Journal of Analytical Chemistry, Vol. 55, No. 3, 2000, pp. 294-299. Translatedfrom Zhurnal Analiticheskoi Khimii, VoL 55, No. 3, 2000, pp. 329-334. Original Russian Text Copyright 9 2000 by Zolotov.

IN T H E S C I E N T I F I C C O U N C I L ON A N A L Y T I C A L C H E M I S T R Y O F T H E RUSSIAN A C A D E M Y O F S C I E N C E S

Analytical Chemistry in 1998" Yu. A. Zolotov Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Leninskii pr. 31, Moscow, 117907 Russia The situation in Russian fundamental and applied science did not improve in 1998. Moreover, difficulties grew after August 17, 1998, and a balance barely before (while at a low level) was disturbed. The problems of financial support, logistics, staffing, and information provision remained unsolved or even increased. Nevertheless, the research and development work in analytical chemistry continued in Russia. This is true for institutes of the Russian Academy of Sciences, higher educational institutions, and even specialized institutes, which suffered most heavily during the years of socalled reforms. Numerous noteworthy results, which were often of importance and interest, were obtained. The volume of the written annual report of the Scientific Council became even larger than usual. Our colleagues from the CIS countries and the Baltic States are faced with great difficulties, which are often more severe than those in Russia. As for analytical chemistry on a global scale, it is under intensive development, and new concepts, methods, and unique technical or mathematical solutions appear almost every year. In particular, this was demonstrated at important conferences, such as Euroanalysis X in Basel and Pittcon in Orlando, which were held in September 1998 and March 1999, respectively. Russian instrument-making companies actively participated at the Pittcon and InCom conference exhibitions and at the Eureka Fair exhibition in Brussels; this was almost not the case previously. Miniaturization of analysis is among the branches that have attracted considerable attention of specialists in analytical chemistry worldwide. This is reflected in the fact that analytical instrumentation is improved so that it becomes possible to change from measurements at a minilevel to those at a micro- or even a nanolevel. Along with customary microscopes, instruments that should be properly termed nanoscopes were developed. We can observe patterns in which individual atoms can be really seen, and the terms nanoscale chemical analysis, micro-Raman spectroscopy, and laser ablation (nanoscale laser sampling) became commonly used. After pioneering studies at Ciba in Basel, multifunctional microanalytical instmments based on electronic chips, in particular, capillary electrophoresis instru*A lecture delivered at the annual session of the Scientific Council on Analytical Chemistry of the Russian Academy of Sciences on April 6, 1999.

ments, are under development in a number of countries. In Russia, these works were started at the Institute of Analytical Instrument Making of the Russian Academy of Sciences. A great number of presentations at the Euroanalysis conference were devoted to microinstruments, because the conference was held where this line of investigation originated. Of the works on microanalysis covered by the report of the Scientific Council, mention should be made of the development of an electron-probe technique for determining light elements (from boron to fluorine) in highpurity materials and compounds with a locality of several micrometers and a detection limit of 10-1~ g. These results were obtained by M.N. Filippov and other researchers at several institutions in Moscow. A new calibration procedure was developed for determining the above elements. The analyte concentrations varied from 2 to 97 wt %. The procedure can be applied to the analysis of local impurities, first of all, to the analysis of electronic materials. Much attention is focused on analysis in the field, i.e., out-of-laboratory analysis at the sites where test materials occur. In principle, this goal can be accomplished in several ways. Among them is the development of mobile analytical laboratories. Several companies manufacture these laboratories, which are equipped, as a rule, with the common analytical instruments, which may be smaller and more stable to vibrations than the usual instruments. In Russia, mobile laboratories installed on a boat (St. Petersburg) and an automobile (Moscow-Kaluga) were designed. The second line of out-of-laboratory analysis is the development of portable and handheld instruments. Of course, portable instruments weighing between 5 and 20 kg have been known fairly long; however, presently, a great number of companies manufacture pocket-sized analyzers. They are designed particularly for analyzing gas mixtures; instruments capable of determining several gases rather than a single gas are currently available. Instruments of this kind for determining dissolved oxygen in water and other components of liquid media are also known. Of handheld instruments developed in Russia, mention should be made of portable gas and ion chromatographs of the Tsvet series and mercury analyzers (Lyumeks and Vernadsky Institute of Geochemistry

