Review: mass spectrometry in Russia.

V.G. Zaikin and A.A. Sysoev, Eur. J. Mass Spectrom. 19, 399–452 (2013) Received: 21 October 2013 n Accepted: 6 December 2013 n Publication: 12 December 2013

399

EUROPEAN JOURNAL OF MASS SPECTROMETRY

Review

Mass spectrometry in Russia Vladimir G. Zaikina,* and Alexander A. Sysoevb a A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky prospect 29, 119991 Moscow, Russian Federation. E-mail: [email protected] b

National Research Nuclear University MEPhI, Kashirskoe Shosse 31, 115409 Moscow, Russian Federation

The present review covers the main research in the area of mass spectrometry from the 1990s which was about the same time as the Russian Federation emerged from the collapse of the Soviet Union (USSR). It consists of two main parts—application of mass spectrometry to chemistry and related fields and creation and development of mass spectrometric technique. Both traditional and comparatively new mass spectrometric methods were used to solve various problems in organic chemistry (reactivity of gas-phase ions, structure elucidation and problems of identification, quantitative and trace analysis, differentiation of stereoisomers, derivatization approaches etc.), biochemistry (proteomics and peptidomics, lipidomics), medical chemistry (mainly the search of biomarkers, pharmacology, doping control), environmental, petrochemistry, polymer chemistry, inorganic and physical chemistry, determination of natural isotope ratio etc. Although a lot of talented mass spectrometrists left Russia and moved abroad after the collapse of the Soviet Union, the vitality of the mass spectral community proved to be rather high, which allowed the continuation of new developments in the field of mass spectrometric instrumentation. They are devoted to improvements in traditional magnetic sector mass spectrometers and the development of new ion source types, to analysis and modification of quadrupole, time-of-flight (ToF) and ion cyclotron resonance (ICR) analyzers. The most important achievements are due to the creation of multi-reflecting ToF mass analyzers. Special attention was paid to the construction of compact mass spectrometers, particularly for space exploration, of combined instruments, such as ion mobility spectrometer/mass spectrometer and accelerating mass spectrometers. The comparatively young Russian Mass Spectrometry Society is working hard to consolidate the mass spectrometrists from Russia and foreign countries, to train young professionals on new appliances and regularly holds conferences on mass spectrometry. For ten years, a special journal Mass-spektrometria has published papers on all disciplines of mass spectrometry. Keywords: mass spectrometry in Russia, application to chemistry, application to biochemistry and medicine, mass spectral identification, mass spectra treatment, development of mass spectrometric equipment, multi-reflecting ToF analyzers, compact and combined instruments

Introduction The present review covers the main investigations in mass spectrometric areas beginning from the 1990s, almost from the same time as the Russian Federation emerged after the collapse of the Soviet Union (USSR). It is interesting that at that time, two powerful ionization methods—electrospray/ ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)—had been invented, which made mass spectrometry a unique analytical and experimental tool that, in ISSN: 1469-0667 doi: 10.1255/ejms.1248

fact, created the basis for such new sciences as proteomics, genomics, metabolomics, lipidomics, glycomics, petroleomics etc. Before turning to the mass spectrometric studies in Russia, we will briefly mention the most important advances made during the Soviet period. Development and production of mass spectrometric equipment in the USSR had a long foundation. The Soviet Union was one of the main countries where a number of © IM Publications LLP 2013 All rights reserved

400 Review: Mass Spectrometry in Russia

types of mass spectrometer for different applications had been developed and manufactured and a pleiad of scientists and engineers were involved in this field. The first mass spectrometric studies began in 1924 when Viktor Kondratiev, being young student and working in the laboratory headed by Nikolai Semenov (Nobel Prize laureate in chemistry, 1956) at the State Physiko-Technical Institute (later named by A.F. Ioffe) in Leningrad, constructed the first mass spectrometer in the USSR.1 At that time it was the third apparatus in the world [the first is known as Dempster’s mass spectrometer (1918) and the second one as Aston’s mass spectrograph (1919)]. Kondratiev mass spectrometer can be considered as the fourth one, taking into account Thomson’s parabola spectrograph (1910). Proper attention had not been paid to the creation of mass spectrometry equipment until the atomic project, within the scope of which the first mass instruments were built with the help of German specialists. The experience accumulated within the bounds of atomic project allowed wider application and instrumental development of mass spectrometric equipment. The scientists of the State Physiko-Technical Institute made a great contribution to the development of dynamic mass spectrometry. The principle of magnetic resonant mass spectrometery developed by Boris Mamyrin allowed the determination of trace amounts of 3H in the atmosphere and other gaseous samples.2 Boris Mamyrin created the first Russian time-of-flight (ToF) mass spectrometer in the earlier 1950s.3 This linear ToF instrument had low resolution owing to energy spread of ions generated in an ion source. To increase the resolution of ToF analyzers, Alikhanov4 theoretically justified and Mamyrin constructed reflectron, which is now a standard accepted by manufactures of ToF mass spectrometers all over the world. This invention was defended by a Soviet Inventor’s Certificate in 1967 and published in 1973.5 Mamyrin received the American Society for Mass Spectrometry Distinguished Contribution in Mass Spectrometry Award (2000) and Gold Medal of Russian Society for Mass Spectrometry (2005). The method for compensation of time aberrations at over focusing of ion packets and partial time focusing of ions by energies in axial-symmetric electric fields has been suggested by Alexander Sysoev and co-workers.6,7 It has been further improved by Poshenrider8 and later became the basis of multi-reflecting ToF mass spectrometers with sector axialsymmetric electric analyzers. The outstanding Russian scientist Lidiya Gall’ should be considered as an inventor of the electrospray/ionization (ESI) method that is now the most popular mass spectrometric instrument used in various fields of life sciences. This method called “Extraction of ions from solutions under atmospheric pressure” has been described and instrumentally designed9 in earlier works by J. Fenn, who received the Noble award for ESI method in 2002. Although the first articles of Gall’ and Fenn appeared in the same year (1984), Gall reported the first application of the method in 1982 and 1983 for the case of antibiotics and amino acids. However, Fenn’s main contribution

to ESI is its application to the analysis of large biomolecules and he was awarded the Nobel Prize with the wording “for their development of soft desorption ionization methods for mass spectrometric analyses of biological macromolecules”. Lidiya Gall’ has many other achievemnents for creation of Soviet and Russian mass spectrometric techniques (development of new ionization methods, participation in the construction of mass spectrometric devices etc.). She received the Gold medal of the Russian Society for Mass Spectrometry (2009). Georgii Tantsirev actually created a new mass spectrometric field—secondary ion mass spectrometry (SIMS) of organic compounds.10 This discipline deals with the interaction of fast ions (or atoms) with solid surfaces and the analysis of large polyatomic molecules. Later, he suggested the use of a glycerol matrix to dissolve an analyte. Georgii Tantsirev, Victor Tal’roze and Vladimir Raznikov were the first to combine a capillary chromatographic column with a mass spectrometer and suggested recording the chromatograms using two or more selected ions from mass spectra (in fact, the principle used further for selected ion monitoring). Igor’ Revelsky and his co-workers were the inventors of atmospheric pressure photoionization and photochemical ionization mass spectrometry.11 These methods generate only molecular or pseudomolecular ions and allow the analysis of complex mixtures without separation. They were accepted by many manufacturers of commercial instruments. Revelsky continues his successful investigations in the field of analytical mass spectrometry. For his achievements in the field of mass spectrometry, he received the Gold medal of the Russian Society for Mass Spectrometry (2011). Although the first orthogonal-injection ToF mass spectrometer was described in 1964 [G.J. O’Halloran, R.A. Fluegge, J.F. Betts and W.J. Everett, Technical Report prepared by the Bendix Corporation Research Laboratories Division, Southfield (Contract Nos AF33(616)-8374 and AF33(657)11018, A.F. Materials Laboratory Research and Technology Division, Air Force Systems Command) (1964)], only the works of Alexander Dodonov et al. rediscovered this invention and the instruments began to gain popularity. It should be noted that Dodonov could not receive the certificate in 1985 because the Institute of Patent Expertise of the USSR rejected his invention on the application of ToF mass spectrometer with orthogonal inlet and only in 1987 was the patent received. 12 Also note that the first investigations in the field of proteomics in Russia were performed with the aid of ESI mass spectrometers. A great contribution to the development and organization of Soviet mass spectrometry has been made by Victor Tal’roze, a famous Russian physical chemist. For many years he has headed the Commission of Mass Spectrometry at the Academy of Sciences. During investigation of ion–molecular reactions, he discovered (1952) the formation of methonium cation (CH5+)—one of the most reactive particles in chemical ionization mass spectrometry. For his contribution to the development of mass spectrometry, Victor Tal’rose received the International Mass Spectrometry Foundation Thomson Medal (2003).

V.G. Zaikin and A.A. Sysoev, Eur. J. Mass Spectrom. 19, 399–452 (2013) 401

Although during the Soviet period a significant achievement in the development and production of the domestic mass spectrometers was made, until the 1990s the country did not have sufficient economical and technical opportunities for the extensive continuation of this activity. As a result, a number of talented Russian scientists moved abroad, involved in the development of new mass spectral techniques in various companies and have achieved great success. We would like to mention some of them. Among these scientists is the particularly notable physicist, Alexander Makarov. Having moved to Peter Derrick’s group at the University of Warwick in England, he started his work on the Orbitrap mass analyzer. He joined HD Technologies which was acquired by Thermo Electron Corporation in 2000 and he provided outstanding results on the creation of the orbital trap as a new type of mass analyzer, that was the basis of the Orbitrap.13 This development led to the commercial release of the LTQ Orbitrap tandem mass spectrometer in 2005. Alexander Makarov now works at Thermo Fisher Scientific in Bremen (Germany). He has been a recipient of several awards for his research: the Heinrich-Emmanuel Merck award (2007), the Gold Medal of the Russian Society for Mass Spectrometry (2007), award of the American Society for Mass Spectrometry for The Distinguished Contribution in Mass Spectrometry (2008), the Curt Brunnee research award of the International Society for Mass Spectrometry (2009), the Science and Technology Award of the Human Proteome organization (2011) and the International Mass Spectrometry Foundation Thomson Medal (2012). It should be mentioned that some theoretical research leading to the creation of “Orbitrap” mass spectrometer have been carried out by Alexander Makarov in Russia.14 Roman Zubarev, in collaboration with Fred McLafferty, invented a method called electron capture dissociation (ECD) as efficient version of tandem mass spectrometry.15 The method involves the direct addition of low energy electrons to trapped gas-phase multi-protonated peptide ions and resulting polycation radicals can decompose in a specific ways. ECD allows accurate determination of not only amino acid sequence but also post-translational modifications. For a long time, the method was used only in combination with ion-cycotron resonance Fourier transform (ICR-FT) mass spectrometry but later it was included in ion trap systems. Roman Zubarev works now at Department of Medical Biochemistry and Biophysics, Karolinska Institutet (Sweden). In 2007, he was awarded the Biemann Medal that recognizes a significant achievement in basic or applied mass spectrometry. He has also been a recipient of Curt Brunnee research award of International Society for Mass Spectrometry (2006). Anatoly Verentchikov (MS Consulting, Montenegro) began his fruitful activity in mass spectrometry during the Soviet period, participating in the development of the first ESI mass spectrometer in Leningrad. At the beginning of the 1990s, he moved abroad (Canada, USA, Montenegro) where he continued his work in the development and commercialization of orthogonal injection ToF mass spectrometers with ESI ion

source. From the beginning of 2000, his main activity was directed towards the development of multi-reflecting ToF mass spectrometers.16 This work created the basis for commercial ToF mass spectrometers (resolution 100,000, speed of spectra recording 100 spectra s–1, ESI and electron ionization sources) produced by the LECO company that received the Gold Pittcon Medal in 2012. The Russian physicist Vyacheslav Artaev took part in the design of the instrument. Various interesting investigations are bering performed by Julia Laskin (Pacific Northwest National Laboratory, Richland, USA). Her most outstanding achievements lie in the study of fundamental aspects of activation and dissociation of complex molecular ions, soft-landing of mass selected ions on surfaces etc. She received the Biemann Medal that recognizes a significant achievement in basic or applied mass spectrometry (2008). Anzor Mikaia (National Institute of Standards and Technology, Gaithersburg, USA) makes a fundamental contribution to the development, improving the quality and expansion of the comprehensive NIST/EPA/NIH Mass Spectral Library that is most popular all over the world. Igor Kaltashov (University of Massachusetts Department of Chemistry, USA) is a famous scientist in the field of mass spectrometry-based study of architecture, dynamics and interaction of biomolecules. Andrej Shevchenko (Max Planck Institute of Molecular Cell Biology and Genetics, Germany) is a well-known scientist in the field of application of mass spectrometry to proteomics and lipidomics. Yury Tsybin (Institut des sciences et ingénierie chimiques, Lausanne, Switzerland) conducts efficient developments of new techniques for the characterization of peptides and proteins in mass spectrometry through ion cyclotron resonance (ICR). Victor Ryzhov (Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, USA) conducts research in the field of gas-phase ion chemistry and energetics, ion–molecule reactions and reactivity of radical ions. Natalia Tretyakova (Department of Medicinal Chemistry, University of Minnesota, USA) actively investigates the structural basis for promutagenic and anticancer activity of DNA-modifying agents with the aid of ESI-MS, cap HPLC/MS, MS/MS, and MALDI-ToF-MS. Unfortunately, we were not able to name other mass spectrometrists successfully working abroad and we apologize to them. The most well-known centers in Russia dealing with the development of mass spectral techniques and methodology as well as with extensive application of mass spectrometry are follows: Chemistry Department of M.V. Lomonosov Moscow State University (CD-LMSU, Moscow), Institute of Analytical Instrumentation, Russian Academy of Sciences (IAI RAS, St Petersburg), Institute of Energy Problems of Chemical Physics, Russian Academy of Sciences (IEPCPh RAS, Moscow), M.M. Schemyakin and Yu.A. Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences (IBOCh RAS, Moscow), A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences (TIPS RAS, Moscow), N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences


IOEC RAS with participation of Yurii Nekrasov. Researchers considered the ionization chamber (IC) of a mass spectrometer as a chemical reactor where bimolecular reactions (not involving ions) can occur, provided the corresponding reactants are introduced in the IC in sufficiently high amounts. Fullerenes (C60 and C70) were chosen as the main substrates that are capable of catching radical species. Most likely the observed reactions proceeded on the walls of the ion chamber which was held at a temperatures of 300–300oC. The reactions relate to homolytic ones since radicals are often formed under the energetic influence upon molecules in an IC. The developed method has been called a homolytic reactive mass spectrometry of fullerenes and was considered as a tool for prediction of the reactions of fullerenes in solution (or in solid state/phase). It has been shown that both C60 and C70 reacted with either the Scherer radical (perfluorodiisopropylethylmethyl, C9F19) or other fluorinated radicals in the IC of a mass spectrometer (the reaction being accompanied by hydrogen addition) and the ions for trifluoromethylation products were recorded in the mass spectra.27 Formation of poly(trifluoromethylated) fullerenes has been also detected when using Hg(CF3COO)2 as a source of CF3 radicals. It is interesting to note that heating the mixtures of the reagents under argon at 300–310°C also yielded trifluoromethylated fullerenes. 28 A number of organo- and organoelement mercurials has been also Organic and small bio-organic molecules tested.29 Correlation with solution reactions has been also found for some mercurial substrates. In other works, the Extensive mass spectrometric investigations of various homolytic reactive mass spectrometry of fullerenes has been organic and small bio-organic compounds, mainly with the investigated using ketones30,31 and aromatic aldehydes.32,33 In use of electron ionization (EI), began in the Soviet Union at the end of the 1950s. Such works, also involving other ionization the case of ketones RCOR1 the main products were due to the techniques, are still going on in Russia. addition of R and R1 radicals to the fullerenes with hydrogen For many years, one of the interesting investigations has been addition or loss. The same products were obtained in solution performed by Al’bert Lebedev and co-workers at CD-LMSU. under UV irradiation. They have been devoted to finding the correlations between In the course of a joint long-term project together with the gas-phase reactivity of some organic molecules under American scientists on the quality improvement and the mass spectrometric conditions and liquid phase reactions. extension of the National Institute of Standards and Technology/ These investigations have been directed to create rapid National Institute of Health/Environmental Protection Agency mass spectrometric methods for the prediction of particular (NIST/NIH/EPA) Mass Spectral Library, 34 a great number solution reactions. For example, such a correlation has been of various new derivatives have been synthesized and their found for EI-induced cyclization of thioamidomethyl pyridine electron ionization (EI) mass spectra have been measured ylides and isoquinoline ylides17 of dithiocarbamate derivatives at TIPS RAS under Vladimir Zaikin’s guidance. This project includes computer-assisted “manual” evaluation of every of polyhalopyridines,18 of ortho-cyclopropylphenylacetamides spectrum that requires a knowledge of many fragmentation and benzamides, 19,20 of N,N-dialkyldithiocarbamate and pathways. In this case, the recognition of new unexpected alkylxanthate derivatives of polyhalogenated pyridines,21 of EI-induced reactions, that could not be explained on the basis the substituted N-(ortho-cyclopropylphenyl)-N¢-aryl ureas and thioureas, 22 of 2-[2-pyrrolidin-1-yl and piperidin-1- of known mass spectral rules, may be particularly helpful. Examples of such unexpected fragmentations has been ylbenzilidene]malononitrile.23 It has been shown that chemical found in the analysis of EI mass spectra of secondary ionization and atmospheric pressure chemical ionization alcohol methoxyacetates.35 In collaboration with American provide a closer similarity with reactions in solution than EI in the case of cyclization of a-diazo-arylsulphonylaminoalkan- mass spectrometrists at NIST, a new kind of EI-induced 2-ones24 and N-(ortho-cyclopropylphenyl) arylamides.25 At “para-effect” has been discovered for a series of specially synthesized bis(perfluoroacyl) derivatives of o-, m- and the same time, EI mimics solution reactions of 2-acyl- and p-phenylenediamines,—hydroxybenzeneamines and 2-thioacylaminobenzylcyclopropanes better than ESI.26 mercaptobenzeneamines RCOX–C 6 H 4 –NHCOR (X = NH, A series of investigations demonstrating the potential of using an EI mass spectrometer as a tool for prognosis of liquid S, O; R = CF3, C2F5, C3F7). Only the para-isomers revealed or solid state chemical reactions has been accomplished in successive loss of a radical RCO.and a molecule RCN, leading (IOCh RAS, Moscow), Anti-Doping Center (ADC, Moscow), A.N. Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences (IOEC RAS, Moscow), N.N. Blokhin Russian Cancer Research Center, Russian Academy of Medical Sciences (RCRC RAMS), V.N. Orekhovich Institute of Biomedical Chemistry, Russian Academy of Medical Sciences (IBMCh RAMS), N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences (IBChPh RAS, Moscow), G.K. Skryabin Institute of Biochemistry and Physiology of Microorganisms, Russian Academy of Sciences (IBChPM RAS, Pushino), A.N. Severtsov Institute of Ecology and Evolution, Russian Academy of Sciences (IEE RAS, Moscow), Space Research Institute, Russian Academy of Sciences (SRI RAS), National Research Nuclear University MEPhI (MEPHI), Ryazan State Radio Technical University (RSRTU) Recently, in Novosibirsk, the Access Center of Siberian Branch of RAS “Mass Spectrometric Studies” was created where proteomic and metabolomic investigations are performed with the aid of HPLC/MS and MALDI-ToF MS. Mass spectrometric groups in St Petersburg, Yfa, Kazan’, Tomsk, Irkutsk, Ekaterinburg, Vladivostok should be also mentioned.

