V. M. Martynenko

Photoreduction of graphite oxide

The photoreduction of graphite oxide (GO) films and solutions by UV light was studied. The electrical resistance of a GO film decreases upon irradiation by more than an order of magnitude. The threshold of photoreduction was determined to be 3.2 eV. The photoreduction is accompanied by an increase in absorption in the visible spectral region, and the CO, CO2, O2, and H2O molecules were found in the gas phase above the irradiated GO film.

Facile preparation of amine and amino acid adducts of [60]fullerene using chlorofullerene C60Cl6 as a precursor.

We report a general synthetic approach to the preparation of highly functionalized amine and amino acid derivatives of [60]fullerene starting from readily available chlorofullerene C(60)Cl(6). The synthesized water-soluble amino acid derivative of C(60) demonstrated pronounced antiviral activity, while the cationic amine-based compound showed strong antibacterial action in vitro.

Carbon nanomaterial produced by microwave exfoliation of graphite oxide: new insights

We present detailed characterization of graphene-like material obtained through microwave stimulated exfoliation of graphite oxide (GO). Properties of this material were studied by multiple techniques including, among others, X-ray photoelectron spectroscopy, mass-spectroscopy, infrared and Raman spectroscopy, scanning electron microscopy and broadband dielectric spectroscopy. Specific surface area and volume of microwave exfoliated graphite oxide reached 600 m2 g−1 and 6 cm3 g−1, respectively. It is shown that during such an explosive reduction process the sample emits CO2, CO and H2O and, in some cases, SO2 gases. The resulting reduced material exhibits IR spectra similar to that of graphite and a dc-conductivity of 0.12 S cm−1.

[Fe2(μ-SC5H4N)2(NO)4] as a New Potential NO Donor: Synthesis, Structure, and Properties

A new potential donor of nitrogen monoxide, a binuclear iron sulfur nitroso complex, was prepared by exchange reaction of Na2Fe2(S2O3)2(NO)4 with pyridine-2-thiol in the presence of sodium thiosulfate at pH 12. The molecular and crystal structures of [Fe2(μ-SC5H4N)2(NO)4] were studied by X-ray diffraction analysis. The type of iron coordination by pyridine-2-thiol in the presence of a coordinated NO molecule was determined. In vacuum, the structure of the complex is destroyed, which is accompanied by NO evolution, while exposure to UV radiation results in decomposition of the complex and in a release of N2O.

Fabrication and characterization of fluorinated single-walled carbon nanotubes

The optimum conditions for the fluorination of single-walled carbon nanotubes (SWCNT) in the atmosphere of gaseous fluorine with the nanotube structure remaining intact up to a stoichiometry of CFx, x ∼ 0.5 were determined. The kinetics of fluorination was examined. The fluorinated SWCNTs were characterized by various methods, including transmission electron microscopy, measurements of specific surface area and accessible internal volume, NMR spectroscopy, IR spectroscopy, X-ray absorption and photoelectron spectroscopies, thermal stability, and analysis of gaseous products by mass-spectrometry. The structure of fluorinated SWCNT was preserved up to brutto-composition CF0.5 but degree of fluorination of SWCNT bundles was decreased with distance from the SWCNT surface to its core. Such a decrease becomes evident at ∼1.5 nm distance. It means that the degree of fluorination depends on the degree of its dispersion.

Harnessing Electron Transfer from the Perchlorotriphenylmethide Anion to Y@C82(C2v) to Engineer an Endometallofullerene‐Based Salt

We show that electron transfer from the perchlorotriphenylmethide anion (PTM(-)) to Y@C82(C2v) is an instantaneous process, suggesting potential applications for using PTM(-) to perform redox titrations of numerous endohedral metallofullerenes. The first representative of a Y@C82-based salt containing the complex cation was prepared by treating Y@C82(C2v) with the [K(+)([18]crown-6)]PTM(-) salt. The synthesis developed involves the use of the [K(+)([18]crown-6)]PTM(-) salt as a provider of both a complex cation and an electron-donating anion that is able to reduce Y@C82 C2v). For the first time, the molar absorption coefficients for neutral and anionic forms of the pure isomer of Y@C82(C2v) were determined in organic solvents with significantly different polarities.

