Evolution of Water State in the "Ionic Liquid EAN/Al(NO)/HO" System Depending on Temperature and Aluminum Salt Concentration.

Although lithium salts are the most successful materials for electrochemical devices so far, there is growing interest in electrolytes containing divalent and trivalent salts, which are characterized by a much higher energy density than lithium systems. For this purpose, the physical and chemical properties of solutions of aluminum nitrate in ethylammonium nitrate (EAN) were studied in a number of works. However, it was demonstrated by the H NMR method that solutions contain water (from aluminum crystallohydrates) in the first solvated shell of the Al cation even after usual drying procedures, and this solvated water cannot be directly detected by the standard Karl Fischer analysis.

Density Fluctuations Inside an Individual Polymer Coil.

More than five hundred images of individual macromolecules of random styrene-butadiene copolymers and styrene-isoprene block copolymers dissolved in a polystyrene matrix were analyzed. The presence of density fluctuations inside the macromolecular coil has been established. Within the framework of the model of harmonic oscillations, the radial distribution of such density fluctuations is estimated.

Methods of Formation of Protective Inhibited Polymer Films on Tungsten.

A comparative study of anticorrosive inhibited polymer films on the tungsten surface formed from an aqueous solution of inhibited formulations (INFOR) containing organosilane and corrosion inhibitors was carried out by means of the prolonged exposure of a tungsten product in a modifying solution and by the method of cataphoretic deposition (CPD). Depending on the method of forming films on tungsten, the molecular organization of the near-surface layers was studied (ATR-FTIR), and the subprimary structure of the films was explored (TEM). The optimal modes of cataphoresis deposition (CPD duration and current density applied to the sample) for the formation of a protective inhibited polymer film on the tungsten surface were established by means of SEM.

The State of Water in "Ionic Liquid [bmim]Cl/AlCl/HO" Systems.

The unique physical and chemical properties of ionic liquids (ILs) determine their numerous applications in "green" chemistry and material science. Recently, systems based on ILs have been considered to be promising for use in a new generation of electrochemical devices. The results of a nuclear magnetic resonance (NMR) study of the microstructure of 1-butyl-3-methylimidazolium chloride (IL)/water mixtures in the presence of Al cations are presented.

The Effect of Divinylbenzene on the Structure and Properties of Polyethylene Films with Related Radiation Chemical Grafted Polystyrene and Sulfocationite Membranes.

In the present work, the effect of divinylbenzene (DVB) on the kinetics of post-radiation chemical graft polymerization styrene (St) on polyethylene (PE) film and its structural and morphological features were investigated. It has been found that the dependence of the degree of polystyrene (PS) grafting on the DVB concentration in the solution is extreme. An increase in the rate of graft polymerization at low concentrations of DVB in the solution is associated with a decrease in the mobility of the growing chains of PS.

Effect of the Coat Protein N-Terminal Domain Structure on the Structure and Physicochemical Properties of Virions of Potato Virus X and Alternanthera Mosaic Virus.

The amino acid sequences of the coat proteins (CPs) of the potexviruses potato virus X (PVX) and alternanthera mosaic virus (AltMV) share ~40% identity. The N-terminal domains of these proteins differ in the amino acid sequence and the presence of the N-terminal fragment of 28 residues (ΔN peptide) in the PVX CP. Here, we determined the effect of the N-terminal domain on the structure and physicochemical properties of PVX and AltMV virions.

Evaluation of Optic Disc Edema in Long-Duration Spaceflight Crewmembers Using Retinal Photography.

Background: Long-duration spaceflight crewmembers are at risk for spaceflight-associated neuro-ocular syndrome (SANS). One of the earliest manifestations of SANS is optic disc edema (ODE), which could be missed using the subjective Frisén scale. The primary objective of this study is to determine the inter-rater and intrarater reliability of Frisén grade for SANS-induced ODE among a trained observer cohort.

Spectra of Internal Friction in Polyethylene.

The study of spectra of internal friction λ=fT and temperature dependencies of frequency of freely damped ν=fT oscillatory process excited in investigated samples of polyethylene with different degree of crystallinity in the temperature range from -150 °C to +150 °C. It is established that four local dissipative processes of different intensity shown in different temperature intervals are observed on the spectra λ=fT. These are μ, β, α, βk processes.

Al solvation in solutions of aluminum nitrate in a protic ionic liquid: Nuclear magnetic resonance verification of the solvation shell composition.