Organic chemistry


to very intense peaks in the spectra.36 In the other work,37 mono-, di- and trialkyl derivatives of “sulfabenzamide” (N-4-aminophenylsulfonylbenzamide) have been prepared and their EI mass spectra examined. It was found that the fragmentation of N-alkylsulfabenzamides (alkyl = CH 3 to n-C 5H 11) proceeds via a very specific rearrangement process giving rise to stable N-alkylphenylcyanide cations [RN+ = CC6H5]. The findings were confirmed by exact mass measurements, tandem mass spectrometry experiments and deuterium labeling. Investigations on the application of new gas reagents in chemical ionization mass spectrometry were accomplished by Oleg Chizhov and Valentin Kadentsev at IOCh RAS. The main attention has been paid to the study of gas-phase interaction of trimethylsilyl cation with various polyfunctional compounds,38 ethers and esters of cyclohexanediols, 39 various nitrocompounds40–42 and substituted monosaccharides.43,44 Later, tandem mass spectrometry has been used to study the behavior of derivatives in the estrane series under ESI conditions.45,46 For several decades, beginning from the Soviet period, investigations in the field of negative ion mass spectrometry have being performed at some institutes of the Bashkirian Branch of RAS in Ufa. These works, initiated by Viktor Khvostenko and Victor Mazunov, were directed at the investigation of negative ions generated from organic compounds through resonance electron capture and lasted for two decades. Note the papers devoted to the determination of electron affinity of carbonyl radicals,47 to the behavior of negative ions generated from derivatives of cyclopropyl urea,48 chlorinated propanes49 and some typical MALDI matrices through the capture of slow electrons.50 ESI and collision-induced dissociation have been used for detection of both the cations and anions in ionic liquids.51,52 The same methods allowed the formation of cluster ions as well as cation deprotonation and reduction in the case of diquat and paraquat to be observed.53 Lev Sidorov and co-workers at CD-LMSU have investigated some organic derivatives of fullerene by MALDI-ToF mass spectrometry including post-source decay technique. In the case of tert-butyl esters of fulleroprolines, which are promising reagents for the synthesis of fullerene-modified peptides, new unexpected double-caged bicycloadducts as admixtures have been discovered.54 Similar bicycloadducts, in which the fullerene cages are bound by two joined cycles were also observed in negative ion MALDI spectra of some products after synthesizing ethyl and tert-butyl esters of non-substituted fulleroproline. 55 For fullerene derivatives such as C 60(CF 2) n[C(COOEt) 2] m and C 60[CH(R)N(R¢)CHR²] n, mainly negative ion MALDI mass spectra have been recorded and they also enabled multi-caged fullerene derivatives to be identified.56

Organo-element compounds Analytical potentials of various conditions in ESI experiments have been shown by Yurii Nekrasov and co-workers at IOEC RAS, who used ferrocene (FcH), ferrocenium triiodide [FcH]+I3¯,

dimethylaminomethylferrocene FcCH2NMe2 and its trimethylammonium salt [FcCH2NMe3]+I¯ as examples.57 They investigated the behavior of these compounds under the conventional conditions of ESI (the analyte solution was subjected to spraying) and in two versions of desorption electrospray ionization (DESI), when the sprayed solvent bombarded the surface of solid or liquid analytes. In addition, the behavior of neutral compounds under ESI of vapors of the studied compounds in the gas phase (ESI_V) has been investigated. Using ferrocene and its dimethylaminomethyl derivative, it has been demonstrated that the detection limits for the compounds occurring in the gas phase were comparable within the order of magnitude with their detection limits under ESI and DESI conditions of solid and liquid samples. Thus, ESI should be considered as a universal method for study of a compound in any aggregation state, that is, solid, liquid and gas. Using ferrocenylalkyl azoles and deuterium-labeled experiments, the same authors have discovered new mechanisms of ion production in ESI called ‘‘activating protonation”.58,59 As has been shown earlier, these compounds under ESI conditions underwent oxidation, protonation, fragmentation and ferrocenylalkylation to form molecular ions [M]+•, protonated molecules [M + H]+, ferrocenylalkyl cations [FcCHR]+ and bisferrocenylalkyl azole cations [(FcCHR)2X]+, respectively. 60,61 On the basis of special experimental techniques (deuterated solvents, saturation of the ionic source of an ESI mass spectrometer by the vapors of deuterated and unlabeled solvents, the experiments under ‘‘inverse” ESI conditions when the solvent is subjected to electrospray in the presence of ferrocenylalkyl derivative vapors) and quantumchemical calculations, the scheme of the formation of these ions in a gas phase was suggested. In particular, it has been concluded that all mentioned ions are formed through the protonation stage at the expense of hydroxonium ions in a gas phase. Analogies between the reactivity of compounds in conditions of EI, ESI and acid catalysis were established.62 Note joint investigations performed at IOEC RAS and the Institute of Organic Chemistry (Ufa Research Center of RAS) on the application of negative ion mass spectrometry to organoelement compounds. One such work has been devoted to resonance capture of electrons to cyclopentadienyltricarbonylmanganese and -rhenium derivatives.63 It has been shown that successive decarbonylation was the main fragmentation process for precursor molecular anion-radicals. EI-induced fragmentation of various poly(triorganosilyl) alkanes and alkenes has been studied at TIPS RAS. 64,65 These compounds were obtained and characterized by pyrolysis-GC/MS.

Stereoisomers Study of stereoisomeric effects in mass spectra was one of the interesting fields arising from the very beginning of mass spectrometry in many countries. In the Soviet Union, such investigations with the aid of electron ionization mass spectrometry started in the middle of the 1960s at IBOCh RAS. The main objects of the study, performed with the participa-


tion of Vladimir Zaikin, were stereoisomeric carbocyclic and heterocyclic alcohols. Later, similar objects were subjected to analysis by chemical ionization (CI) and tandem mass spectrometry.66 For example, the pronounced stereospecificity of ion–molecule reactions with proton-donating gas-reagents has been observed in the series of 17-and 17a-epimeric 17a-alkyl-17a-hydroxy-d-homo-estra-1,3,5(10),8-tetraenes, 17-alkyl-17-hydroxy-estra-1,3,5(10)-trienes and their acetates.67 The observed quantitative differences between CI mass spectra of stereoisomers were explained by steric hindrance for the attack of proton-donating cations. Similar “approach control” was suggested to explain the stereospecificity of the protonation of tertiary alcohols in the transdecahydro-4-hydroxyquionoline series.68,69 It has been also demonstrated that CI mass spectrometry can be used for the determination of the configuration of the chiral C-4 center in 2,6-diaryl-substituted pyperidin-4-ol silyl ethers.70 For the investigation of stereospecificity of EI-induced fragmentation, methyl(trideuteromethyl) esters of substituted 6-phenylcyclohex-3-ene-carboxylic acids have been synthesized directly in a GC column of a GC/MS system by successive introduction of acids and CH3OH(CD3OH)/BF3-etherate.71 Interesting investigations on mass spectrometric discrimination of chiral compounds have been performed by joint collaboration of a number of institutes with the participation of Eugene Nikolaev. 72 Using enantiomeric dimethyl tartrates and direct probing, the vapors of the analyte at the atmospheric pressure conditions (corona discharge chemical ionization and surface thermoionization), it has been shown that both ionization methods produce cationized dimers and trimers of dimethyltartrate molecules with pronounced effects of chiral discrimination. In the case of corona discharge ionization, the chirality affected the formation of both H3O+ and H2O+ based adducts of dimers and trimers.

Derivatization Development of various derivatization approaches to mass spectrometric analysis of organic compounds was one of the important fields of investigation. As is known, this methodology is widely used in conjunction with various instrumental methods. It is particularly useful for the determination of polar, thermally unstable and slightly gas chromatographicallyseparated compounds by GC/MS when preliminary chemical modification significantly changes physical-chemical properties of an analyte or provide additional structural information from mass spectra. Precise quantification of trace and minor components frequently requires preliminary derivatization as well. In a number of Russian works, traditional derivatization reagents have been tested for analysis of various particularly important compounds. For instance, Igor’ Revelsky and co-workers at CD-LMSU have carried out a comparative investigation of derivatization of thermally unstable pharmaceutical substances with the use of various reagents—N,O-bis(trimethylsilyl)trifluoroacetamide, N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide,

pentafluorobenzyl bromide, isobutyl chloroformate, benzyltrimethylammonium hydroxide—for analysis by GC/MS. As a result, the most efficient reagents have been selected.73 This team of scientists has proposed a new approach to establishing the yield of derivatization reactions of difficultto-derivatize steroids (for example, 17-methyltestosterone).74 Reproducibility of EI mass spectra of trimethylsilyl and tertbutyl-dimethylsilyl derivatives of fatty acids, dicarboxylic acids, hydroxyacids, oxoacids and amino acids has been studied.75 Application of the same derivatives to the determination of amino acids by atmospheric pressure photochemical ionization (APPhCI) has also been investigated.76 Considerable attention to domestic research in the field of GC/MS has been paid to the development and testing of new reagents for derivatization. In particular, Vladimir Zaikin and his colleagues at TIPS RAS have presented cycloorganosilyl chlorides (cycloorganosilyl = trimethylene-, tetramethyleneand pentamethylenesilyl) as a new class of silylating reagents for the analysis of alcohols and acids by CG/MS.77,78 N-Cycloalkylcarbonyl (cycloalkyl = cyclopropyl to cyclohexyl) methyl esters have been shown to be useful derivatives for the analysis of amino acids.79 Among known reagents, Hušek reagents comprising of alkyl(aryl) chloroformate/alkanol mixtures have attracted special attention for GC/MS analysis of amino acids, small peptides and other amino and carboxyl group containing compounds. The main feature of the agents is that they allow chemical modification of analytes in water media and, hence, biological liquids. This has been clearly demonstrated by Igor’ Revelsky and his co-workers at the CD-LMSU in the course of comparison of amino acid derivatizations by silylation with BSTFA and MTBSTFA and reaction with isobutyl chloroformate/ isobutanol mixture giving rise to N(O,S)–isobutoxycarbonyl derivatives of amino acid isobutyl esters.80,81 The latter reaction appeared to be useful not only for identification but also for quantitation of amino acids, fatty acids and dicarboxylic acids in a single run with the aid of CI mass spectrometry.82 Similar reagents composed of various alkyl chloroformates and alkanols have been tested by Zaikin’s group in the investigation of amino acids and dipeptides by electron ionization (EI) and chemical ionization (CI) GC/MS and tandem mass spectrometry. Recommendations have been given for the use of the most appropriate composite reagents providing the differentiation of isomeric leucine and isoleucine both in an individual state83 and within dipeptides.84 In the majority of cases, chemical modification of the analytes under investigation is performed prior to introduction into a gas chromatograph by using reactions in solution. Chemical or physical–chemical conversion, however, may be accomplished directly in the inlet system of a mass spectrometer (on-line) by using gas-phase reactions. Such an approach developed by Anzor Mikaya and Vladimir Zaikin at TIPS RAS is less time-consuming and suitable for the determination of sub-microgram amounts of compounds. 85 This version of GC/MS methods called “reaction GC/MS” is predominantly a domestic development and is widely used in analytical


practice. The method involves hydrogenation, dehydrogenation, oxidation, exchange reactions that may be carried out directly in a flash heater of a chromatograph, in a gas-phase microreactor situated before a chromatographic column or between a column and a mass spectrometer. Derivatization can also be achieved directly in a gas chromatographic column.86 It should be noted that the use of soft-ionization mass spectrometry does not commonly require the additional derivatization of analytes. However, such an approach is useful for reliable solutions of qualitative and quantitative problems especially in proteomics. Russian developments in this field will be given below.

Trace and minor component analysis. Doping-control One of the most important areas of research in the field of GC/MS and LC/MS was to develop approaches that significantly increase the sensitivity of the method for the determination of minor components and trace amounts of substances. The most interesting investigations in this field were performed by Igor’ Revelsky and co-workers at CD LMSU and by the research group at ADC in Moscow. For example, a method involving the concentration of analytes and the analysis of the concentrates by GC/MS with negative ion chemical ionization has been proposed by the former research group for the screening of samples containing polychlorinated dibenzodioxines and biphenyls at the level n × 10–13–10–11% (depending on the substance) in the presence of chlorinated pesticides.87 In another case the detection limit was reduced by two to three orders owing to the analysis of the whole concentrate. In this case, entering the derivatization reagent into an analytical system was avoided owing to its replacement by inert solvent.88 A similar approach, involving exchange of the reagent mixture (pyridine and BSTFA) for tert-butylmethylether, has been used in the development of a highly sensitive method for analysis of steroids by gas chromatography/time-of-flight mass-spectrometry.89 The method included off-line sorption concentration of derivatives from large sample volume and injection of solvent-free products in a gas chromatograph. APPhCI has been recommended for highly sensitive determination of dialkyl phthalates in complex organic mixtures90 and esters of phosphoric and phosphonic acids.91 Very low detection limits for the latter compounds have been achieved by using GC/MS-MS.92 This scientific team has proposed a method for the determination of moderately volatile organic impurities in pharmaceutical tablet preparations and hairs based on a combination of solvent-free supercritical fluid extraction and GC/MS.93,94 Another developed approach involved a combination of capillary chromadistillation with EI mass spectrometry.95 It allowed highly sensitive determination of compounds with different volatility. For detection of trace amounts of organic compounds in solutions, direct analysis in real time (DART) mass spectrometry has also been recommended.96 A combination of high-performance liquid chromatography (HPLC) and high-resolution mass spectrometry (HRMS)

opens up entirely new opportunities. In particular, at ADC, this variant of the method has been realized with the aid of orbital ion trap (LTQ Orbitrap) that allowed elemental compositions of analytes on the basis of accurate mass measurement (error about 2 ppm) to be determined. Such an approach including atmospheric pressure photoionization (APPI) has been developed for ultra-trace detection and selective determination of compounds, including agents with antiestrogenic activity, b2 agonists, exogenous anabolic steroids and their metabolites in urine and other biological fluids for doping-control. Low detection limits (3 × 10–13–1.2 × 10–12 g) have been achieved in real samples.97–101 Researchers from ADC have developed an approach allowing the maximization of the number of compounds that can be determined with high sensitivity in a single run.102 It involves so-called “wrong-way-round ionization” in ESI for the simultaneous detection of multiple classes of doping substances (stimulants, diuretics, b2-agonists, b-blockers, antiestrogens, glucocorticosteroids and anabolic agents) without the need to switch the polarity. For the analysis, enzymatic hydrolysis, liquid–liquid extraction and detection by LC/orbitrap mass spectrometry were used. The thermal desorption/ambient chemical ionization method has been suggested by Eugene Nikolaev and co-workers at IECPh RAS for the detection of traces of organic explosives on cotton swabs or in particulate samples.103 It involves the transfer of ions into a mass spectrometer after thermal desorption and corona discharge chemical ionization in ambient air.

Problems of mass spectral identification As with other structural–analytic methods, mass spectrometry is successfully employed for identification of organic compounds. The latter operation means some kind of matching of the quantitative (here mass spectrometric) properties of an analyte and known compound. However, the only comparison of mass spectrometric characteristics is not always sufficient for this purpose (for example, to differentiate isomers or stereoisomers) and a more efficient procedure requires the use of additional information. Such problems and approaches to their solving in both chemical and mass spectrometric analysis have been described and discussed in a number of papers published by Boris Milman from D.I. Mendeleyev Institute for Metrology (St Petersburg).104–108 The author considers a “chemical identification as the combination of experimental and calculated procedures and intellectual operations followed by the decision-making of the analyst as expert and the search for similarity in at least two different properties/features between the analyte and one of the known chemical compounds”. One of the important elements of the identification procedure includes the selection of candidates for identification according to high values of their chemical literature citation and co-citation (papers, patents, Chemical Abstract Service, Internet etc.). For example, this data processing method is validated by counting citations and co-citations for detected impurities in pure n-hexane and


naphthalene, polycyclic aromatic hydrocarbons in waste gas tigations were concentrated in the Institute for Chemistry of and the compared analytes were pre-identified by GC/MS. Natural Products, USSR Academy of Sciences in Moscow Boris Milman has analyzed a library of MSn spectra acquired (presently, IBOCh RAS). Rather short synthetic and tryptic peptides, as well as depsipeptides and cyclodepsipeptides, mainly using ion trap (IT) and triple-quadrupole (QqQ) have been the main objects and conventional mass specinstruments and composed of numerous collections/sources trometry, utilizing EI, was employed. As a rule, all the inves(ionization methods: ESI, CI, APCI).109,110 He has demonstrated tigations included derivatization of peptides (N-acylation and that MS2 spectral libraries containing sufficiently numerous O-alkylation) in order to improve volatility and to enhance the different entries for each compound are effective for the structure information content gained from the mass spectra. identification of unknowns and suitable for use with different In many cases, EI mass spectra provided reliable information tandem mass spectrometers. regarding the primary structure of peptides. However, special Another efficient approach which is particularly helpful mass spectrometric methods (such as chemical ionization, in structure identification is based on the use of retention DADI, field desorption, plasma desorption, high resolution) indices (RI) in combination with mass spectrometric data. The have also been tested for solving structural problems in the GC/MS technique is now recognized as the most informative tool in structure elucidation of individual volatile or semi- peptide and protein series. As was noted in the Introduction, the first example of ESI volatile compounds. Its application is based on the availability mass spectrometers were described by Lidiya Gall’ et al. in of well organized mass spectral libraries (NIST/EPA/NIH 1984.9 The application of this magnetic-sector ESI instrument library is the most efficient and comprehensive). However, the problem arises when isomeric or stereoisomeric compounds to the analysis of peptide hydrolyzates and verification of the revealing qualitatively and quantitatively undistinguishable results of amino acid sequencing determined by the chemical EI mass spectra need to be identified. In such cases, the (Edman) method has recently been reported. 121,122 The use of additional data, mainly RI, is of particular help. The same instrument was employed by Mirgorodskaya et al. in approach of joining interpretation of mass spectrometric and St Petersburg for solving some problems of medical biology, gas chromatographic data has been extensively developed for example, for the determination of substrate specificity by Igor Zenkevich at the Chemical Research Institute of St of proteinases. 123 The authors have also used orthogonal Petersburg State University (St Petersburg).111 The suggested injection reflecting ToF mass spectrometer with an ESI source (invented by Alexander Dodonov in IEPCPh RAS) for peptide principle implies the evaluation of a set of RI increments for mass mapping.124,125 hypothetical replacement of structural fragments by simpler substituents, for example, methyl. In this case, not only initial The creation and extensive development of new mass compounds but their structural analogs can be identified. spectrometric methods (ESI, MALDI) stimulated the This approach has been employed for identification of the emergence of proteomics as an independent science the main chlorination products of aliphatic ketones,112,113 of chloro goal of which is to achieve the large-scale analysis of proteins by unambiguous identification and correct quantification of derivatives of dialkyl ethers, 114 of condensation products as many proteins as possible in a biological system (whole derived from aliphatic carbonyl compounds115,116 and the organism, tissue, cells, sub-cellular structures). At present, products of free-radical chlorination of cyclohexanes by GC/ proteomics researchers employ two main approaches to MS.117,118 In the latter case, the modified additive scheme for the study of proteins: (a) the “bottom-up” approach includes precalculation of RI for chloro cyclohexanes was based on the preliminary enzymatic hydrolysis of proteins and mass data for congeners with less numbers of chlorine atoms. The spectrometric analysis of resulting tryptic peptides; (b) the same approach can be recommended for identification of the products (isomers and congeners, including diastereomers) ”top-down” approach which includes mass spectrometric of other non-selective (regio and stereo) organic reactions. analysis of the whole protein with the use of its induced fragmentation by various collision methods. Until now, the The proposed algorithm of using both mass spectral data and former approach was the most distributed and involved mass RIs for the identification of unknown compounds has been fingerprinting or peptide mass mapping, accurate mass tags or expanded to organic halogenides.119 de novo peptide sequencing. The latter approach is the most distributed and involves various tandem mass spectrometric methods (for example, low- or high-energy collision-induced dissociation (CID), MALDI-MS/MS or MALDI-post-sourcedecay) and further application of sophisticated algorithms (for example, SEQUEST, MASCOT, PROFOUND) for identifying Oligopeptides and proteins, proteomics proteins from such peptide MS/MS data. Interesting investigations in this field are being carried out in Russia as In the former USSR, attempts to develop mass spectrometric well. methods for the structure determination of proteins have The fundamental cycle of studies of peptides in amphibia been undertaken practically from the beginning of organic and skin has been conducted by Al’bert Lebedev and Tat’yana bioorganic mass spectrometry. As was noted in the excellent historical review by Boris Rozynov,120 up to 1985 such inves- Samgina and their collaborators at CD-LMSU (Moscow)

