Structure of 5-nitro-2-tosylaminobenzaldehyde di(morpholin-4-yl)aminal Complex with Carbon Tetrachloride

The 5-nitro-2-tosylaminobenzaldehyde di(morpholin-4-yl)aminal forms a stable complex with carbon tetrachloride in the crystal phase. X-ray structural study of this complex indicates an essentially shortened intermolecular contact of 2.89 Å between the oxygen atom of the nitro group and one of the chlorine atom of the CCI4 molecule. Quantum-chemical calculations by semiempirical AMI method showed that the formation of such complex did not cause considerable decrease of system energy or change of charge distribution in molecules. It was supposed that this associate has van der Waals character

Особливості взаємодії 3-(2-амінофеніл)-6-R-1,2,4-триазин-5(2H)-онів та циклічних ангідридів несиметричних дикарбонових кислот

The peculiarities of the reaction between 3-(2-aminophenyl)-6-R-1,2,4-triazin-5(2H)-ones and cyclic anhydrides of non-symmetric (2-methylsuccinic, 2-phenylsuccinic and camphoric) acids have been described in the present article. The influence of electronic and steric effects of substituents in the anhydride molecule on cyclisation processes has been discussed. The results have shown that the interaction of 3-(2-aminophenyl)-6-R-1,2,4-triazin- 5(2H)-ones mentioned above with 2-methylsuccinic and 2-phenylsuccinic acid anhydrides proceeded non-selectively and yielded the mixtures of 2-R1-3-(2-oxo-3-R-2H-[1,2,4]triazino[2,3-c]quinazoline-6-yl)propanoic acids and 1-(2-(5-oxo-6-R-2,5-dihydro-1,2,4-triazin-3-yl)phenyl)-3-R1-pyrrolidine-2,5-diones. It has been found that low regioselectivity of the acylation process may be explained by insignificant electronic effects of substituents (of the methyl and phenyl fragment) in position 2 of the anhydride molecule on the electrophilic reaction centre. It has been also determined that the reaction between 3-(2-aminophenyl)-6-R-1,2,4-triazin-5(2H)-ones and camphoric anhydride proceeds regioselectively and yielded 1,2,2-trimethyl-3-(3-R-2-oxo-2H-[1,2,4]triazino[2,3-c]quinazolin- 6-yl)cyclopentan-1-carboxylic acids. Regioselectivity of the interaction mentioned above may be explained by the steric effect of the methyl group. Identity of compounds has been proven by LC-MS, the structure has been determined via a set of characteristic signals in 1H NMR, 13C NMR spectra and position of cross peaks in the correlation HSQC-experiment. Mass spectra of the compounds synthesized have been also studied, the principal directions of the molecule fragmentation have been described. The structure of 1,2,2-trimethyl-3-(3-methyl- 2-oxo-2H-[1,2,4]triazino[2,3-c]quinazolin-6-yl)cyclopentane-1-carboxylic acid has been proven by X-ray analysis.Описаны особенности реакции между 3-(2-аминофенил)-6-R-1,2,4-триазин-5(2H)-онами и ангидридами несимметричных дикарбоновых кислот (2-метилянтарной, 2-фенилянтарной и камфорной) кислот. Проведено обсуждение влияния электронных и стерических эффектов заместителей на процессы цик- лизации. Результаты показали, что взаимодействие приведенных выше 3-(2-аминофенил)-6-R-1,2,4- триазин-5(2H)-онов с ангидридами 2-метилянтарной и 2-фенилянтарной кислот протекало не региоселективно с образованием смесей 2-R 1-3-(2-оксо-3-R-2H-[1,2,4]триазино[2,3-c]хиназолин-6-ил)про- пановых кислот и 1-(2-(5-оксо-6-R-2,5-дигидро-1,2,4триазин-3-ил)фенил)-3-R1-пиролидин-2,5-дионов. По- казано, что низкая региоселективность процесса ацилирования может быть объяснена незначительными электронными эффектами заместителей (метильного и фенильного фрагмента) в положении 2 молекулы ангидрида на электрофильный реакционный центр. Также установлено, что реакция между 3-(2-аминофенил)-6-R-1,2,4-триазин-5(2H)-онами и ангидридом камфорной кислоты протекает регио- селективно и приводит к образованию 1,2,2-триметил-3-(3-R-2-оксо-2H-[1,2,4]триазино[2,3-c]хиназолин- 6-ил)циклопентан-1-карбоновых кислот. Селективность реакции в данном случае может быть объяснена стерическим эффектом метильной группы. Индивидуальность соединений подтверждена ме- тодами LC-MS, структуру установлено по положению характеристических сигналов в 1H ЯМР и 13С ЯМР-спектрах и по положению кросс-пиков в корреляционном HSQC-эксперименте. Также были иссле- дованы масс-спектры синтезированных соединений и описаны основные направления фрагментации молекулярных ионов. Структуру 1,2,2-триметил-3-(3-метил-2-оксо-2H-[1,2,4]триазино[2,3-c]хиназолин- 6-ил)циклопентан-1-карбоновой кислоты было доказано с помощью рентгеноструктурного анализа.Описані особливості реакції між 3-(2-амінофеніл)-6-R-1,2,4-триазин-5(2H)-онами з ангідридами несимет- ричних дикарбонових кислот (2-метилбурштинової, 2-фенілбурштинової та камфорної) кислот. Обго- ворено вплив електронних та стеричних ефектів замісника у молекулі ангідриду на процеси циклізації. Результати показали, що взаємодія наведених вище 3-(2-амінофеніл)-6-R-1,2,4-триазин-5(2H)-онів з ангідридами 2-метилбурштинової та 2-фенілбурштинової кислот перебігала нерегіоселективно з утворенням суміші 2-R1-3-(2-оксо-3-R-2H-[1,2,4]триазино[2,3-c]хіназолін-6-іл)пропанових кислот та 1-(2- (5-оксо-6-R-2,5-дигідро-1,2,4триазин-3-іл)феніл)-3-R1-піролідин-2,5-діонів. Показано, що низька регіосе- лективність процесу ацилювання може бути пояснена незначними електронними ефектами замісників (метального та фенільного фрагменту) у положенні 2 молекули ангідриду на електрофільний реакційний центр. Також встановлено, що реакція між 3-(2-амінофеніл)-6-R-1,2,4-триазин-5(2H)-онами та ангідридом камфорної кислоти перебігає регіоселективно та приводить до утворення 1,2,2-триметил-3-(3- R-2-оксо-2H-[1,2,4]триазино[2,3-c]хіназолін-6-іл)циклопентан-1-карбонових кислот. Селективність за- значеної вище реакції може бути пояснена стеричними ефектами метальної групи. Індивідуальність сполук підтверджена методом LC-MS, структуру встановлено за положенням характеристичних сигналів у 1H ЯМР та 13С ЯМР-спектрах та за положенням крос-піків у кореляційному HSQC-експерименті. Також були досліджені мас-спектри синтезованих сполук та описані основні напрямки фрагментації молекулярних іонів. Структуру 1,2,2-триметил-3-(3-метил-2-оксо-2H-[1,2,4]триазино[2,3-c]хіназолін-6-іл) циклопентан-1-карбонової кислоти було доведено за допомогою рентгеноструктурного дослідження