The closest environment of Al cations was analyzed in detail in solutions of aluminum nitrate in the prototypical protic ionic liquid ethyl ammonium nitrate (EAN) using H and N nuclear magnetic resonance (NMR) spectra. For Al (NO ) -EAN mixtures with different water content, a quantitative analysis of the integral intensities of the H and N signals was carried out and the composition of the first solvation shell of the aluminum cation was refined.

Structural Rearrangement of Dps-DNA Complex Caused by Divalent Mg and Fe Cations.

Two independent, complementary methods of structural analysis were used to elucidate the effect of divalent magnesium and iron cations on the structure of the protective Dps-DNA complex. Small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-EM) demonstrate that Mg ions block the N-terminals of the Dps protein preventing its interaction with DNA. Non-interacting macromolecules of Dps and DNA remain in the solution in this case.

Influence of Genipin Crosslinking on the Properties of Chitosan-Based Films.

Chitosan is a promising environment friendly active polymer packaging material due to its biodegradability, exceptional film forming capacity, great mechanical strength, appropriate barrier property along with intrinsic antioxidant and antimicrobial features. Bifunctional reagent was used for producing water insoluble chitosan films. Biopolymeric films crosslinked by Genipin (Gp), which is a reagent of natural origin, should have high potential in food packaging.

pH-Dependent Gelation of a Stiff Anionic Polysaccharide in the Presence of Metal Ions.

Cross-linking of polysaccharides by metal ions provides polymer gels highly required by industrial applications. In this article, we study the rheological properties and microstructure of solutions of a stiff anionic polysaccharide xanthan cross-linked by chromium (III) ions, and we demonstrate that their properties are highly sensitive to the preparation pH. Stable gels are obtained in a wide range of pH from 2.

Local dynamics in LiCl-CsCl-DO water-in-salt solutions according to NMR relaxation.

The main purpose of this study was to investigate the local structure and dynamics in 'water-in-salt' solutions, namely the ternary concentrated LiCl-CsCl-D2O electrolytes. Water based electrolyte solutions are components of natural waters, they are very widespread and possess many practical abilities. NMR was applied as the main technique to study the local structure of the solutions as well as ion and solvent dynamics.

Translational Diffusion in a Set of Imidazolium-Based Ionic Liquids [bmim]A and Their Mixtures with Water.

As the development of the work ( (10), 2362-2372), we have investigated the translational mobility in the same set of dried imidazolium-based ionic liquids (ILs) [bmim]A (A = BF, NO, TfO, I, Br, and Cl) in a wide temperature range using the NMR technique. It is shown that for the [bmim] cation, the temperature dependencies of product η do not follow the Stokes-Einstein relation for most systems studied, that is, the so-called "diffusion-viscosity decoupling" was realized. The correlation between local and translational mobility in pure IL of the [bmim][A] type was investigated using the data on NMR relaxation rates and diffusion coefficients.

Cell theory, intrinsically disordered proteins, and the physics of the origin of life.

Cell theory, as formulated by Theodor Schwann in 1839, introduced the idea that the cell is the main structural unit of living nature. Later, in solving the problem of cell multiplication, Rudolf Virchow expanded the cell theory with a postulate: all cells only arise from pre-existing cells. But what did the very first cell arise from? This paper proposes extending the Virchow's law by the assumption that between the nonliving protocell and the first living cell the continuity of fundamental physical properties (the principle of invariance of physical properties) is preserved.

Molecular Mobility in a Set of Imidazolium-Based Ionic Liquids [bmim]A by the NMR-Relaxation Method.

The detailed investigation of the local mobility in a set of dried imidazolium-based ionic liquids (1-butyl-3-methylimidazolium) in a wide temperature range and varying anions (BF, I, Cl, Br, NO, TfO) is presented. The measurements of temperature dependencies of the spin-lattice relaxation times of H and C nuclei are motivated by the need to obtain a fundamental characterization of molecular mobility of the substances under study, namely, to estimate the correlation times, τ, for the motion of individual molecular groups. In particular, it follows from obtained results that the mobility of the hydrocarbon "tail" is higher (smaller τ) than that of the imidazole ring, and this expected tendency is quantified.

Open problems, questions and challenges in finite- dimensional integrable systems.

The paper surveys open problems and questions related to different aspects of integrable systems with finitely many degrees of freedom. Many of the open problems were suggested by the participants of the conference 'Finite-dimensional Integrable Systems, FDIS 2017' held at CRM, Barcelona in July 2017.This article is part of the theme issue 'Finite dimensional integrable systems: new trends and methods'.

