High-pressure phase and transition phenomena in ammonia borane NH3BH3 from X-ray diffraction, Landau theory, and ab initio calculations

Structural evolution of a prospective hydrogen storage material, ammonia borane NH3BH3, has been studied at high pressures up to 12 GPa and at low temperatures by synchrotron powder diffraction. At 293 K and above 1.1 GPa a disordered I4mm structure reversibly transforms into a new ordered phase. Its Cmc21 structure was solved from the diffraction data, the positions of N and B atoms and the orientation of NH3 and BH3 groups were finally assigned with the help of density functional theory calculations. Group-theoretical analysis identifies a single two-component order parameter, combining ordering and atomic displacement mechanisms, which link an orientationally disordered parent phase I4mm with ordered distorted Cmc21, Pmn21 and P21 structures. We propose a generic phase diagram for NH3BH3, mapping three experimentally found and one predicted (P21) phases as a function of temperature and pressure, along with the evolution of the corresponding structural distortions. Ammonia borane belongs to the class of improper ferroelastics and we show that both temperature- and pressure-induced phase transitions can be driven to be of the second order. The role of N-H...H-B dihydrogen bonds and other intermolecular interactions in the stability of NH3BH3 polymorphs is examined.Comment: 23 pages, 7 figure

Creation of operation algorithms for combined operation of anti-lock braking system (ABS) and electric machine included in the combined power plant

The paper considers the Anti-lock Braking System (ABS) operation algorithm, which enables the implementation of hybrid braking, i.e. the braking process combining friction brake mechanisms and e-machine (electric machine), which operates in the energy recovery mode. The provided materials focus only on the rectilinear motion of the vehicle. That the ABS task consists in the maintenance of the target wheel slip ratio, which depends on the tyre-road adhesion coefficient. The tyre-road adhesion coefficient was defined based on the vehicle deceleration. In the course of calculated studies, the following operation algorithm of hybrid braking was determined. At adhesion coefficient ≤0.1, driving axle braking occurs only due to the e-machine operating in the energy recovery mode. In other cases, depending on adhesion coefficient, the e-machine provides the brake torque, which changes from 35 to 100% of the maximum available brake torque. Virtual tests showed that values of the wheel slip ratio are close to the required ones. Thus, this algorithm makes it possible to implement hybrid braking by means of the two sources creating the brake torque

НОВЫЕ ПАЛЕОМАГНИТНЫЕ ДАННЫЕ ПО СИЛУРИЙСКИМ И ДЕВОНСКИМ ОСАДОЧНЫМ ПОРОДАМ ПОДОЛИИ (ЮГО-ЗАПАДНАЯ УКРАИНА) И КИНЕМАТИКА ВОСТОЧНО-ЕВРОПЕЙСКОЙ ПЛАТФОРМЫ В СРЕДНЕМ ПАЛЕОЗОЕ

