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. The circular dichroism spectra of these viruses differed significantly, and the melting point of PVX virions was 10-12°C higher than that of AltMV virions. Alignment of the existing high-resolution 3D structures of the potexviral CPs showed that the RMSD value between the Cα-atoms was the largest for the N-terminal domains of the two compared models. Based on the computer modeling, the ΔN peptide of the PVX CP is fully disordered. According to the synchrotron small-angle X-ray scattering (SAXS) data, the structure of CPs from the PVX and AltMV virions differ; in particular, the PVX CP has a larger portion of crystalline regions and, therefore, is more ordered. Based on the SAXS data, the diameters of the PVX and AltMV virions and helix parameters in solution were calculated. The influence of the conformation of the PVX CP N-terminal domain and its position relative to the virion surface on the virion structure was investigated. Presumably, an increased thermal stability of PVX virions vs. AltMV is provided by the extended N-terminal domain (ΔN peptide, 28 amino acid residues), which forms additional contacts between the adjacent CP subunits in the PVX virion.

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. The secondary objective is to propose a standardized evaluation process for SANS-induced ODE across International Space Station Partner Agencies. METHODS: Retrospective, double-blinded diagnostic study. Preflight and postflight fundus photographs were presented to subject matter experts who identified and graded ODE. Pairs of images were also compared side-by-side for disc ranking. Grader concordance was assessed for Frisén grading and disc ranking. RESULTS: Expert graders identified Grade 1 ODE in 17.35% of images from 62 crewmembers (9 female, mean [SD] age, 47.81 [5.19] years). Grades 2 and 3 were identified less than 2% of the time. Concordance in Frisén grades among pairs of graders was 70.99%. Graders identified a difference in preflight and postflight fundus photographs 17.21% of the time when using disc ranking. Pairs of graders had complete concordance in disc ranking 79.79% of the time. Perfect intrarater agreement between Frisén grade and disc ranking occurred 77.7% of the time. CONCLUSIONS: These findings demonstrate intergrader and intragrader variability when using the Frisén scale to identify SANS-induced ODE, which is typically milder in presentation than terrestrial cases of idiopathic intracranial hypertension. It is possible to miss early ODE on fundoscopy alone, making it insufficient as a sole criterion for the diagnosis of SANS. A more sensitive and objective method of surveillance is necessary to monitor international crewmembers for ODE, perhaps using a multimodal approach that includes technology such as optical coherence tomography.

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 energy and thermochemical characteristics (sessile drop and DSC methods), as well as operational (adhesive behavior) and protective filming ability (EIS and corrosion behavior), according to the method of formation of inhibited polymer film, were determined. Based on the combined characteristics of the films obtained by the two methods and the deposition modes, the CPD method showed better performance than the electroless dipping method.

Al3+ solvation in solutions of aluminum nitrate in a protic ionic liquid: Nuclear magnetic resonance verification of the solvation shell composition.

The closest environment of Al3+ cations was analyzed in detail in solutions of aluminum nitrate in the prototypical protic ionic liquid ethyl ammonium nitrate (EAN) using 1 H and 14 N nuclear magnetic resonance (NMR) spectra. For Al (NO3 )3 -EAN mixtures with different water content, a quantitative analysis of the integral intensities of the 1 H and 14 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 Mg2+ 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. The subsequent addition of the chelating agent (EDTA) leads to a complete restoration of the structure of the complex. Different effect was observed when Fe cations were added to the Dps-DNA complex; the presence of Fe2+ in solution leads to the total complex destruction and aggregation without possibility of the complex restoration with the chelating agent. Here, we discuss these different responses of the Dps-DNA complex on the presence of additional free metal cations, investigating the structure of the Dps protein with and without cations using SAXS and cryo-EM. Additionally, the single particle analysis of Dps with accumulated iron performed by cryo-EM shows localization of iron nanoparticles inside the Dps cavity next to the acidic (hydrophobic) pore, near three glutamate residues.

