Water/organic liquid interface properties with amine, carboxyl, thiol, and methyl terminal groups as seen from MD simulations.

Molecular dynamics simulations were performed to study structural and dynamic properties of polar butanamine/water/butanamine, pentanoic acid/water/pentanoic acid, butanethiol/water/butanethiol, and nonpolar pentane/water/pentane systems. The mass density profiles along the interface normal to the organic liquid/water system, the difference in the local structure of H 2 O molecules in bulk and in the vicinity of interface, as well as the diffusion behavior of water molecules at the interface with above-mentioned organic liquids have been investigated. Our MD simulation has shown that the diffusion of water molecules across the water/organic liquid interface is influenced by the hydrogen bonds n HB between water molecules and the terminal groups of organic liquids. It was found that the loss of the hydrogen bonds n HB in the nonpolar organic liquid leads to a decrease in the value of the normal component of the diffusion coefficient D z , while the tangential diffusion coefficients, both D x and D y , increase.

Skeletal photoinduced rearrangement of diarylethenes: ethene bridge effects.

A skeletal photorearrangement involving UV-induced 6π-electrocyclization of diarylethenes with various ethene bridges has been studied. It has been found that deprotonation is the predominant step among the three possible alternative reaction pathways (radical abstraction, deprotonation, or sigmatropic shift) following 6π-electrocyclization, and incorporation of an electronegative carbonyl group into the geminal position to the phenyl residue results in a reduction in the reaction time and an increase in the yield of the desired product. The significant increase in the reaction time in less polar solvents (toluene, TCM) also indicates a large contribution of the deprotonation step to the skeletal photorearrangement of diarylethenes. Performing the reaction in toluene in the presence of tertiary amines leads to a reduction in the reaction time and an increase in the yield of the desired product. The best results were achieved when the reaction was carried out in toluene in the presence of DIPEA. The experimental results are in good agreement with the DFT calculations.

Charge Fluctuations on a Flat Interface between Dielectric and Electrolyte or Dense Plasma.

An interface between a dielectric and a medium containing charge carriers with moderate mobility is considered. In equilibrium, stochastic fluxes of positive and negative particles toward the surface have equal average current density j0, and we suppose that the surface absorbs all falling charges. All over the surface, this results in the emergence of oppositely charged spots of various sizes D fluctuating and interacting with each other. Fourier expansion reduces this collection of interacting spots to the ensemble of independently fluctuating charge density waves. An exact solution of the Poisson equation for a single wave on a flat surface was obtained and provided strict proof that a fluctuating electric field is quite strong just above each charge spot but diminishes exponentially with the distance from the plane. The lifetime τ of a charge spot is inversely proportional to the density j0 of the stochastic current while proportional to j0τ fluctuation's amplitudes independent of j0. The fluctuation's parameter dependence on the charge spot's size D can vary according to the conducting medium properties.

Photochemical rearrangement of diarylethenes: synthesis of functionalized phenanthrenes.

A novel protocol for the synthesis of functionalized phenanthrenes through photocyclization of diarylethenes (DAE) under UV irradiation is proposed. The reaction proceeds through 6π-electrocyclization with the formation of a cyclic (closed) intermediate that undergoes a rearrangement affording unsymmetrical phenanthrenes in good yields. However, in contrast to benzene derivatives, the photocyclization of naphthalene diarylethenes proceeds more slowly, which is confirmed by DFT calculations. The transformation was performed on a 1 mmol scale. The scalability showed that the diarylethenes bearing oxazole, thiazole, pyrazole and imidazole as aryl moieties are more prone to photorearrangement and can be used in preparative organic synthesis.

Nonmechanical principle for producing a flow in a homogeneously aligned microfluidic nematic channel.

