and still produced in several countries as Arsenaso III (V. I. Kuznetzov, S. B. Savvin). The theory of interaction of organic reagents with metal ions was developed beginning with works by L. A. Chugaev who suggested dimethylglyoxime as a reagent for nickel and formulated some postulates of metal chelate chemistry. Table 2 gives examples of analytical reactions and reagents suggested by Russian chemists. Research Centers. There are several institutes of the Russian Academy of Sciences which developed AC. The Vernadskii Institute of Geochemistry and Analytical Chemistry (Moscow) includes the Analytical Division with many research laboratories and small groups (see Figure 5). They developed spectrometric, chromatographic (mostly for ions), electrochemical, and nuclear methods as well as solved practical problems concerning noble metals and transuranium elements. For instance, A. A. Grechnikov develops mass spectrometry

Figure 3. Kumakhov X-ray lens. Permission of the Institute of X-ray Optics. 8350

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Analytical Chemistry Table 2. Some Analytical Reactions and Reagents Suggested by Russian Chemists analyte

reaction, reagent

authors

year

ref (source) and comments

Phosphorus Aromatic hydrocarbons

Ammonium molibdate β-Dinitroantraquinone

G. V. Struve, G. Svanberg Yu. F. Fritzsche

1850 1863

Halides in organic compounds

Green flame under heating in the presence of copper oxide Xanthates 1-Nitrozo-2-Naphtol

F. F. Beilstein

1872

41 15, “Fritzsche reagent” 15, “Beilstein test”

P. N. Akhmatov M. A. Il’inskii, G. Knorre L. A. Chugaev, F. V. Tserevitinov L. A. Chugaev N. S. Poluektov V. I. Kuznetsov S. B. Savvin

1870 1885 end of XIXth century 1905 1933 1941 1959

42 43 16, “Tserevitinov method” 44 45 46 47, popular reagent

Cu, Ni, Co Cobalt Mobile hydrogen atom in organic amperends Nickel Potassium Uranium Many metal ions

Dimethylglioxime Dipicrylamine Thoron (Thorin, Arsenazo) Arsenazo III

Figure 5. Vernadskii Institute of Geochemistry and Analytical Chemistry, Moscow. Permission of the Scientific Secretary of the Institute.

G. I. Tsisin, S. G. Dmitrienko), and rapid tests for field analysis (E. I. Morosanova, Yu. A. Zolotov) being mentioned. Significant results in thermooptical techniques are obtained, especially in thermal lens spectrometry (M. A. Proskurnin). N. V. Alov deals with total reflection X-ray fluorescence (TRXRF) spectrometry. gas chromatography-mass spectrometry (GCMS) and liquid chromatography-mass spectrometry (LC-MS) techniques are developed by I. A. Revelskii, O. A. Shpigun, and others. Analytical chemistry is successively developed in three divisions of Sankt-Petersburg University: analytical chemistry (L. N. Moskvin, O. V. Rodinkov), organic chemistry (I. G. Zenkevich, L. A. Kartsova), and radiochemistry (Yu. G. Vlasov). Nanoanalysis is developed in many centers, maybe especially in Saratov University (S. N. Stykov). Publications. Zhurnal Analitichescoi Khimii (Journal of Analytical Chemistry) is published since 1946 in two versions, Russian and English, with the latter one distriluted by Springer. There are also other journals: Analitika i Kontrol (Analytics and Control), Sorbtzionie i Khromatograf icheskie Processi (Sorption and Chromatographic Processes), Zavodskaya Laboratoria (Plant Laboratory), Zhurnal Prikladnoi Spectroskopii (Journal of Applied

(mostly surface-assisted laser desorption ionization (SALDI)). B. K. Zuev developed the original technique called oxythermoanalysis. L. A. Gribov developed expert systems for the identification of organic molecules. B. F. Myasoedov developed methods for the determination of transplutonium elements. The institute has modern analytical instruments. ISEs, flow injection analysis (FIA), X-ray fluorescence (XRF), and electron microprobe spectrometry are developed in the Kurnakov Institute of General and Inorganic Chemistry (also in Moscow). Other Moscow academic institutes including the Institute of Petrochemical Synthesis (gas chromatography (GC), high-pressure liquid chromatography (HPLC), TLC, analytical metrology), the Institute of Chemical Physics (analysis of polymers, chemometrics) can be noted. There is research work in AC also in other institutes of the Academy and not only in Moscow. There are several hundred universities, with about 50 separate divisions (chairs) of AC. One of the biggest chairs belongs to Lomonosov Moscow State University. There are many directions developed in the division, with chromatography (O. A. Shpigun), enzymatic methods (A. A. Karyakin, T. N. Shekhovtsova), sorption preconcentration (Yu. A. Zolotov, 8351