Bioorganic chemistry and biochemistry


beginning in 2006.126–128 These peptides are known to be anti-microbial compounds and act as part of the amphibian immune defense and skin regulatory systems. Some of them are distinguished by the fact that they contain intramolecular disulfide bonds (“Rana box”) that hinder the direct mass spectrometric sequencing. To overcome the problem with mass spectrometric de novo sequencing of such peptides by MALDI-ToF/ToF, the preliminary opening of a disulfide cycle is particularly promising. Two derivatization approaches, namely, reduction with dithiothreitol followed by alkylation of free thiol groups by iodoacetamide and oxidation by performic acid to form sulpho-groups, have been comparatively elucidated.129,130 Using five natural peptides isolated from ranid skin secretions of European frog species of Rana ridibunda and Rana arvalis, the authors have concluded that both processes are relevant for the elucidation of the amino acid sequence inside the seven-member cystine ring at the C-terminus. However, the oxidation procedure led to notably higher abundances of b- and y-ions. In addition, one-step oxidation appeared to be simplier, reproducible and did not require additional purification. The other approach to de novo sequencing of peptides from R. ridibunda included oxidation of the disulfide bond and acylation of the terminal NH2 group. A combination of HPLC with ESI tandem mass spectrometry and ECD was used for manual interpretation of spectra.131 For the sequencing of skin secretion peptides from the brown frog Rana temporia (Zvenigorod, Russia), ICR-MS and two methods of fragmentation activation [collision-induced dissociation (CID) and ECD) have been employed. In the case of disulfide-cycle containing peptides, preliminary disulfide bond opening by reduction/alkylation or oxidation by performic acid have been used. As a result, the peptide profile in the particular frog skin has been obtained and ornithokinin (one of two known kinin receptors of non-mammals) has been discovered.132 The same mass spectrometric methods and derivatization approaches have been applied for the analysis of skin secretory peptidome of the European brown frog Rana arvalis inhabiting the Moscow region in Russia130,133 and European frog Rana lessonae.134 In the peptidome of the latter species, 49 peptides have been identified and the structure of 19 peptides have been elucidated for the first time. The same authors have recently demonstrated the technical advantage of a nano-HPLC-ESI-OrbiTrap instrument (as compared to FT-ICR-MS) which allowed them to obtain detailed and rich information on the composition of skin peptidomes of ranid frogs Rana temporia.135 Without using the preliminary derivatization but involving HCD and ETD spectra, 76 natural nontryptic peptides were identified in the skin secretion of the frogs. The sequences of brevinin 2Tf, temporin N and [Hyp3] temporin M and the discovery of 49 peptides belonging to bradykinin family were reported for the first time. One of the popular approaches used in qualitative and quantitative proteomics is based on preliminary derivatization of various end- or side chain functional groups in peptides and proteins followed by mass spectrometric analysis. In the case of disulfide cycle containing peptides, this methodology

is particularly efficient. As noted above, reductive opening of disulfide cycles gives rise to dithiol grouping that can be further modified to protect sulfhydrile groups. In addition to the abovementioned iodoacetamide, various N-arylmaleimides readily reacting with thiol groups in cycteine have been synthesized, tested and their influence on signal yields in MALDI mass spectra has been investigated.136 Later, the same authors137 extended a set of derivatizing agents for use in sequencing the long disulfide-containing peptides brevinins 1E and 2Ec. The latter peptides were reduced and alkylated with novel and known derivatizing maleimide agents and analyzed further by MS/MS (FT-ICR and Orbitrap mass spectrometers with the aid of higher-energy (HCD) collisionally induced dissociation or ECD/ETD techniques). It was shown that ECD/ETD and MS/MS fragmentation revealed complementary sequence information and HCD sufficiently enhanced y-ion formation. Novel tags [N-benzyl- and N-(2,6-dimethylphenyl)maleimide] along with known N-phenylmaleimide and iodoacetic acid showed high total sequence coverage for even long peptides (34 amino acid residues) if the combined ETD and HCD fragmentation was analyzed. It is interesting that reduction of the disulfide cycle with dithiothreithol followed by alkylation of the SH groups with the same N-arylmaleimides can be easily accomplished directly on the MALDI target.138 The need for application of a special derivatization has originated in mass spectrometric study of short peptides from the tryptophyllin family presenting the major portion of the European Tree frog Hyla arborea.139 The problem was in that b-ions, formed from monoprotonated peptides, undergo head-to-tail cyclization and opening of a formed ring can give rise to several linear structures, thus complicating de novo sequencing due to sequence scrambling. Even though no rearrangements were observed in FT-ICR-MS and MALDI-ToF/ ToF spectra, the latter were not suitable for sequencing due to the low sequence coverage. To overcome the problem, preliminary acetylation and sulfobenzoylation of an N-amino group or its transformation to 2,4,6-trimethylpyridinium by interaction with 2,4,6-trimethylpyrillium tetrafluoroborate were tested. Although all three reagents block scrambling and provide spectra better than the intact peptide, acetylation was the one particularly recommended because it is simple and suitable for mass spectrometric sequencing of short peptides by manual or automatic algorithms. Preliminary acetylation in conjunction with nano-ESI-FTICR mass spectrometry and ECD and CID techniques were successfully applied for de novo sequencing of peptides from the leaf frog Hyla arborea schelkownikowi.140 In this respect, a recent paper should be noted demonstrating that low-energy (CAD) collisionally induced fragmentation and HCD mass spectra of doubly protonated tryptic peptides revealed only negligible sequence scrambling due to b-ion cyclization.141 Recent work has demonstrated the potential of high‐ resolution tandem mass spectrometry in the structure elucidation of bradykinin‐related peptides from skin secretions of various Russian ranid frogs.142 Among a total of 44 bradykinins identified, a novel peptide named “lessonakinin”


and a group of its C‐terminally extended analogs were discovered. It is interesting that mass spectrometric peptide sequencing, developed in the present work, can support the cDNA cloning approach and make it more accurate. The same team of authors has recently shown that routine LC-ESI-MS/MS low-energy CID analysis of naturally long peptides with a terminal disulfide cycle revealed a new fragmentation pathway that is helpful in sequencing within the disulfide cycle.143 This fragmentation includes the opening of S–S loop via amide bond cleavage and becomes pronounced in the case of proton-deficient precursor ions, in the presence of basic residues at the C-terminus or acidic protons of Asp and Glu residues neighboring the “Rana box.” Interesting work has been performed on the investigation of stress influence on peptide composition of amphibian skin secretion with the aid of off-line HPLC separation and MALDI mass spectrometry express-profiling.144 For example, the contact of amphibian species with Micricoccus luteus and Staphyllococcus aureus saprotrophic bacteria has been found to stimulate the release of antimicrobial peptides and maintained the high bradykinin and related peptide levels. The same group of researchers has suggested a new method of mass spectral data analysis and visualization that presents a comprehensive picture of the peptide content including relative abundances and grouping into families.145 The method uses the 2D mass mapping that includes putting the molecular masses onto a 2D bubble plot, with the relative monoisotopic mass defect and isotopic shift being the axes and with the bubble area proportional to the peptide abundance. Each peptide is represented by a spot with its position based on elemental composition of the peptide, its color related to the particular family of the peptides and its size based on its quantity in the secretion. As a result, peptides belonging to the same family form a compact group on such a plot. The performance of the method has been demonstrated on the high-throughput analysis of skin secretion from three frogs.146 Interesting works have been carried out at CD-LMSU on identification of enzymes by MALDI-ToF mass spectrometry.147 A comparative analysis of spectra of low-molecular products resulting from the hydrolysis of native collagen I by collagenases of various classes has shown the presence of common ion peaks and a unique set of peaks characterizing each enzyme. Some important investigations in the field of proteomics have been accomplished at IBOKh RAS. One of the works was devoted to structure elucidation of a low-molecular-weight cationic protein that can bind human and rabbit immunoglobulins G and isolated from Yersinia pseudotuberculosis cells.148 Tryptic hydrolysis followed by MALDI-ToF mass spectrometry for proteolytic peptide profiling as well as the peptide fingerprint, molecular mass, N-terminal sequence and the use of bioinformatic resources allowed the protein to be identified as Y. pseudotuberculosis periplasmic chaperone Skp. The same approach, as well as cloning and sequencing cDNAs for the first time, encoding cysteine-rich proteins found in animal venom has been used for complete sequencing of such

proteins (consisting about 220 amino acid residues) from 30 snakes of the Viperinae sub-family.149 In collaboration with Taiwan scientists, complex methods (ESI-MS, MALDI-ToF-MS, tryptic hydrolysys, Edman degradation, circular dochroism) have been employed for structure elucidation of strong anticoagulating venom phospholipases A2 from the steppe viper Vipera ursinii renardi venom glands.150 Using ESI and MALDI mass spectrometry and bioinformatics engines, 323 peptides, which are the fragments of 79 proteins, have been isolated and identified from protoplasts of moss Physcomitrella patens.151 Important research in the field of proteomics have been performed at the Institute of Protein Research, Russian Academy of Sciences (Pushchino, Moscow Region). One of the theoretical works has demonstrated that the same fundamental parameter (namely the gas-phase basicity of backbone carbonyl groups) lies behind such disparate phenomena as the folding of proteins in solution and fragmentation of peptide cations in the gas phase. This parameter relates to the free energy of accepting a proton and it is responsible for protonation of polypeptides in electrospray ionization.152 Another paper has described a comparison of experimental and theoretical data on the number of sites of deuteration for 10 globular proteins. Experiments on H/D exchange with D 2O have been carried out using nanoelectrospray mass spectrometry.153 The latter method has also been used for characterization of flagellar filaments of Haloalcura marismortui, an archaeal species previously considered to be non-motile.154 In Russian investigations, attention was also paid to the detection of post-translationally modified proteins and to the determination of the sites and levels of such modifications. An example of such investigations was given by the work from IMBCh RAMS155 where post-translational modifications in the coat protein of potato virus X were studied by MALDI-ToF mass spectrometry. Detailed mass spectrometric study of the modified peptide and its fragments in combination with direct carbohydrate analysis data revealed that one monosaccharide residue (galactose or fucose) was linked to the acetylated serine residue in the first position. The same method, including the tandem version, has been applied to the determination of sequence and acylation character of the C-terminal anchoring segment from influenza viruses.156,157 Using a LC-MS/MS 7-Tesla LTQ-FT Ultra mass spectrometer equipped with a nano-ESI ion source, Eugene Nikolaev’s group has investigated light-induced changes in the distribution of phosphorylated and nitrated proteins in the thylakoid membrane of Arabidopsis thaliana leaves adapted to growth light and subsequently exposed to high light (HL).158 As a result, eight protein phosphorylation sites were identified in the photosystem and the phosphorylation level of seven of them was determined. In addition, the changes in the nitration level of 23 tyrosine residues in five photosystems were determined. With the aid of polyacrylamid gel electrophoresis, HPLC, MALDI ICR-mass spectrometry, several rarely expressed and stress induced chlorophyll binding proteins have been identified.


Changes in localization of early light induced protein families and formation of assembled/disassembled subcomplexes under light stress conditions have been discovered.159 In another work,160 126 tyrosine and 12 tryptophan nitration sites in 164 nitrated proteolytic peptides as well as 140 oxidation products of tyrosine, tryptophan, proline, phenylalanine and histidine residues have been identified in particular photosystems. Comparatively recently, derivatization and particularly stable isotope coding or “isotopic tagging” became an important tool in quantitative proteomics. Of course, the efforts to develop suitable derivatives for quantitative peptides determination by soft ionization mass spectrometry have been undertaken in Russia. For example, a novel mass spectrometry-based method has been suggested involving the selective modification of cysteine residues of proteins with N-phenylmaleimide containing light (D0) or heavy (D5) isotopes followed by the covalent enrichment of labeled peptides on a solid matrix. The latter process includes the modification of labeled peptides with hydrazine followed by reaction of the resulted hydrazones with the immobilized benzaldehyde.161 A known method of isotopic coding by hydrolysis of proteins with H218O, allowing the introduction of labels into carboxyl groups, has been suggested for absolute quantification of proteins and peptides in biological environments and kinetic studies of metabolism and enzyme activity.162 As was noted above, tryptic peptide mixtures are most frequently analyzed by HPLC/MS including tandem mode. Proteomic studies, in this case, require comparison of different experimental data. Identification of chromatographic peaks of the same peptide in different chromatograms is complicated if peptides are analyzed in different experiments because retention times of the same peptides would vary from one experiment to another due to inevitable differences in experimental conditions (type of chromatographic columns, changes in flow rates of a mobile phase or in a solvent concentration etc.). Eugene Nikolaev’s and Mikhail Gorshkov’s teams at IEPCPh RAS have developed the promising technologies for “shotgun” proteomics that was called Accurate Mass and Time (AMT) tag. The approach is based on the generation of a universal scale for the chromatography data using a multiple point normalization method. It provided a reliable method for selection of peaks that corresponded to the same peptides from chromatography/mass spectra for the subsequent alignment of retention times.163,164 The method can be applied to alignment of chromatograms that are obtained in different laboratories on various experimental equipments. In recent years, Mikhail Gorshkov and co-workers at IEPCPh RAS were developing an approach to sequence-dependent retention time prediction of peptides based on the concept of liquid chromatography at critical conditions (LCCC).165–168 Being applied to biopolymers (BioLCCC), this methodology, in combination with mass spectrometry, provides an efficient tool to solve problems wherein the protein sequencing is essential. Contrary to alternative additive models for retention time

prediction based on summation of the so-called “retention coefficients”, the BioLCCC approach takes into account the location of amino acids within the primary structure of a peptide, thus allowing the identification of the isomeric peptides having the same amino acid composition. Inversion of the order of peptide elution in reversed-phase liquid chromatography under changing separation conditions such as a gradient slope has also been considered.169 Qualitative and quantitative description of peptide elution order inversion has been demonstrated using a model of LCCC. The same team of scientists was developing the alternative methods for verifying the results of the mass spectrometric identification of peptides in shotgun proteomics database search.170,171 Three criteria were introduced for the verification of peptide identification: retention times of peptides, the mean number of missed tryptic cleavages per peptide and the difference between theoretical and experimentally measured peptide masses. In order to estimate the false discovery rate (FDR) for identified peptides, the same authors introduced an empirical approach that is based on the FDR-like functions of sets of peptide spectral matches (PSMs).172 All of these (based on three complementary sources of data: chromatography, mass spectrometry and sequences of identified peptides) have close values for equal-sized sets with the same FDR and depend monotonically on the FDR of a set. Recently, a set of reusable generic components was designed allowing accomplishment of a large variety of specialized tasks on the basis of popular “Pyteomics” providing efficient tools for rapid proteomics software development.173 A number of important methodological mass spectrometric research in the field of peptides and proteins has been performed in IBOCh RAS. For example, the valuable analytical method for monitoring of recombinant human insulin and maybe other recombinant proteins production has been developed.174 It included the high-performance separation micro-techniques [narrow-bore reversed-phase (RP)-HPLC, high-performance capillary electrophoresis (HPCE)] and MALDI-ToF mass spectrometry and enabled the unambiguous information about purity and primary structure of all intermediates to be gained. In another work,175 sensitive approaches have been developed for micro-level analysis of some unusual amino acids (phosphorylated and hydroxylated) as well as of some genetically non-encoded amino acids. The suggested scheme allowed their identification in the peptide and protein amino acid sequence by using narrow-bore column HPLC, HPCE, MALDI mass spectrometry and automatic protein gas-phase sequencing. In a recent paper,176 a method for preliminary fractionation of blood serum for use in subsequent analysis by MALDI-ToF mass spectrometry has been described. The purpose was to provide desorption of low-molecular weight (LMW) peptides from abundant blood proteins. The method included heating diluted blood serum to 98°C for 15 min, resulting in dissociation of LMW peptides from the most abundant blood proteins. Its application significantly increases the number of LMW peptides detected by MALDI-ToF mass spectrometry and offers a useful approach for the analysis


of blood serum to search of peptide biomarkers for various pathological processes.

Lipidomics In Russia there not too many works devoted to the application of mass spectrometry to lipidomics been carried out. Some are listed below. In the joint work of several institutions, ESI-MS has been suggested for quantitative analysis of prostaglandins and polyunsaturated fatty acids with carbon chain length C18– C22. 177 The validated method allowed the simultaneous analysis of the compounds in a nanomolar concentration range without preliminary chromatographic separation to be made. Rather interesting investigation in the field of lipidomics has been performed at the Pacific Institute of Bioorganic Chemistry RAS (Vladivostok).178 MALDI mass spectrometry in negative ion mode has been used for structure elucidation of outmost lipid layer of bacterial cells (marine bacterium Marinomonas vaga ATCC 27119T ). Three lipid species were detected, one of which contained only a single glucosamine moiety. Repeated cell cultivation in conjunction with the FT-ICR-MS techniques allowed the conclusion to be made that the cell mutation proceeded through shunting the biosynthesis pathway in the lipid moiety of the bacterial lipopolysaccharide. Some investigations have been performed on identification of the molecular species of different phospholipid classes (glycerophospholipids, sphingolipids) as well as individual molecular species of ceramides derived from human erithrocytes with the aid of HPLC-MS and HPLC-MS/MS.179,180 The presence of sphingonine, in addition to sphingosine as a unit of several molecular species, has been confirmed and unknown molecular fraction Cer24:2/S18 has been identified.

Medical chemistry Extremely high sensitivity, a possibility of combining with various separation techniques and of accurate quantitative measurements of biological compounds at molecular level are increasingly using mass spectrometry as a unique and powerful tool in medical sciences. The most important research is devoted to finding various biomarkers that, in perspective, can be used in daily clinical laboratory diagnostics. Two groups of scientists at RCRC RAMS and IBOCh RAS are heavily involved in searching for peptide and protein biomarkers of various diseases. The former group, headed by Valery Shevchenko, is making efforts to find biomarkers of cancer. No satisfactory plasma biomarkers had been discovered until the work of this group for the early detection and monitoring of the most frequently encountered lung cancer. The main goal of the study of the group was to establish a MALDI-ToF-MS based approach to obtain specific pattern of proteins expression in plasma at different stages of tumor development on the assumption that lung cancer modifies the plasma proteomic expressions

profile. Recently, they have presented a new unified and approved methodology for the search of tumor markers of the cancer, involving profiling the low-molecular plasma proteomes (1−20 kDa) of blood. The new approach includes three basic components: robotic pre-preparation of samples, MALDI-ToF-MS and bioinformatics software for mass spectral data processing. As a result of the research, peptides/proteins which can be used in future for detecting this pathology have been suggested.181 Continuing the work, the same authors have applied the pre-fractionation of EDTA plasma samples by using magnetic bead kits and ClinProTools bioinformatic software for statistically analyzing the MALDI-ToF mass spectra. Up to 441 peaks/spectrum have been detected in a mass range 1000–20,000 Da among which 33 proteins had statistically different expression levels and can be considered as potential biomarkers.182 Similar approaches have been used for the search of differential signs of squamous cell lung carcinoma. Profiling of blood plasma and bioinformatics tools allowed the selection of 15 mass spectral protein peaks that may potentially serve for the early diagnosis of the disease.183 To identify potential biomarkers of ovarian cancer, mass spectrometric proteome profiling of tumor pleural effusion (TPE) liquid fraction from patients has been performed. 184 Methodology of analysis of the TPE protein composition included removal of high-abundant proteins by affine chromatography, additional fractionation of the low-abundant proteins based on their lipophilicity and high-resolution mass spectrometric analysis. Application of several criteria for data analysis allowed the generation of a group of 26 proteins which are promising candidates for testing as ovarian cancer biomarkers. Mass spectrometric mapping has been applied to plasma proteome from patients with renal cell carcinoma (RCC).185 As a result, a total of 247 proteins were identified; the expression of 12 of these proteins increased and 14 proteins decreased on going from the controls to patients with Stages I–II and III–IV RCC. The authors concluded that among these 26 proteins, seven proteins belong to acute-phase ones, three proteins are associated with the intercellular matrix and they can be potential markers for RCC. A scientific group in the IBOCh RAS has applied MALDIToF-MS for the search of biomarkers of ovarian cancer. 186 Using reverse-phase (MB-HIC 8 and HB-HIC 18) weak cation exchange (MB-WCX) and metal affinity ClinProt magnetic beads, peptides and protein factions were isolated from human sera. Proteome profiling of sera from I–IV stage ovarian cancer patients and from healthy women has been made by allowing calculation of the best diagnostic models based on the Genetic Algorithm and Supervised Neural Network classifiers. Statistical mass spectrometry analysis of peak areas included with the diagnostic classifiers showed three mass spectral peaks distinctive to ovarian cancer and four peaks-for ovarian and colorectal cancer. Recently, the same authors performed similar MALDI-ToF-MS profiling of blood serum of patients with Guillain–Barre syndrome and chronic inflammatory demyelinating polyneuropathy in order


to identify potential biomarkers of autoimmune demyelinating polyneuropathies.187 Using the genetic algorithm and taught neural network, this group has created mathematical models that were able to distinguish groups of the MALDI mass spectrometric sample profiles in ovarian cancer from those in healthy women and patients with adenomyosis.188 A series of important proteomic investigations has been accomplished in the field of the pathogenesis of Alzheimer’s disease (AD). In these works, scientists, including Eugene Nikolaev, from a number of institutes (IBChPh RAS, IEPCPh RAS, IBMCh RAMS and V.A. Engelhardt Institute of Molecular Biology of the Russian Academy of Sciences) took place. 189–191 Main attention was paid to the investigation of the amyloid-b peptide (Ab) that plays a crucial role in the pathogenesis of AD. It has been shown that Asp7 isomerization is a standard posttranslational modification and isomerized Ab peptide is accumulated in AD brain lesions and is associated with AD progression. Asp7 Isomerization gives rise to significant conformational changes of Ab and these two isoforms can be differentiated by using tandem mass spectrometry or ICR-FT-MS. Because the isoAsp 7-containing isomer (isoAb) is assumed to be a potential biomarker of AD that can be identified in the blood, a mass spectrometric method for quantitative determination of the ratio of normal and isomerized Ab fragments 1–16 in their binary mixtures was tested. In addition, with the aid of ESI-MS it has been shown that Asp7 isomerization gives rise to a new function of the Ab zinc-binding domain: namely, its ability to oligomerize upon interactions with zinc ions. Joint investigation, performed at N.M. Emanuel Institute of Biochemical Physics of RAS and other institutes, involved LC/MS for quantitative analysis of lipids extracted from blood plasma of patients with Alzheimer’s disease.192 It was shown that medical treatment with rivastigmine (exelon) and memantin resulted in similar changes in phospholipid spectra of blood plasma. The method allowed the detection of the alteration of each molecular species of different lipids during medical treatment. A group of scientists from the same institute has accomplished a cycle of investigations on gaining information about peptide and protein contents in various biological fluids (such as urine, blood, exhaled breath, tear). The main idea was to search for protein biomarkers of early stages of various diseases. For identification of human urinary proteins and peptides, a method has been developed that was based on the accurate mass and time tag (AMT) and does not use tandem mass spectrometry.193 A database of AMT tags containing more than 1381 AMT tags of peptides has recently been constructed. In addition, software for database filing with AMT tags, normalizing the chromatograms, database application for identification and quantification of proteins and peptides has been developed. This approach has recently been extended by the additional involvement of an economical procedure of triptic peptide labeling with isotope 18O by hydrolysis with the aid of heavy