Nonmechanical fluid pumping principle has been developed utilizing the interactions of both the director [Formula: see text] and velocity v fields and temperature T redistribution across a two-dimensional homogeneously-aligned nematic (HAN) microfluidic channel under the influence both of a heat flux [Formula: see text] and the surface electric field E0, originating from the surface charge density [Formula: see text]. The heat flux [Formula: see text] is caused by the laser beam pulse focused on the channel's boundary, whereas the normally directed electric field is due to electric double layers, that is naturally created within the liquid crystal near a charged surface. Calculations, based upon the nonlinear extension of the classical Ericksen-Leslie theory, with accounting the entropy balance equation, show that due to the coupling between the [Formula: see text] and [Formula: see text], in the HAN microfluidic channel the vortical flow [Formula: see text] may be excited. The direction and magnitude of [Formula: see text] is influenced by [Formula: see text] and E0, as well as by the thickness of the HAN microfluidic channel.

Photocyclization of diarylethenes: the effect of imidazole on the oxidative photodegradation process.

We have studied the photoreaction of 1,2-diarylethenes under aerobic conditions in the presence of various amines to prevent side processes promoted by singlet oxygen. It has been found that the most amines quite effectively deactivate processes associated with singlet oxygen, but primary and secondary amines unlike tertiary ones, react with substrates resulting in various side products. Among the studied amines, the most effective additive for preventing side processes, including those associated with singlet oxygen is imidazole, which is practically not consumed in photoreaction. It was shown that imidazole can also prevents the photodegradation of organic photochromes in solutions. The results obtained can be used in various branches of science, technology and medicine to improve the photostability of photosensitive organics (dyes).

Structural and optical properties of free-standing smectic films.

We have carried out a complex numerical study of the structural, thermodynamic and optical properties of the partially fluorinated 5-n -alkyl-2-(4-n-(perfluoroalkyl-metheleneoxy)phenyl) free-standing smectic film in air under the action of the external electric field [Formula: see text]. Calculations, based upon the extended McMillan's mean-field theory with anisotropic forces, show a stepwise reduction of the value of the Helmholtz free energy and the reflectivity of the partially fluorinated smectic film in air, as the temperature is raised above the bulk smectic-A-isotropic transition value. It has been shown, by solving the self-consistent nonlinear equations for the orientational and translational order parameters, that the electric field [Formula: see text] may not only affect the layer-thinning transition sequences, but also change the first multilayer jump in the film thickness, whereas practically does not affect the reflectivity R(N) of the partially fluorinated N -layer smectic film in air. In the range of film thicknesses investigated, the reduction of the R(N) is, at least, qualitatively in agreement with the experimentally observed decrease of the optical reflectivity with the decrease of N.

Local structural ordering in surface-confined liquid crystals.

The effect of the interplay between attractive nonlocal surface interactions and attractive pair long-range intermolecular couplings on molecular structures of liquid crystals confined in thin cells with flat solid surfaces has been studied. Extending the McMillan mean field theory to include finite systems, it has been shown that confining surfaces can induce complex orientational and translational ordering of molecules. Typically, local smectic A, nematic, and isotropic phases have been shown to coexist in certain temperature ranges, provided that confining cells are sufficiently thick, albeit finite. Due to the nonlocality of surface interactions, the spatial arrangement of these local phases can display, in general, an unexpected complexity along the surface normal direction. In particular, molecules located in the vicinity of surfaces can still be organized in smectic layers, even though nematic and/or isotropic order can simultaneously appear in the interior of cells. The resulting surface freezing of smectic layers has been confirmed to occur even for rather weak surface interactions. The surface interactions cannot, however, prevent smectic layers from melting relatively close to system boundaries, even when molecules are still arranged in layers within the central region of the system. The internal interfaces, separating individual liquid-crystal phases, are demonstrated here to form fronts of local finite-size transitions that move across cells under temperature changes. Although the complex molecular ordering in surface confined liquid-crystal systems can essentially be controlled by temperature variations, specific thermal properties of these systems, especially the nature of the local transitions, are argued to be strongly conditioned to the degree of molecular packing.

The effect of surfaces on molecular ordering in thin liquid-crystal systems.