Paleomagnetic data are the priority source of information for global paleotectonic reconstructions representing horizontal movements of the crustal blocks. Upon receipt of new paleomagnetic data, kinematic models of the East European platform in the Paleozoic are regularly revised and improved. The article presents results of the paleomagnetic study of sedimentary gray-colored and red beds of the Silurian and Lower Devonian sequences located in the Dniester river basin, Podolia region, SW Ukraine. The study covered 17 outcrops that are stratigraphically correlated with the Wenlock, Ludlow, Pridoli states of the Sillurian and the Lochkovian stage of the Devon. Over 400 samples of grey limestone, argillite, dolomite, red limestone and sandstone were analyzed, and two components of natural remnant magnetization (NRM) were revealed. The first component with SSW declination and negative inclination is revealed in the majority of the samples during AF- and T-magnetic cleaning. Its pole positions, that are calculated separately for each series, are trending to the Permian segment of the apparent polar wander path (APWP) published by Torsvik et al. [2012] for Baltica / Stable Europe. Considering its chemical origin, this NRM component is related to formation of authigenic minerals due to rock remagnetization. The second component is revealed only in some samples taken from the red beds (during thermal demagnetization in the range of unblocking temperatures from 590 to 690 °С) and in few samples of grey limestone (in AF fields from 30 to 70 mT or in the range of unblocking temperatures from 300 to 460 °С). This component has SW declination and positive inclination, goes to the origin of coordinates of the diagrams, and has all the indicators of primary magnetization of sediments. Calculated positions of the poles (0 ºS and 329 ºE for grey limestone of the Tiverskaya series, 2.3 °S and 338.4 °E for red beds of the Dniestrovskaya series, etc.) are well correlated with the Devonian segments of APWP for Baltica / Stable Europe. The same is true for the Silurian poles. The new results suggest that in the Ludlow, the East European platform was located at the near-equatorial latitudes of the Southern Hemisphere, and in the Pridoli, it moved to the north towards the equatorial latitudes of the Southern Hemisphere. Later on, the drifting mode was changed, and the platform moved to the south. In the Lochkovian, its position was stabilized at the equatorial latitudes of the Southern Hemisphere. Drifting of the platform can be described by counterclockwise rotation by 16° around the Euler pole (Φ=34 °S, Λ=247 °E). Палеомагнитным данным отводится приоритетная роль при глобальных палеотектонических реконструкциях, которые отображают горизонтальные перемещения отдельных блоков земной коры. Построенные на их основе кинематические модели миграции Восточно-Европейской платформы (ВЕП) в палеозое по мере поступления нового фактического материала постоянно уточняются. В работе приводятся результаты палеомагнитных исследований осадочных сероцветных и красноцветных отложений силура и нижнего девона юго-запада Украины (район Подолии, бассейн реки Днестр). Для палеомагнитных исследований были выбраны 17 обнажений, которые стратиграфически сопоставимы с венлокским, лудловским, пржидольским отделами силура и лохковским ярусом девона и представлены сероцветными известняками, аргиллитами, доломитами и красноцветными известняками и песчаниками. В результате исследований коллекции более 400 образцов были выделены две компоненты естественной остаточной намагниченности (ЕОН). Первая выделяется на большинстве образцов при Н- и Т-чистках, имеет юг-юго-западное склонение и отрицательное наклонение. Соответствующие ей палеомагнитные полюсы, рассчитанные для каждой серии отдельно, тяготеют к пермскому сегменту сегмента траектории кажущейся миграции полюса (ТКМП) для Балтики / стабильной Европы [Torsvik et al., 2012]. Эта компонента химической природы связана с образованием аутигенных минералов при перемагничивании пород. Другая компонента, выделяемая в только в отдельных образцах красноцветов (при температурной чистке в диапазоне деблокирующих температур 590–690 °С) и в единичных образцах сероцветов (в переменных полях 30–70 мТл либо в диапазоне деблокирующих температур 300–460 °С), имеет юго-западное склонение и положительное наклонение, идет к началу координат диаграмм и характеризуется всеми признаками первичной намагниченности. Рассчитанные палеомагнитные полюса (0 °S, 329 °E для сероцветов тиверской серии, 2.3 °S, 338.4 °E для красноцветов днестровской серии и др.) хорошо согласуются с нижнедевонским фрагментом ТКМП для Балтики / стабильной Европы. Это же справедливо и для силурийских полюсов. Согласно новым результатам, в лудлове ВЕП располагалась в приэкваториальных широтах Южного полушария, в пржидольское время перемещалась к северу в экваториальные широты Южного полушария. Далее характер дрейфа изменяется – происходит перемещение уже в южном направлении, и в лохковское время положение ВЕП стабилизируется в приэкваториальных широтах Южного полушария. Характер дрейфа платформы можно описать поворотом против часовой стрелки на 16º вокруг полюса Эйлера, с координатами Φ=34 °S, Λ=247 °E.

Microevolution of tick-borne encephalitis virus in course of host alternation

AbstractTwo tick-borne encephalitis (TBE) virus variants were studied: mouse brain-adapted strain EK-328 and its derivate adapted to Hyalomma marginatum ticks. The tick-adapted virus exhibited small-plaque phenotype and slower replication in PEK cells, higher yield in ticks, decreased neuroinvasiveness in mice, increased binding to heparin-sepharose. A total of 15 nucleotide substitutions distinguished genomes of these variants, six substitutions resulted in protein sequence alterations, and two were in 5′NTR. Two amino acid substitutions in E protein were responsible for the observed phenotypic differences. Data obtained during reverse passaging of the tick-adapted virus in vivo and in vitro suggest that TBE virus exists as a heterogeneous population that contains virus variants most adapted to reproduction in either ticks or mammals. Host switch results in a change in the ratio of these variants in the population. Plaque purification of the tick-adapted virus resulted in the prompt emergence of new mutants with different virulence for mammals

The peculiarities of cross-correlation between two secondary precursors - radon and magnetic field variations, induced by stress transfer changes