water H 2 18 O. 194 The latter approach has been combined with AMT tags for quantification of peptides in human urine proteome. Interesting work with the use of LC/FT-ICR-MS has been performed on the comparative investigation of the urine protein compositions for six Russian cosmonauts (male, aged 35–51) having long flight missions (between 169 and 199 days) at the International Space Station.195 Preliminary cleaning and concentration of proteins were accomplished with the aid of MB-HICC8 magnetic particles. The method of precise mass markers and retention times was also used and interpretation of MS2 spectra of peptides was based on the Mascot search system. In other work, the parameters of urine sex steroid profiles, along with quantification of a number of endogenous steroids and their metabolites in healthy human urine (volunteers during isolation in a pressurized compartment), have been investigated by GC using mass-selective detection.196 The dependence of the healthy human profile parameters of urine steroids and their individual and group variability on vital activity factors (diet, water consumption, physical activity, etc.) has been found. The main attention has focused on technologies for the direct profiling of serum samples using magnetic beads with different functional surfaces and microchromatographic C18 zip-tips.197 Another investigation performed in IBChPh RAS, has shown that mass spectrometry offers new possibilities for the proteomic analysis of exhaled breath condensate (EBC) as a simple non-invasive method of diagnosing respiratory diseases. 198 This method can be an alternative to the traditional endoscopic method and includes trypsinolysis of concentrated protein mixture, analysis of peptides by nanoflow HPLC-MS/MS with a 7-Tesla Finnigan LTQ-FT mass spectrometer and suitable bioinformatics. It was found that major proteins in EBC were cytoskeletal keratins (mostly exogenous components of exhaled air).199 The suggested procedure of proteome monitoring can allow one to look for biomarkers of different disease states. In particular, this procedure has been used for EBC analysis of a patient with lung dystrophy at different times before and after bilateral lung transplantation. Qualitative protein composition of EBC samples obtained during the first month correlates with the clinical data on the acceptance of the transplanted lungs (allograft).200 The joint work of several institutions with Eugene Nikolaev’s participation has been devoted to determination of the hepatitis C virus (HCV) genotype from HCV-positive blood sera or plasma.201 The developed method involved minisequencing followed by MALDI-ToF mass spectrometry for registering the particles of the expected molecular weights. The method for HCV RNA typing can be efficiently used to discriminate the major HCV genotypes. A quite promising trend in the use of isotope ratio mass spectrometry for the diagnosis of various diseases was demonstrated by Anatoly Zyakun at IBChPM RAS. For example, the use of the labeled 13C-glucose breath test based


on the feeding of safe doses of labeled glucose, followed by measurement of the content of the 13C-label in exhaled CO 2 enabled the discovery of new quantitative diagnostic criteria characterising the utilization of glucose in patients with insulin-independent diabetes mellitus.202 A similar approach has been developed for highly sensitive non-invasive diagnostics of Helicobacter pylori, the most frequent human infection. Detection of urease activity and, hence, the presence of Helicobacter pylori in humans, is based upon measurement of the elevated 13C isotope content in exhaled CO 2 after administration of 13C-urea.203 Work carried out where mass spectrometry has been used for controlling the amount of inhalation anesthetics sevoflurane in the patient breathing circuit of an inhalation anesthesia machine should be noted.204 Time dependence of the concentration of the anesthetic gas to different period of anesthesia has been demonstrated. Mass spectrometry has also been suggested for real-time non-invasive control of concentrations of intravenous hypnotic propofol in blood by its quantification in exhaled air during the course of complex anesthesia.205

Pharmacology, drugs and metabolites A number of scientific groups in Russia have tested mass spectrometric approaches to solving various problems of pharmacology, pharmacokinetics, drug and metabolite analysis. The traditional GC/MS method combined with preliminary derivatization has been employed for analysis of active substances and impurities in pharmaceutical substances. However, the possibilities of using DART mass spectrometry 206,207 and DESI 208 for the same purposes have also been investigated. On the basis of ESI-MS, a highly sensitive method has been developed that allows quantitative determination of antiarrhythmic drugs in blood plasma without preliminary chromatographic separation.209 A combination of HPLC and tandem MS has opened up great prospects for rapid determination of metabolites of drugs in vitro and such techniques have been developed in Russia. For example, one investigation has been performed on a ESI-triple quad mass spectrometer permitting multiple reaction monitoring to be used.210 It has been demonstrated that metabolites formed upon standing the particular drugs (such as diclofenac, omeprazole and dextromethorphane) with microsomal proteins or recombinant cytochromes can be determined at qualitative and quantitative levels. In another paper, it has been shown that HPLC/MS was more efficient than GC/MS in the investigation of metabolites of synthetic cannabinoid JWH–018 as a part of the smoking mixture. 211,212 The former method allowed the detection of a greater number of metabolites the principal of which contained a hydroxyl group in the indole ring. In other works, GC/MS method hasproved to be very efficient for

the study of pharmacokinetics and metabolism of various anestetics.213,214

Environmental In Russian research, much attention is paid to environmental objects. A lot of work has been done using GC/MS. Al’bert Lebedev and co-workers at CD-LMSU have investigated pollutants in various objects near Lake Baikal which is considered to be the largest reservoir of fresh natural water in the world. As a result of qualitative and quantitative analysis of sediments, phytoplankton, zooplankton, sponges, aquatic plants, algae, muscles of various fish species and birds’ eggs, more than 40 individual organic pollutants (polycyclic aromatic hydrocarbons, phenols, organochlorine compounds) have been discovered. The results showed that there was pronounced bioaccumulation of persistent organochlorine compounds along the trophic chain, leading to substantial residues of organochlorine compounds in seals.215,216 Taking into account the high metabollic rate of certain of these compounds in birds, the main route into higher trophic levels has been proposed. GC/MS and ICP-MS methods have been used by the same group for monitoring various organic ecotoxicants (petroleum hydrocarbons, organic acids and alcohols, phthalates and phenols ) and metals in snow collected near the Kostomuksha iron factory (Karelia, Russia),217 in snow of urban and rural Russia and Finland 218 and in snow along the perimeter (109 km) of the Moscow belt road.219 Recently, a novel simplified sample preparation for quantitative analysis of polycyclic aromatic hydrocarbons (PAH) in water samples by GC/MS was proposed.220 The important feature of the method was the use of a Pegasus GC-HRT instrument operating in high resolution mode (25,000). The method requires just 1 mL of water and 1 mL of dichloromethane and provides the detection limits of PAH with the use of high-resolution GC/MS of about 1 µg L–1, while the limits of quantification is 10 µg L–1. All these limits correspond to those for the standard 8270 method of the US Environmental Protection Agency. Special works on detection and structure determination of various polysulfides as environmental organic pollutants from sediment samples from the Eastern Gulf of Finland have been accomplished in Saint-Petersburg Center of Ecological Safety Russian Academy of Sciences (St Petersburg).221–223 In these studies, a combination of GC with low- and high-resolution mass spectrometry were employed. For qualitative and quantitative analysis of ecologically important compounds, high performance two-dimensional GC × GC/MS was efficiently applied. The method has found wide application in studies conducted at the Chemistry Department of Moscow State University under the guidance of Al’bert Lebedev. A striking example of the effectiveness of the method is the detailed investigation of the products of water chlorination of diesel fuel under conditions approaching real processes of disinfection during water treatment.224,225 More than 1500 compounds have been identified and it has


been shown that only aromatic compounds were subjected to chlorination. Particularly important are the investigations performed by Efim Brodskii et al. at IEE RAS on the determination of trace amounts of various pollutants.226 Special attention has been paid to polychlorinated dibenzo-p-dioxines, dibenzofuranes, biphenyls (PCB) and chlorinated pesticides. Reliable determination of trace concentrations of such compounds, the monitoring of which must be carried out in accordance with the Stockholm Convention, requires high sensitivity and selectivity of the methods used. The most efficient method using GC/high-resolution MS providing the highest sensitivity and selectivity with the use of isotope-labeled standards has been developed. The principal advantage of the method compared with the combination of GC/low resolution MS is that it allows one to separately detect isobaric ions with the same mass but different elemental composition. One of the works has demonstrated that the procedure allows the determination in one injection the dioxin-like and indicator PCBs and other chloro‑ and bromo-containing pesticides and an increase in the reliability of rutine analysis.227 The same methodology has been used for the determination of polychlorinated dibenzo-p-dioxines, dibenzofuranes and PCBs in Russian Baltic fish228 and in Moscow soil.229 One of the widely distributed and dangerous pollutions is due to spills of oil and petroleum products. They appear in soil, water and atmosphere as a result of oil spills during petroleum production, fuel transportation and storage etc. Identification of the sources of such pollutions is a very important task. Efim Brodskii et al. have extensively used GC/MS for the detection of oil spill residue in stream sediments in the area of emergency mazut overflow from industrial enterprise.230,231 The employed complex method adopted the peaks of n-alkanes, the ratio between n-alkanes with even and odd numbers of carbon atoms, the peaks of biomarkers (isoprenanes, steranes, triterpanes etc.), the predominance of methyl- and alkyl-substituted mono-, biand polynuclear aromatic hydrocarbons over unsubstituted aromatic hydrocarbons and other features. Other types of ecologically significant compounds to be detected and determined in various matrices are warfare agents, toxic and mutagenic substances, their metabolits and transformation products.232 Useful analytical methods using HPLC/MS have been developed at CD-LMSU for the determination of nerve agent markers233 and asymmetrical dimethylhydrazine transformation products with low detection limits and high selectivity.234 Of special interest is the use of isotope ratio mass spectrometry in environmental studies. One such work, performed by Anatolii Zyakun et al., concerned the biogeochemical studies of bacterial methanogenesis and methane oxidation processes occurring at a dump of solid domestic waste.235 On the basis of quantitative and isotopic characteristics of the carbon from methane and carbon dioxide, the quality of methane released into the atmosphere each year in the particular region of Russia has been determined.

Petroleum chemistry During the Soviet period, oil component compounds were the first organic objects subjected to mass spectrometry investigation. Two famous scientists—Ada Polyakova and Ryurik Khmel’nitskii—were the first to have been involved in the work. Their most important achievements concerned the development of mass spectrometric structure-group analysis of oil compounds and the products of petroleum treatment. Both low-resolution and high-resolution mass spectra were used for this purpose. Recently, Efim Brodskii and co-workers at IEE RAS suggested new representation of the results of such analysis on the basis of specific treatment of GC/MS data.236 Specific representation of mass spectra of complex mixtures as a table of 14 homologous raw materials allows the selection of ion clusters which are characteristic of compound types. On the mass chromatograms of homologous ion series, these ion clusters form peculiar three-dimensional chromatographic peaks (homologous raw vs number of carbon atoms vs intensity). Recent work performed by Eugene Nikolaev et al. at IEPCPh RAS and IBChPh RAS should be considered as the first Russian investigation in the field of new science petroleomics. The work was devoted to a detailed analysis of heteroatomic compounds in recently discovered very young oil (about 50 years old) with the aid of FT-ICR-MS combined with an ESI source.237 Using Kendrick mass defect, main homologous classes of sulfurand oxygen-containing compounds in the volcanic oil were identified. Comparative analysis of the results with the aid of a Krevelen diagram showed that the oil possesses low amounts of oxygenated compounds and a large amount of unsaturation. On the basis of the diagram, the authors concluded that the oil is of bioorganic origin, most likely from lipid-containing raw materials.

Macromolecules Application of mass spectrometry to the investigation and analysis of polymers and plastics in the former USSR began almost with the appearance of organic mass spectrometry. The majority of mass spectrometric works included preliminary off-line degradation of macromolecules to low-molecular weight oligomers mainly by pyrolysis. Thermal degradation of polymers, desorption of additives and volatile impurities directly in a mass spectrometric device (pyrolysis-MS) have also been developed. These approaches are still used. For example, atactic polypropylene was recently investigated by using a combination of incomplete off-line thermal-oxidative destruction and GC/MS in order to develop useful components for new composite materials.238 At the beginning of 1990s, Zaikin and his colleagues at TIPS RAS have started extensive investigation of a potential of on-line pyrolysis-GC/MS (Py-GC/MS) for the determination of polymer structures. Using this combined method, mass


spectrometric structure elucidation and gas chromatographic separation and quantification of pyrolysis products are achieved. Much attention has been focused on the determination of microstructure (unit sequence distribution, branching, differentiation of statistics, alternating, random, block and block-random co-polymers, end-group analysis, character of joining of monomer units etc.).239 For the determination of unit sequence distribution in co-polymers, the yields of dimeric, trimeric and other pyrolysis products can normally be used. For instance, only dimeric products have been involved in the case of vinylcyclohexane/ styrene co-polymers. 240,241 Dimeric products comprised various dimers which are formed from Ziegler–Natta catalysis of vinylcyclohexane, polystyrene and hybrid dimers whose structures were established on the basis of EI mass spectrometry. Chromatographic peak areas of respective dimeric products and first order chain Markov’s theory have been employed for calculations. Determination of unit sequence distributions in butadiene(BD)/isoprene (IP) co-polymers by Py-GC/MS was based on the analysis of trimeric pyrolysis products.242,243 Monitoring of molecular ions for all possible combinations of BD and IP in trimers allowed the registration of chromatographic peaks whose areas were proportional to concentrations of corresponding triads. Py-GC/MS has also been employed for differentiation of random and random-block copolymers of ethylene/ vinylcyclohexane prepared in different ways. 244,245 It was shown that the copolymers prepared using Ziegler–Natta catalysts were random whereas copolymers obtained under non-stationary conditions contained blocks of vinylcyclohexane. It has been demonstrated that Py-GC/MS allows the distinction of polyvinylcyclohexane samples prepared using different catalytic systems and the estimation of content of “head-totail” and “head-to-head” units.246 Later, Zaikin and Borisov at TIPS RAS began new research on the application of MALDI-ToF-MS to synthetic oligomers and polymers. For example, co-polyamides specially synthesized from aliphatic diamines (1,3-propanediamine and 1,4-butanediamine) and dichlorides of aliphatic carboxylic acids (adipic and sebacic acid dichlorides) have been characterized by this method. 247 The presence of NH2-NH2, NH2-COOH or COOH-COOH end groups in individual oligomers and the absence of cyclic structures have been proved. The composition of oligomers have been determined and the relative reactivities of homologous co-monomers in polycondensation reaction have been estimated. It is well-known that ordinary MALDI-ToF-MS allows recording of only peaks for protonated, deprotonated or cationized molecules. Such peaks are suitable for the determination of molecular-weight distribution or the sum mass of end groups but they provide limited information regarding the structure of the macromolecules. Only the use of tandem mass spectrometry (CID or PSD) allows some structural information to be deduced. To increase the efficiency of the methods, derivatization of polymers may be

helpful. Zaikin and Borisov have suggested the application of simple derivatization (silylation, acylation, alkylation) of functional groups that has rarely been applied to the analysis of polymers and oligomers by MALDI-ToF-MS. It has been shown that silylation of silsesquioxanes allowed enumeration of hydroxyl groups in each individual oligomer and, hence, differentiation of “ladder”-type and 3D-type structures to be made.248,249 Preliminary silylation by BSTFA and acylation by capryloyl chloride followed by MALDI-ToF-MS have been shown to be efficient method for the determination of the number of end hydroxyl groups and the distinction of cyclic and linear dehydration products among minor components in poly(alkylene) glycols.250 An approach to the determination of number of primary amine groups in amine-containing polymers involving derivatization with carbonyl compounds to form Schiff bases followed by MALDI-ToF-MS has been suggested. Derivatization of polyethyleneimine with 2,3-dihydroxybenzaldehyde and the use of DHB as matrix appeared to be the most efficient. The suggested approach seems to be the only tool for the determination of a number of NH2 groups in branched polyethyleneimine molecules at the molecular level.251 For structure characterization and molecular weight distribution of polyethyelenes containing terminal iodine atom, GC/MS and MALDI-MS have recently been employed252,253 The latter method was involved after preliminary derivatization of substrates by triarylphosphine, trialkylamine or N-heteroarenes to form covalently bonded charge. Various aspects of derivatization of polymers with hydrolytically labile bonds and “matrix effects” have been investigated.254–256 Scope and limitations of derivatization principles for the investigation of polymers by MALDI-ToF-MS and other “soft” ionization techniques have recently been reviewed.257

Physical chemistry Application of mass spectrometry to solving various physical-chemical problems (thermochemistry, kinetics, mechanisms etc) in reactivity of gas phase organic and inorganic ions and related fields had a place in domestic investigations. For example, using photoionization mass spectrometry, Vyacheslav Takhistov and co-workers at the Centre of Ecological Safety of the Russian Academy of Sciences (St Petersburg) have measured ionization and appearance energies and determined enthalpy of formation of a large number of ions generated from polysubstituted cyclopropenes.258,259 A useful approach to the analysis of H/D exchange kinetics of active hydrogen atoms in polyfunctional compounds for reactions in both solution and gas phase has been suggested by Valery Raznikov and co-workers at IEPCPh RAS (Branch) in Chernogolovka (Moscow Region, Russia).260 It was based on the monitoring of mass spectra of biomolecules during exchange reactions and estimating the exchange probabilities for each H-atom at a fixed time. Another team from the same Institute has studied the H/D-exchange reaction kinetics


in polypeptide molecules by using D2O or ND3 and a highresolution orthogonal time-of-flight mass spectrometer261 or the segmented RF-quadrupole as an ion–molecule reactor.262 A principal possibility to distinguish different mobile H-atoms in peptides using a statistical approach and reaction rates has been shown. The scientific team of Lev Sidorov at CD-LMSU has accomplished a lot of measurements on thermodynamic properties of inorganic compounds. Using Knudsen cell mass spectrometry and ion–molecule electron exchange reactions, electron affinity (EA) values for fullerene derivatives С60(CF3)10 and the S6 isomer of C60(CF3)12 as well as for C60(CF3)6,8,10 were estimated.263–265 The same values were also determined experimentally for higher fullerenes and metallofullerenes. 266–269 A similar experimental technique has been applied to the determination of saturated vapor pressure and sublimation enthalpy for a number of unsubstituted and fluorinated fullerenes,270,271 for calculation of EA values for various inorganic compounds and the heats of formation of respective anions (see, for example, References 272–274).

Statistical analysis, databases, treatment of mass spectral data Russian scientists actively participate in the development of mass spectral databases in the application of various statistical approaches to the identification of organic compounds by mass spectrometry, to the prediction of mass spectra and to efficient treatment of chromatography/mass spectrometry data. Since 1994, Zaikin and his co-workers have been involved in the process of improving and expanding an EI mass spectral library, prepared by the National Institute of Standards and Technology (Gaithersburg, USA).34 To date, the work is continuing to improve the quality of the NIST library by computer-assisted “manual” evaluation of spectrum-by-spectrum. In addition, a lot of EI mass spectra of newly synthesized compounds and derivatives of important compounds as well as their retention indexes are measured and added into the NIST/EPA/NIH Mass Spectral Library (last version NIST 2011). Among the available software for chromatography/mass spectrometry data processing, software AMDIS, supplied with mass spectral database NIST (last version NIST 2011), is often used in mass spectrometric practice in Russia. It is particularly useful when analyzing the micro and trace amounts of compounds. However, AMDIS software also appeared to be useful for the analysis of complex mixtures of Fischer–Tropsch synthesis, allowing the automatic and semi-automatic identification of various hydrocarbon types, including co-eluted compounds, and the determination of retention indices and concentrations to be made.275

Some interesting statistical approaches to identification and treatment of mass spectral data have been suggested by Igor’ Revelsky et al. at CD-LMSU. For example, a method for the extraction of “pure” mass spectra from chromatographically co-eluted compounds of a mixture has recently been suggested.276 The method of main components allows the extraction of spectra at chromatographic peak resolution less than 0.05. Resulting mass spectra provide reliable identification by computerized searching in available mass spectral libraries. In another work,277 the possibility of identifying unknowns on the basis of comparison of experimental EI mass spectra for unknown compounds with those simulated by Mass Frontier software has been shown. Structure candidates were ranked according to “similarity measure” of their simulated and experimental mass spectra. Principal component analysis has been applied for distinguishing between isomeric o-, mand p-xylenes and ethylbenzene which have very close EI mass spectra.278 The developed new mathematical approach based on using principal component analysis has been suggested for unbiased and reliable comparison of EI mass spectra recorded under identical experimental conditions. Applicability of the method has been demonstrated using the examples of isomeric xylenols. It has been underlined that the approach allows increasing identification reliability of traces of organic compounds with the aid of EI mass spectrometry.279 Yurii Nekrasov and co-workers at IOEC RAN have suggested a general approach to revealing correlations between the structure of molecules and their gas-phase reactivity under EI conditions based on the use of generalized structural and mass spectral features.280–283 The characteristics were obtained using information theory, molecular graphs and absolute reaction rates. Information topological indices of molecular graphs were used as generalized structural characteristics of molecules. The gas-phase process of fragmentation of molecules under EI was accepted as a general reaction. Using various organic and organometallic compounds, linear correlations between the information indices of the mass spectra and the information topological indices of the appropriate molecular graphs or electronic parameters of molecules have been found. Special investigations have been performed in order to predict EI mass spectra of new highly toxic compounds in the series of O-alkylalkylfluorophosphonates and O-alkyl-N,Ndialkylphosphoramido cyanides subjected to control under the Chemical Weapons Convention.284,285 EI mass spectra of the former group, for example, may be divided into two sub-spectra (phosphorus containing ions and olefinic ions) and the spectrum of an individual compound is considered as a sum of an generalized spectral image of these sub-groups. Valery Raznikov and co-workers at IEPCPh RAS (Branch) in Chernogolovka (Moscow Region, Russia) have suggested an approach to reliable and fast measurement of m/z ratios and intensities of overlapping mass spectral peaks for sector field and time-of-flight mass spectrometers. The method of quasispline deconvolution was involved in the search, subtraction and correction of individual peak contributions.286,287 Further


development of the approach has led to its application for the analysis of multiply-charged ions generated from biopolymers under ESI conditions.288–290