A theoretical method for analyzing the interplay between pair long-range intermolecular forces and nonlocal, relatively short-range, surface interactions in liquid crystals, confined between plates of thin planar cells, is developed. It is shown that this method, as involving the concept of local orientational and translational order parameters, enables detailed investigations of the emergence of smectic A, nematic, and isotopic phases, as well as yields an insight into phase transitions between them, in cases of systems strongly affected by surfaces. The evidence of various surface effects, including the coexistence of different phases and the inward propagation of surface melting under the increase of temperature, is also given. The underlying numerical procedure, based on the algorithm of self-consistent calculations of local order parameters, is found to be very effective, allowing one to consider model systems of rather large thicknesses, corresponding to thicknesses of real sample cells.

Orientational relaxation in free-standing smectic C film driven by rotating circular frame.

The pecularities in the cˆ-director reorientation in free-standing smectic C film without of defects and stretched between two circular frames, the rest outer and rotating inner, have been investigated theoretically based on the hydrodynamic theory including the cˆ-director motion and with accounting for backflow. Since the orientation of the cˆ-director is fixed at the rims of the smectic film, the shear flow induced by rotating frame winds up of the cˆ-director field. It is found that the higher shearing flow produces the greater twisting rotation of the cˆ-director around the normal to the smectic film directed in the opposite sense with respect to the direction of the angular velocity. Calculations also show that the relaxation dynamics of the cˆ-director field depends crucially on the curvature of the inner rotating frame.

Squeezing-out dynamics in free-standing smectic films.

We have carried out a theoretical study of the dynamics of the removal of one smectic layer from the N-layer free-standing smectic film during the layer-thinning process. Squeezing-out is initiated by a thermally activated nucleation process in which a density fluctuation forms a small hole. The dynamics of the bounding area during the layer-thinning transition N → N - 1, when the nucleation occurs in the center of the circular smectic film and the squeezed-out area increases up to the edge of the circular smectic area, is studied by the use of the conservation laws for mass and linear momentum. The disjoining pressure is the main factor that is responsible for the driving out of one smectic layer from the N-layer smectic film.

Comparison of the expression of immunomodulatory factors in cultures of mesenchymal stromal cells from human extraembryonic tissues.

mRNA of genes (tgfß, il6, il10, il1ß, and vegf165) involved in cell proliferation, inflammatory, anti-inflammatory, and angiogenic processes were detected and quantified in cultures of mesenchymal stromal cells of different passages derived from human extraembryonic tissues (amniotic sac, umbilical cord, chorionic villi and trophoblast of the placenta). The concentrations of IL-10, IL-6, IL-1ß, and TGFß were measured.

Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: a mean-field treatment.

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature TAI(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers. The effects of surface "enhanced" pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained - by means of optical microscopy and ellipsometry techniques - data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained.

Surface tension and disjoining pressure of free-standing smectic films above the bulk smectic-A-isotropic transition temperature.

We have carried out a numerical study of both the structural and thermodynamic properties of free-standing smectic films for the case of enhanced pair interaction in the bounding layers. Calculations, based upon the extended McMillan's mean-field theory with anisotropic forces, show that the layer-thinning transitions are characterized by abrupt drops to lower values, both for a disjoining pressure and a fluctuation-induced long-range interaction between the smectic film surfaces, and then continues to increase with a larger positive slope. Reasonable agreement between the theoretically predicted and the experimentally obtained data on the surface tension of the partially fluorinated 5-n-alkyl-2-(4-n-(perfluoroalkyl-metheleneoxy)phenyl) film has been obtained.

Gamma oscillations in the somatosensory cortex of newborn rats.