Peculiarities of spectral reflectance of fractions with sizes from 20 to 5,000 microns in soil samples

By the example of arable horizon samples taken from three soil types (sod-podzolic, gray forest, and leached chernozem) the peculiarities of electromagnetic waves reflection from their different particle size fractions were studied. The extraction of fractions by dry sieving was carried out using Retsch AS 200 BASIC equipment. As a result, 14 fractions ranging in size from less than 20 microns to more than 5,000 microns were isolated. Spectral reflectance was determined for each fraction and for the soil sample before sieving in the electromagnetic wave range from 350 to 2,500 nm using a SR-6500 field spectroradiometer (Spectral Evolution, USA). Analysis of similarities and differences in the obtained spectral reflectance curves of individual fractions was carried out using their visual analysis, the method of similarity dendrogram construction, as well as regression analysis between light reflectance and fraction particle size. It was confirmed that at a more detailed level of analysis compared to the one carried out by other researchers earlier, the general patterns of light reflectance of the samples do not change. A higher reflection of waves by thinner fractions and a lower reflection by more coarse fractions are observed. At the same time, spectral reflection curves for individual fractions are out of the general pattern, the level of intensity of local extremes of the curves’ changes. This confirms the difference of the material composition, which forms the color of soils, of these fractions from others. The color of the mixed sample is a spectral mixture of colors of its separate fractions. Presumably, this is the main reason for such a phenomenon as change of spectral reflectivity of open surface of soils under the influence of atmospheric precipitation

