Publications on the project |
036 Monomer/dimer dependent modulation of reduction of the cationic dye methylene blue in negatively charged nanolayers as revealed by mass spectrometry |
Authors: | V.S. Shelkovsky, M.V. Kosevich, O.A. Boryak, V.V. Chagovets, I.V. Shmigol, V.A. Pokrovskiy | |
Summary: | The possibility to control the reduction rate of redox-active dyes incorporated into nanostructures is of interest for nanotechnology and biomedicine. We propose a novel mass spectrometric approach to study the aggregation-dependent modulation of cationic dye methylene blue (MB) reduction in the case of its inclusion into negatively charged nanolayers, which is based on detecting the difference in the redox activity of monomers and dimers of the MB cation (Cat+). A regular reproducible recording of either intact Cat+ in the case of MB present in its monomeric form, or one- and two-electron reduction products [Cat + H] +• and [Cat + 2H]+ in the case of MB dimer formation, is observed for three different anionic nanostructures with varied content of MB, tested by three mass spectrometric methods: (1) an anionic surfactant sodium dodecyl sulfate (SDS) monolayer with adsorbed MB cations at the liquid–gas interface, probed by fast atom bombardment; (2) dried shells of soap bubbles blown from an SDS and MB aqueous solution, tested by laser desorption/ionization; (3) a nanotextured surface of porous silicon modified by –SO3- groups with adsorbed MB cations, studied by a desorption/ionization on silicon technique. The requirement for MB cations to be in the form of dimers or higher aggregates for reduction to be observed under mass spectrometric conditions is justified for the listed systems, where only another MB cation can serve as a source of the electrons and protons (or hydrogen radical H•) necessary for reduction reaction. The proposed method can be applied to mass spectrometric imaging of stained biological
materials, supplying information not only about the localization, but also the MB aggregation state as well.
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Keywords: | Methylene blue dye, SDS, mass spectrometry, reduction, monomers and dimers, nanolayers | |
Edition: | RSC Advances | | | 2014,
60260–60269,English |
036 Mass spectrometric study and computer modeling of noncovalent interactions of cytosine with polyethylene glycol oligomers |
Authors: | V.G. Zobnina, V.V. Chagovets, O.A. Boryak, M.V. Kosevich | |
Summary: | Data on noncovalent intermolecular interactions of nitrogen bases as nucleic acid components with organic polyethers are of interest both for fundamental molecular biophysics and applied tasks of production of pharmaceutical organic nanoparticles. In the present work systems composed of pyrimidine nitrogen base cytosine (Cyt) or its methylderivatives and polyethylene glycol PEG-400 oligomers Mn are examined by mass spectrometry with electrospray ionization (ESI) and fast atom bombardment. Recording of a set of associates of Mn·Сyt·H+ type (n = 3–17) in the ESI mass spectra evidences formation of protonated complexes of the base with oligomers of various chain length in all systems studied. Computer modeling by means of molecular dynamics provided answers to questions concerning stability and structure of these complexes under different conditions. It is shown that Mn·Сyt·H+ clusters in the gas phase (vacuum) adopt a compact structure with a quasi-cyclic or quasi-helical self-organization of a polymeric chain around the protonated base. It is established that the compact structure of M8·Сyt·H+ complex characteristic of its gas phase state is preserved in liquid medium of methanol (utilized as a solvent in ESI). The results of simulation of evolution of methanol droplet in vacuum, which mimics the droplet disintegration under ESI conditions, have shown that the M8·Сyt·H+ complex initially present in the droplet does not disintegrate in the process of droplet evaporation. After completion of desolvation the complex returns to the conformation characteristic of the gas phase state. Thus, the evidence is found to the fact that M8·Сyt·H+ clusters recorded on the ESI mass spectra reflect adequately the presence of the corresponding noncovalent complexes in the analyzed liquid solution. | |