A model of precursor manifestation mechanisms, stimulated by tectonic activity and some peculiarities of observer strategy, whose main task is the effective measurement of precursors in the spatial area of their occurrence on the Earth's daylight, are considered. In particular, the applicability of Dobrovolsky's approximation is analyzed, when an unperturbed medium (characterized by the simple shear state) and the area of tectonic activity (local inhomogeneity caused by the change only of shear modulus) are linearly elastic, and perturbation, in particular, surface displacement is calculated as a difference of the solutions of two independent static problems of the theory of elasticity with the same boundary condition on the surface. Within the framework of this approximation a formula for the spatial distribution (of first component) of magnetic field variations caused by piezomagnetic effect in the case of perturbed regular medium, which is in simple shear state is derived. Cogent arguments in favor of linear dependence between the radon spatial distribution and conditional deformation are obtained. Changes in magnetic field strength and radon concentrations were measured along a tectonomagnetic profile of the total length of 11 km in the surroundings of the "Academician Vernadsky" Station on the Antarctic Peninsula (W 64{\deg}16', S 65{\deg}15'). Results showed a positive correlation between the annual surface radon concentration and annual changes of magnetic field relative to a base point, and also the good coincidence with theoretical calculation.Comment: 27 pages, 11 figures, 3 tables (a substantially revised and extended edition; v3 -- some analysis of recent publications added

Nature of the bonding in metal-silane σ-complexes

The nature of metal silane σ-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp′Mn(CO)2(η2-HSiHPh2)] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate a trigonal bipyramid; salient bond distances and angles are Mn−H(1) 1.575(14), Si−H(1) 1.806(14), Si−H(2) 1.501(13) Å, and H(1)−Si−H(2) 148.5(8)°. This complex is similar to [Cp′Mn(CO)2(η2-HSiFPh2)] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these σ-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn−H distances for 1 and 2 in solution have been estimated using NMR T1 relaxation measurements, giving a value of 1.56(3) Å in each case, in excellent agreement with the distances deduced from neutron diffraction. Density functional theory calculations have been employed to explore the bonding in the Mn−H−Si unit in 1 and 2 and in the related system [Cp′Mn(CO)2(η2-HSiCl3)] 3. These studies support the idea that the oxidative addition of a silane ligand to a transition metal center may be described as an asymmetric process in which the Mn−H bond is formed at an early stage, while both the establishment of the Mn−Si bond and also the activation of the η2-coordinated Si−H moiety are controlled by the extent of Mn → σ*(X−Si−H) back-donation, which increases with increasing electron-withdrawing character of the X substituent trans to the metal-coordinated Si−H bond. This delocalized molecular orbital (MO) approach is complemented and supported by combined experimental and theoretical charge density studies: the source function S(r,Ω), which provides a measure of the relative importance of each atom’s contribution to the density at a specific reference point r, clearly shows that all three atoms of the Mn(η2-SiH) moiety contribute to a very similar extent to the density at the Mn−Si bond critical point, in pleasing agreement with the MO model. Hence, we advance a consistent and unifying concept which accounts for the degree of Si−H activation in these silane σ-bond complexes

Rh-POP Pincer Xantphos Complexes for C-S and C-H Activation. Implications for Carbothiolation Catalysis

The neutral Rh­(I)–Xantphos complex [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i>, <b>4</b>, and cationic Rh­(III) [Rh­(κ³-_P,O,P-Xantphos)­(H)₂]­[BAr^F₄], <b>2a</b>, and [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂]­[BAr^F₄], <b>2b</b>, are described [Ar^F = 3,5-(CF₃)₂C₆H₃; Xantphos = 4,5-bis­(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C₆H₃(CF₃)₂ = 9,9-dimethylxanthene-4,5-bis­(bis­(3,5-bis­(trifluoromethyl)­phenyl)­phosphine]. A solid-state structure of <b>2b</b> isolated from C₆H₅Cl solution shows a κ¹-chlorobenzene adduct, [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂(κ¹-ClC₆H₅)]­[BAr^F₄], <b>3</b>. Addition of H₂ to <b>4</b> affords, crystallographically characterized, [Rh­(κ³-_P,O,P-Xantphos)­(H)₂Cl], <b>5</b>. Addition of diphenyl acetylene to <b>2a</b> results in the formation of the C–H activated metallacyclopentadiene [Rh­(κ³-_P,O,P-Xantphos)­(ClCH₂Cl)­(σ,σ-(C₆H₄)­C­(H)CPh)]­[BAr^F₄], <b>7</b>, a rare example of a crystallographically characterized Rh–dichloromethane complex, alongside the Rh­(I) complex <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η²-PhCCPh)]­[BAr^F₄], <b>6</b>. Halide abstraction from [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i> in the presence of diphenylacetylene affords <b>6</b> as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ³-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh­(κ³-_P,O,P-Xantphos)]⁺ fragment and facilitates <i>ortho</i>-directed C–S activation in a number of 2-arylsulfides to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-Ar)­(SMe)]­[BAr^F₄] (Ar = C₆H₄COMe, <b>8</b>; C₆H₄(CO)­OMe, <b>9</b>; C₆H₄NO₂, <b>10</b>; C₆H₄CNCH₂CH₂O, <b>11</b>; C₆H₄C₅H₄N, <b>12</b>). Similar C–S bond cleavage is observed with allyl sulfide, to give <i>fac</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η³-C₃H₅)­(SPh)]­[BAr^F₄], <b>13</b>. These products of C–S activation have been crystallographically characterized. For <b>8</b> in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of <i>fac</i>-κ³-<b>8</b>, which then proceeds to isomerize to the <i>mer</i>-isomer. With the <i>para</i>-ketone aryl sulfide, 4-SMeC ₆H₄COMe, C–H activation <i>ortho</i> to the ketone occurs to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-4-(COMe)­C₆H₃SMe)­(H)]­[BAr^F₄], <b>14</b>. The temporal evolution of carbothiolation catalysis using <i>mer</i>-κ³-<b>8</b>, and phenyl acetylene and 2-(methylthio)­acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed <i>fac</i>-isomer of the C–S activation product is considerably more active than the <i>mer</i>-isomer (i.e., <i>mer</i>-<b>8</b>), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data