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Analytical Chemistry Spectroscopy). Many papers are also published in other Russian journals (and, of course, in international ones). Many monographs and text books are published. As an example, two recent monographs can be mentioned, on ionselective electrodes48 and biosensors.49 The Scientific Council on Analytical Chemistry (see below) prepares a series of collective monographs “Problems of Analytical Chemistry”. In total, 20 volumes have been published including books on outof-laboratory analysis50 and capillary electrophoresis.51 Several modern text books have been recently published, which were prepared in Moscow52 and St. Petersburg53 Universities and in Moscow University of Fine Chemical Technologies.54 Instrumentation. There were several original ideas, approaches, and developments in the field of analytical instrumentation. Electrospray for MS was developed in St. Petersburg Institute of Analytical Instrumentation (L. N. Gall and others) simultaneously with J. Fenn, maybe earlier (By the way, the former researcher of this institute, A. Makarov, is the main author of the Orbitrap MS of the Thermo Co.). The first atomic absorption (AA) spectrometer with a continuous spectrum source was made in the Vernadskii Institute in the 1970s, but manufacturing was not organized. Domestic companies and state organizations manufacture instruments for X-ray (XR), atomic emission (AE), AA spectrometric (AE without ICP) and electrochemical analysis and GC isotope MS. There are no good domestic GC-MS, ICP-AES, or ICP-MS manufacturers, so laboratories must purchase these instruments from international companies. Coordination of Research and Information. At present, the only coordinating unified body leading Russian analysts is the Scientific Council on Analytical Chemistry of the Russian Academy of Sciences. The Council organizes conferences and seminars, publishes the mentioned series “Problems of Analytical Chemistry”, develops Russian terminology, influences education in analytical chemistry, and has international contacts. The council includes many subject commissions and several regional branches. Solving Practical Problems. There are analytical control systems in industry (chemical, petroleum, pharmaceutical, in metallurgy, electronics, etc.), agriculture, environmental protection, health, national defense, and so on. Some such analytical services are powerful enough. For example, an excellent analytical survey is the geological survey with the leading All-Russian Institute of Mineral Raw Materials in Moscow. Analytical control of metallurgical processes are almost completely automated, and it is based on using ICPOES, ICP-MS, AAS, and XRF spectrometry. Analysis in the pharmaceutical industry is carried out with the wide application of HPLC and UHPLC. There are several laboratories with significant experience in the analysis of high-purity materials. There are many successes in AC with noble metals. There is, of course, a network of laboratories for environmental control. Education in Analytical Chemistry. AC is taught in about 300 Russian universities. In total, all chemistry students takes approximately 300 academic hours of AC. There are many textbooks, mostly domestic, and sometimes translated textbooks (from English and, seldomly, German) are also used. As an example, let us to consider the education system in the Chemistry Department of Lomonosov Moscow State University. Every year, about 230 students enter the Chemistry Department. They are divided into 12−13 groups with 16−20 persons in each group, and every group is subdivided into two parts (8−10 students) and each part has its own teacher in

chemistry (for seminars, laboratory work, control tasks), an Associate or Assistant Professor. Lectures for students are delivered by Full Professors. Undergraduate students have four basic courses of chemical disciplines: the first year (semesters 1 and 2), inorganic chemistry; the second year (semesters 3 and 4), analytical; the third year (semesters 5 and 6), organic; the third and fourth year (semesters 6 and 7), physical chemistry. Each basic course has the same number of hours for teaching, namely, 390. Beginning from the sixth semester, students have many other chemical disciplines (chemical technology, chemistry of high molecular weight compounds, chemistry of natural compounds, electrochemistry, colloid chemistry, etc., see schematics). Chemical courses at the Chemistry Department of Moscow University (1−10 are semesters) are shown in Table 3. Table 3. Education Structure in Chemical Department of Moscow University semester

courses

1 2 3 4 5 6

inorganic chemistry inorganic chemistry analytical chemistry analytical chemistry organic chemistry organic chemistry physical chemistry special courses colloid chemistry crystal chemistry physical chemistry special courses chemical technology special courses history of chemistry special courses prediploma practice diploma work

7

8 9

10

Distribution of teaching hours (%) for AC is shown in Table 4. Table 5 shows the distribution of teaching hours between different subject topics. Table 4. Distribution of Teaching Hours of AC semester

lectures

seminars

laboratory works

total

third fourth total

36 36 72

32 32 64

126 128 254

194 196 390

At the end of each block (lectures + seminars + laboratory work) devoted to one topic or group of topics, students have to pass a colloquium (small oral examination) and write a control work on the same topic. At the end of the year, students have to pass an oral examination for the whole course of analytical chemistry. There are some difficulties in education. Sometimes it is difficult to answer the question: what is AC? There are some contradictions in training chemists and teaching modern AC (which is not chemistry alone). International Contacts. The international contacts of Russian analysts are diverse. It is possible to mention the participation in international organizations: IUPAC, DAC/ 8352

