


Vol 50, No 6 (2016)
- Year: 2016
- Articles: 11
- URL: https://journal-vniispk.ru/0018-1439/issue/view/9537
General Aspects of High Energy Chemistry
Application of deuterium–hydrogen exchange to study the secondary structure of oligonucleotide ions in a gas phase
Abstract
At present, the secondary structure of oligonucleotide ions in a gas phase is almost not understood. One of the main points is the retention of a hairpin secondary structure during ionization. In this work, we used a deuterium–hydrogen exchange reaction in a gas phase at atmospheric pressure for studying the conformational dynamics of oligonucleotide ions formed as a result of electrospray ionization. The exchange reactions of two oligonucleotides, which consisted of the identical sets of nucleotides but differed in their sequence, have been studied. One of these oligonucleotides formed a hairpin secondary structure, but the other did not. It has been found that both of the oligonucleotides demonstrate similar reaction dynamics of deuterium/hydrogen exchange in the gas phase; thereby indicating that the secondary structure has been completely destroyed during ionization.



Radiation Chemistry
Resonance electron capture by the molecules of α- and β-C(14)-methoxy isomers of 10,12-dehydro-8,9-seco-8,9-dioxolappaconine and its oxo derivative
Abstract
The formation of negative ions of some diterpene alkaloid molecules having conjugated πС=С and πС=О bonds in their structure by resonance electron capture has been studied. The mass spectra of these compounds are due to electron capture onto the lowest unoccupied molecular orbital (LUMO), which is π*-С=С or π*-С=О in nature. It has been found that the partial conversion of the test compound molecules into the enol form is possible on transferring into a gas phase; for this purpose, the appearance potentials of the ions (M–H)– and (M–OCH3)– have been compared with the calculated thermodynamic thresholds of their appearance in the keto and enol forms.



Photonics
Chemiluminescence accompanying solid-phase interaction of terbium(III) sulfate with xenon difluoride
Abstract
It has been found that solid-phase interaction of anhydrous terbium(III) sulfate powder with xenon difluoride at room temperature is accompanied by chemiluminescence (CL). The formation of terbium( IV) and ozone in the course of the reaction has been observed spectrophotometrically. Two CL emitters, xenon in the Xe(I)* oxidation state (540, 580 nm) and Tb(III)* (490, 545, 590 nm), have been revealed. Emission by the former is observed at the beginning of the reaction. After the consumption of xenon difluoride, the emission is due to excited Tb(III) generated as a result of reduction of the Tb(IV) intermediate.



Photoinduced processes in bis(diethylaminobenzylidene)cyclohexanone and its bis(aza-18-crown-6)-containing analogue in acetonitrile
Abstract
Photoinduced processes in bis(diethylaminobenzylidene)cyclohexanone (CH1) and its bis(aza-18-crown-6) derivative (CH2) in acetonitrile at ambient temperature and 77 K have been studied. The absorption, fluorescence, and phosphorescence spectra of CH1 and CH2 are similar. The probability of the formation of the triplet state is higher for CH2 molecules (λT-Tmax = 660 nm, lifetime τT ~ 20 μs). The lifetime of the CH1 molecule in the triplet state is estimated at τT ~ 2–3 μs. Photoisomers of CH1 and CH2 are formed along with the triplet state. According to DFT calculation results, the formation of trans–cis photoisomers of CH1 and CH2 is the most energetically favorable.



Influence of gold nanoparticles on nonradiative energy transfer in nanoclusters of colloidal quantum dots InP@ZnS
Abstract
The influence of gold nanoparticles on the efficiency of nonradiative resonance energy transfer between InP@ZnS quantum dots composed of nanoclusters, a new type of organized structures consisting of hydrophobic quantum dots and gold nanoparticles, has been experimentally studied.



Nanostructured Systems and Materials
Crystal structure as the basis for the lack of enantiotropic mesomorphism in 3-hydroxy-4-propionylphenyl-4′-n-alkyloxybenzoates
Abstract
Features of the molecular structure and crystal packing of the mesogenic compounds 3-hydroxy-4-propionylphenyl esters of 4-n-amyloxy (1), 4-n-hexyloxy (2), 4-n-heptyloxy (3), and 4-n-octyloxybenzoic acid (4) have been analyzed on the basis of X-ray diffraction (XRD) data. Comparison of the results of XRD and DSC studies of these compounds has shown that the crystalline modification studied for each of the compounds is not a precursor to the mesophase. The possibility of mesophase formation from the melt is discussed.



Plasma Chemistry
Formation of composite membranes containing hydrophobic polymer layers by electron-beam sputter deposition
Abstract
The chemical structure and the contact and morphological properties of composite membranes prepared by electron-beam sputter deposition of a polytetrafluoroethylene layer on the surface of track-etched polypropylene membrane have been studied. It has been found that the application of such layers results in bilayer composite membranes with both the layers having hydrophobic properties. It has been shown that an increase in the thickness of the deposited polytetrafluoroethylene layer leads to development of its roughness, resulting in the formation of a polymer with superhydrophobic properties on the surface of the initial membrane.



Synthesis of titanium nitride and carbonitride nanopowders in confined-jet flow plasma reactor
Abstract
The synthesis of titanium nitride and carbonitride nanopowders from titanium tetrachloride vapor in a stream of hydrogen–nitrogen plasma, generated by an arc torch, in confined-jet flow reactor has been experimentally studied. Single-phase nanopowders with a NaCl-type cubic crystal lattice as assemblies of preferably cube-shaped nanoparticles of a 20–150 nm size and aggregates based on them have been obtained in the experiments. By varying the synthesis parameters, it has been possible to prepare titanium nitride nanopowders with a specific surface area in the range of 11–39 m2/g containing 18.8–22.5 wt % nitrogen, which corresponds to the empirical formula TiN0.79–TiN0.99. The titanium carbonitride nanopowders had a specific surface area of 13–23 m2/g and carbon and nitrogen contents of 7.5–13.6 and 13.5–5.1 wt %, respectively.



The possible role of X-rays during radiofrequency discharge plasma treatment of polymer films



Short Communications Radiation Chemistry
Radiation telomerization of tetrafluoroethylene in trifluoroethanol solution with ethanol



Letter to the Editor
On the changes in mass of fluoropolymer films exposed to near-space factors