Relationship between various pathways of cellular death at distinct stages of ontogenesis in normal state and systemic diseases of connective tissue

The aim of our research  was to reveal quantitative ratios existing between  the pathways of cellular death in normal state, as well as in immunocomplex pathology. The proportion of different pathways of cell death (autophagy, apoptosis, necrosis) in autoimmune (systemic  connective tissue diseases (SDCT) – rheumatoid arthritis (RA), systemic lupus erythematosus (SLE)  and systemic scleroderma (SSD) is a subject of age-related changes. On the one hand, aging process can be considered a genetically determined overall decrease in adaptive potential of the body, and a systemic  age-related chronic inflammatory response, with a pronounced cytokine proinflammatory shift. On the other hand, a polygenic decrease in energy and information capacity  of the cells, represent the basis of multisystem and multiorgan functional and metabolic disorders  in SDCT.Blood plasma  samples were analyzed  in the patients of two age groups. The first group consisted of 10 SLE cases (4 men and 6 women, average age 43.8 years), 13 patients with RA (5 men and 8 women, average age 45.6 years),  7 SSD (women, average age 35.8 years),  and 10 healthy  donors  (6 men and 4 women, average age 40.7 years). The second age group consisted of 9 SLE cases (2 men and 7 women, average age 69.8 years), 10 patients with RA (5 men and 5 women, average age 65.6 years), 5 patients with SSD (women, average age 65.7 years) and 12 healthy  donors  (normal biological  aging – 7 men and 5 women, average age 64.7 years). The data presented in this paper  were obtained with informed consent of the  patients. When  carrying  out  biomedical research, we followed  internationally recognized ethical  standards of the Helsinki Declaration (International Medical Association, 1996, revision  2013). The proportion of various cell death  types (autophagy, apoptosis, necrosis) in  autoimmune disorders  (systemic  diseases  of connective tissue,  SDCT), i.e.,  rheumatoid arthritis (RA), systemic  lupus erythematosus (SLE), and systemic  scleroderma (SSD) proved to be subject to age-dependent changes. Close  interaction were revealed  between  the  ways of cellular  death  in SDCT (most  pronounced in SLE), correlating with age changes and clinical  manifestations of autoimmune process. In SDCT, the affected tissues exhibit all types of cellular  death, however, degree of their expression  depends on the disease nosology. Upon systemic diffuse pathology of connective tissue, autophagy (especially in case of SLE and RA) is directly involved in development of immune response  and inflammatory process.In normal biological  aging, like as in SDCT, one may observe a sharply increased activity of the metabolic trigger – AMP-activated protein kinase (AMPK), a sensor of intracellular energy, along with shifted acid-base equilibrium. The quantity of active oxygen radicals  increases, oxidoreductive potential of the cells is changed, with  activation of cellular  destruction components. Activity  of cytokine system  in the  organism  is changed causing  apoptosis regulation; expression  of chaperons is decreased, and  the immune-oxygenase homeostasis is also displaced. Inhibition of genetically determined process of death  of cells (apoptosis) comprises the basis for development of autoimmune diseases. Transition of late apoptosis into secondary necrosis  is accompanied by decrease of antioxidant protection and  development of autoimmune pathology. The  chaperon-mediated induction of immune response as the signaling mechanism of autophagy, being evolutionarily fixed in mammals only, may be the common central  link and “the  molecular switch”  causing both development of autoimmune diseases of connective tissue, and aging processes

Ассоциация полиморфизма гена аполипопротеина Е и липидного спектра с различными типами инсульта в Сибири

The present research aimed at studying association between Apo E polymorphism and certain types of stroke and also association factors of lipid profile’s results and different types of stroke it depends on sex and conditions of living in typical West Siberian megapolis (Novosibirsk).The causes of brain stroke were registered in representative population with population about 150 000 in according to standarts of WHO program MONICA and previous program «Register of stroke». From 2003 to 2007 among new registered and repeated causes of stroke was form at random 15% sample (261 patients). The average age of stroke attack is 61,3 ± 1,0 for men and 61,3 ± 1,0 for women.Independent influence of APOE gene's genotypes polymorphism on development at different stroke patients has not been revealed.Представлено исследование ассоциации полиморфизма гена APOE с определенными типами инсульта, а также ассоциации показателей липидного профиля и различных типов инсульта в зависимости от пола в условиях крупного города Западной Сибири (г. Новосибирск).Cлучаи мозгового инсульта регистрировались в репрезентативной целевой популяции с общей численностью жителей около 150 тыс. человек в соответствии с критериями программы Всемирной организации здравоохранения MONICA и предшествующей программы «Регистр мозгового инсульта». В 2003—2007 гг. среди выявленных новых и повторных случаев инсульта была сформирована случайная 15%-я выборка (261 человека). Средний возраст развития инсульта у мужчин составил (61,3 ± 1,0) года, у женщин — (66,1 ± 0,9) года.У больных различными типами инсульта не выявлено независимого влияния полиморфизма генотипов гена APOE на развитие определенных типов инсульта