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Analytical Chemistry Table 5. Distribution of Teaching Hours between Teaching Topics (AC) block

lectures (% of 72)

third semester Homogenic equilibria (acid basic, complexation, redox); Titrimetry 25 Methods of identification and separation; Gravimetry; Sample 17 pretreatment; Heterogeneous equilibria Metrology of analysis 8 Analysis of natural or industrial samplesa − fourth semester Spectrocopic methods 22 Electrochemical methods 14 Chromatographic methods 14 Final course workb −

1 2 3 − 4 5 6 − a

topics

seminars, control works (% of 64) 30 19

laboratory work (% of 254)

total part (% of 390) 20 17.5

10 −

15.5-titrimetry 13.5-separation, identification, 6-gravimetry − 15

15 13 13 −

17.5 13.5 4 15

18.5 14 7.5 10

2.5 10

Different for each student, individual task. bSmall scientific study. (12) Lidov, A. P., Bunge, N. A. Gas Analysis Using Bunsen-Deier Method. Kiev, 1894 (in Russian). (13) Budreiko, A. A. Proceedings of the Institute of History of Nature Science and Technique, Moscow, 1960, 30. (14) Gustavson, G. G.Zhurn. Russ. fiziko-khim. ob-va (J. Russian Physico-Chem. Society). Part Chem., 1886, 18 (8). (15) Zolotov, Yu.A. Who Was Who in Analytical Chemistry in Russia and USSR. URSS Publishing House: Moscow, Russia, 2006 (in Russian). (16) Volkov, V. A., Kulikova, M. V. Russian Professors. XVIII: The Beginning of XX Centures Chemical Sciences, Biographical Dictionaries; RKhGI: St. Petersburg, Russia 2004 (in Russian). (17) Senchenkova, E. M.; Semenovich, M. Tswett−The Creator of Chromatography; Yanus-K Publ. House: Moscow, Russia, 1997 (in Russian). (18) Ettre, L. S. LC−GC Eur., 2003, September, pp 2−7. (19) Tswett, M. S. Selected Works; Zolotov, Yu. A., Ed.; Nauka: Moscow, Russia, 2013 (in Russian). (20) Izmailov, N. A.; Schreiber, M. S. Farmatsiya 1938, No. 3, 1−6. (21) Davankov, V. A.; Rogozhin, S. V. J. Chromatogr. 1971, 60, 280− 283. (22) Malakhov, V. V.; Sidelnikov, V. N.; Utkin, V. A. Dokl. Akad. Nauk SSSR 1993, 329, 749−751. (23) Moskvin, L. N.; Gorshkov, A. I.; Gumerov, M. F. Dokl. Akad. Nauk SSSR 1982, 265, 378−382. (24) Moskvin, L. N. Dokl. Akad. Nauk SSSR 1994, 334, 599−602. (25) Moskvin, L. N. J. Chromatogr. 1994, 669, 81−87. (26) L’vov, B. V. Spectrochim. Acta 1961, 17, 761−770. (27) L’vov, B. V. Spectrochim. Acta, Part B 1978, 33, 153−193. (28) Christian, G. D., Dasgupta, P., Schug, K. Analytical Chemistry, 7th ed.; Wiley: New York, 2013. (29) L’vov, B. V. J. Anal. Chem. 2005, 60, 382−392. (30) Engelscht, V. S.; Urmanbekov, K.; Zheenbaev, Zh. Zh. Zavodskaya Laboratoria 1976, 42, 174−176. (31) Zayakina, S., Anoshin, G. Dual Stream Plasmatorch in Analytical Spectrometry; Lap Lambert Academic Publishing GmbH & Co. KG: Saarbrücken, Germany, 2013 (in Russian). (32) Kumakhov, M. A. Nucl. Instrum. Methods Phys. Res., Sect. B 1990, 48, 283−286. (33) Shpolskii, E. V.; Il’ina, A. A.; Klimova, L. A. Dokl. Akad. Nauk SSSR 1952, 87, 935−938. (34) Mamyrin, B. A.; et al. J. Exp. Theor. Phys. 1973, 64, 82−88. (35) Di Natale, C., D’Amiko, A., Vlasov, Yu. G., Legin, A. V., Rudnitskaya, A. M. Proceedings of the International Conference on Eurosensor IX, Stockholm, Sweden, 1995; p 512. (36) Vlasov, Yu.A.; et al. Sens. Actuators, B 2000, 65, 235−236. (37) Sholz, F., Ed. Electrochemistry in a Divided World. Innovations in Eastern Europe in the 20th Century. Springer: Heidelberg, Germany, 2015. (38) Yatsimirskii, K. B. Kinetic Methods of Analysis; Goskhimizdat: Moscow, Russia, 1963 (in Russian).

