The review covers the use of mass spectrometry with soft ionization methods in proteomics. The principles of mass spectrometric analysis of proteins, the possibilities of mass spectrometry in the identification of proteins and peptides, in the search and identification of post-translational modifications, and in comparative quantitative analysis are described.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

In this review the MALDI mass-spectrometry opportunities in respect to the analysis of peptide nature toxins produced by bacteria, some kinds of plants, sea organisms, insects, arthropoda and snakes are considered. The advantages and disadvantages of the present method are showed.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

In this review the possibilities of application of gas chromatography—mass spectrometry method are considered. The principles of the method and application areas of it were described.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

The possibility of mass-spectrometry using for complex analysis of medical products containing streptokinase is showed. The protein composition and target protein – streptokinase - content are determined. The identification and quantitative estimation of streptokinase content were carrying out by MALDI-MS on exhaustive tryptic cleavage products. For the quantitative estimation, ¹⁸O-isotopic tracers of streptokinase tryptic peptides with known concentration were added to the analysis samples as internal standard. The analyzable protein concentration was calculated on the intensities ratio of isotopic distribution of the analyzable protein and ¹⁸O labeled internal standard. The streptokinase biological activity was estimated by its capability to activate plasminogen in human blood serum. The plasminogen activation is accompanied by the appearance of esterase activity which was determined by the cleavage rate of synthetic substrate TAME. The formation of hydrolytic cleavage product TA was determined with ESI-MS in the presence of radio labeled TA as an internal standard. All isotope tracers used as internal standards were obtained by isotopic exchange of products containing carboxyl (peptides and tozilarginin) in the medium H₂¹⁸O.

¹Institute for Analytical Instrumentation RAS, Saint-Petersburg. ²Institute of biomedical chemistry RAMS, Moskow. ³Institute of bioorganic chemistry RAS, Moskow. ⁴Institute of influenza RAMS, Saint-Petersburg.

The practical method for detecting of pharmaceuticals (caffeine, ketoprofen, diclofenac, ciprofloxacin) in natural water samples is presented. The solid-phase extraction (Oasis HLB cartridges) and method of high-performance liquid chromatography with high resolution tandem mass-spectrometry (LTQ OrbiTrap, ThermoFinnigan) were used. The method has been tested on standard solutions. The detection limit (5–10 ng/l), stable detection threshold and recovery for standard solutions have been estimated. The results of the analysis of the standard solutions on two types of TOF mass-spectrometers (MX 5310, IAI RAS and LCMS-IT-TOF, Shimadzu) are also presented.

¹Saint-Petersburg Research Center of Ecological Safety RAS.
²Institute for Analytical Instrumentation RAS, Saint-Petersburg.

By means of the instrument complex consisting of the time-of-flight mass-spectrometer МХ 5310 and the liquid chromatograph Milichrome A-02, the analysis of medical products composition was carried out. The possibility of sensitivity increasing chromato-mass spectrometric analysis of medical compounds in comparison with chromatographic analysis is shown.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

The possibility of interaction of acetylsalicylic acid with purified human and rat globin in vitro was investigated. The rat globin can be modified with acetylsalicylic acid on aminoacid residues K-17 and K-57 in alpha subunit as well as on K-96 in beta subunit. The human globin can be modified with acetylsalicylic acid on aminoacid residues K-17, K-41 and K-57 in alpha subunit as well as on K-18 and K-121 in beta subunit.

¹Institute for Analytical Instrumentation RAS, Saint-Petersburg.
²Research Institute of Hygiene, Occupational Pathology and Human Ecology, Saint-Petersburg.

The covalent adducts formation of sulfur mustard (HD) with rat globin have been investigated in vitro. A number tryptic peptides of rat globin, namely EFTPCHDAQAAFQK (1444.62 Da), GTFAHLSELHCHDDK (1561.66 Da), IGGHGGEYGEHDEALQR (1676.78 Da) alkylated with HD were identified by MALDI-TOF mass-spectrometry on globin amino acid residues C126, С93 and E27, respectively.

¹Institute for Analytical Instrumentation RAS, Saint-Petersburg.
²Research Institute of Hygiene, Occupational Pathology and Human Ecology, Saint-Petersburg.