Isotopic (isotope ratio) mass spectrometry During the last decades, the natural isotopic signature (ratios C/12C, 15N/14N, 34S/32S, 2H/1H) became more and more used in various studies. This was stimulated by the creation of highly precise mass spectrometric devices including systems allowing on-line decomposition of organic compounds to small molecules (CO2, N2, H2O etc.) that retain corresponding isotope composition of initial compounds. Some examples of the application of precise isotopic mass spectrometry (isotopic ratio mass spectrometry, IRMS) in Russia have been given in the sections on Medical chemistry and the Environment. Gas chromatography/combustion/isotope ratio mass spectrometry has been used in many other applications as well. Extensive research in the field of IRMS has been performed by Anatoly Zyakun and co-workers at IBChPM RAS. One interesting area of research was directed to the investigation of carbon isotopes 12C and 13C fractionation by various microorganisms. For example, the degree of such fractionation has been investigated for photoautotrophically growing cultures of purple sulfur bacteria (Ectothiorhodospira shaposhnikovii, Lamprocystis purpureus and Thiocapsa sp.) and the green sulfur bacterium Prosthecochloris sp. isolated from meromictic water bodies. 291 In this work, carbon stable isotope compositions in total soil organic pools, transformation products and labile components (microbial biomass and active pools) were estimated. The investigations have demonstrated that degradation of soil organic matter (SOM) can reach a significant level as a result of an influx of organic nutrients into soil. In one of the works, the effect of glucose (a readily consumable substrate) on the activation of microbial degradation of organic substances in arable soil and the features of molecular oxygen as an electron acceptor in this process have been studied with the use of carbon isotope composition.292 The hydrocarbon oxidizing potential of soil microbiota and hydrocarbon oxidizing microorganisms introduced into soil has been studied based on the quantitative and isotopic characteristics of carbon in products formed in microbial degradation of oil hydrocarbons.293 By determining carbon isotopes ratio of cumulative CO 2 resulting from hydrocarbon mineralization, the dynamics of microbial degradation of exogenous contaminants, n-hexadecane and its primary microbial oxidized metabolite, n-hexadecanoic acid, has been studied for topsoils, under agricultural management and in beech forests.294 Based on the carbon isotope ratio characteristics and a comparison of the rates of microbial CO 2 formation in native soil and crude oil hydrocarbons, polluted soil, it has been shown that the sources of metabolic CO 2 , which were crude oil hydrocarbons and pollution,

13

enhance the SOM mineralization. The authors have made very interesting conclusion that microbial transformation of oil hydrocarbons into products could be a source of organic fertilizers stimulating plant growth.295 For the purposes of rapid monitoring of the microbial degradation of petroleum hydrocarbons (n-hexadecane and naphthalene) in the environment, isotope compositions of the carbon dioxide, biomass and exometabolites produced during the growth of microbes were tested.296 Oher papers297,298 presented evidence that using the carbon isotopes 12C and 13C ratio, it is possible to determine the degree of microbial oxidation of methane in the course of its passing through the aerated landfill horizons covered with a sand–clay layer and the rate of methane emission into the atmosphere. The papers published by Anatoly Zyakun et al. have also to be noted where fractionation of chlorine isotopes in dichloromethane in the presence of aerobic methylobacteria Methylobacterium dichloromethanicum DM4 and Albibacter methylovorans DM10 was reported.299,300 One more application of isotope ratio mass spectrometry was the determination of authenticity of wine and grape plants.301 On the basis of measurement of 13C/12C abundance ratios in the samples of vegetative (roots, grapevine, leaves) and generative (berries) parts of the vine as well as in ethanol and the dry residue of wine, it has been concluded that the ratios reflected the relationship between wine and vine plant. A very interesting application of the method is the development of a way to identify geographical places of origin of narcotic substances on the basis of isotope analysis of carbon and nitrogen. 302 For discrimination between endogenous and exogenous origin of urinary steroids and detection of administration of some prohormonal supplements, the use of 13C/ 12C carbon isotope ratio measurement by gas chromatography/combustion/isotope ratio mass spectrometry has been suggested.303 Recently, 304 a solid electrolyte reactor, containing ZrO2 and Y2O3 as the stabilizer, for the determination of hydrogen isotope ratio in water and hydrocarbon gases by continuous flow isotope ratio mass spectrometry was described. For isotope analysis of other elements in inorganic compounds, ICP-MS can be used. For example, multicollector ICP-MS has been applied at the Institute of Ore Deposits, Petrography, Mineralogy and Geochemistry RAS (Moscow) for simultaneous precise determination of 88Sr/86Sr and 87Sr/86Sr ratios in various geological samples.305

Inorganic chemistry and elemental analysis One of the fruitful approaches, actively developed by Lev Sidorov and co-workers at CD-LMSU, was the use of a mass spectrometer equipped with a Knudsen cell as a chemical reactor for studies of solid-state reactions of fullerenes.306 The approach allows in situ generation and simultaneous EI mass


spectrometric detection and characterization of the volatile products. In addition, information on the dynamics of formation and the distribution of products at varying reaction conditions can be obtained which promotes the rapid development of synthetic fullerene chemistry. Among the tested reactions were the fluorination of C60 with MnF3 to form mainly C60F36,307 with molecular fluorine to form C60F18 and C60F36,308,309 with KMnF4 to form isomers of C60F8,310 with K2PtF6 to form C60F18 and AgF2 to form C60F44, with K2PtF6, K3CoF6, and K2NiF6 etc. Higher fullerenes have also been involved in similar fluorination reactions.311 Other interests of the team have been directed to mass spectrometric investigation of fullerenes, their fluorinated, chlorinated, trifluoromethylated and pentafluoroethylated derivatives with the use of the on-line Knudsen cell technique. For instance, the first recording and interpretation of EI mass spectrum for fluorinated fullerene C60F 48 has been made.312 Some mass spectrometric studies of fluorinated and trifluoromethylated fullerenes by resonant electron capture have been carried out in conjunction with the Institute of Physics of Molecules and Crystals (Ufa Research Center of RAS).313,314 Mixtures of trifluoromethylated C60 derivatives have been analyzed by EI, MALDI, ESI, thermal surface ionization and electron capture mass spectrometric techniques. For the first time, ionization energy and electron affinity values have been used to explain the differences in the results obtained by different ionization methods.315 In the last decade, the main attention has been paid to MALDI-ToF mass spectrometry of fullerenes derivatives. In addition to traditional matrices, new ones, sulfur and 9-nitroantracene appeared to be useful for the study of halogenated fluorenes in particular.316,317 Variously fluorinated, trifluoromethylated, pentafluoroethylated and chlorinated fullerenes have been the subjects of MALDI-ToF mass spectrometric investigations. Unimolecular decompositions of positive and negative ions have been observed using PSD and explained using thermochemical data (ionization and appearance potentials, electron affinities etc.).318 One of the interesting findings of this scientific group has been the discovery of multi-caged fullerene compounds in a number of synthetic products by MALDI-MS in both positive and negative ion modes. For example, double-caged and even three-caged compounds were formed during the reaction of C60 with trifluoromethylated fullerenes or C60F18. In the latter case, the formation of a double-caged [2 + 2]-cycloadduct consisting of the C60F16 and C60 fragments connected along [6,6]-double bonds has been proved by X-ray analysis. Origin of the groups attached to fullerene and the bridges binding the cages were established by PSD study on the basis of fragmentation of fluorinated fullerene derivatives.319,320 As has been shown by the same team, MALDI mass spectrometry was a method of choice for observation of stable trifluoromethylated fullerene radicals C60(CF3)15 and C60(CF3)17 generated by UV irradiation of C60(CF3)n mixture.321 They have extremely long lifetimes since they were registered after the

long-term (several weeks) storage of their solutions in air. The presence of ions with an odd number of substituents has also been mentioned in the case of similarly irradiated pentafluoroethylated fullerenes and the ions were recognized as free radicals whose existence was proved by ESR analysis. Among the considerable works of this team, the first recording of MALDI mass spectra of carbon nano-tubes should be mentioned.322,323 Various other mass spectrometric techniques have been used in domestic works for analysis of inorganic compounds. For example, ICP-MS has been applied at Ural Electrochemical Integrated Plant (Novouralsk, Sverdlovsk oblast) for direct determination of B, Si, P, S, Cl and Br, Fe, Ca, K, Th, Sm, Gd, etc. at low levels in uranium materials.324–326 Special systems for gaseous impurity concentration built-in-to the EI mass spectrometer inlet system has been developed at this Plant in order to increase the performance of mass spectrometry methods for inorganic impurity analysis.327 An absolute method for the determination of isotopic composition of substances in multiple collector mass spectrometers has been proposed and demonstrated on the samples of uranium hexafluoride having 235U within a wide range of concentrations.328 At St Petersburg University, for the determination of elements in various materials (for example, nitrogen in steels), ToF mass spectrometry with glow discharge has been applied.329,330

Mass spectrometry technologies As was noted in the Introduction, after the dissolution of the USSR, construction, development and production of mass spectrometric instruments no longer had any support from the state at the first stage and started to decline. Many scientific groups started to break up and many scientists moved abroad and began their successful work with foreign firms and teams. At the same time, the vitality of the mass spectral community turned out to be very high, allowing it to overcome the initial state of shock. According to expert judgment, nowadays about 100–150 mass spectrometers of different types are produced in Russia annually. The majority of them are based on home developments.

Magnetic mass spectrometers and their elements

Single focusing mass spectrometers

In spite of the fact that starting from the 1960s, dynamic mass spectrometers have seriously pressed magnetic equipment, the latter are still in demand in many applications. First, there is a concern in isotopic analysis where special accuracy of measurement is needed and high resolution is necessary for isotopic analysis of low mass ions. Developments carried out at IAI RAS by scientific team under leadership of Lidiya Gall are the most significant in this field. This scientific school has long-term highly professional traditions ascending to activity


in the former USSR. The majority of developments of magnetic mass spectrometers, manufactured in the Soviet Union, has originated from this school. The main attention has been paid to two lines of magnetic mass spectrometers. One of them included the devices for the solution of nuclear industry tasks, in particular, for the analyses of easy and heavy elements. It is typical for the Lidiya Gall School to apply the integrated approach that presupposes joint consideration of the ion source, the analyzer and the detector during the design of analytical parts of magnetic mass spectrometers. One of the problems which is important to solve for high-accuracy isotopic analysis is the understanding of the mechanisms causing mass discrimination in electron ionization sources.331 Authors considered different mechanisms leading to discrimination of ions on mass (specified initial kinetic energies of atoms/ molecules in the ionization chamber, discrimination due to magnetic field in the latter, influence of the size of ionic optics of the source defining coherence of the source emittance with mass analyzer acceptance). Considering the mutual influence of initial energies of ions in the direction of movement for the ionization chamber, having a pushing out electrode, the authors came to the conclusion that there was a considerable decrease in efficiency of an ion yield from the source with a change in their initial energy from 0.05 eV to 1 eV and a start direction from 0о to 90о. Efficiency decreases still more for fragmental ions. Although the influence of a magnetic field in the source on ion discriminations is a well-known fact, the computational simulation allowed the determination of the ratio between the emittance of an ion source and acceptance of the analyzer for the “short” and “long” ion optics of the source sometimes called an immersion lens.332 An attempt to use the concept of phase space for simultaneous optimization of resolution and transmission was stopped for a long time due to the absence of developed hardware and software. At the same time, this concept is a key to achieving high analytical characteristics of a mass spectrometer and, in particular, optimum transmission and, as a result, the maximum sensitivity of the device. This concept has been further developed in more detail.333 SIMION 3D 7.0 was used as the basic software.334 To expand its capabilities, the authors developed additional interface modules GenIO for simulation of inlet parameters of an ion beam and SimDraw for the phase analysis of the source emittance and the analyzer acceptance. It has been demonstrated that if the design of the EI ion source and MSD-650 mass analyzer was optimized separately, the aggregate result of arriving ions to the collector for their joint action gave transmission of only 6-8%. However, the optimization of the source emittance and the analyzer acceptance increases the percentage of ions reaching the collector up to 50–60%. In last decade in Russia, intensive efforts were undertaken in development of a line of single-focusing mass spectrometers for the analysis of gaseous and solid samples for control of technological processes at the nuclear-fuel cycle of enterprises. Specialists of the Russian Academy of Sciences

and nuclear branch took part in the development. The technical solutions put in a design of mass spectrometers provided the basis for creating a line of magnetic mass spectrometers with different functions.335 The ion-optic scheme with a radius of an average trajectory of r0 = 250 mm and dispersion in mm Dg = 7.3 for 1% of the difference of DM/M permitted the application of multiple-collector detectors for basic model of a new generation of precision isotope mass spectrometers.336 At a deflecting angle of ions in a magnetic field Y = 90° the analyzer had inclined borders einput = 27° and eoutput = 34.5°—for input and output, respectively. The borders had the radius of R input = 198 mm (convex) and R output = 432 mm (concave). Such curvatures of borders allowed minimizing geometrical aberrations as second and third orders, and to get resolution R = 500 at the slit width of a source and a collector equal to Ss = 0.2 mm and Scol = 1 mm, respectively. An EI open type ion source has been put in the basic MTI-350G mass spectrometer model. A constant magnet was applied to electron focusing. To reduce memory and to increase measurement accuracy, the system of molecular inlet of gas into a source was used. Functioning of a molecular gas puffing system is ensured by two cryogenic traps that work autonomously for 72 hours. The mass spectrometer was equipped with the four-collector ions detector for simultaneous registration of isotopes 234U, 235U, 236U, 238U. For an exact adjustment, collectors (Faraday cylinders) can be moved perpendicular to an ion beam. In the process of diagnostics of all main functional units, their impact on a discrimination of measurement data and reproducibility of the analysis was defined. These units are: a needle-shaped metering valve located in the system of sample preparation and injection; EI ion source; the chamber of the magnetic mass analyzer with the aperture diaphragms; multiple-collector ion detector. 337 The most important characteristics of the basic model can be found in Reference 338. When creating the second model of a MTI-350GS mass spectrometer for technological control of production of uranium hexafluoride sublimate, the authors have considered the necessity to measure such gases, as HF, N2, O2, F2, Ar, UF6. In this case, simultaneous registration of ions which differ more than 15 times by mass was necessary.339.340 Resolution for group of light masses has to be R = 200 (at the level of 10%) at high absolute and isotopic sensitivity. The magnetic analyzer offered by the authors represents, inherently, a symbiosis of two analyzers—for light and heavy masses with the general input border and two output borders oriented on radically difference position focusing.339 The first part is a “light masses analyzer”, a symmetric 90° magnetic analyzer with an average trajectory radius of r 0 = 125 mm. Tilt angles made e inpt = 27° for input border and e outpt = 30° for output, respectively, and the input arm length equaled l1 = 100 mm; the output one l2 = 108.4 mm. Mass dispersion equaled Dg = 84.9 mm for 1% DM/M. Inclinations of input and output border provide a high transmission of the beam thanks to its axial focusing. To form an ion beam a Nier type source,


characterized by the minimum number of the electrodes, the reduced length of ion optics and strict angle collimation of an ion beam were chosen.340 The ion source forms an ion beam with angular dispersion 2a = 2° in the radial direction and 2b = 4° in the axial direction. Energy of the electrons emitted by the cathode can be regulated in the range of 60–150 eV. The electron gun provides the electron current of more than 200 mka with anefficiency of use not lower than 75%.341 The direct sample puffing was used in the MTI-350GS mass spectrometer. The design of the puffing system is made to provide the minimum distortions of an electric field in the ionizing chamber. It is important that an open-type ionization chamber was applied. Two types of ion detectors can be used: a multi-collector ion detector for registration of light components and an ion detector for heavy components. The former is intended for simultaneous and independent registration of ion currents for five components of the mixture being analyzed at five separate collectors (Faraday cylinders): HF+ (20 amu), N2+ (28 amu), O2+ (32 amu), F2+ (38 amu), Ar+ (40 amu). Input diaphragms of collectors with 0.8 mm width are located in the focal plane which makes an angle of 38° with an optical axis of the analyzer. The central collector is fixed stationary, the others can move by means of manual drives from without. The range of measured ion currents is 10–9–10–16 A. The single-collector detector of heavy mass ions is intended to register simultaneously the ion currents of all spectral components of uranium hexafluoride UF6 (UF6+, UF5+, UF4+, UF3+, UF2+, UF+, U+), that means from U (238 amu) to UF6 (252 amu). The main design decisions in the described model of the mass spectrometer are the same as in the basic model. The most essential differences belong to the vacuum chamber of the analyzer, the design of the magnet, the collector blocks and the ion source. A magnetic mass spectrometer (model MTI-350T) has been developed for solid state analyses. 342 The main analytical unit of the instrument as well as the unified electronic blocks were the basis of its design. In addition, new units and units redeveloped according to new functions of the instrument were included. For example, the structure of analytical parts included a revolving two-emitter ion source, with 11 positions.335 Rotation of a drum and precise positioning of ion sources were made remotely by means of the drive using the step motor and the precision position controller. The ion source, analyzer and ion collector regions were pumping by high-speed turbo-molecular and ion-getter pumps. The ion detector is equipped with nine collectors in the form of Faraday cylinders—one rigid (central) and eight actuated (four on each side). Movement of the collectors is carried out by means of individual drives without vacuum trouble. The instrument had the following characteristics: the top value of mass range (at accelerating voltage of 8000 V) of 300 amu; resolution 800; the threshold of isotopic sensitivity for 238U better than 1 × 10–5; limit of the allowed relative standard deviation (RSD) of a random error for the measurement of

atomic fraction of an isotope 235U in the range (0.5–1.0)—0.04%; limit of allowed RSD of a random error for the measurement of atomic fraction of an isotope 234U and 236U in the range (0.0005–0.006)—5%. Another model of a mass spectrometer, the MTH-350GP, was intended for the analysis of impurity in gas samples of uranium hexafluoride, such as derivatives of rhenium (ReF6), tungsten (WF 6 ), molybdenum (MoF 6 ), phosphorus (PF 5 , POF 3), chrome (CrO 2F 2), sulfur (SF 6, SOF 2, SO 2F 2), silicon (SiF4), boron (BF 3), air components (N 2, O2, Ar, CO 2), light impurities—hydrogen fluoride, light organic compounds.335 The mass spectrometer was created with the basic analytical units of the MTI-350G and uses the unified electronic blocks. In the instrument the gas ion source with the reduced discrimination and adjustable width of an output collimating split and the ion detector with a wide dynamic range of measured ion currents were used. The mass spectrometer includes a special system for sample preparation, such as the impurity concentrator which allows decreasing the threshold of impurity detection. Single-collector ion detection and magnetic scanning were used. The range of recorded masses was 10–450 amu The general design ideology was employed for the creation of a line of mass spectrometers belonging to MTI-350 series. It naturally included creating hardware and software of the automated complexes.343–345

Double focusing mass spectrometers In the 1990s, at IAI RAS, a new static double focusing mass spectrometer was developed. Originally, the mass spectrometer was applied to operate together with the “Crystal” chromatograph and was intended for the solution of a wide range of tasks in ecology, medical biochemistry and some other areas where the analysis of organic compounds is required. Later, the device was equipped with a glow discharge ion source346 and its application was extended to the area of element analysis as well.347 Nier–Johnson’s ion-optical scheme for the combination of electrostatic and magnetic analyzers was used as its basis. However, principal corrections were included using a toroidal condenser with a sector angle YE = 90° as the electrostatic analyzer and magnetic analyzer with a deviation angle YM = 54°. This fact, as well as the corresponding choice of borders of the magnetic analyzer, provided double focusing of the second order and considerably increased the analyzer transmission at the expense of axial focusing. In addition, the magnification of an ion-optical system was reduced to 0.778. The EI ion source was used in the instrument. Owing to special design of ion optics, ion beam focusing in two orthogonally related directions and higher stability of ion current in the wide range of pressure and ionizing electrons current have been achieved. Resolution was R = 16000 at 10% level and R = 25000 at 50% level of peak height. The range of the measured ion masses equals DM = 650 aem at an accelerating voltage of 5 kV and 1300 amu at an accelerating voltage of 2.5 kV. Dynamic range of registration system is 1–109.


Successes in developing units of mass spectrometers An original ion source with glow discharge has been developed. 348,349 It can operate at a much stronger discharge current, creating more dense plasma, than in sources used before. The authors used the special design of the hollow cathode limited by a diaphragm with a hole. For such a design, more dense plasma hinders streaming of working gas from an internal cathode area to the discharge chamber making ionization more intensive in the internal cathode area before the diaphragm. Due to the pressure reduction in the discharge chamber by several digits the efficiency of a desorption pollution from its walls is reduced and, hence, the level of the mass spectrometer background decreases as well. For different organic molecules the intensity of the background decreases from several tens to several hundred times in the mass range from 14 Da to 84 Da. The developed source allows a considerable expansion in the range of analyzed substances. In particular, it can be used for the trace element analysis of liquids and non-conductive solids.350 Another new type of ion source, namely, the magnetically strengthened radio-frequency (RF) pulsed discharge or the planar magnetron, has been presented in the paper. 351 It was intended for the direct element analysis of glass and ceramics. Its use allows an increase in the analytical signal by approximately four times in comparison with a usual radiofrequency source and lowers the background signal up to ten times. The analytical characteristics of a mass spectrometric method including the suggested source are estimated with the usage of glass standards (NIST SPM): limits of detection reach 10–100 ng g–1, convergence of results of definitions of sr without sample changes was from 0.04 to 0.10, repeatability of measurements of sr by sample changes increased to 0.06– 0.15.