Local dynamics in LiCl-CsCl-D2O 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. The characteristic reorientation times (τc) were calculated from spin-lattice relaxation times for 2H, 7Li, and 133Cs nuclei. The diffusion coefficients (D) for 1H, 7Li, and 133Cs nuclei were also obtained. We have confirmed that most of the molecules and ions are combined into dynamic clusters, 'cybotactic groups', with lifetimes long enough for them to diffuse as a whole unit. Thus, the results provide direct experimental confirmation of the existence of 'cybotactic groups' predicted earlier for concentrated electrolyte solutions. The precise self-diffusion coefficients show the state of ions in the system and can be used as a reference for modelling of such systems.

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 1 H and 13 C NMR relaxation.

Temperature dependences are compared for 1 H and 13 C NMR 1/T1 curves relaxation rates in three imidazolium-based ionic liquids (ILs), namely, in [bmim]PF6 , [bmim]BF4 , and [emim]CH3 COO. 13 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 1 H curves differ strongly from corresponding 13 C ones and also have different shapes for different ILs. For the first time, we have detected the specific, two-maximum shape of 1 H relaxation curve for hydrogen atom of C(2)H group of the [emim]CH3 COO. Assuming that this maximum reflects the correlated rotation of several adjoining ion pairs, we have tried to destroy this rotation by addition of glycerol to the [emim]CH3 COO. The second, high-temperature maximum has disappeared in the [emim]CH3 COO-glycerol mixture, and this fact confirms our assumption. Copyright © 2017 John Wiley & Sons, Ltd.

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. It is shown that the position of the maximum of 1/T1(ω) depends on the location of the segments inside the dendrimer. This dependence of the maximum is explained by the restricted flexibility of the dendrimer. Such behavior has been predicted recently by the analytical theory based on the semiflexible viscoelastic model. The simulated temperature dependences of 1/T1 for terminal and inner groups in PLL dendrimers of n = 2 and n = 4 generations dissolved in water are in good agreement with the NMR experimental data, which have been obtained for these systems previously by us. It is shown that in the case of PLL dendrimers, the traditional procedure of the interpretation of NMR experimental data - when smaller values of 1/T1 correspond to higher orientation mobility - is applicable to the whole accessible frequency interval only for the terminal groups. For the inner groups, this procedure is valid only at low frequencies.

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. Thus the applicability of (13)C NMR relaxation rate measurements to the calculation of the characteristic times for reorientation of all the carbons of the [bmim](+) cation was confirmed and our findings have shown that a (13)C NMR relaxation technique allowed its application to ionic liquids to be equally successful as for other liquid systems.

The State of Water in "Ionic Liquid [bmim]Cl/AlCl3/H2O" 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 Al3+ cations are presented. For the first time, the splitting of spectral lines of water in such systems has been recorded. Comparing the 1H and 27Al NMR data, we have detected the existence of different solvate complexes of Al3+ with Cl- and estimated the characteristic times of exchange processes. For the system under study, a model of the Al3+ cation environment and its evolution with temperature and water content has been described. Quantum-chemical calculations have been performed to substantiate the model.

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.

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. A decrease in the rate of graft polymerization at high concentrations of DVB is associated with a decrease in the rate of diffusion of St and iron(II) ions in the cross-linked network structure of macromolecules of graft PS. A comparative analysis of the IR transmission and multiple attenuated total internal reflection spectra of the films with graft PS shows that graft polymerization of St in the presence of DVB leads to the enrichment of the film surface layers in PS. These results have been confirmed by the data on the distribution of sulfur in these films after sulfonation. The micrographs of the surface of the grafted films show the formation of cross-linked local microphases of PS with fixed interfaces.

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, ß, α, ßk processes. The theoretical analysis of the relationship between the anomalous changes of the vibrational process frequency ν=fT and the shift modulus defect ΔG=fT and the internal friction mechanisms for each of the dissipative loss processes detected on the spectrum λ=fT is carried out. The influence of supramolecular structures on local dissipative ßk process in polyethylene is estimated.

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. It was found that the temperature of 1/T(1H) maximum is practically independent of the number of generations, G; therefore, the theoretical prediction was confirmed experimentally. In addition, the average time of the internal spectrum of carbosilane dendrimers was found to be near 0.2 ns at room temperature, and this value correlates well with the values previously obtained for other dendrimer structures using other experimental techniques.

Native aggregation as a cause of origin of temporary cellular structures needed for all forms of cellular activity, signaling and transformations.