1061-9348/00/5503-0294525.00 9 2000 MAIK "Nauka/Interperiodica"

ANALYTICAL CHEMISTRY IN 1998 and Analytical Chemistry, Russian Academy of Sciences). Test methods and relevant test kits with disposable components are also important for solving the problem of on-site analysis. A set of rapid tests for environmental analysis, food analysis, etc., was developed at Moscow State University. For example, test methods were proposed for determining free chlorine residues in drinking water and water of swimming pools; these methods are based on the use of the simplest indicator tubes and can be used by a layperson. Indicator tubes of a novel type (test solution enters them under the action of capillary forces) were developed for determining copper and iron in wines and brandies; they can be used for the identification of these products and for the determination of ascorbic acid in juices and biological fluids. An enzyme assay for determining very low concentrations of phenol is included in recommended procedures. Extremely low concentrations of lead can be determined in natural water using another enzyme test method. A wide variety of test kits were developed for analyzing drinking water by request of the Government of Moscow. A set of individual tests for detecting more than 20 narcotics, psychotropic drugs, and toxic substances out of laboratory should be particularly mentioned; foreign analogs of these tests are unknown (A.V. Gaevskii, Russian Research Institute of Organic Chemistry and Technology). New types of indicator paper test strips sealed in polymer films were proposed for determining AI, V(V), Fe(II), Fe(III), Cd, Cu(II), Bi, Ni, Ag, Hg(II), Pb, Zn, Ti(IV), Ge, Mo(VI), W(VI), I-, CI-, Br-, SCN-, S O42-, F-, and POJ- by putting one end of a test strip into the test solution and measuring the length of a colored or decolorized zone on the strip. The analytical range is 0.01-1000 mg/L (RSD = 10-30%). The test strips were recommended for rapid analyses of wastewater, natural water, soil extracts, and atmospheric precipitates under field conditions. Indicator paper compositions and devices were developed for the rapid determination of AI, Ti(IV), Mo(VI), W(VI), V(V), Fe(II), Fe(III), Ag, Cu(II), Zn, Cd, Pb, Hg(II), and S2- in natural water at a level of maximum permissible concentrations (MPCs). These devices are intended for monitoring water of fish-farming reservoirs under field conditions (Vladimir University). The first doctoral dissertation on test methods was defended by V.G. Amelin. The design of chemical sensor systems for the multicomponent analysis of gas and liquid media is an intensely developing line over the world. A set of nonselective sensors is used, and signals from these sensors are mathematically treated on the basis of pattern recognition and other mathematical techniques. Such devices for gas analysis were named the "electronic nose." A great number of papers and special sessions at JOURNALOF ANALYTICALCHEMISTRY Vol. 55

295

the latest Pittsburgh Conference were devoted to electronic noses. Books under relevant titles were issued. By analogy, devices for the multicomponent analysis of solutions were designated as the "electronic tongue" A device developed at the University of Texas for the analysis of liquids by detecting receptor color changes can serve as an example. Another device based on the use of a combination of ion-selective electrodes was developed at the St. Petersburg State University; Yu.G. Vlasov repeatedly reported on this development work. In 1998, this group established principles for the assessment of cross sensitivity of sensors, including solid chalcogenide electrodes, cation-sensitive film electrodes based on poly(vinyl chloride), etc. An electronic tongue was used for the simultaneous determination of bath components in electroplating shops (acid etching, nickel plating, and copper-lead-tin alloy plating). A flow-injection system was designed with the use of a multisensor cell based on chalcogenide glass electrodes for the simultaneous determination of lead, cadmium, copper, and chromium in the smoke of refuse incinerators; this system passed laboratory tests. It was found that the electronic tongue can be used in analyses of grape wines and mineral water. This technique can distinguish wines of the same kind from different winemakers, recognize various types of mineral water, and determine their mineral composition. Progress was also achieved toward the development of commonly used individual chemical sensors. Thus, piezoelectric resonance sensors for mercury vapor and unsymmetrical dimethylhydrazine (UDMH) were developed at the Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences. Sensors for methane and natural gas, which can perform remote measurements at a distance of 1 km, were designed at the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences. One sensor is based on an ingenious principle, namely, the use of a low-frequency thermoresistive generator and a pyroelectric film transducer. A thermocatalytic sensor developed at the Sochi Research Center of the Russian Academy of Sciences can continuously determine ammonia in air in the presence of other gases. Analytical quality control and quality assurance is another rapidly developing general line. As to this subject matter, a dozen books were published, a journal is being issued, and conferences are being held. A rubric on the metrology and quality assurance in chemical analysis was organized in the journal Zavodskaya Laboratoriya. An issue of the journal Accreditation and Quality Assurance published in April 1999 was compiled of papers by Russian authors. Considerable changes associated with the use of the uncertainty concept take place in the metrology of chemical analysis. This concept should be clarified, and the utility of its introduction should be assessed. An invited paper on this subject by Professor R. Kaiser will