Quadrupole instruments, ion traps There are some scientific centers in Russia where the development of quadrupole mass spectrometry is being undertaken. In the modern history of Russia, it is necessary to note RSRTU, where the development of quadrupole mass spectrometers is carried out under the leadership of Ernst Sheretov. The main attention of the team was paid to the creation of compact ion traps, particularly for space research. Numerous original scientific and technical decisions are reflected in a number of patents from the Russian Federation among which it is possible to specify the following ones.352–354 The theory of the trapping particles in hyperboloidal mass spectrometers of a 3D trap type, as one of the key factors influencing the parameters of the analyzer, was described in References 355 and 356 The authors analyzed the features of capturing particles as well. Using a mode of phase input, the ratio describing a form of mass peak was obtained. It was shown that for resolution of more than 100 it is not rational to choose the duration of an ionizing impulse of electron current more than 7% from HF-voltage period. The influence of initial speeds of trapped ions on the efficiency of their restraint by a high-frequency

field at the equally probable position of a vector of the speed was shown. New opportunities of quadrupole flight mass spectrometers (a monopole, a three-pole and a filter of masses), called the 3D focusing mode (3DFM) have been discussed in the paper.357 They showed that modulating the feeding RF-voltage with an additional RF-voltage with a period, multiple to the basic feed, it is possible to unroll the line of quasi-stability into instability bands that cut all the general zones of stability into stability islands. Sheretov and co-workers have presented an exhaustive theory of emergence of a linear parametrical resonance that is widely used now in quadrupole mass spectrometry equipment.358 They found also the thin spiking structure of dependence of ion fluctuations from b0 value and developed the correct theory of this phenomenon.359,360 Using the results of theoretical research, this team suggested two-dimensional spatial focusing along with phase focusing. Such a method of the analysis allows a considerable increase in sensitivity of a mass spectrometer. At the same time, the resolution increases significantly by using double focusing on both coordinates, orthogonal to the analyzer’s axis. So, for the chosen l = 1.2416 at realization of the offered method, the resolution on a half-height of the peak reaches 2000. For the chosen value l the ion transmission achieves a value of 75%. Along with in-depth theoretical studies, some experimental models of hyperboloid mass spectrometers have been developed. 361 For example, the design of the monopole analyzer with an angular electrode was offered. It enabled three to four times higher resolution and two orders higher sensitivity which reach up to 10–5 relative unit. Higher resolution was achieved when the length of the analyzer was 200 mm and using the same operating mode as the traditional and new type of monopoles. Work should be noted362 where the possibilities of designing linear ion traps from simple electrodes have been investigated. These electrodes are comparatively cheap and handy for manufacturing and at the same time capable of providing resolving power of mass analysis similar to commercial ion traps. By means of computer simulations and optimization of resonance ejection scan it was shown that for manufacturing linear ion traps, electrodes of triangular cross-section with ejection slit width of 16% of the trap inscribed radius can be used and they provide a resolving power greater than 18,000. Titov, at the All-Russian Research Institute of Technical Physics and Automation, has performed the detailed modeling of operation of the quadrupole mass-analyzer. 363–367 He considered the most important aspects of dynamics of ionic beams in phase space by transformation of the solution of the Mathieu equation taking into account the distortions of electric fields. Simulation of ion separation in the field of the quadrupole analyzer was carried out taking into account different types of distortions and was based on the principles of statistical mechanics that allowed the investigation of dynamics of an ionic beam in phase space of coordinates and speeds. Results of simulation confirmed that injection of ions into the analyzer at a zero phase in each cycle of HF-field by


supplying to the analyzer a heterogeneous variation field with linear distribution along an axis of ions movement increases transmission by 10–100 times depending on resolution and field distortion. Various aspects of simulating results of an ion beam dynamics in phase space of coordinates and speeds for quadrupole mass analyzers were discussed.366,367 Nikolay Konenkov and co-workers at Ryazan State Pedagogical University investigated features of the application of the second area of the stability chart at a pulse feeding of the analyzer.368,369 At the number of fluctuation cycles of the HF-field n = 50, resolution R0.1 = 2900 was reached, but the additional filter of masses with the resolution of R0.1 = 1 to remove heavy ions was required. Theoretical research of auxiliary HF field influence on the form of mass peak has been also studied.370 Earlier, the question of dividing properties of quadrupole mass analyzers while using several zones of stability was discussed in the paper.371 The cycle of works from RSRTU was devoted to development of hyperboloidal mass spectrometers with unidimensional an ion mass separation. 372–375 As a result of theoretical consideration of ion separation in such fields and mathematic relation for analytical parameters and the instrument function of the device, an experimental model of a monopole mass spectrometer with hyperboloidal and conicalshaped electrodes was provided. Resolution of such mass spectrometer was R0.5 = 500. It was observed that the form of mass peaks is strictly limited, sorting speed is increased by three to five times. The author also investigated the possibility of increasing the resolution to 1.2 × 103. One of the directions in the field of quadrupole mass spectrometry performed at RSRTU is the development of time-of-flight mass-selective separation of charged particles in linear HF fields.375,376 By forming electric fields with the specified potential distribution in electrode systems with flat discrete electrodes in combination with a HF-voltage of these, such systems reveal new ion-optical properties. It was shown that a mass analyzer with flat electrodes and with lineardiscrete potential distribution on thes is more effective. It was established that to obtain resolution of more than R = 103, error of potential distribution shouldn’t exceed d = 10–4. The authors established focusing properties of HF-fields with various energies, original coordinates, angles and input phases of ions. Using simulation, it was shown that such analyzers can provide resolution at a level 1.65 × 104 for transmission about 100%.377

Time-of-flight mass spectrometers

Mass spectrometers with orthogonal inlet of ion beam

Despite the rapid development of ToF mass spectrometry in the last decades, its opportunities were limited over a period of time as far as the direct inlet to an analyzer was concerned. As was noted in the Introduction, Alexander Dodonov and co-workers have received the Soviet Union patent12 for a ToF mass spectrometer with orthogonal inlet of an ion beam. The priority of the invention was also confirmed by an international

patent in 1989.378 Calculations of such analyzers and their potentials were given in the paper.379 The mass spectrometer included an ion source with atmospheric pressure ionization, containing ion optics for formation of a quasiparallel ion beam with ion energies 5–25 eV. This beam was injected into the ion package forms called the accumulation unit. After it is filled out, the ions are ejected in the orthogonal direction by an electric impulse. To separate the ions in ToF mode, a mass reflectron was used. Numerical calculations showed that it is possible to obtain resolution of a mass spectrometer at the level of 150,000– 280,000. The authors noted a unique attribute of massreflectron ToF-MS with orthogonal inlet of an ion beam, the ability to compensate simultaneously negative influence on a resolution of spatial and energy spread of ions with the help of electrostatic fields. In the case of ideal grids, resolution can be R = 5 × 104 for an ion source with ionization at atmosphere pressure, with an input diameter of the skimmer dsk = 0.5 mm and input energy Einput = 25 eV. For real grids with parallel wires and distance between them of 0.5 mm, the resolution is R = 20000. Later, this team described a home-built ToF mass spectrometer with orthogonal inlet of an ion beam. 380 A molecule-ion reactor (MIR) was a part of an electrospray ionization interface. Electrosprayed ions pass through a gas curtain and through a nozzle into the MIR chamber and through a skimmer to the orthogonal-ToF mass analyzer. The latter provided a routine mass resolving power ~10,000 and an accuracy of the mass measurement of 10 ppm. A new model of a ToF mass spectrometer with time focusing on energies and with orthogonal inlet of the ion beam produced in an ESI ion source was created. 381 The instrument includes four main units: source of ions with ESI, MIR, radio-frequency traffic quadrupole and a ToF massspectrometer with orthogonal inlet of an ion beam. In the instrument, the produced ions are injected into an MIR that consists of a sequence of quadrupole lenses. The oscillating high-frequency electric voltage and also the constant voltage providing formation of electric field of accelerating ions in the direction of their movement to the ToF-MS is put on a rod of lenses. MIR is the first cascade of the interface between the source and ToF-MS. The ions then enter the second stage of the interface containing transport quadrupole and system of focusing diaphragms. The ion beam was focused, transformed into a parallel one with the help of special diaphragms. Ions fill the ion accumulator and are pushed out to the orthogonal direction into the time-of-flight analyzer. The accumulator unit consists of flat parallel one monolithic and two grid electrodes. Ions are pushed out by two impulses of opposite polarity so that a homogeneous electric field intensity is formed in both gaps. Then the ion packet is accelerated in an accelerating gap of 6 kV. Using gramicidin solution (10–5 mole) as example, the author demonstrated ToF-MS parameters (resolution R50% = 19,700 and R 10% = 9800 for mass about M = 572). Accuracy of measurement of mass was not worse DM = 10–20 ppm. On


the basis of orthogonal mass spectrometer, a new method for studying the kinetics of ion decay reactions in a radio frequency with resonance rotation excitation was suggested.382

Membrane inlet mass spectrometry (MIMS) A series of interesting developments has been made at MEPHI by Alexander Sysoev and co-workers. One of them—a fast membrane inlet ToF mass spectrometer—was based on conventional two-stage mass reflectron with an EI ion source.383 Sampling was performed by flow-through direct membrane inlet utilizing capillary polydimethylsiloxane membrane. ppb and sub-ppb range limits of detection were shown for organic analytes in aquatic samples. The instrument has been demonstrated to be a perspective tool for determination of isotopic composition of carbon dioxide in 13C-labeled urea breath tests in medical diagnostics.384 It can also be applied for the determination of carbon isotope composition in breath air. The results of analysis for both standard gas samples and breath tests demonstrate satisfactory reproducibility and precision of 12C/13C ratio determination. The obtained precision is quite close to statistical fluctuation of the number of ions (0.002% for 200,000 ions). A mathematical model and computer code were developed in MEPHI to study the dynamic response of the hollow fiber membrane probe in fast MS instruments.385 The depletion layer formation at sample/membrane interface was taken into consideration by the mathematical model for the liquid mobile phase. The code produced concentration profiles within a sample feed stream and in the membrane. Flux values at the vacuum side of the membrane were calculated as a function of time. The method was applied both for gas and liquid feed streams. Concentration profiles in a mobile phase and the flux of analytes through the hollow fiber membrane inlet was studied with this simulation technique as a function of the liquid phase flow rate. The influence of the formation of a layer of the analyte depletion during the dynamic response was considered. The described numerical simulation model was shown to be a good tool for determination of permeation parameters of organic compounds.386 Diffusivities were determined by calculating permeation curves at various diffusivity values and searching for a value of diffusivity that gave the best correlation of the theoretical curve with the experimental permeation curves. The model was postulated to be applicable over a concentration range in which membrane transport obeys ideal diffusion law and there is linear sample/membrane partitioning. Comparison of the simulated results showed generally good agreement with the experimental ones and the expected behavior of permeating flux as a function of sample flow rate was observed. In Reference 387, analytical performance of a miniaturized micro array quadrupole instrument equipped with membrane inlet was compared with MIMS based on a conventional quadrupole mass spectrometer. The major advantage of the MIMS micro array quadrupole system is the small size, especially when as small pumps as possible are used. The

whole equipment is easily portable. The major disadvantage is the non-unit resolution of the analyzer, which makes the system suitable for monitoring simple sample streams only. The possibility of applying an electromembrane technique for the production of ions of biological molecules at atmospheric pressure was demonstrated.388 This technique has previously only been used for extraction of ions from liquids directly into vacuum. The membrane technique for ion extraction at atmospheric pressure was tested with both time-offlight and Fourier transform ion cyclotron resonance mass spectrometers. The mass spectra of intact molecular ions obtained from aqueous solutions of peptides and proteins are presented. The new technique is promising for achieving absolute sensitivity (charging every analyte molecule) and for performing spatially-resolved analysis of liquid biological samples.

Compact laser ToF mass spectrometer One such kind of mass spectrometers, namely linear laser timeof-flight mass spectrometer LAZMA, has been described.389 The device has axial symmetric ion optics and rather small dimensions. The main analytical units of the device were: optical system, laser ions source, ToF analyzer, detector and recording system. Reflectron had a symmetric configuration relative to the axis passing perpendicularly through the center of a target. Behind the reflectron in the vacuum camera there is a window for input of laser radiation which, after passing the reflectron grids and the central hole in the detector, also located symmetrically relative to the analyzer axis, is focused on a sample. The detector is the secondary-electronic multiplier with an amplifying coefficient of about 106. In front of MKP there is the grid assembly consisting of three grids. Full length of ions drift in the analyzer equals 28 cm. In the instrument, the laser (YAG) with the working element Nd3+ is applied. The laser has the following characteristics: (i) impulse duration—10 ns; (ii) wavelength—1.06 µm; (iii) radiant energy—20 mJ. The authors offered an original method to increase the sampling of solids during one laser shot. A six-sector splitter was used to divide an initial laser beam into six equal beams. The target is irradiated perpendicular to the surface; ions enter the analyzer without additional acceleration. The detecting system is collected from ring assemblies of microchannel plates with a hole for the passing of a plasma bunch. Generated plasma freely expands and part of it enters the reflectron where electrons are cut and ions, after reflection and subsequent drift, arrive through grid assembly on the detector. The authors developed a special method to increase accuracy of the element analysis. It includes two independent, but complementary stages for a series of measurement or a single mass spectra. The first stage of measurement is carried out in a mode of a wide energy window when ions with energies from 0 to Emax are detected and their quantity is equated to 100%. According to these data, relative distribution of intensities, separate peaks or their groups is determined if they are badly divided or are not divided completely. The


described instrument was tested experimentally in the analyses of solid alloys and high-quality glass NBS-610 and NBS-612 reference samples. It has the following technical characteristics: (i) mass range is from 1 amu to 250 amu, (ii) mass resolution is 600, (iii) relative sensitivity at summation of spectra is 5 × 10–7.

Laser time-of-flight mass spectrometers with axial-symmetric mass-analyzer One of the lines in the development of laser ToF mass spectrometry involved the use of sector electrostatic fields. The first realization of such a concept has been described by Alexander Sysoev et al.390 The capabilities of such a type of laser-ionization mass spectrometers, called LAMAS-technology by the authors, were presented in the paper.391 The main advantage of the analyzers is the possibility of ensuring threefold temporary focusing: (i) by radial divergence angles, (ii) by coordinates of ion exit from a source and by energy spread of ions. Theory of such analyzers was considered and possibility of obtaining resolution 1000–2000 on a half-height of mass peak was shown.392 Unlike mass-reflectron, such analyzers have no grids on the drift way of the ion packages and, by using additional focusing lenses, their transmission can come nearer to 100%. As followed from calculation, 392 the number of turns in the condenser can be any number. However, in this case, the length of free drift of ions significantly increases in proportion to deviation angle. To overcome this difficulty, it was suggested to provide a drift of ions with different energies for different sections of the analyzer. Later393,394 in the time-of-flight analyzer the cylindrical condenser with the angle of sector

Y = 4p / 2 = 509.2° was used. To simplify input and output of ion packages from the analyzer, the source and the detector are shifted in the axial direction relative to each other, and the ions move inside the analyzer on spiral trajectories. Radiuses of the middle trajectory, of internal and external electrodes of the condenser were, respectively, equal to: r0 = 100 mm, r1 = 80 mm, r2 = 120 mm. In the condenser, there is an energy window providing a transmission of ions with energy dispersion of ±2%. A laser operating in a mode of modulated quality factor and allowing one to obtain light impulses lasting 7 ns on an impulse half-height with energy of the laser 5–50 mJ was used to obtain laser plasma bunches in the source. When focusing the laser beam into a spot with diameter of d f ~ 50–70 µm the radiation capacity varies within (3–6) × 1010 W cm–2. To obtain optimum power of radiation of a sample (1–5) × 109 W cm–2, the filters weakening radiation intensity approximately at order were installed at the exit of the laser. The plasma bunch with a density of 1013 cm–3 was formed at interaction of laser radiation with a solid freely scattering on some drift way.395 A part of the bunch passes through a hole in the skimmer of the source and gets into the accelerating gap where plasma collapses,

and ions accelerate. The created ion packet goes into the electrostatic analyzer. In the special work, 396 new approaches for the creation of a detecting and recording system for the ToF mass spectrometer, providing significant expansion of dynamic range and increase in accuracy of the isotope and element analysis, are offered. Analytical capabilities of a considered laser ToF mass spectrometer were shown in References 393 and 397 The limit of impurity detection in different matrixes reached ppb level. Real dynamic range, depending on the ion mass and the type of analyzed sample reached 3 × 107–3 × 108. The relative standard deviation varies from 0.4% for the main components to 26% for micro impurity (at the concentration level of 0.001–0.01%). Use of scanning by ion energies allowed the reproducibility and accuracy of measurement to improve. One of the problems of laser ToF mass spectrometers is the presence of free drift space for laser plasma. This is why it was not possible to achieve time focusing during the whole way of the ion flight from the place of plasma generation to the injection in an ion detector. In Reference 398, the conditions under which the space of plasma drift in a focusing condition can also be taken into account was also considered.

Tandem-type laser mass spectrometer Igor’ Kovalev has developed a laser-ionization mass spectrometer (LIMS) for determination of gas-forming impurities in compact materials.399 The ion-optical scheme of the mass spectrometer was constructed on the basis of free scattering of plasma. For the mass analyzer, a time-of-flight analyzer from two sequentially located “mass-reflectrons” was used. Both steps were situated in one vacuum chamber, but separated by dense screens. After the first step, where ions were recorded in analog mode, intensive ion packages were locked by the electrodynamic valve. After secondary step of separation the impurity ion are recorded in a count mode by the detector.400 As intensive ion packages were locked after the first step, the background of intense ion packages decreases by some orders after passing the second step. A special laser that emits two consecutive impulses of radiation with an interval no more than 1 ms has been developed for cleaning the solid surface from the adsorbed atoms. Radiation from the first impulse clears the solid surface of superficial pollution; the second laser evaporates the cleared site of the solid, and the formed plasma is used for the analysis of gas-forming impurities. At the outlet of the laser two impulses of radiation lasting 15 ns with identical mode structure, separately adjustable energy and with a frequency of repetition of 12–50 Hz are formed. This allows the reduction of the background conditioned by adsorbed gases below the level ~10–7%. Time of impulse delays in experiments was determined the minimum, equal to 400 ms. Impulses of the radiation are focused on the surface of a sample by one lens that provids precision combination of craters from them at any fluctuation of a relief of a sample surface. Density of radiation power was 1 × 109 W cm–2 for the first impulse of the laser and 5 × 109 W cm–2 for the second. The diameter of the


focusing spot of the laser was equal of 50 µm. To increase the stability of an ion current from the source, a stabilization system is used. The latter is based on maintaining the constancy of the relation of intensity of one- and two-charging ions of the basic component of analyzed samples. When using such anapproach to ion stabilization, the reproducibility of analysis increases more, than five times.401 The effective length of ions drift—4.5 m, transmission–10–7, for a single mass spectrum were recorded for ~105 ions that corresponded to sensitivity of 10–3% for 10 ions. Resolution equaled 200 for a single mass spectrum. Special attention was paid to the instrument’s own background which equalled ~10–8%.402 The mass spectrometer allows one to determine gas-containing impurity at the level of 1 × 10–2–n × 10–7 mass % with a relative random error of 0.33 near the lower bound of concentration. The convergence and reproducibility of results of the analysis in the specified range is characterized by relative standard deviation 0.05–0.23.

Time-of-flight mass spectrometer with pulsed glow discharge Alexander Ganeev and co-workers at St Petersburg State University have carried out a series of works on the creation of a ToF mass spectrometer with an ion source on the basis of pulse glow discharge in the hollow cathode for element analysis.403–407 The ion-optical scheme of the mass analyzer was constructed on the basis of the classical “mass-reflectron” analyzer. The ions produced in the source are formed in a narrow ion beam that is orthogonally entered into the pushing-out zone of the mass-reflectron. In the drift space and in a reflecting gap, ions are focused in time on energies and, being separated on masses, are detected by means of microchannel plates. To maintain stable conditions of the analysis, the buffer-gas pressure was stabilized by means of the pressure sensor mounted in a discharge region. The effect of the addition of He and H2 on the nature of mass spectra was investigated. The authors concluded that the suggested design of the ion provides considerably smaller dispersion of coefficients of relative sensitivity as compared with the constant glow discharge ion source and with other methods of ion generation. Limits of detection varied within 0.3–1.0 ppm. Reproducibility of the analysis results made 1–12% depending on a type of impurity.