The covalent adduct of organophosphorus compounds with serum albumin are perspective biomarkers of organophosphorus compounds intoxication. In the work the method of purification of phosphonylated peptides from biological samples was proposed. The combination of affinity chromatography on Cibacron Blue for purification of serum albumin and immobilized metal ion affinity chromatography (IMAC) on Fe3+ sorbent was used for purification of paraoxon-phosphonylated peptides of serum albumin. The identification of paraoxon-phosphonylated peptides was performed by MALDI TOF-TOF mass-spectrometry. The paraoxon-phosphonylated peptides of rat serum albumin contained Y-150 and Y-411 were identified by the method from sera in vivo exposured rats.

¹Institute for Analytical Instrumentation RAS, Saint-Petersburg.
²Research Institute of Hygiene, Occupational Pathology and Human Ecology, Saint-Petersburg.

The method of synthesis of complex oxide LiCoO₂ with the structure stabilized by the magnetic dilution in LiGaO₂ was developed. For the first time the qualitative elemental analysis of solid solutions of Li_1-xNa_xCoO₂—LiGaO₂ by MALDI MS was carried out.

¹Saint-Petersburg state university. ²Institute for Analytical Instrumentation RAS, Saint-Petersburg.

In this study the results of the liquid chromatography/mass-spectrometric detection of cyanobacterial toxins such as anatoxine-a and microcystin-RR, obtained on the equipment with ion traps of different types are compared. The results, obtained on LCMS-IT-TOF (Shimadzu corp.) and LTQ OrbiTrap (ThermoFinnigan) are considered. The investigations were carried out using the solutions of standards and model systems.

¹Saint-Petersburg Research Center of Ecological Safety RAS.
²Institute for Analytical Instrumentation RAS, Saint-Petersburg

This paper is devoted to the comparison of nanospray and electrospray ion sources for mass-spectrometer МХ 5310 (IAI RAS). The new ionization block allows to low down sample consumption in routine analysis (50–100 nl/min). It has been drawn a comparison between efficiencies of developed nanospray ionization block and regular one by testing compound reserpine. The derived system makes it possible to work with nano amounts of testing samples (10^–9 M). The capability of MX 5310 equipped nanospray ion source to analyze samples with multistage biochemical treatment by example of serum albumin fragments modified by insecticide paraoxon was also confirmed.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

In the work the gas-dynamic interface time-of-flight mass spectrometer MX 5311 with orthogonal input of ions and the ESI ion source is described. The results of the research of gas-dynamic interface bandwidth TOFMS MX 5311 are presented. It is shown that the complete loss of ion current during the passage of gas-dynamic interface from the field ionization chamber to the mass analyzer is less than 6 orders of magnitude.

Institute for Analytical Instrumentation RAS, Saint-Petersburg Saint-Petersburg.

In this work the results of researches of the transportation system of the ionic bunches are presented. The ions were being formed at atmospheric pressure and transported to high-vacuum area of the mass analyzer by the transportation system. The radio-frequency transporting system working at essentially different pressure of residual gas is investigated. This system works with use of two quadruples with the system of the differential pumping out. The possibility of ionic current control at pressure of the order of 1–5 Torr is shown. The possibility of ion transportation in cooling radio-frequency quadruple at pressure of the order of several 1–10 mTorr is also shown. The analysis of experimental data confirming efficiency of use of such system is carried out.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

The method of polymerase-chain reaction (PCR) in the gel is one of modern and relevant molecular diagnostic technique which has several advantages over classical PCR method in the liquid. To realize this method the prototypes of microchip devices (cartridges- microchip) with polyacrylamide gel in the reaction chamber were designed and created. They possess the appropriate physics and chemical characteristics (for example, optical). The article discusses the features of the manufacture of such microchips.

Institute for Analytical Instrumentation RAS, Saint-Petersburg.

A new approach to the solution of mathematically incorrect inverse problem of elipsometry for ultra thin superficial films based on the using of measurements corresponding to angles of incidence set of a light beam is proposed. Parameters-criterion are introduced which allow to find the optimal solution of an inverse problem, the nearest to the exact solution. The results of the numerical experiment showed the great accuracy of the optimal solution during parameters determination of ultra thin films. The errors influence in assigning substrate optical constants on the accuracy of the optimal solution is studied. The general analysis of features of the inverse problem of simultaneous parameters determination of a reflecting single-layer system with ultra thin films is given.

¹Institute of Applied Physics NAS, Ukraine, Sumy.
²Institute for Analytical Instrumentation RAS, Saint-Petersburg.