Synthesis of Trifluoromethylated Monoterpene Amino Alcohols.

For the first time, monoterpene trifluoromethylated ß-hydroxy-benzyl-O-oximes were synthesized in 81-95% yields by nucleophilic addition of the Ruppert-Prakash reagent (TMSCF3) to the corresponding ß-keto-benzyl-O-oximes based on (+)-nopinone, (-)-verbanone and (+)-camphoroquinone. Trifluoromethylation has been determined to entirely proceed chemo- and stereoselective at the C=O rather than C=N bond. Trifluoromethylated benzyl-O-oximes were reduced to the corresponding α-trifluoromethyl-ß-amino alcohols in 82-88% yields. The structure and configuration of the compounds obtained have been established.

Synthesis and Oxidative Transformations of New Chiral Pinane-Type γ-Ketothiols: Stereochemical Features of Reactions.

Chiral γ-ketothiols, thioacetates, thiobenzoate, disulfides, sulfones, thiosulfonates, and sulfonic acids were obtained from ß-pinene for the first time. New compounds open up prospects for the synthesis of other polyfunctional compounds combining a biologically active pinane fragment with various pharmacophore groups. It was shown that the syntheses of sulfanyl and sulfonyl derivatives based on 2-norpinanone are characterized by high stereoselectivity in comparison with similar reactions of pinocarvone. The conditions for the preparation of diastereomerically pure thioacetyl and thiobenzoyl derivatives based on pinocarvone, as well as for the chemoselective oxidation of γ-ketothiols with chlorine dioxide to the corresponding thiolsulfonates and sulfonic acids, were selected. The effect of the VO(acac)2 catalyst on the increase in the yields of thiosulfonates was shown. A new direction of the transformation of thiosulfonates with the formation of sulfones was revealed. In the case of pinocarvone-based sulfones, the configuration is inversed at the C2 atom. An epimerization scheme is proposed.

Pollen data from bottom sediments of a tundra lake in the Yerkuta River basin on the Yamal Peninsula.

This article extends the findings of our previous research "Preliminary reconstruction of climate changes and vegetation cover inferred from pollen study of the arctic lake bottom sediments from the southwestern part of the Yamal Peninsula" (G.R. Nigamatzyanova, N.M. Nigmatullin, B.I. Gareev, O.N. Tumanov, L.A. Frolova, 21st International Multidisciplinary Scientific GeoConference SGEM. 4 (2021) 415-421. https://doi.org/10.5593/sgem2021/4.1/s19.53) [1]. The Late Holocene vegetation history of the southern part of the Yamal Peninsula was reconstructed using the pollen data obtained from bottom sediments of the tundra lake K1 (68°15.320' N, 69°07.675' E) near the Yerkuta research station in the Yerkuta River basin. A 30-cm-long sediment core was drilled during the expedition to the lake in 2014. A total of 15 samples were taken at 1-cm intervals for palynological analysis. To extract pollen grains, prior chemical treatment of the samples by the standard methods. The palynological dataset was exported in Excel sheets, one listing the raw pollen counts and the other containing the pollen percentages determined with respect to the total pollen counts for all taxa. The palynodiagram illustrating the variations in pollen and spore percentages with depth is given. These palynological records yield insight into the vegetation dynamics on the Yamal Peninsula in response to the climate forcing and may be of practical importance in regional syntheses of the vegetation history in the region.

Increasing the Efficacy of Treatment of Staphylococcus aureus-Candida albicans Mixed Infections with Myrtenol.

Infectious diseases caused by various nosocomial microorganisms affect worldwide both immunocompromised and relatively healthy persons. Bacteria and fungi have different tools to evade antimicrobials, such as hydrolysis damaging the drug, efflux systems, and the formation of biofilm that significantly complicates the treatment of the infection. Here, we show that myrtenol potentiates the antimicrobial and biofilm-preventing activity of conventional drugs against S. aureus and C. albicans mono- and dual-species cultures. In our study, the two optical isomers, (-)-myrtenol and (+)-myrtenol, have been tested as either antibacterials, antifungals, or enhancers of conventional drugs. (+)-Myrtenol demonstrated a synergistic effect with amikacin, fluconazole, and benzalkonium chloride on 64-81% of the clinical isolates of S. aureus and C. albicans, including MRSA and fluconazole-resistant fungi, while (-)-myrtenol increased the properties of amikacin and fluconazole to repress biofilm formation in half of the S. aureus and C. albicans isolates. Furthermore, myrtenol was able to potentiate benzalkonium chloride up to sixteen-fold against planktonic cells in an S. aureus-C. albicans mixed culture and repressed the adhesion of S. aureus. The mechanism of both (-)-myrtenol and (+)-myrtenol synergy with conventional drugs was apparently driven by membrane damage since the treatment with both terpenes led to a significant drop in membrane potential similar to the action of benzalkonium chloride. Thus, due to the low toxicity of myrtenol, it seems to be a promising agent to increase the efficiency of the treatment of infections caused by bacteria and be fungi of the genus Candida as well as mixed fungal-bacterial infections, including resistant strains.