Multi-reflecting time-of-flight mass spectrometers In the last decade, ToF mass spectrometers with multireflecting in electrostatic mirrors (so-called reflective time-offlight mass spectrometers) have undergone intensive development. In such instruments with small dimensions, the length of the way of ion flight can reach some tens of meters that are necessary for a radical increase in resolution. Active research in this field are conducted at IAI RAS where Mikhail Yavor and Anatoly Verenchikov (mentioned in the Introduction) play the main role. Original multi-reflecting mass spectrometers with planar geometry have been offered408,409

and theoretical consideration of such analyzers, ion-optical schemes of multi-reflecting ToF-MS and the prospect of their development and application were analyzed in detail.410–414 The technical realization, consisting of two planar, in parallel mounted mirrors, was used as the basis for the ToF analyzers. Each mirror contains a row of four pairs of plane-parallel plates with a reflector in the form of a box. On the pairs of plates, constant potentials are fed so that ion packages, getting to such a configuration at an angle, were focused and reflected in the direction of the same mirror, making W-shaped movements between mirrors. Along the symmetry axis between mirrors, periodic two-dimensional lenses are mounted. Periodic fields of mirrors and lenses lead to the steady movement of ion packages similar to limitation of ion movement by radio-frequency fields.415 One attractive features of the offered ion-optical scheme is the ability to repeatedly reproduce W-shaped reflections of ions between the same mirrors at the expense of reflection of ion packages from the analyzer end faces.416 In this case, the restriction of length of ion movement is due only to dissipation of ions and the corresponding decrease in transmission. Such fields can provide obtaining ultrahigh values of resolution. At a reasonable assessment of an initial time spread of Dt of 2 ns and at energy of ions 2 kV the achievement of the resolution of R = 100,000 demands flight time in the analyzer of not less than 400 ms. For an ion mass of 100 Da, it corresponds to a flight length of 8 m. In addition, the resolution is limited by broadening a peak duration at the expense of the detector caused by temporary non-stabilities of the feeding electrode potential. Numerical evaluations show that mass resolution at the level of 100,000 on a half-height of peak demands stability of the feeding electrode potential at the level of 10–5. The first experimental results of test of the ion-optical scheme suggested in Reference 416 for multi-reflecting timeof-flight mass spectrometers were described.417,418 The mirrors of the instrument are assembled on a massive base frame having thick the plates of 1 mm made of stainless steel. The plates are isolated by dielectric washers and pulled together with plastic cores. The plates are collected in blocks of 25 mm to create a five-electrode reflecting configuration of a mirror. Accuracy of production and installation of elements in a mirror is not worse than 10 µm. Between the mirrors, the block of electrostatic lenses consisting of five identical flat lenses is symmetrically located. At the chosen sizes of the analyzer and an angle of ion entry, equal to 3° lenses are mounted with a step of 30 mm. One of lateral plates of the block of lenses is executed in the form of a flat wedge with a corner of 3° that is used for installation of the caesium gun that is an ion source of the analyzer. Pulse signals were recorded and measured by means of a digital oscillograph with the time resolution of 1 ns and capacity of 8 bits. The research confirmed the expected results. In each mass spectrum isotopes 39K, 41K, 85Rb, 87Rb were reliably recorded at a ratio of amplitudes close to natural, and containing in range of 10–5–10–6. The peak intensity of ion 41 K was only 3 × 10–6 from the peak intensity of caesium.


To demonstrate the opportunities of a planar ToF mass spectrometer, the authors used a method of increased timeof-flight of ions by short circuit of ionic trajectories in cycles. Two modes were used. Using specified methods, the authors reach times-of-flight of 80–90 ms for ion energy of 100 eV that corresponds, in the first case, to about 170 oscillations of an ion package between mirrors and to about 800 oscillations in the second one. As a result, the authors reached resolutions of about 180,000–200,000 at a half-height of peak of caesium ions. Further improvement in the technology of planar time-offlight mass spectrometers has proceeded in several directions. In some cases,419 they reached a resolution of R = 1,000,000. However, the main efforts were directed on improvement of analytical characteristics by use of various modifications of additional elements. For example, a well-known principle of orthogonal input was used for conversion of a continuous ion beam into pulse packages.420 In addition, the applications of a planar mass spectrometer with ESI sources and crown discharge ionization were described. Thus, in a mode with a narrowed mass range for R = 100,000 the accuracy of measurement of ion mass at the level of 1 ppm is reached. To increase the conversion efficiency of a constant pulse ion beam in the ion package, the so-called “pulsar” scheme was used that allows one to increase the intensity of an analytical signal up to 50–100 times. The advanced system of input of an ion beam into the analyzer was offered.421 To transform an ion beam, the original scheme of a radio-frequency ion trap with an axial output of ions was used. In intervals between impulses, ions are collected in the ion trap placed at the outlet of radio-frequency ion guide. By means of additional electrodes in this zone, the longitudinal electrostatic well is created. In this scheme nearly 100% efficiency in transformation of an ion beam into ion packages is reached. As a result the following characteristics were reached: resolution of more than 70,000 in the full mass range, the accuracy of mass measurement at the level of 1-2 ppm, sensitivity similar to the sensitivity of mass-reflectron with a running cycle of 20%.

Ion cyclotron resonance mass spectrometers One of the remarkable achievements of Russia scientists in the field of developing mass spectral instruments is connected with the use of ion-cyclotron resonance. They are mainly due to the research of the scientific team from IEPCPh RAS. This team has a long tradition and was earlier headed by Victor Tal`roze and later by Eugene Nikolaev. One should underline the fundamental approach to developments in this field where the authors’ interests included in-depth theoretical studies with broad computer model operation, the development of the interface facilities defining ions input, formed by different types of ions sources. Success of the work of the collective in the contemporary history of Russia can obviously be traced. In the 1990s, the attention of authors was concentrated on the perception of ways of increasing the resolution of ICR mass spectrometers.422,423

The problem of a choice of an optimum radius of ion gyration for obtaining high resolving power was also considered and the performed calculations showed the dependence of gyration radius with magnetic intensity H. A number of works have been devoted to theoretical research and simulation of the problem of forming mass peaks and mechanisms influencing such processes.424–427 In particular, this concerns space charge effects in ion inlet systems.428–431 The dependence of resolution on the size of energy spread of ions has been studied.423 At small values of energy spread, the satisfactory resolution of mass spectrometers can be achieved. However, it imposes the corresponding restrictions on ion formation in the source and in their transportation system via the interface of the ion input in a cell of an ICR mass spectrometer. At the same time, a dependence of resolution from energy can be used as a useful application, in particularly, for separation of molecular fragments by energy.432 In the paper,433 the authors have demonstrated the influence of harmonics on resolution and sensitivity of an ICR mass spectrometer. Theoretical and experimental results indicate that for simultaneous increase of resolution in sensitivity, the minimization of magnetron gyration is a very expedient procedure as the form of the mass peak improves. Analysis of functioning in the cell was carried out in References 434 and 435. One of the achievements of the team was the development of a new principle of formation of distribution of an effective electric field in a penning trap.436 The concept is based on averaging of space potential, taking into account optimization of cyclotron gyration of the charged particles. The cylindrical surface of the ICR-cell is divided into segments with a square potential distribution along an axis of the cyclotron gyration orbits in the directions at any radius of this gyration. The first experimental results have demonstrated its higher potential opportunities in comparison with traditional cells.437 A resolution of more than 20,000,000 was achieved for M/q = 609 amu for a magnetic field with an induction of H = 7 Tesla, created by means of a superconducting magnet with extremely high uniformity in a magnetic field. In Mikhail Gorshkov’s team, a permanent magnet on the basis of NdFeB alloy with a longitudinal magnetic field for a ICR mass spectrometer has been developed.438 The magnet creates a cylindrically symmetrical magnetic field, B = 0.89 Tesla in size and has an inlet hole of 42 mm. Inhomogeneity of a magnetic field along an axis of a magnet equals B –1 dB/dr = 5.6 × 10 –4 cm –1 in the central volume of 1 cm3. Additional correction of a magnetic field using a system of coils allows one to increase uniformity up to the sizes over 5.6 × 10–5 cm–1 for the central area. Despite high characteristics of a magnetic field, the size of the design does not exceed 250 mm in each direction and the weight of the magnet is less than 40 kg. For further improvement in magnetic field uniformity, additional inductance coils that are built in the working space of a magnet were used. Thereby, minimization of the electric current necessary for correction of uniformity of a magnetic field to values of 0.01% and above


was reached. The authors believe that detecting a signal at an increased frequency by means of a multi-electrode ICR trap allows the resolution to be improved by several times the resolution. Thus the cost of such magnets and their maintenance is significantly lower in comparison with superconducting-coil electromagnets. The suggested design of a magnet allows one to create a small-sized ICR mass spectrometer with atmospheric sources of ionization, such as MALDI and ESI, which are widely used in a biological mass spectrometry. The results of development of a small-size hybrid mass spectrometer with ICR on the basis of a permanent magnet with atmospheric sources of ionization of electro-spray and MALDI have been described.439 Note that such sources are used in classic ICR mass spectrometers.440 The design of a permanent magnet is based on the technology of a reversible magnetic field that allows the creation of longitudinal magnetic fields of 1–1.5 Tesla and uniformity of 5 × 10–4 cm–1 in the central volume of 1 cm3. Preliminary accumulation and fragmentation of ions are carried out in the linear radio-frequency quadrupole ion trap located in a third stage of differential pumping. The developed mass spectrometer showed a resolving power of about 80,000 and up to 30,000 for multiply charged ions of peptides; accuracy of measurement of peptide masses (in the range of m/z 300–1200) of 5–10 ppm. Mass spectral characteristics of the mass spectrometer were investigated both for electron ionization and ESI. In the case of ESI of peptides from Bradykinin (the mass spectrum has several peaks corresponding to the natural concentration of isotopes of 13C), the value of resolution was about 30,000 on a half-height of peaks. The results of the development of a source of atmospheric ionization on the basis of DESI for a small-size hybrid ICR mass spectrometer have been presented.441 The source was tested using low-molecular samples, mainly pharmaceutical ones.

Mass spectrometers for space exploration Russia has a long tradition in the field of development of mass spectrometers for space research. In this direction, leading positions are taken by ISR RAS. Within the Phobos–Grunt program some such instruments have been developed—these are devices for the analysis of a solid and gaseous components for the Maras satellite. Under the leadership of Georgii Managadze, two devices have been developed for the analysis solid samples.442,443 The “Lazma” laser ToF mass spectrometer is intended for an elemental and isotopic analysis of the non-atmospheric surface layer of regolith. After installation of regolith samples on a rotating disk at the distance that equal to a focal distance of a laser radiator, the sample is irradiate by the laser for 7 ns and a power density of ~109 W cm–2. Such action causes atomization and ionization of samples and strong overheating causes emission of the generated ions being in the structure of a target in the form of a plasma torch. High-speed ions are directed to a ToF mass-analyzer.

The ions are detected by a secondary electron multiplier. The structure of the Lazma instrument includes optical module, analyzer, soil receptor unit and electronic blocks. Main characteristics of the mass spectrometer are as follows: (i) range of masses is of 1–250 amu, (ii) resolution is of 380, (iii) the relative sensitivity is of 10–4, (iv) dynamic range is of 105, (v) accuracy is of 10%, (vi) the weight of the instrument is of 2.6 kg. The Managa-F instrument443 is a ToF mass spectrometer that allows the determination of element and isotope composition of the secondary ions generated from a surface of Phobos under the influence of primary ions from the solar wind. “Managa-F” consists of the following units: an analyzer including the form of an ion flow, a system of ion mirrors, a reflectron and a detector like the secondary-electron multiplier consisting of two sequentially located microchannel plates; management and feeding module; protective cover. To increase the sensitivity and to decrease the total dimensions in the analyzer, the system of reflecting ion mirrors that provides reliable protection for the detector against UF-radiation is used. After acceleration, the ion package arrives in the ToF analyzer. The main characteristics of the mass spectrometer are as follows: (i) the mass range is from 1 amu to 1000 amu, (ii) mass resolution is not worse than 100, (iii) the relative sensitivity is 0.1–1 ppm, (iv) dynamic range is 106, (v) the area of the entrance target is 15.43 cm2. The MAL-1F mass spectrometer has been developed for the definition of a gas component and measurement of isotope ratios of volatile elements in studied gases. A monopole analyzer 361 and electronic block 444 are used as the mass analyzer in MAL-1F. The mass spectrometer has resolution R 0.1 = 250, the dynamic range of the mass spectrometer achieved 10 3 and the weight is about 180 g. This mass spectrometer was created by the V.I. Vernadsky Institute of a Geochemistry and Analytical Chemistry of the Russian Academy of Sciences. The design of the electrode system of the monopole mass-analyzer of “MAL-1F”, which is a part of the mass spectrometer equipment was developed for space research in the PHOBOS–Grunt project by RSRTU under the leadership of Ernst Sheretov. At the Samara State Aerospace University, named after S.P. Korolyov, an on-board dust-impact mass spectrometer for determination of element composition of micrometeorites has been developed.445 The ToF analyzer was constructed according to the original ion-optical scheme including two combined electrostatic reflectrons between which the semi-transparent target bombarded by high-speed particles is located. The surface of the target is covered with a silver film. The secondary electron multiplier, in the form of a microchannel plate surrounded with two spherical concentric grids, is used as the detector. The resolution of the instrument varies from several tens of units to several hundred, depending on the design and impact parameters. The created mass spectrometer has diameter of 240 mm, a length of 280 mm and mass of 11.3 kg. The range of speeds of high-speed particles was 1–20 km s–1.


Combined mass spectral equipment

Ion mobility spectrometers/time-of-flight mass spectrometers At MIPHI, works on the creation of a complex instrument on the basis of an ion mobility spectrometer/ time-of-flight mass spectrometer were carried out. The instrument includes four main parts: an ion source, ion mobility spectrometer, a gasdynamic interface and a ToF mass spectrometer. The general idea of the instrument was explained in the papers.446,447 As the drift module, the high-resolution ion mobility spectrometer was used.448,449 The ion mobility spectrometer is adjusted to operate in a fast mode of acquisition with an inlet duration ion bunch of 500 µs during a period of 50 ms. The gas-dynamic interface (GDI) provides transportation of ion bunches with minimum losses and a minimum broadening from the atmospheric pressure area, at which the ion mobility spectrometer is operated, to areas of high vacuum. GDI contains two stages which are operated under pressure of 4 Torr and 5 × 10–4 Torr and pumped out by the sliding vane rotary pump and turbo-molecular pump, respectively. In the first stage of the interface the first transport quadrupole is located. In the second stage the second transport quadrupole and the ion lens are located. The ToF mass spectrometer represents a combination of the sector axial-symmetric analyzer with the orthogonal accelerator and an ion drift area. The accelerating field of the orthogonal accelerator is matched to compensate for a time aberration on the second order of energy in the sector time-of-flight analyzer. The analyzer operates under pressure of 5 × 10–7 Torr and has resolution of 2000. The ions entering the orthogonal accelerator in the direction of an X axis with energy of 20 eV, are pushed out in the Y direction by an impulse voltage of 400 V and accelerate to an energy of 3.5 keV in the direction of an electrostatic analyzer. In the analyzer, ions moving on a spiral about the X axis in the axial-symmetric electric field, turn on a corner of 254° with an average trajectory of a beam of 150 mm. Then they continue to move in the linear field-free area preceding the detector. The range of the analyzed mass of the used mass spectrometer reaches 50–900 amu. If the measurements of higher masses are necessary, then a required mass range can be recorded by fragments. In this case, the transport quadrupole of the differential pumping interface is adjusted during the recording of the passage of only chosen fragments in the mass range. The total time of the analysis from sample inlet to obtaining a mass spectrum depends on the number of hardware-summed distributions of mobility. This value ranges from 6 s to 100 s.450,451

Accelerating mass spectrometer Siberian physics, under the leadership of Vasilii Parkhomchuk at G.I. Budker Institute of Nuclear Physics of the Siberian Branch of the Russian Academy of Science, have begun to create of first Russian accelerating mass spectrometer (AMS) which enables dating archeological finds and geological breeds with high precision and to study the composi-

tion of atmosphere and tissues of live organisms from the different historical periods. Despite a rather long history in creating AMS in the world (about 30 years), the represented instrument adds new opportunities for a decrease in the isobaric background limiting sensitivity of the analyzer.452 Thus the concentration of radioactive isotopes, for example, 14 C, can achieve 10−12−10−14 relative units in comparison with the main isotope. The negatively ionized atoms are accelerated in an ion source with the output diaphragm of under zero potential, up to energy of injection. Further ions turn in a magnetic field on 90° and are accelerated by an electric field with voltage from units to tens of millions of volts in the first linear accelerator to the positive potential of the high-voltage terminal. In the accelerator terminal, an ions beam passing through very thin film loses electrons and ions turn into positive particles. After the ions turn on 180° in the electrostatic axial-symmetric analyzer, they are further accelerated in the second accelerator and after turning in 90° magnetic analyzer go to the detector. However, due to much larger energies, it is possible to use the following effects for separation of elements and isotopes. Nitrogen, for example, does not form negatively ionized atoms. Use of a source of negatively ionized atoms allows a radical decrease in influence on the background of an isobar 14N. The suppression of molecular ions occurs at a stage of its turning into positively ionized atoms. Thus, further ions with high charging numbers, +3 and higher, are selected. Molecules and radicals do not exist in such conditions, as they are dissociated on atoms. In the presented instrument, the attention has been focused on the fact that the stream of background particles can be lowered significantly using the filter on energy in the highvoltage terminal. In the existing complexes of AMS, the filter on energy is located either on an entrance to the accelerator, or on accelerator escaping, or both. However, using the filtration effect, these options are not equivalent. The reason is as follows: in spite of the fact that the negatively ionized atoms of nitrogen are unstable, atoms of nitrogen can form molecular compounds of nitrogen in the accelerator where the negatively ionized atoms are formed. If molecular ions are formed in an ion source, the installation of the suppressing filter on energy in the inlet canal considerably lowers this noise. A bison bone became one of the first samples to be tested for dating using a method of radio-carbon analysis by means of the AMS. The accelerating mass spectrometer defined the age of the find to about 27,000 years. The accuracy of dating achieved is within about 100 years. The created accelerating mass spectrometer is one of the most important tools at the Center of Collective Use of the Siberian Branch of the Russian Academy of Science “Cenozoic geochronology”. 453 The first measurements carried out on concentration of radio carbon in test samples showed that the accelerating mass spectrometer is different due to the increased reliability in identification of ions of radio carbon. The real mode of an accelerating mass spectrometer operation at accelerating voltage of


1 MV is reliable enough. Coincidence of the measured concentration of radio carbon in the pressed filaments for carbon fabric (the modern sample) is 1%. The first measurements of the content of radio carbon in annual rings of a tree from Academgorodok (Novosibirsk) have been carried out. During 2011, a test dating of 154 samples from various organic materials (fossil bones, wood, wood charcoal, carbonates, ground settlings etc.) were carried out. In 2012, dating of about 500 samples was carried out. More than 50 verifying measurements of samples with allegedly known age were carried out.

Society for mass spectrometry, conferences and principal publication activities in Russia The Russian Society for Mass Spectrometry (RSMS) (www. vmso.ru) was founded in 2003. The main purpose of the Society is to promote the development of domestic mass spectrometry as a modern fundamental and applied science, to unite the science, engineering and technical community to solve actual problems of mass spectrometry and the use of its achievements, the expansion and deepening of international contacts and cooperation. The Society has about 500 life members from Russia and abroad. Congresses of the Society meet every two years, where the president and the board of the Society are elected. Congress awards the Gold medal of Russian Society for Mass Spectrometry “For outstanding achievements in the field of mass spectrometry”. The medal has been awarded to Boris Mamyrin (2005), Alexander Makarov (2007), Lidiya Gall’ (2009) and Igor’ Revelskii (2011). Parallel to the Congresses, scientific conferences with international participation “Mass Spectrometry and its Applied Problems” take place. In addition the International Mass Spectrometry Conference on Petrochemistry, Environmental and Food Chemistry, “Petromass 2011” was organized in TIPS RAS in 2011. Each year, the Society organizes the Workshops “Practical Aspects of Application of GC/MS and HPLC/MS” and “Practical Aspects of Application of Mass Spectrometric Element and Isotope Analysis”. It should be noted that four conferences on mass spectrometry (“Fundamental Basics of Mass Spectrometry and its Analytical Application”) have been organized by IEPCPh RAS. Since 2004, the Society has published the scientific journal Mass-spektrometria in Russian which is also published in English as complementary issues to the Journal of Analytical Chemistry. The journal publishes papers on all areas of mass spectrometry. Since the 1990s, Russian mass spectrometrists have published a number of books 454–462 and comprehensive reviews 463–486 in both Russian and English on various fundamental and applied aspects of mass spectrometry.

Conclusion The review covers the most important and systematic investigations in various fields of technical development of equipment and diverse applications of mass spectrometry in many areas of science, medicine or industry that have been performed during the last 20 years in Russia. Naturally, we could not give comprehensive information on all the studies and have not given a complete list of papers. However, the material presented here provides an overview of trends in research in the field of mass spectrometry carried out in Russia.

Acknowledgement The authors are most greatful to our colleagues-mass spectrometrists who have contributed to this review with their comprehensive publication lists, bibliographic information and helpful discussion.

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63. V.K. Mavrodiev, I.I. Furtei, A.Sh. Sultanov, Yu.S.

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84. R.S. Borisov, V.G. Zaikin, B.V. Vas’kovskii and L.Yu.