Keywords: | nitrogen base, cytosine, polyethylene glycol PEG-400, noncovalent complexes, mass spectrometry, electrospray ionization, computer
simulation, molecular dynamics | |
Edition: | | | | 2014,
97–106,Russian |
036 Chapter Seven: Interactions of Biologically Active Redox-Sensitive Dyes with Nanomaterials: Mass Spectrometric Diagnostics |
Authors: | M.V. Kosevich, O.A. Boryak, V.V. Chagovets, V.S. Shelkovsky, V.A. Pokrovskiy | |
Summary: | A problem of intermolecular interactions of biologically active molecules with nanomaterials, addressed by approaches of modern nanobiophysics, is of both basic and applied importance. Useful functional properties of nanocomposites of redox-active organic dyes with carbon nanoparticles and nanotextured surfaces of inorganic materials are provided namely by their peculiar intermolecular interactions. A novel mass spectrometric approach to study of such interactions at the nano-level is overviewed and discussed in the present review. The novelty of the method is in possibility of evaluation of elementary steps of electrons and proton transfer within the nanocompostes of redox-sensitive dyes, essential for their functioning. Recent achievement of the proposed mass spectrometric approach in monitoring of reduction reactions of imidazophenazine derivatives and cationic methylene blue dye deposited on carbon nanoparticles, mesoporous dioxide films, nanostructured graphite surface, and organic monolayers are highlighted. | |
Keywords: | nanobiophysics, nanotechnology, nanomaterials, nanodevice, redox-sensitive dyes, imidazophenazine dyes, methylene blue, mass spectrometry, ,molecular dynamics simulation, quantum chemistry | |
Edition: | Nanobiophysics: Fundamental and Applications. – Singapore: Pan Stanford Publishing | | | 2014,
179–216,English |
036 Study of nanocomposites of amino acids and organic polyethers by means of mass spectrometry and molecular dynamics simulation |
Authors: | V.G. Zobnina, M.V. Kosevich, V.V. Chagovets, O.A. Boryak | |
Summary: | A problem of elucidation of structure of nanomaterials based on combination of proteins and polyether polymers is addressed on the monomeric level of single amino acids and oligomers of PEG-400 and OEG-5 polyethers. Efficiency of application of combined approach involving experimental electrospray mass spectrometry and computer modelling by molecular dynamics simulation is demonstrated. It is shown that oligomers of polyethers form stable complexes with amino acids valine, proline, hisidine, glutamic and aspartic acids. Molecular dynamics simulation has shown that stabilization of amino acid-polyether complexes is achieved due to winding of the polymeric chain around charged groups of amino acids. Structural motives revealed for complexes of single amino acids with polyethers can be realized in structures of protein-polyether nanoparticles currently designed for drug delivery. | |
Keywords: | nanocomposites, nanoclusters, nanoparticles, amino acids, organic polyethers, PEG, self-assembly, electrospray mass spectrometry, molecular dynamics simulation | |
Edition: | Nanomaterials Imaging Techniques, Surface Studies, and Applications - New York: Springer | | | 2013,
327-338,English |
036 Grid Infrastructure of B. Verkin ILTPE NASU and its practical use in scientific research |
Authors: | V.I. Belan, L.F. Belous, S.A. Egupov, V.G. Zobnina, A.Yu. Ivanov, V.A. Karachevtsev, M.V. Kosevich, V.D. Natsik, V.M. Polyakov, Yu.V. Rubin, S.N. Smirnov, S.G. Stepanian, E.Yu. Torgonin, V.V. Chagovets | |
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Edition: | Collection of scientific papers of International Conference “Parallel and Distributed Computing Systems”, PDCS 2014, 4–6 March, 2014, Kharkiv, Ukraine. – Kharkiv: ISMA Publishing House, 2014 | | | 2014,
27-40,Russian |
036 Application of HPC-technologies at B. Verkin ILTPE NAS of Ukraine |
Authors: | V.I. Belan, L.F. Belous, G.E. Grechnev, E.S. Zarudnev, V.G. Zobnina, A.Yu. Ivanov, M.V. Karachevtsev, M.V. Kosevich, Yu.V. Rubin, V.V. Slavin, S.N. Smirnov, S.G. Stepanian, V.V. Chagovets | |
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Edition: | Collection of scientific papers of International Conference “Parallel and Distributed Computing Systems”, PDCS 2013, 13-14 March, 2013, Kharkiv, Ukraine. – Kharkiv: ISMA House | | | 2013,
23-40,Russian |