Unraveling the Mechanism of Platelet Aggregation Suppression by Monoterpenoids.

Platelet aggregation causes various diseases and therefore challenges the development of novel antiaggregatory drugs. In this study, we report the possible mechanism of platelet aggregation suppression by newly synthesized myrtenol-derived monoterpenoids carrying different heteroatoms (sulphur, oxygen, or nitrogen). Despite all tested compounds suppressed the platelet aggregation in vitro, the most significant effect was observed for the S-containing compounds. The molecular docking confirmed the putative interaction of all tested compounds with the platelet's P2Y12 receptor suggesting that the anti-aggregation properties of monoterpenoids are implemented by blocking the P2Y12 function. The calculated binding force depended on heteroatom in monoterpenoids and significantly decreased with the exchanging of the sulphur atom with oxygen or nitrogen. On the other hand, in NMR studies on dodecyl phosphocholine (DPC) as a membrane model, only S-containing compound was found to be bound with DPC micelles surface. Meanwhile, no stable complexes between DPC micelles with either O- or N-containing compounds were observed. The binding of S-containing compound with cellular membrane reinforces the mechanical properties of the latter, thereby preventing its destabilization and subsequent clot formation on the phospholipid surface. Taken together, our data demonstrate that S-containing myrtenol-derived monoterpenoid suppresses the platelet aggregation in vitro via both membrane stabilization and blocking the P2Y12 receptor and, thus, appears as a promising agent for hemostasis control.

Data on taxa composition of freshwater zooplankton and meiobenthos across Arctic regions of Russia.

We present the presence/absence species list (Table 1) of rotifer, cladoceran, and copepod (Calanoida, Harpacticoida, and Cyclopoida) fauna from seven Arctic regions of Russia (the Kola Peninsula, the Pechora River Delta, the Bolshezemelskaya tundra, the Polar Ural, the Putorana Plateau, the Lena River Delta, and the Indigirka River Basin) based on our own and literature data. Our own records were obtained by analyzing samples of zooplankton, meiobenthos, and two cores of bottom sediments (from the Kola Peninsula and the Bolshezemelskaya tundra lakes) that we collected once in July or August in 1992, 1995-2017. To supplement the list, we used relevant literature with periods of research from the 1960s to the 2010s. The list is almost identical to "Dataset 2: Zooplankton and Meiofauna across Arctic Regions of Russia", which was analyzed but not published in [1]. The detailed analysis of this list revealed the specific composition of the aquatic fauna associated with the climatic and geographical factors [1]. The data provide information on the current state of biodiversity and species richness in Arctic fresh waters and can serve as the basis for monitoring these environments and predicting how they are likely to change in the future.

Design, Spectral Characteristics, and Possibilities for Practical Application of BODIPY FL-Labeled Monoterpenoid.

This article describes the design and biological properties of a BODIPY FL-labeled monoterpenoid BF2-meso-(4-((1″R)-6″,6″-dimethylbicyclo[3.1.1]hept-2″-ene-2″)yl-methoxycarbonylpropyl)-3,3',5,5'-tetramethyl-2,2'-dipyrromethene conjugate (BODIPYmyrt). The fluorophore was characterized using X-ray, NMR, MS, and UV/vis spectroscopy. The conjugate exhibits a high quantum yield (to ∼100%) in the region 515-518 nm. BODIPYmyrt effectively penetrates the membranes of the bacterial and fungal cells and therefore can be used to examine the features of a broad spectrum of Gram-positive and Gram-negative bacteria and pathogenic fungi as well. Moreover, BODIPYmyrt exhibits a moderate tropism to the subcellular structures in mammalian cells (e.g., mitochondria), thereby providing an attractive scaffold for fluorophores to examine these particular organelles.