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chromatography, highperformance capillary electrophoresis and matrix-assisted laser desorption ionisation time-of-flight mass spectrometry”, J. Chromatogr. A 907(1–2), 131 (2001). doi: 10.1016/S0021-9673(00)01016-5 175. A.R. Ivanov and I.V. Nazimov, “Identification of unusual (modified and non-encoded) amino acid residues in peptides by combinations of high-performance liquid chromatography and high-performance capillary electrophoresis with matrix-assisted laser desorption ionization time-of-flight mass spectrometry”, J. Chromatogr. A 870(1–2), 255 (2000). doi: 10.1016/S00219673(99)01058-4 176. R. Ziganshin, G. Arapidi, I. Azarkin, E. Zaryadieva, D. Alexeev, V. Govorun and V. Ivanov, “ New method for peptide desorption from abundant blood proteins for plasma/serum peptidome analyses by mass spectrometry”, J. Proteomics 74(5), 595 (2011). doi: 10.1016/j. jprot.2011.01.014 177. Yu.O. Karatasso, S.E. Aleshin, N.V. Popova, V.V. Chistyakov, M.G. Sergeeva and S.D. Varfolomeev, “Quantitative analysis of prostaglandins and polyunsaturated fatty acids using electrospray ionization mass spectrometry”, Mass-spektrometria 4, 173 (2007) (in Russian). 178. Yu.N. Elkin, B.A. Budnik, V.B. Ivleva, E.L. Nazarenko, H.B. O’Connor and C.E. Costello, “Elucidation of composition of the outmost lipid layer of bacterial cell: mass spectrometric approach”, Mass-spektrometria 8, 273 (2011) (in Russian). 179. D.A. Korzhenevskii, ,V.N. Kuptsov, V.A. Mityanina, A.A. Selishcheva, S.V. Savel’ev and T.Yu. Kalashnikova,”Identification of the individual molecular species of ceramides derived from human erythrocytes using HPLC/MS and HPLC/MS/MA”, Mass-spektrometria 7, 188 (2010) (in Russian) [J. Anal. Chem. (Engl. Transl.) 66, 1270 (2011). doi: 10.1134/S1061934811130053]. 180. D.A. Korzhenevskiy, A.A. Selischeva and S.V. Saveliev, “An approach to the identification of molecular fractions of human erythrocyte phospholipids using HPLC with mass spectrometric detection”, Biochem. (Moscow) Supplement Series B: Biomed. Chem. 4(3), 296 (2010). doi: 10.1134/S1990750810030121 181. V.E. Schevchenko, N.E. Arnotskaya, O.P. Trifonova, A.S. Dashkevich, V. A. Yurchenko and D.G. Zaridze, “Profiling of low molecular weight proteoms of blood plasma for the detection of potential markers of lung cancer”, Mass-spektrometria 4, 245 (2007) (in Russian). 182. V.E. Schevchenko, N.A. Arnotskaya and D.G. Zaridze, “Detection of lung cancer using plasma protein profiling by matrix-assisted laser desorption/ionization mass spectrometry”, Eur. J. Mass Spectrom. 16(4), 539 (2010). doi: 10.1255/ejms.1080 183. M.A. Pyatnitskiy, A.V. Lisitsa, S.A. Moshkovskii, N.E. Arnotskaya, B.B. Akhmedov, D.G. Zaridze, B.E. Polotskii and V.E. Shevchenko, “Identification of differential signs of squamous cell lung carcinoma by means of

the mass spectrometry profiling of blood plasma”, Mass-spektrometria 8, 99 (2011) (in Russian) [J. Anal. Chem. (Engl. Transl.) 66(14), 1369 (2011). doi. 10.1134/ S1061934811140139]. 184. V.E. Schevchenko, D.E. Makarov, S.V. Kovalev, N.E. Arnotskaya, N.R. Pogosyan and K.I. Zhordania, “Tumor pleural effusion proteome profiling for ovarian cancer biomarkers mining”, Mass-spektrometria 9, 167 (2012) (in Russian). 185. V.E. Schevchenko, S.V. Kovalev, V.A. Yurchenko, V.B. Matveev and D.G. Zaridze, “Human plasma proteome mapping in health and clear cell carcinoma of the kidney”, Onkourologiya 1, 65 (2011) (in Russian). 186. R.N. Ziganshin, D.G. Alexeev, G.P. Arapidi, V.T. Ivanov, V.M. Govorun and S.A. Moshkovskii, “Serum proteome profiling for diagnostics of ovarian cancer using ClinProt magnetic technique and MALDI-ToF mass spectrometry”, Biochemistry (Moscow) Suppl. Series B: Biomed. Chem. 2, 335 (2008). (in Russian). 187. R.H. Ziganshin, G.P. Arapidi, I.V. Azarkin, I.P. Balmasova, O.L. Timchenko, Yu.A. Fedkina, E.A. Morozova, M.A. Piradov, N.A. Suponeva, N.D. Yuschuk and V.M. Govorun, “Proteomic technologies for identification of serum biomarkers of potential autoimmune demyelinating polyneuropathies”, Bioorganicheskaya Khimiya 37, 36 (2011) (in Russian) [Russian Journal of Bioorganic Chemistry (Engl. Transl.) 37(1), 30 (2011). doi: 10.1134/ S1068162011010171]. 188. A.Sorokina, R. Ziganshin, G. Arapidi, O. Ivanova, V. Radzinsky and V. Govorun, “Search for biomarkers specific for ovarian cancer by MALDI mass spectrometry”, Vratch (Phisician) 1, 39 (2012) (in Russian). 189. Ph.O. Tsvetkov, I.A. Popov, E.N. Nikolaev, A.I. Archakov, A.A. Makarov and S.A. Kozin, “Isomerization of the Asp7 residue results in Zinc-induced oligomerization of Alzheimer’s disease amyloid (1–16) peptide”, ChemBioChem 9(10), 1564 (2008). doi: 10.1002/ cbic.200700784 190. I.Yu. Toropygin, E.V. Kugaevskaya, O.A. Mirgorodskaya, Y.E. Elisseeva, Y.P. Kozmin, I.A. Popov, E.N. Nikolaev, A.A. Makarov and S.A. Kozin, “The N-domain of angiotensin-converting enzyme specifically hydrolyzes the Arg-5-His-6 bond of Alzheimer’s Ab-(1–16) peptide and its isoAsp-7 analogue with different efficiency as evidenced by quantitative matrix-assisted laser desorption/ionization time-of-flight mass spectrometry”, Rapid Commun. Mass Spectrom. 22(2), 231 (2008). doi: 10.1002/ rcm.3357 191. M.I. Indeykina, I.A. Popov, S.A. Kozin, A.S. Kononikhin, O.N. Kharybin, Ph.O. Tsvetkov, A.A. Makarov and E.N. Nikolaev, “Capabilities of MS for analytical quantitative determination of the ratio of a- and bAsp7 isoforms of the amyloid-b peptide in binary mixtures”, Anal. Chem. 83, 3205 (2011). doi: 10.1021/ac103213j 192. Yu.O. Karatasso, C. Sullards, Ya.B. Fedorova, A.A. Korotaeva, S.I. Gavrilova, S.D. Varfolomeev and A.V.


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mii (Mass Spectrometry in Organic Chemistry). Binom, Moscow, Russia (2003) (in Russian). 456. B.L. Mil’man, Vvedenie v Khimicheskuyu Identificatsiyu (Introduction in Chemical Identification), VVM, St-Petersburg, Russia (2008) (in Russian). 457. V. Zaikin and J. Halket, A Handbook of Derivatives for Mass Spectrometry. IM Publications, Chichester, UK (2009). 458. V.G. Zaikin, Mass-Spectrometria Sinteticheskikh Polimerov (Mass Spectrometry of Synthetic Polymers), VMSO, Moscow, Russia (2009) (in Russian). 459. A.M. Zyakun, Teoreticheskie Osnovi Izotopnoi Mass Spectrometrii v Biologii (Theoretical Basics of Isotope Mass Spectrometry in Biology), OOO-Foton-Vek, Pushino, Russia (2010) (in Russian). 460. B.L. Milman, Chemical Identification and Its Quality Assurance. Springer, Heidelberg, Germany (2011). 461. A.T. Lebedev (Ed.), Comprehensive Environmental Mass Spectrometry. ILM Publications, Hertfordshire, UK (2012). 462. A.T. Lebedev, K.A. Artemenko and T.Yu. Samgina, Basics of Mass Spectrometry of Proteins and Peptides. Technosphera, Moscow, Russia (2012). 463. A.T. Lebedev, “Mass spectrometry of diazo compounds”, Mass Spectrom. Rev. 10(2), 91 (1991) doi: 10.1002/ mas.1280100202 464. L.N. Sidorov, “High temperature studies”, Int. J. Mass Spectrom. Ion Proc. 118/119, 739 (1992). doi: 10.1016/0168-1176(92)85083-C 465. E.S. Chernetsova, A.I. Revelsky, I.A. Revelsky, I.A. Mikhasenko and T.G. Sobolevsky, “Determination of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls by gas chromatography/mass spectromtry in the negative chemical ionization mode with different reagent gases”, Mass Spectrom. Rev. 21(6), 373 (2002). doi: 10.1002/mas.10037 466. J.M. Halket and V.G. Zaikin, “Derivatization in mass pectrometry—1. Silylation”, Eur. J. Mass Spectrom. 9(1), 1 (2003). doi: 10.1255/ejms.527 467. V.G. Zaikin and J.M. Halket, “Derivatization in mass pectrometry—2. Acylation”, Eur. J. Mass Spectrom. 9(5), 421 (2003). doi: 10.1255/ejms.576 468. J.M. Halket and V.G. Zaikin, “Derivatization in mass pectrometry—3. Alkylation (arylation)”, Eur. J. Mass Spectrom. 10(1), 1 (2004). doi: 10.1255/ejms.619 469. V.G. Zaikin and J.M. Halket, “Derivatization in mass pectrometry—4. Formation of cyclic derivatives”, Eur. J. Mass Spectrom. 10(4), 555 (2004). doi: 10.1255/ejms.653 470. J.M. Halket and V.G. Zaikin, “Derivatization in mass spectrometry—5. Specific derivatization of monofunctional compounds”, Eur. J. Mass Spectrom. 11(1), 127 (2005). doi: 10.1255/ejms.712 471. V.G. Zaikin and J.M. Halket, “Derivatization in mass spectrometry—6. Mixed derivatization”, Eur. J. Mass Spectrom. 11(6), 611 (2005). doi: 10.1255/ejms.773

472. J.M. Halket and V.G. Zaikin, “Derivatization in mass spectrometry—7. On-line derivatization/degradation”, Eur. J. Mass Spectrom. 12(1), 1 (2006). doi: 10.1255/ ejms.785 473. V.G. Zaikin and J.M. Halket, “Derivatization in mass spectrometry—8. Soft ionization mass spectrometry of small molecules”, Eur. J. Mass Spectrom. 12(2), 79 (2006). doi: 10.1255/ejms.798 474. V.V. Lobodin and A.T. Lebedev, “Analogies in monomolecular transformations of organic compounds in a solution and in a mass spectrometry experiment”, Mass-spektrometria 2, 91 (2005) (in Russian). 475. J.M. Halket and V.G. Zaikin, “Analyte Derivatization Strategies for GC–MS”, The Encyclopedia of Mass Spectrometry, Volume 8 (Hyphenated methods), Ed by W.M.A. Niessen. Elsevier, Amsterdam, The Netherlands, p. 61 (2006). 476. A.T. Lebedev, “Mass spectrometry in identification of ecotoxicants including chemical and biological warfare agents”, Toxicol. Appl. Pharmacology 207(2), S451 (2005). doi: 10.1016/j.taap.2005.02.040 477. V.G. Zaikin and J.M. Halket, “Derivatization in Mass Spectrometry”, The Encyclopedia of Mass Spectrometry, Volume 6 (Ionization Methods), Ed by M. Gross. Elsevier, Amsterdam, The Netherlands (2007). 478. A.T. Lebedev and V.G. Zaikin, “Organic mass spectrometry at the beginning of the 21st century”, J. Anal. Chem. 63(12), 1128 (2008). doi: 10.1134/S1061934808120022 479. A.T. Lebedev and V.G. Zaikin, “Recent problems and advances in mass spectrometry”, Inorg. Mater. 44(14), 1482 (2008). doi: 10.1134/S0020168508140033 480. E.D. Kan’shin, I.E. Nifant’ev and A.V. Pshezhetskii, “Mass spectrometric analysis of protein phosphorylation”, Mass-spektrometria 6, 103 (2009) (in Russian) [J. Anal. Chem. (Engl. Transl.) 65, 1295 (2010). doi: 10.1134/ S1061934810130010]. 481. A.M. Zyakun, “Isotopologs and isotopomers: new analytical aspects of isotopic mass spectrometry in biology”, Mass-spektrometria 7, 165 (2010) (in Russian) [J. Anal. Chem. (Engl. Transl.) 66(13), 1243 (2011). doi: 10.1134/ S1061934811130119]. 482. A.V. Gusakov, M.V. Semenova and A.P. Sinitsyn, “Mass spectrometry in the study of extracellular enzymes produced by filamentous fungi”, Mass-spektrometria 7, 5 (2010) (in Russian) [J. Anal. Chem. (Engl. Transl.) 65(14), 1446 (2010). doi: 10.1134/S1061934810140030]. 483. I.V. Dobrokhotov, L.Kh. Pastushkova, I.M. Larina and E.N. Nikolaev, “Study of the urine proteome in healthy humans”, Human Physiology 37(7), 777 (2011). doi: 10.1134/S0362119711070097 484. V.G. Zaikin, “Chromatography-mass spectrometry”, J. Anal. Chem. 66(12), 1210 (2011). doi: 10.1134/ S1061934811110177 485. V.Yu. Markov, A.Ya. Borschevsky and L.N. Sidorov, “MALDI mass spectrometry of fullerene derivatives”,


Int. J. Mass Spectrom. 325–327, 100A.S. (2012).Kononikhin, doi: 10.1016/j. M.I. Indeykina spectrometry 486.E.N. Nikolaev, I.A. Popov, andanalysis E.N. of peptides and proteins”, ijms.2012.05.014 Russian Chem. Rev. 81(11), 1051 (2012). doi: 10.1070/ Kukaev, “High-resolution mass spectrometry analysis of peptides and proteins”, RC2012v081n11ABEH004321 486. E.N. Nikolaev, I.A. Popov, A.S. Kononikhin, M.I. Russian Chem. Rev. 81, 1051 (2012). doi: 10.1070/RC2012v081n11ABEH004321 Indeykina and E.N. Kukaev, “High-resolution mass

Biographical details Bibliographic details Vladimir Zaikin

chemical synthesis. From theoretical point of view, his cycles of investigations of reactivity of gaseous ions generated from Professor Vladimir G. Zaikin various organic compounds is interesting. Among his works obtained his Master of one can find the results of mass spectrometric determinaScience degree in organic tion of thermochemical parameters of various molecules and chemistry in 1965 from the unstable particles, the development of methods for microsynChemical Department of thesis of derivatives and deuterated compounds, for monitoring M.V. Lomonosov Moscow and mechanistic studies of heterogeneous and homogeneous State University. While still catalytic reactions with the aid of mass spectrometry. Together a student, he joined the with Anzor Mikaia he developed a “reaction GC/MS” method newly established mass including on-line chemical or physico–chemical transformation spectrometric laboratory of analytes. As a result, a number of methods have been develheaded by Professor N.S. oped for structure determination of alcohols, amines, carboxylic Wulfson in the Institute for Chemistry of Natural Products USSR acids, amino acids, peptides, synthetic polymers. His more Academy of Sciences (present name M.M. Shemyakin and Yu.A. recent research deal with MALDI mass spectrometric analysis Ovchinnikov Institute of Bioorganic Chemistry Russian Academy of synthetic polymers and low-molecular weight compounds of Sciences) and began his research in electron ionization mass Professor Vladimir Zaikin(steroids, obtainedalkaloids, his Master of Science degree in organic including derivatization approaches. He pays special attention spectrometry of naturalG. products terpeto recording “high quality” noids, amino acids, peptides etc.). He obtained his PhD degree chemistry in 1965 from Chemical Department of M.V. Lomonosov Moscow State electron ionization mass spectra of important organic compounds and their derivatives. A lot of from this Institute in 1968 in the area of stereoisomeric effects University. still aalcohols. student, he he joined the newly established mass in the most popular NIST/NIH/EPA such spectra are included in mass spectraWhile of carbocyclic In 1973, was invited mass spectral library by the A.V. Topchiev Institute of Petrochemical Synthesis RAS to spectrometric laboratory headed by Prof. N.S. Wulfson in the Institutewhose for evaluation is accomplished jointly with National Institute of Standards and Technology (USA) organize mass spectrometric investigations where he obtained Chemistry Natural Products USSR of Sciences (present name Vladimir M.M. Zaikin has published more than beginning in 1994. his Doctor ofof Science degree in 1978. Until Academy now, he continues 300 scientific papers and six tutorial books. He has supervised to work at the Institute as a head of the Laboratory for Spectral Shemyakin and Yu.A. Ovchinnikov Institute of Bioorganic Chemistry Russian a number of students for their PhD degree. He is the EditorResearch. His main investigations deal with the application Academy of Sciences) and organic, began his researchesand in electron mass Mass-spektrometria and editor of in-Chief ionization of Russian journal of mass spectrometry to various organoelement European Journal of Mass Spectrometry bioorganic compounds, synthetic polymers, products of petro-

spectrometry of natural products (steroids, alkaloids, terpenoids, amino acids, peptides etc.). He obtained his PhD degree from this Institute in 1968 in the area of

Alexander A. Sysoev

of secondary ions beam stereoisomeric effects in mass spectra of carbocyclic alcohols. In 1973, he was

focusing by monocrystal Professor Alexander A. Sysoev obtained his Master of Science invitedin by A.V. Institute Physics of Petrochemical Synthesis RAS for surface was experimentally degree physics fromTopchiev Moscow Engineering Institute confirmed for first time. (nowadays National Research Nuclear University MEPhI) in 1962. He began his scientific career researching thermody- In 1969–1973 he studied kinetics and mechanisms namics of high temperature carbide uranium evaporation in o f o rg a n i c s u b s t a n ce 1962–1964. In 1964–1967, under the supervision of Professor G.Y. Shchepkin, he developed an electrostatic sector time- polymerization initiated by electron and ion bombardof-flight mass spectrometer with double time focusing. He ment. Basic theory was also obtained his PhD in 1967 from the Moscow Engineering Physics developed for a single stage Institute. In collaboration with Doctor of Science V.E. Yurasova from M.V. Lomonosov Moscow State University, in 1967–1969, and double stage static mass analyzer with crossed he studied anisotropy of spattering a face-centered lattice electric and magnetic fields copper monocrystal by ion beams. V.E. Yurasova’s mechanism

Professor Alexander A. Sysoev obtain

from Moscow Engineering Physics Inst University

MEPhI)

in

1962.

He


on the basis of polyparametric series. Later (1974–1975) the mentioned approach was taken as a basis for the development of a theory of multi-convolution time-of-flight mass analyzer with triple time focusing. In the same period, the author developed a mass spectrometer and the method for analysis of biology aerosols including a combination of programmable thermal analysis and quadrupole mass spectrometry. In 1981, he defended a second Doctor of Science dissertation in physics and mathematics. Between 1981 and 1988, Alexander Sysoev carried out investigations for the development of a mass spectrometric method and instrumentation for studying space dust in near Earth space. From 1989 to 1999, he developed a laser time-of-flight mass spectrometer for the analyses of solid and powder substances (LAMAS-technology). Between 2001 and 2006, the method for determining isotope composition of nitric oxide was developed for light isotope production. During recent years he has jointly, with Associate Professor Alexey A. Sysoev, developed an ion mobility time-of-flight mass spectrometer. On the basis of modern achievements in pedagogy

and psychology, in 1985-2012 he developed an ImitationalActivity Technique of Engineering Education for the National Research Nuclear University MEPhI. Disciples of Professor Alexander A. Sysoev, such as Dr A.A. Makarov and V.B. Artaev, are working at leading mass spectrometry companies abroad from Russia. Between 1970 and 2012 he supervised 15 postgraduates defend PhD theses. From 1970 to 1992 he was a Dean of the Special Faculty for Retraining Specialists by New Areas in Science and Technology. Since 1996 he has been an Academician of the International Academy of Science of High Education. He is an Inventor of USSR. He is also an Honorable Official of Higher Education of the Russian Federation. He is an author of more than 300 scientific works, including 4 monographs, more than 10 tutorials, more than 150 papers, 30 inventions for the USSR and 7 patents. He is a member of the Presidium and Counsel of the Russian Mass Spectrometric Society, a member of the editorial board of the journals Massspektrometria and Problems of Atomic Science and Technology.

Mass spectrometry imaging for plant biology: a review.

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The 12th Asilomar conference on mass spectrometry: Elemental mass spectrometry.

Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

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Mass spectrometry for steroids.

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Mass spectrometry of triglycerides.

Mass spectrometry pittCon®'96.

Electrospray ionization mass spectrometry.

Mass Spectrometry Analysis and Pharmacokinetic Assessment of Ponatinib in Sprague-Dawley Rats.

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mass spectrometry.

mass spectrometry of lipids.