EuChMS, Eurachem, CITAC, Eurachem, and others. Joint scientific projects, organization of training and advertising centers of transnational companies in Russia, membership in editorial or advisory boards of international journals, and exchange of visits for lecturing should be also mentioned. Joint Japan−Russia symposia on analytical chemistry have been held every two years for the past 20 years. Regular Analytical Russia−Germany−Ukraine Symposia on analytical chemistry (ARGUS) took place between 1992 and 2005.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The author declares no competing financial interest.



ACKNOWLEDGMENTS This article was prepared under financial support from the Russian Science Foundation, Grant Number 14-23-00012.



REFERENCES

(1) Batalin, A. Kh. Zavodskaya Laboratoria 1951, No. 10, 1155− 1162. (2) Batalin, A. Kh. Assays in History of Analytical Chemistry in the USSR; Orenburg Agricultural Institute: Orenburg, Russia, 1961 (in Russian). (3) Zolotov, Yu. A., Vershinin, V. I. History and Methodology of Analytical Chemistry; Academia: Moscow, Russia, 2007 (in Russian). (4) Lowitz, T. E. Selected Works on Chemistry and Chemical Technology; Publishing House of the Academy: Moscow, Russia, 1955 (in Russian). (5) Figurovskii, N. A., Ushakova, N. N. Tovii Yegorovich Lowitz 1757−1804; Nauka: Moscow, Russia, 1988 (in Russian). (6) Severgin, V. M. Chemical Assay, or Handbook on Chemical Testing Metal Ores and Other Raw Materials; Publishing House of the Academy: St. Petersburg, 1801 (in Russian). (7) Soloviev, Yu. I. Herman Ivanovich Hess; Publishing House of the Academy: Moscow, Russia, 1962 (in Russian). (8) Claus, C. C. Beiträge zur Platinmetalle. Festschritt zur jubëlfeier des fünfzigjährigen Bestehens der Universität Kazan ; Kazan University: Kazan, Russia, 1854. (9) Ivanov, N. A. Introductory Basis of Qualitative and Quantitative Analysis; in 3 volumes, 1854 (in Russian). (10) Rozen, B.Yu.; Khrapkovskii, A. I. Zavodskaya Laboratoria 1955, 21, 675−676. (11) Palm, U. V. From the History of Nature Science and Technique of Baltics. Riga, 1970. 2. 8353

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Analytical Chemistry (39) Malakhov, V. V.; Vasilyeva, I. G. Russ. Chem. Rev. 2008, 77, 370−392. (40) Malakhov, V. V. J. Solid State Electrochem. 2012, 16, 2295−2307. (41) Struve, G. V.; Svanberg, L. Z. Prakt. Chemie 1848, 44, 291. (42) Akhmatov, P. N. About Reactions of Xanthates with Compounds of Some Metals; Moscow, 1874 (in Russian). (43) Il’inskii, M. A.; Knorre, G. Ber. Dtsch. Chem. Ges. 1884, 17, 2581−2593. (44) Chugaev, L. A. Selected Works, Vol. 1−3, Akademiia Nauk SSSR: Moscow, Russia, 1962. (45) Poluektov, N. S. Kalii 1933, 10, 44. (46) Kuznetsov, V. I. Zhur. Analit. Khim. 1952, 7, 226. (47) Savvin, S. B. Dokl. Akad. Nauk SSSR 1959, 127, 1231. (48) Mikhelson, K. N. Ion-Selective Electrodes, Lecture Notes in Chemistry, Vol. 81; Springer: Heidelberg, Germany, 2013. (49) Evtugin, G. Biosensors: Essentials, Lecture Notes in Chemistry, Vol. 84; Springer: Heidelberg, Germany, 2014. (50) Out-of-Laboratory Chemical Analysis, Problems in Analytical Chemistry, Vol. 13; Zolotov, Yu. A., Ed.; Nauka: Moscow, Russia, 2010 (in Russian). (51) Capillary Electrophoresis, Problems of Analytical Chemistry, Vol. 18; Kartsova, L .A., Ed.; Nauka: Moscow, Russia, 2014 (in Russian). (52) Fundamentals of Analytical Chemistry, 6th ed.; Zolotov, Yu. A., Ed.; Academia Publishing Centre: Moscow, Russia, 2014 (in Russian). (53) Analytical Chemistry; Moskvin, L. N., Ed.; Academia Publishing Centre: Moscow, Russia, 2008; Vols. 1 and 2; 2010, Vol. 3 (in Russian). (54) Analytical Chemistry and Physico-Chemical Methods of Analysis; Ishenko, A. A., Ed.; Academia Publishing Centre: Moscow, Russia, 2010 (in Russian).

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