Archive for October 30, 2017

Green Chemistry, 2017, 19, 3032–3041

G. Werner, K.S. Rodygin, A.A. Kostin, E.G. Gordeev, A.S. Kashin, V.P. Ananikov

“A solid acetylene reagent with enhanced reactivity: fluoride-mediated functionalization of alcohols and phenols”

Green Chemistry, 2017, 19, 3032–3041
DOI: 10.1039/C7GC00724H


The direct vinylation of an OH group in alcohols and phenols was carried out utilizing a novel CaC2/KF solid acetylene reagent in a simple K2CO3/KOH/DMSO system. The functionalization of a series of hydroxyl-group-containing substrates and the post-modification of biologically active molecules were successfully performed using standard laboratory equipment, providing straightforward access to the corresponding vinyl ethers. The overall process developed involves an atom-economical addition reaction employing only inorganic reagents, which significantly simplifies the reaction set-up and the isolation of products. A mechanistic study revealed a dual role of the F additive, which both mediates the surface etching/renewal of the calcium carbide particles and activates the C[triple bond, length as m-dash]C bond towards the addition reaction. The development of the fluoride-mediated nucleophilic addition of alcohols eliminates the need for strong bases and may substantially extend the areas of application of this attractive synthetic methodology due to increasing functional group tolerance. As a replacement for dangerous and difficult to handle high-pressure acetylene, we propose the solid reagent CaC2/KF, which is easy to handle, does not require dedicated laboratory equipment and demonstrates enhanced reactivity of the acetylenic triple bond. Theoretical calculations have shown that fluoride-mediated activation of the hydroxyl group towards nucleophilic addition significantly reduces the activation barrier and facilitates the reaction.

Science of The Total Environment 2018, 615, 1229–1238

R. Vasilevich, E. Lodygina, V. Beznosikova, E. Abakumov

“Molecular composition of raw peat and humic substances from permafrost peat soils of European Northeast Russia as climate change markers”

Science of The Total Environment 2018, 615 (In Progress, Available online 17 October 2017), 1229–1238
DOI: 10.1016/j.scitotenv.2017.10.053


Humic substances (HSs) from the mire peat soils of the forest-tundra zone of the European northeast part of Russia have been characterized in terms of molecular composition. This was accomplished using solid-state 13C nuclear magnetic resonance (13C NMR) techniques and electron spin resonance (ESR) spectroscopy. The composition depended on the intensity of cryogenic processes in the active layer, the quality of the humification precursors (the degree of peat material transformation), and the biochemical selection of aromatic fragments during humification. Humic acids (HAs) and fulvic acids (FAs) of the peat soils showed the presence of compounds with a low extent of condensation and a low portion of aromatic fragments, which increased with depth. A higher proportion of aliphatic carbon species was found in the HAs, indicating a low degree of organic matter stabilization. Based on the data from the two types of peat soils, we suggest that particular changes in the proportion of aromatic and unoxidized aliphatic fragments on the border of the bottom of the active layer and permafrost layers can be used as markers of current climatic change.

Journal of Molecular Structure, 2017, 1146, 554–561

A. M. Afanasenko, D. V. Boyarskaya, I. A. Boyarskaya, T. G. Chulkova, Y. M. Grigoriev, I. E. Kolesnikov, M. S. Avdontceva, T. L. Panikorovskii, A. I. Panin, A. N. Vereshchagin, M. N. Elinson

“Structures and photophysical properties of 3,4-diaryl-1H-pyrrol-2,5-diimines and 2,3-diarylmaleimides”

Journal of Molecular Structure, 2017, 1146, 554–561
DOI: 10.1016/j.molstruc.2017.06.048


Structural features of 3,4-diaryl-1H-pyrrol-2,5-diimines and their derivatives have been studied by molecular spectroscopy techniques, single-crystal X-ray diffraction, and DFT calculations. According to the theoretical calculations, the diimino tautomeric form of 3,4-diaryl-1H-pyrrol-2,5-diimines is more stable in solution than the imino-enamino form. We also found that the structurally related 2,3-diarylmaleimides exist in the solid state in the dimeric diketo form. 3,4-Diaryl-1H-pyrrol-2,5-diimines and 2,3-diarylmaleimides exhibit fluorescence in the blue region of the visible spectrum. The fluorescence spectra have large Stokes shifts. Aryl substituents at the 3,4-positions of 1H-pyrrol-2,5-diimine do not significantly affect fluorescence properties. The insertion of donor substituents into 2,3-diarylmaleimides leads to bathochromic shift of emission bands with hyperchromic effect.

Delegation from Thailand


The delegation led by the Princess Maha Chakri Sirindhorn of Thailand has visited St Petersburg University. The delegation visited some of the Resource Centres. the Director of the Magnetic Resonance Research Centre (CMR) Petr Tolstoy has presented main research methods realized in CMR. Peter Tolstoy also has told about collaboration experience in research with the foreign scientists.
More about visit of the delegation


Total in September 1938 service applications were carried out.
All together measured:

  • 1821  1H spectra
  • 296  13C spectra
  • 72  DEPT spectra
  • 22  COSY spectra
  • 22  NOESY spectra
  • 27  31Р spectra
  • 142  19F spectra

219 applications were carried out.