036 Observation of poly(ethylene glycol) clusters with the chlorine anion in the gas phase under electrospray conditions |
Authors: | M.V. Kosevich, V.G. Zobnina, V.V. Chagovets, O.A. Boryak | |
Summary: | It is demonstrated herein that poly(ethylene glycol) (PEG) oligomers can form stable complexes with the chlorine anion in the gas phase as evidenced by results from electrospray ionization mass spectrometry (ESI-MS) and molecular dynamics simulation. While the formation of crown-ether-like structures by acyclic polyethers in their complexes with alkali metal cations coordinated by the ether oxygen atoms has been extensively studied, the possibility of forming ‘inversed’ quasi-cyclic structures able to bind a monoatomic anion has not been proved till now. We have observed the formation of stable gas-phase complexes of oligomers of PEG-400 with the Cl− anion experimentally by ESI-MS for the first time. It is suggested that a necessary precondition for obtaining the polyether-chlorine anion clusters is the prevention of the formation of neutral ion pairs. Molecular dynamics simulation has demonstrated the wrapping of the Cl− anion by the PEG chain, to stabilize the PEGn•Cl− clusters in the gas phase. The conformation of the polyether chain in such quasi-cyclic or quasi-helical complexes is ‘inversed’ compared with that in the complexes with cations: that is its hydrogen atoms are turned towards the central anion. Awareness of the possibility of the Cl− anion being trapped in quasi-cyclic PEG structures may be of practical importance when considering the intermolecular interactions of PEGs. | |
Keywords: | polyethylene glycol, chlorine anion, clusters, electrospray mass spectrometry, molecular dynamics simulation | |
Edition: | Rapid Communications in Mass Spectrometry | | | 2011,
713–718,English |
036 Intermolecular interactions of polyethers oligomers with amino acid histidine |
Authors: | V.G. Zobnina, M.V. Kosevich, O.A. Boryak, V.V. Chagovets | |
Summary: | In the framework of a problem of interactions of protein components – amino acids – with polymer
compounds on the level of intermolecular complexes a model system: «histidine – oligomers of oxyethylated
glycerol OEG-5» was studied. Sets of protonated associates of histidine molecule with one and two oligomers of
OEG -5 – ОЕGn•His•Н+ and ОЕGn•ОЕGm•His•Н+ – were registered by experimental mass spectrometriс technique in the positive ion mode. Structures of such complexes, determined by molecular dynamics simulation, are proposed. It is found that in clusters with histidine the wrapping of the polymer chains around the charged groups of amino acid takes place. | |
Keywords: | histidine, oxyethylated glycerol, intermolecular interactions, mass spectrometry, molecular dynamics | |
Edition: | | | | 2011,
88–93,Russian |
036 036
The events in the framework of the project |
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036 1.4. Diagnostics and modeling of nanosystems Purpose:Development of new approaches to diagnostic of the structure of nanoparticles using up-to-date capabilities of mass spectrometry combined with computer modeling and their application to study of nanoparticles of organic polymers and inorganic clusters aimed at discovering the mechanisms of their formation and stabilization, determination of structural, energetic and electronic characteristics of such nanomaterials. Expected results:Issue of new types of products: methods, theories Stage 1:Experimental mass spectrometric study of nanoparticles based on organic polyethers with inorganic and organic ions. Stage 2:Experimental study and computer modeling of composites of organic polymers and inorganic nanoparticles by means of quantum chemistry and molecular dynamics. Stage 3:Development of cryotechnology methods for manufacturing of nanoparticles and development of low temperature mass spectrometry method of monitoring of successivestages of the nanomaterials formation. Stage 4:Mass spectrometry diagnostics of composites of polymers with nanoforms of carbon and inorganic nanoclusters. Stage 5:Study of tunnel effects in nanoparticles and their components and elaboration of the complex method of combined experimental and calculation diagnostics of nanoparticles.
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