Here we addressed a question of whether gamma oscillations previously described in the whisker-related barrel cortex are a universal pattern of activity in the somatosensory cortex of newborn rats. Intracortical recording of local field potentials and action potentials in neurons using multisite silicon electrodes in 2-7-day-old rats showed that mechanical stimulation of single fingers or specific areas on the plantar or back side of the foot evoked early gamma oscillations followed by spindle-burst oscillations in the corresponding regions of the somatosensory cortex. Early gamma oscillations had maximum amplitude in layer IV of the somatosensory cortex and effectively synchronized action potentials in layer IV neurons. It was concluded that early gamma oscillations evoked by activation of the topographic sensory input are a universal activity pattern of the entire somatosensory cortex of newborn rats.

[The interactions along the microbiota-gut-brain axis in the regulation of circadian rhythms, sleep mechanisms and disorders]. / Rol' vzaimosvyazei po osi mozg­kishechnik­mikrobiom v regulyatsii tsirkadiannykh ritmov, mekhanizmakh sna i ikh narushenii.

The bidirectional relationship between cerebral structures and the gastrointestinal tract involving the microbiota embraces the scientific concept of the microbiota-gut-brain axis. The gut microbiome plays an important role in many physiological and biochemical processes of the human body, in the immune response and maintenance of homeostasis, as well as in the regulation of circadian rhythms. There is a relationship between the higher prevalence of a number of neurological disorders, sleep disorders and changes in the intestinal microbiota, which actualizes the study of the complex mechanisms of such correlation for the development of new treatment and prevention strategies. Environmental factors associated with excessive light exposure can aggravate the gut dysbiosis of intestinal microflora, and as a result, lead to sleep disturbances. This review examines the integrative mechanisms of sleep regulation associated with the gut microbiota (the role of neurotransmitters, short-chain fatty acids, unconjugated bile acids, bacterial cell wall components, cytokines). Taking into account the influence of gut dysbiosis as a risk factor in the development of various diseases, the authors systematize key aspects and modern scientific data on the importance of microflora balance to ensure optimal interaction along the microbiota-gut-brain axis in the context of the regulatory role of the sleep-wake cycle and its disorders.

Dynamics of the modulated distortions in confined nematic liquid crystals.

The peculiarities in the dynamics of the director reorientation in confined nematic liquid crystals (LCs) under the influence of a strong electric field E have been investigated theoretically based on the hydrodynamic theory including the director motion with appropriate boundary and initial conditions. Analysis of the numerical results for the turn-on process provides an evidence for the appearance of the spatially periodic patterns in confined LC film, only in response to the suddenly applied strong E. It has been shown that there is a threshold value of the amplitude of the thermal fluctuations of the director over the LC sample which provides the nonuniform rotation mode rather than the uniform one, whereas the lower values of the amplitude dominate the uniform mode. During the turn-off process, the reorientation of the director to the direction preferred by the surfaces is characterized by the complex destruction of the initially periodic structure to a monodomain state.

Molecular structure and elastic properties of thermotropic liquid crystals: integrated molecular dynamics--statistical mechanical theory vs molecular field approach.

The connection between the molecular structure of liquid crystals and their elastic properties, which control the director deformations relevant for electro-optic applications, remains a challenging objective for theories and computations. Here, we compare two methods that have been proposed to this purpose, both characterized by a detailed molecular level description. One is an integrated molecular dynamics-statistical mechanical approach, where the bulk elastic constants of nematics are calculated from the direct correlation function (DCFs) and the single molecule orientational distribution function [D. A. McQuarrie, Statistical Mechanics (Harper & Row, New York, 1973)]. The latter is obtained from atomistic molecular dynamics trajectories, together with the radial distribution function, from which the DCF is then determined by solving the Ornstein-Zernike equation. The other approach is based on a molecular field theory, where the potential of mean torque experienced by a mesogen in the liquid crystal phase is parameterized according to its molecular surface. In this case, the calculation of elastic constants is combined with the Monte Carlo sampling of single molecule conformations. Using these different approaches, but the same description, at the level of molecular geometry and torsional potentials, we have investigated the elastic properties of the nematic phase of two typical mesogens, 4'-n-pentyloxy-4-cyanobiphenyl and 4'-n-heptyloxy-4-cyanobiphenyl. Both methods yield K3(bend) >K1 (splay) >K2 (twist), although there are some discrepancies in the average elastic constants and in their anisotropy. These are interpreted in terms of the different approximations and the different ways of accounting for the structural properties of molecules in the two approaches. In general, the results point to the role of the molecular shape, which is modulated by the conformational freedom and cannot be fully accounted for by a single descriptor such as the aspect ratio.