No. 3

2000

296

ZOLOTOV

be published in the Zhurnal Analiticheskoi Khimii

(Journal of Analytical Chemistry). A systematic approach to the identification of unknown compounds in complex mixtures separated from environmental samples was suggested for GC and GC-MS determinations. This approach consists of the determination of a particular component system with the use of several identified compounds; the test system consists of a set of compounds originating from a common source or simultaneously present in test samples (homologous series, isomer sets, industrial process products, decomposition products of naturally occurring compounds, groups of emission components from a particular plant, etc.). Thereafter, the other components of these systems are searched for. The use of internal standard substances in the analysis of multicomponent organic mixtures and in environmental analysis was optimized for the purposes of quantitative determinations and analytical quality control (Institute of Evolution and Ecology Problems, Russian Academy of Sciences). High-level studies concerning sorption and extraction techniques for separation and preconcentration were performed. Studies performed at the Moscow State University on the sorption, extraction, membrane transport, and determination of organic compounds, including ecotoxicants, are of profound interest. The development of unique devices for analyte extraction from solid samples (Institute of Evolution and Ecology Problems, Russian Academy of Sciences) and for membrane fractionation of solid samples and water components, and a new design of planet centrifuge for countercurrent chromatography (Institute of Analytical Instrument Making, Russian Academy of Sciences, and Vernadsky Institute of Geochemistry and Analytical Chemistry) should also be mentioned. Modified polymeric matrices with selective properties are widely used for sorption preconcentration. On this basis, procedures for extracting, separating, and determining elements were developed. Among these matrices are xerogels prepared by the sol-gel technology. Reagents are immobilized on these matrices. Quinone imine indicators immobilized on reversedphase silica gels were applied to the solid-phase spectrophotometric determination of active chlorine residues in drinking water and water from swimming pools (Moscow State University). A procedure for preparing fibrous adsorbents as a nonwoven fabric modified with Arsenazo I and Arsenazo III groups was developed at the Vernadsky Institute on the basis of a polyacrylonitrile fiber containing amidoxime and hydrazine groups. Basic selection criteria for sorption systems were proposed, and a procedure for calculating the optimal conditions of dynamic sorption preconcentration of trace elements was developed to achieve the maximum preconcentration coefficients. A unified measurement system including a 48-channel ICP-AES spectrometer, a flow-injection