Research and Development of the pyrochemical processing for the mixed nitride uranium-plutonium fuel

A mixed nitride U-Pu SNF pyrochemical reprocessing technology was suggested. It includes the following basic operations: dissolution of key components using the CdCl2 or PbCl2 oxidizer in chloride melt and their subsequent deposition as oxides. The obtained product, which is a mixture of actinides and rare-earth metals, may be additionally purified using hydrometallurgical processes (combined technology) or using pyrochemical methods. The mixture of actinides oxides is reduced to metal ("metallization"), additionally purified from fission products during electrorefining and then Am and Cm are separated using the potentiostatic electrolysis in order to obtain products that may be used for pure fuel fabrication. © 2020 IOP Publishing Ltd. All rights reserved

Revealing Josephson vortex dynamics in proximity junctions below critical current

Made of a thin non-superconducting metal (N) sandwiched by two superconductors (S), SNS Josephson junctions enable novel quantum functionalities by mixing up the intrinsic electronic properties of N with the superconducting correlations induced from S by proximity. Electronic properties of these devices are governed by Andreev quasiparticles [1] which are absent in conventional SIS junctions whose insulating barrier (I) between the two S electrodes owns no electronic states. Here we focus on the Josephson vortex (JV) motion inside Nb-Cu-Nb proximity junctions subject to electric currents and magnetic fields. The results of local (Magnetic Force Microscopy) and global (transport) experiments provided simultaneously are compared with our numerical model, revealing the existence of several distinct dynamic regimes of the JV motion. One of them, identified as a fast hysteretic entry/escape below the critical value of Josephson current, is analyzed and suggested for low-dissipative logic and memory elements.Comment: 11 pages, 3 figures, 1 table, 43 reference

Transparent dense sodium

Under pressure, metals exhibit increasingly shorter interatomic distances. Intuitively, this response is expected to be accompanied by an increase in the widths of the valence and conduction bands and hence a more pronounced free-electron-like behaviour. But at the densities that can now be achieved experimentally, compression can be so substantial that core electrons overlap. This effect dramatically alters electronic properties from those typically associated with simple free-electron metals such as lithium and sodium, leading in turn to structurally complex phases and superconductivity with a high critical temperature. But the most intriguing prediction - that the seemingly simple metals Li and Na will transform under pressure into insulating states, owing to pairing of alkali atoms - has yet to be experimentally confirmed. Here we report experimental observations of a pressure-induced transformation of Na into an optically transparent phase at 200 GPa (corresponding to 5.0-fold compression). Experimental and computational data identify the new phase as a wide bandgap dielectric with a six-coordinated, highly distorted double-hexagonal close-packed structure. We attribute the emergence of this dense insulating state not to atom pairing, but to p-d hybridizations of valence electrons and their repulsion by core electrons into the lattice interstices. We expect that such insulating states may also form in other elements and compounds when compression is sufficiently strong that atomic cores start to overlap strongly.Comment: Published in Nature 458, 182-185 (2009

Spin physics with antiprotons

New possibilities arising from the availability at GSI of antiproton beams, possibly polarised, are discussed. The investigation of the nucleon structure can be boosted by accessing in Drell-Yan processes experimental asymmetries related to cross-sections in which the parton distribution functions (PDF) only appear, without any contribution from fragmentation functions; such processes are not affected by the chiral suppression of the transversity function $h_1(x)$. Spin asymmetries in hyperon production and Single Spin Asymmetries are discussed as well, together with further items like electric and magnetic nucleonic form factors and open charm production. Counting rates estimations are provided for each physical case. The sketch of a possible experimental apparatus is proposed.Comment: Presented for the proceedings of ASI "Spin and Symmetry", Prague, July 5-10, 2004, to be published in Czech. J. Phys. 55 (2005