Molecular mobility in several imidazolium-based ionic liquids according to data of H and C NMR relaxation.

Temperature dependences are compared for H and C NMR 1/T curves relaxation rates in three imidazolium-based ionic liquids (ILs), namely, in [bmim]PF , [bmim]BF , and [emim]CH COO. C curves show alike behavior for all three ILs and follow a well-known Bloembergen-Pound-Purcell (BPP) equation. On the contrary, an essential part of H curves differ strongly from corresponding C ones and also have different shapes for different ILs.

Investigation of Melts of Polybutylcarbosilane Dendrimers by H NMR Spectroscopy.

Melts of polybutylcarbosilane (PBC) dendrimers from third (G3) up to sixth (G6) generations are investigated by H NMR spectroscopy in a wide temperature range up to 493 K. At room temperature, NMR spectra of G3-G5 dendrimers exhibit resolved, solution-like spectra ("liquid" phase). In contrast, the spectrum of the G6 dendrimer is characterized by a single unresolved broad line at whole temperature range, which supports the presence of an anomalous phase state of G6 at temperatures higher than glass transition temperature.

Unexpected Temperature Behavior of Polyethylene Glycol Spacers in Copolymer Dendrimers in Chloroform.

We have studied copolymer dendrimer structure: carbosilane dendrimers with terminal phenylbenzoate mesogenic groups attached by poly(ethylene) glycol (PEG) spacers. In this system PEG spacers are additional tuning to usual copolymer structure: dendrimer with terminal mesogenic groups. The dendrimer macromolecules were investigated in a dilute chloroform solution by (1)H NMR methods (spectra and relaxations).

Molecular dynamics simulation of spin-lattice NMR relaxation in poly-L-lysine dendrimers: manifestation of the semiflexibility effect.

NMR relaxation experiments are widely used to investigate the local orientation mobility in dendrimers. In particular, the NMR method allows one to measure the spin-lattice relaxation rate, 1/T1, which is connected with the orientational autocorrelation function (ACF) of NMR active groups. We calculate the temperature (Θ) and frequency (ω) dependences of the spin-lattice NMR relaxation rates for segments and NMR active CH2 groups in poly-L-lysine (PLL) dendrimers in water, on the basis of full-atomic molecular dynamics simulations.

13C NMR relaxation and reorientation dynamics in imidazolium-based ionic liquids: revising interpretation.

The temperature dependencies of (13)C NMR relaxation rates in [bmim]PF6 ionic liquid have been measured and the characteristic times (τc) for the cation reorientation have been recalculated. We found the origin of the incorrect τc temperature dependencies that were earlier reported for ring carbons in a number of imidazolium-based ILs. After a correction of the approach (13)C T1, the relaxation data allowed us to obtain the characteristic times for an orientation mobility of each carbon, and a complicated experiment, such as NOE, was not required.

Vibrational structure of n-π* transition of the UV absorption spectrum of acryloyl fluoride in the gas phase.

UV absorption spectrum of acryloyl fluoride molecule in the gas phase has been obtained in the region at 32600-35500 cm(-1) with the purpose of the investigation of the hindered internal rotation. The resolved vibrational structure of this spectrum consists of 92 absorption bands, each of which corresponds to a certain transition from the ground (S0) to excited (S1) electronic state. The assignment of all bands has been made.

Average relaxation time of internal spectrum for carbosilane dendrimers: nuclear magnetic resonance studies.

A new theoretical description of the interior mobility of carbosilane dendrimers has been tested. Experiments were conducted using measurements of the (1)H NMR spin-lattice relaxation time, T(1H), of two-, three- and four-generation carbosilane dendrimers with three different types of terminal groups in dilute chloroform solutions. Temperature dependences of the NMR relaxation rate, 1/T(1H), were obtained for the internal CH(2)-groups of the dendrimers in the range of 1/T(1H) maximum, allowing us to directly evaluate the average time of the internal spectrum for each dendrimer.

Cardiac and vascular responses to thigh cuffs and respiratory maneuvers on crewmembers of the International Space Station.

Background: The transition to microgravity eliminates the hydrostatic gradients in the vascular system. The resulting fluid redistribution commonly manifests as facial edema, engorgement of the external neck veins, nasal congestion, and headache. This experiment examined the responses to modified Valsalva and Mueller maneuvers measured by cardiac and vascular ultrasound (ECHO) in a baseline steady state and under the influence of thigh occlusion cuffs available as a countermeasure device (Braslet cuffs).