unit (NITs Akvita), and a personal computer with software was developed in cooperation between Moscow State University and the Vernadsky Institute. The use of this system lowered the detection limits for the analyte elements by a factor of 10-20, as compared with direct ICP-AES determination, at a preconcentration time of 1 min and a relative standard deviation of 2-5% for analyte concentrations of 1-10 ~tg/L. Chromatography remains to be the most commonly used technique in chemical analysis, particularly, in food and pharmaceutical analysis, in the analysis of petrochemicals and petroleum refining products, and in environmental analysis. Five journals on chromatography are issued over the world, not counting a wealth of publications in periodicals concerning analytical chemistry in general. The number of related conferences and even conference series becomes so large that specialists consider to reduce this number. Unfortunately, the friendly Scientific Council on Chromatography of the Russian Academy of Sciences has recently merged with the Scientific Council on Adsorption. Thin-layer gel chromatography is under development (this study seems to be the pioneering work of this kind in Russia) at the Moscow Correspondence Institute of Food Industry; Sephadex sorbents are used, and protein fractions are separated. Acid-base chromatography as a new version of gas chromatography was proposed at the Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences. This version is different from known techniques in that the retention of organic compounds is based on chemical interactions between analyte and carrier-gas molecules. Thus, primary amines (basic compounds) can be selectively retained with the use of acidic carbon dioxide as a carder gas, and organic acids can be retained with the use of ammonia (a base) as a cartier gas. The use of acid-base chromatography can improve separation and is, probably, favorable for the selectively preconcentration of compounds of certain classes. An approach to the determination of toxic organic compounds for which standard reference materials are unavailable was proposed. This approach is based on gas chromatography with an atomic emission detector (AED). Using chlorine- and fluorine-containing pesticides and related physiologically active substances (satin and soman) as examples, it was demonstrated that the above compounds can be determined by GCAED with the use of standard reference samples of other compounds the include similar heteroatoms. Available substances were suggested for use as standard compounds in the determination of pesticides and physiologically active substances. This approach provides the determination of empirical formulas (Saratov State University). A highly selective procedure for determining chlofine-containing pesticides in a mixture with polychlorinated dibenzodioxins or biphenyls by chromatogra-

JOURNAL OF ANALYTICALCHEMISTRY Vol. 55

No. 3 2000

ANALYTICAL CHEMISTRY IN 1998 phy-mass spectrometry was developed; this procedure does not require sample preparation (Moscow State University). Various new efficient adsorbents for ion chromatography and HPLC, primarily, for inorganic analysis, were also developed at Moscow State University. Among electroanalytical techniques, voltammetry and direct potentiometry received primary attention. Interesting studies on stripping voltammetry were performed by Kh.Z. Brainina in Yekaterinburg; these studies gained international acceptance. The number of studies concerning the automation of electrochemical analysis is low; in particular, amperometric responses are insufficiently used for the development of multisensor devices. The development of spectrochemical techniques is restricted by the absence of present-day instruments, particularly, for atomic spectrum analysis, in the majority of institutions. The limit of detection for mercury attained with atomic fluorescence detection using a mercury photometer (Vernadsky Institute of Geochemistry and Analytical Chemistry) with an add-on device for mercury distillation is lower than that in atomic absorption by a factor of five to ten. The use of a gold collector for preconcentration with flash desorption of accumulated mercury increases the analytical signal. The use of argon in place of air as a carrier gas (at a measurement step) makes it possible to attain a detection limit for mercury as low as 1 ng. Mass spectrometry is developing very effectively over the world; many new versions appeared primarily in the area of organic molecular analysis rather than elemental or isotope analysis. Nuclear physics techniques have not received very wide acceptance on a global scale, and no boom is presently observed in this sphere. In Russia, the body of studies on neutron activation analysis was reduced, because a number of reactors were shut down or their operating conditions were changed. Nevertheless, an optimization procedure for instrumental neutron activation analysis of samples of earth and cosmic matter was developed at the Vemadsky Institute. Up to 40 elements can be simultaneously determined in samples of the mass 5 g or lower with the limits of detection at a level of 10-5 to 10-7%. The procedure is based on the simulation of the test sample composition using the measured ),-ray spectra of individual elements and on the use of a computer program package that takes into account the main steps of analysis. The key analytical parameters (sample mass and the times of sample irradiation in solution, cooling, and measurement) can be evaluated; the interference of ),-lines can be reduced; and the experiment can be designed beforehand. The procedure is applicable to the analysis of rocks, minerals, meteorites, and environmental samples, such as soils, plants, and aerosols. In recent years, immunoassay techniques, which belong to biochemical or, probably, biological techJOURNALOF ANALYTICALCHEMISTRY Vol. 55