According to the hypothesis explored in this paper, native aggregation is genetically controlled (programmed) reversible aggregation that occurs when interacting proteins form new temporary structures through highly specific interactions. It is assumed that Anfinsen's dogma may be extended to protein aggregation: composition and amino acid sequence determine not only the secondary and tertiary structure of single protein, but also the structure of protein aggregates (associates). Cell function is considered as a transition between two states (two states model), the resting state and state of activity (this applies to the cell as a whole and to its individual structures). In the resting state, the key proteins are found in the following inactive forms: natively unfolded and globular. When the cell is activated, secondary structures appear in natively unfolded proteins (including unfolded regions in other proteins), and globular proteins begin to melt and their secondary structures become available for interaction with the secondary structures of other proteins. These temporary secondary structures provide a means for highly specific interactions between proteins. As a result, native aggregation creates temporary structures necessary for cell activity."One of the principal objects of theoretical research in any department of knowledge is to find the point of view from which the subject appears in its greatest simplicity."Josiah Willard Gibbs (1839-1903).

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. The influence of the ratio of functional groups in the chitosan-Gp system on film absorption in the visible and ultraviolet regions of the spectrum, sorption, physical, and mechanical properties of the films has been studied. The degree of chitosan crosslinking in the films obtained from solutions containing Gp was estimated using the experimental data on film swelling and water vapor sorption isotherms. It is demonstrated that crosslinking with genipin improves swelling, water resistance, and mechanical properties of the films.

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 2.4 to 7.8. The maximum elastic modulus is observed for the gels made at pH 6.3, and by freeze-fracture transmission electron microscopy it is shown that they are characterized by the most dense network structure. However, out of this pH interval, no gelation is observed. At low pH (< 2.4) it is due to high protonation of carboxylic groups of xanthan preventing their interaction with chromium ions, and to the disappearance of oligomeric ions, which are effective in cross-linking. At high pH (> 7.8) the absence of gelation is caused by the transformation of reactive chromium ions into insoluble chromium hydroxide. At the same time, for the gels initially formed at pH 6.3, subsequent change of pH to strongly acidic (1.4) or basic (8.9) medium does not affect appreciably their properties, meaning that chromium cross-links are stable once they are formed. These observations open a reliable route to produce polysaccharide gels with required mechanical properties in a wide pH range where they initially cannot be prepared. It is also shown that the increase of pH to 6.3 of the initially ungelled solution prepared at pH 1.5 results in gelation. This effect offers a facile way for delayed gelation of polysaccharides, which is especially required by oil industry.

Orientational mobility and relaxation spectra of dendrimers: Theory and computer simulation.

The developed theory of the orientational mobility of individual segments of a perfectly branched dendrimer is used to calculate the relaxation spectrum of a dendrimer. Frequency dependences of NMR relaxation 1/T(1) and of the nuclear Overhauser effect have been theoretically calculated from the Brownian dynamics simulation data. The dendrimer segmental orientational mobility is governed by three main relaxation processes: (i) the rotation of the dendrimer as a whole, (ii) the rotation of the dendrimer's branch originated from a given segment, and (iii) the local reorientation of the segment. The internal orientational mobility of an individual dendrimer segment depends only on the topological distance between this segment and the terminal shell of the dendrimer. Characteristic relaxation times of all processes and their contributions to the segmental mobility have been calculated. The influence of the number of generations and the number of the generation shell on the relaxation times has been studied. The correlation between the characteristic times and the calculated relaxation spectrum of the dendrimer has been established.

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. The protocell is understood here as a cell-shaped physical system on the basis of the self-organized biologically significant prebiotic macromolecules, primarily peptides, having a potential to transform into the living cell. Biophase is considered as the physical basis of the membraneless protocell, the internal environment of which is separated from the external environment due to the phase of adsorbed water. The evidence is given that the first protocells may have been formed on the basis of intrinsically disordered peptides. Data on the similarity of the physical properties of living cells and the following model systems are given: protein and artificial polymer solutions, coacervate droplets, and ion-exchange resin granules. Available data on the similarity of the physical properties of cell models and living cells allow us to rephrase the Virchow's postulate as follows: the physical properties of a living cell could only arise from pre-existing physical properties of the protocell.