[The significance of glymphatic pathway in the relationship between the sleep-wake cycle and neurodegenerative diseases]. / Rol' glimfaticheskogo klirensa v mekhanizmakh svyazi tsikla «son­bodrstvovanie¼ i razvitiya neirodegenerativnykh protsessov.

Selective and progressive death of neurons is a characteristic feature of the process of neurodegeneration and leads to corresponding neuronal dysfunctions. Neurodegenerative diseases represent a heterogeneous group of clinically distinct disorders with similar molecular mechanisms of pathogenesis. They are based on the processes of abnormal aggregation of proteins, the formation of fibrillary insoluble structures and their deposition in the form of histopathological inclusions in the tissues of the nervous system. Disturbance of homeostatic functions that regulate neuronal ion and energy metabolism, biosynthesis and degradation of proteins and nucleotides, chronic hypoxia and the penetration of toxic and inflammatory substances into the brain from the bloodstream not only cause metabolic changes associated with age and disorders in the sleep-wake cycle, but also contribute to the development of neurodegenerative diseases. In animal studies, clearance pathways have been identified in which solutes and specific tracers are excreted perivascular into the meningeal lymphatics. The glymphatic pathway promotes the removal of metabolites, including Aß amyloid and tau protein, from the parenchymal extracellular space of the brain. The glymphatic system is discussed to be more efficient during natural sleep, and fluid dynamics through this pathway exhibit daily fluctuations and are under circadian control. This review systematizes the key aspects and scientific data of recent studies on the role of the glymphatic pathway and astroglial AQP-4 as its main determinant in maintaining homeostatic fluid circulation in the brain in normal and pathological conditions, in particular in relation to the regulatory role of the sleep-wake cycle and in development of neurodegeneration.

[The significance of the glymphatic pathway in the relationship between the sleep-wake cycle and neurodegenerative diseases]. / Rol' glimfaticheskogo klirensa v mekhanizmakh vzaimosvyazi tsikla «son­bodrstvovanie¼ i razvitiya neirodegenerativnykh protsessov.

Selective and progressive death of neurons is a characteristic feature of the process of neurodegeneration and leads to corresponding neuronal dysfunctions. Neurodegenerative diseases represent a heterogeneous group of clinically distinct disorders with similar molecular mechanisms of pathogenesis. They are based on the processes of abnormal aggregation of proteins, the formation of fibrillary insoluble structures and their deposition in the form of histopathological inclusions in the tissues of the nervous system. Disturbance of homeostatic functions that regulate neuronal ion and energy metabolism, biosynthesis and degradation of proteins and nucleotides, chronic hypoxia and the penetration of toxic and inflammatory substances into the brain from the bloodstream not only cause metabolic changes associated with age and disorders in the sleep-wake cycle, but also contribute to the development of neurodegenerative diseases. In animal studies, clearance pathways have been identified in which solutes and specific tracers are excreted perivascular into the meningeal lymphatics. The glymphatic pathway promotes the removal of metabolites, including Aß amyloid and tau protein, from the parenchymal extracellular space of the brain. The glymphatic system is discussed to be more efficient during natural sleep, and fluid dynamics through this pathway exhibit daily fluctuations and are under circadian control. This review systematizes the key aspects and the data of recent research on the role of the glymphatic pathway and astroglial AQP-4 as its main determinant in maintaining homeostatic fluid circulation in the brain in normal and pathological conditions, in particular in relation to the regulatory role of the sleep-wake cycle and in development of neurodegeneration.