297

niques, were brought into use and rapidly gained wide acceptance. Several immunoassay techniques were accepted as standard methods by the US Environmental Protection Agency (EPA); Merck produces test kits for the detection and determination of explosives, aromatic hydrocarbons, and pesticides. The ELISA technique acquired particularly great significance. In Russia, a new method of solid-phase enzyme immunoassay (EIA) was proposed in 1998. This method is based on the use of immobilized water-soluble polyelectrolyte carriers, and it is much more rapid than traditional EIA with the use of the same reagents. A procedure was tested in the determination of herbicide Simazine and insecticide Permethrin at a level of 0.5 ng/mL. It was found that Simazine can be determined in water, milk, and various juices. An immunofiltration system for the rapid determination of pesticides was developed. The competitive binding of a pesticide-containing sample and a pesticide-peroxidase conjugate to antibodies is detected by peroxidase oxidation of the substrate N,N'-diaminobenzidine. The oxidation proceeds with the formation of an insoluble product. The analysis time is 20 min; the detection limit for Simazine is l0 or 1 ng/mL using visual or densitometric detection, respectively (Bach Institute of Biochemistry, Russian Academy of Sciences). A portable immune sensor for determining pesticides (for example, Simazine at a level of 2 ng/mL) was designed. In this sensor, a field-effect transistor is used for measuring the activity of a peroxidase label bound to a membrane (changeable) support (Institute of the Biochemistry and Physiology of Microorganisms, Russian Academy of Sciences, and Bach Institute of Biochemistry, Russian Academy of Sciences). Procedures for the detection of 2,4-dichlorophenoxyacetic acid and Simazine pesticides in aqueous solutions with visual detection were developed; these procedures are based on the use of colloidal particles of textile dyes as an alternative to colloidal gold in membrane test systems (Bach Institute of Biochemistry, Russian Academy of Sciences, and ShemyakinOvchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences). In the last five or six years, the activity of smallscale enterprises was primarily responsible for the development and manufacture of analytical instrumentation in Russia. As a rule, this work was concerned with devices that do not require high production and labor costs (the case in point is, for example, the development of ion-selective electrodes and potentiometers with ion-selective electrodes). The relevant companies simultaneously served as agents for the purchase of instruments from CIS manufacturers and foreign companies. In 1998, the activity of designers at state research institutes and educational institutions became more intensive. This change in the staff of designers also moved the direction of the main design work

No. 3

2000

298

ZOLOTOV

toward the development of instruments based on fundamental studies. In the year under review, a start has been made on the production of the following analytical instruments: an FSL-0.5 Fourier transform spectrometer for measuring infrared spectra of solid, liquid, and gaseous samples (interfaced with a computer, the system can automatically measure spectra, process spectral data, and operate with a spectral database using the software developed) (All-Russia Research Institute of Metrology); a highly sensitive PLS-2A automated polarograph with the software support containing an expert system for the analysis of water, atmospheric air, foods, and products of ferrous and nonferrous metallurgy (Moscow State Institute of Radioengineering, Electronics, and Automation (Technical University) and Infratron); an MGA-915 atomic absorption analyzer; an Infralyum Fourier transform spectrometer and a Kapel' system for capillary electrophoresis (Lyumeks); and an EKhO family of mobile automated multipurpose high-speed gas chromatographs. A BPI-2 sample preparation device (up to four samples simultaneously) was designed for the separation of suspended solids in liquid samples and the production of metal concentrates as solids or solutions. The device can also be used for purifying distilled water, buffer solutions, and alkali and alkaline-earth metal salt solutions (Moscow State University in cooperation with other organizations). Problems of environmental analysis were widely discussed: an All-Russia Conference was held, and the Moscow Workshop was organized. One more journal, Journal of Environmental Monitoring, is now issued. The majority of Russian papers concerning this subject matter were performed at universities and institutes of the Russian Academy of Sciences. The primary attention was focused on the determination of metals in natural samples with the use of spectrochemical and electroanalytical techniques. Procedures for the determination of important pollutants have been insufficiently developed yet. Among these pollutants are toxic inorganic gases (typical of air pollution), such as nitrogen oxides, sulfur oxides, carbon oxides, hydrogen sulfide (and usually concomitant carbonyl sulfide, carbon disulfide, mercaptans, sulfides, etc.), halogens and their derivatives, ammonia, hydrogen cyanide, phosphorus hydride, arsenic hydride, antimony hydride, etc.; organometallic compounds, which are the most toxic metal species (in particular, organotin compounds); aromatic hydrocarbons, aldehydes, and chlorinated hydrocarbons which are the most common urban air pollutants; anilines and aromatic nitro compounds; nitrogen- and phosphorus-containing pesticides; herbicides based on phenoxyacetic acids; and other water pollutants. Although several methodological studies were performed, no general procedure for the monitoring of UDMH in water and soil was developed. UDMH is one