A comparative study of graphene materials formed by thermal exfoliation of graphite oxide and chlorine trifluoride-intercalated graphite

Graphene 3D materials GM1 and GM2 obtained by explosive exfoliation of graphite oxide and graphite intercalated with chlorine trifluoride, respectively, have been studied by elemental analysis, X-ray photoelectron spectroscopy, mass spectrometry, infrared and Raman spectroscopy, and scanning electron microscopy. The specific surface area, the pore size, and electrical conductivity of the materials have been measured. A comparative study has shown that the gas mixture produced during the preparation of GM1 is less hazardous than that in the case of GM2. However, GM2 exhibits a higher conductivity and a larger size of graphene crystallites. The feasibility of isolation of a suspension of graphene nanosheets from the test 3D materials has been demonstrated. Possible applications of these materials are discussed.

Enthalpies of formation of radicals and the mass spectra of the products of tetrafluoroethylene polymerization in acetone

The mass spectra of the dissociative electron-impact ionization products of telomers formed upon the radiation-chemical telomerization of tetrafluoroethylene in acetone were measured over the range of m/z from 1 to 204. The most intense bands at m/z = 43, 51, and 57 were attributed to the CH3CO+, CF2H+ and CH3COCH2+ cations—the main dissociation products of the H(C2F4)nCH2COCH3 telomers. The telomer composition was consistent with a radical telomerization mechanism, in which chain growth and chain transfer are due to the formation of the CH3COCH2· radical. Based on published data supplemented with quantum-chemical calculations, the enthalpies of formation of the radicals R(CF2)n (n = 2–8; R = H, CH3, CH3CO, and CH3COCH2) were tabulated. The formation of telomers with the same terminal groups is consistent with thermodynamic data and a polymerization mechanism in which the chain growth reaction is diffusion-limited and the chain transfer reaction is activated hydrogen-atom transfer.

New polymer electrolytes based on polyethylene glycol diacrylate–LiBF4–1-ethyl-3-methylimidazolium tetrafluoroborate with the introduction of alkylene carbonates

Polymer gel electrolytes based on polyethylene glycol diacrylate (PEG DA), salt LiBF4, and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) were synthesized and studied in the presence of propylene carbonate and ethylene carbonate as solvents. The mechanism of ionic transport in the system was studied using electrochemical impedance spectroscopy, liquid mass spectrometry, pulse-field-gradient spin echo NMR spectroscopy. The range of operating temperatures of the gel electrolytes was determined by DSC. The total conductivity at room temperature in these systems is about 10–3 S cm–1. The self-diffusion coefficients on 7Li nuclei in the systems with a solvent attain the values about 10–10 m2 s–1, and in the PEG DA–LiBF4–EMIBF4 system they range from 10–13 to 10–12 m2 s–1. Ternary associates [(EMI)2(BF4)]+ and [Li+(BF4)2]– were found by liquid mass spectrometry to be the main charge carriers.

LC-MS study of ruthenium catalysts of water oxidation in artificial photosynthesis

Catalysts of water oxidation for artificial photosynthesis, formed from the binuclear oxysulfate ruthenium(IV) complex K4[Ru2(SO4)2(μ-SO4)2(μ-O)2] · 2H2O, are studied via chromatography-mass spectrometry. It is shown that these new catalysts do not contain organic ligands and are more stable and active than the familiar blue dimer [(bpy)2Ru(OH)2]2O4+ and its analogues. It is found that adamantane-like tetra-nuclear and octanuclear ruthenium clusters are active catalysts that oxidize water to oxygen and oxozone O4, respectively.