Structures and Aggregation of the Methylamine−Borane Molecules, MenH3−nN·BH3 (n = 1−3), Studied by X-ray Diffraction, Gas-Phase Electron Diffraction, and Quantum Chemical Calculations

The structures of the molecules methylamine-borane, MeH(2)N.BH(3), and dimethylamine-borane, Me(2)HN.BH(3), have been investigated by gas-phase electron diffraction (GED) and quantum chemical calculations. The crystal structures have also been determined for methylamine-, dimethylamine-, and trimethylamine-borane, Me(n)H(3-n)N.BH(3) (n = 1-3); these are noteworthy for what they reveal about the intermolecular interactions and, particularly, the N-H...H-B dihydrogen bonding in the cases where n = 1 or 2. Hence, structures are now known for all the members of the ammonia- and amine-borane series Me(n)H(3-n)N.BH(3) (n = 0-3) in both the gas and solid phases. The structural variations and energetics of formation of the gaseous adducts are discussed in relation to the basicity of the Me(n)H(3-n)N fragment. The relative importance of secondary interactions in the solid adducts with n = 0-3 has been assessed by the semi-classical density sums (SCDS-PIXEL) approach

NEW PALEOMAGNETIC DATA ON THE SILURIAN AND DEVONIAN SEDIMENTARY ROCKS FROM PODOLIA, SW UKRAINE, AND KINEMATICS OF THE EAST EUROPEAN PLATFORM IN THE MIDDLE PALEOZOIC

Paleomagnetic data are the priority source of information for global paleotectonic reconstructions representing horizontal movements of the crustal blocks. Upon receipt of new paleomagnetic data, kinematic models of the East European platform in the Paleozoic are regularly revised and improved. The article presents results of the paleomagnetic study of sedimentary gray-colored and red beds of the Silurian and Lower Devonian sequences located in the Dniester river basin, Podolia region, SW Ukraine. The study covered 17 outcrops that are stratigraphically correlated with the Wenlock, Ludlow, Pridoli states of the Sillurian and the Lochkovian stage of the Devon. Over 400 samples of grey limestone, argillite, dolomite, red limestone and sandstone were analyzed, and two components of natural remnant magnetization (NRM) were revealed. The first component with SSW declination and negative inclination is revealed in the majority of the samples during AF- and T-magnetic cleaning. Its pole positions, that are calculated separately for each series, are trending to the Permian segment of the apparent polar wander path (APWP) published by Torsvik et al. [2012] for Baltica / Stable Europe. Considering its chemical origin, this NRM component is related to formation of authigenic minerals due to rock remagnetization. The second component is revealed only in some samples taken from the red beds (during thermal demagnetization in the range of unblocking temperatures from 590 to 690 °С) and in few samples of grey limestone (in AF fields from 30 to 70 mT or in the range of unblocking temperatures from 300 to 460 °С). This component has SW declination and positive inclination, goes to the origin of coordinates of the diagrams, and has all the indicators of primary magnetization of sediments. Calculated positions of the poles (0 ºS and 329 ºE for grey limestone of the Tiverskaya series, 2.3 °S and 338.4 °E for red beds of the Dniestrovskaya series, etc.) are well correlated with the Devonian segments of APWP for Baltica / Stable Europe. The same is true for the Silurian poles. The new results suggest that in the Ludlow, the East European platform was located at the near-equatorial latitudes of the Southern Hemisphere, and in the Pridoli, it moved to the north towards the equatorial latitudes of the Southern Hemisphere. Later on, the drifting mode was changed, and the platform moved to the south. In the Lochkovian, its position was stabilized at the equatorial latitudes of the Southern Hemisphere. Drifting of the platform can be described by counterclockwise rotation by 16° around the Euler pole (Φ=34 °S, Λ=247 °E)