of the most important components of rocket fuel. Territories become polluted with this carcinogenic substance in the fall of rockets, as was the case in Altai. Such elements of sample preparation as sample fractionation and cleanup, matrix removal, derivatization, and other operations that can improve the reliability of identification and the quality of analysis in general are often absent. Note that insufficient orientation to practical applications and to the introduction of methods and procedures into ecoanalytical chemistry is typical of many universities. A procedure for the selective gas-chromatographic determination of formaldehyde in ambient and workplace air was developed. The procedure involves passing the air through concentrating tubes containing silica gel moistened with polyethylene glycol, treating the adsorbent with concentrated ammonia under heating for desorption, and the gas-chromatographic determination of the obtained hexamethylenetetramine (HMTA) with thermionic detection. The advantages of this procedure are selectivity (among organic compounds accumulated in the adsorbent, only formaldehyde reacts with ammonia) and a low limit of detection of formaldehyde (~0.1 MPC for atmospheric air). The relative standard deviation of the results of analysis was no worse than 20%. It was found that the quantitative fixation of formaldehyde in HMTA can form the basis for a procedure for passive air sampling in the determination of formaldehyde (St. Petersburg State University). A rapid method for the determination of total organic impurities in water was proposed at the Vernadsky Institute. The method is based on the high-temperature oxidation of organic substances in an oxygeninert gas flow with the coulometric determination of the amount of oxygen consumed for the oxidation. This method formed the basis for the development of a prototype analyzer for the rapid monitoring of organic impurities in natural water, wastewater, and drinking water. Rapidity (the duration of analysis is 3-5 min), the absence of sample preparation, complete automation, safety, and low cost are the advantages of this analyzer. The analyzer can be used in water treatment systems (water stations and water treatment systems for power engineering) and for water purification and environmental monitoring. This development work was awarded a gold medal with honors at the Eureka 98 World's Fair in Brussels. The procedure and device were patented. Procedures for determining opiates in the sweat and adipose egesta of patients by chromatography-mass spectrometry were developed; these procedures can reveal the use of narcotics up to several months after ingestion (Task Group on the Analysis of Narcotic Drugs). A conference on the problems of teaching analytical chemistry was held in Tuapse. An interesting European textbook on analytical chemistry was published in English. A distinguishing feature of another textbook,

JOURNAL OF ANALYTICAL CHEMISTRY

Vol. 55

No. 3

2000

ANALYTICAL CHEMISTRY IN 1998 which was published in Spanish and English in 1998 and 1999, respectively, is that it does not include descriptions of analytical methods. The report of the Scientific Council on Analytical Chemistry of the Russian Academy of Sciences reflects the materials presented by the members of the Council and by leading institutions, and treated by the heads of the corresponding commissions of the Council. Of course, not all that was done in Russia was reflected in the report. Moreover, the heads of some commissions evaluated the material rather subjectively. In 1998, the Ministry of Science and Technologies developed the Program of scientific instrument making within the framework of which the design of several analytical instruments was supported. Professor Ern6 Pungor, a full member of the Hungarian Academy of Sciences, was elected as a honorary professor of the Moscow State University. The presentation of the Diploma and the Medal of Honorary Pro-

JOURNALOF ANALYTICALCHEMISTRY Vol. 55

299

fessor to Pungor was held in February 1999. Academician B.E Myasoedov became deputy chief scientific secretary of the Russian Academy of Sciences. Corresponding Member of the Russian Academy of Sciences L.A. Gribov was designated as deputy director of the Vernadsky Institute of Geochemistry and Analytical Chemistry and became a member of the Bureau of the Scientific Council. Unfortunately, we suffered heavy losses in 1998. N.M. Kuz'min died on July 20, and I.A. Gur'ev deceased on September 9, 1998. Estonian Professor J.L. Haldna, a former member of the Council, also died in 1998. Professor S.V. Lontsikh departed from life in Israel. N.E Losev passed away. In 1999, several anniversary celebrations were held: 275 years of the Russian Academy of Sciences, a 200th birthday ofA.S. Pushkin, and a 60th anniversary of the first All-Union Conference on Analytical Chemistry.

No. 3

2000