Bulk supercooled water versus adsorbed films on silica surfaces: specific heat by Monte Carlo simulation.

Between 150 and 230.6 K, bulk supercooled water freezes upon cooling, and amorphous ice crystallizes upon heating: bulk water thus exists only in its stable ice form. To circumvent this problem, experiments are generally performed on water adsorbed in SiO2 based porous systems. In this work, we take advantage of Monte Carlo simulations to explore this metastable supercooled region inaccessible to experiments. Using three rigid, non-polarizable water models, namely SPC, TIP4P and TIP4P/2005, we investigate the isobaric specific heat capacity (Cp), between 100 and 300 K, of bulk water and water films of few monolayers adsorbed on different SiO2 surfaces: a smooth surface, a non-hydroxylated (0001) surface of quartz, and a fully hydroxylated (001) surface of cristobalite. As Cp is directly related to the entropy fluctuations and we focus on low temperatures, the convergence of the Monte Carlo simulations is a critical point of this work. Also, due to the small mass of the hydrogen atoms, quantum corrections are taken into account, and lead to an excellent agreement of the simulated and experimental Cp values at low temperature (100 K region). Altogether, we conclude that, in bulk, Cp is shown to exhibit a broad peak around 225 K for the SPC and TIP4P models, and around 250 K for the TIP4P/2005 model, in qualitative agreement with the experimentally observed features in Cp measurements. For interfacial water, in all cases, the broad Cp peak disappears. This result, at odds with experimental observations, suggests that disorder and hydrogen bonding at the interface (not yet taken into account) have a fundamental role in confined water transitions.

Nucleon Structure Functions from Operator Product Expansion on the Lattice.

Deep-inelastic scattering, in the laboratory and on the lattice, is most instructive for understanding how the nucleon is built from quarks and gluons. The long-term goal is to compute the associated structure functions from first principles. So far this has been limited to model calculations. In this Letter we propose a new method to compute the structure functions directly from the virtual, all-encompassing Compton amplitude, utilizing the operator product expansion. This overcomes issues of renormalization and operator mixing, which so far have hindered lattice calculations of power corrections and higher moments.

Electric Dipole Moment of the Neutron from 2+1 Flavor Lattice QCD.

We compute the electric dipole moment d(n) of the neutron from a fully dynamical simulation of lattice QCD with 2+1 flavors of clover fermions and nonvanishing θ term. The latter is rotated into a pseudoscalar density in the fermionic action using the axial anomaly. To make the action real, the vacuum angle θ is taken to be purely imaginary. The physical value of dd(n) is obtained by analytic continuation. We find d(n)=-3.9(2)(9)×10(-16) θ e cm, which, when combined with the experimental limit on d(n), leads to the upper bound |θ|≲7.4×10(-11).

Determination of the strange nucleon form factors.

The strange contribution to the electric and magnetic form factors of the nucleon is determined at a range of discrete values of Q^{2} up to 1.4 GeV^{2}. This is done by combining a recent analysis of lattice QCD results for the electromagnetic form factors of the octet baryons with experimental determinations of those quantities. The most precise result is a small negative value for the strange magnetic moment: G_{M}^{s}(Q^{2}=0)=-0.07±0.03µ_{N}. At larger values of Q^{2} both the electric and magnetic form factors are consistent with zero to within 2 standard deviations.

Temperature- and hydration-dependent internal dynamics of stripped human erythrocyte vesicles studied by incoherent neutron scattering.

BACKGROUND: We focus on temperature- and hydration-dependence of internal molecular motions in stripped human red blood cell (RBC) vesicles, widely used as a model system for more complex biomembranes. METHODS: We singled out picosecond local motions of the non-exchangeable hydrogen atoms of RBC vesicles by performing elastic and quasielastic incoherent neutron scattering measurements in dry and heavy water (D2O)-hydrated RBC powders. RESULTS: In dry stripped RBCs, hydrogen motions remained harmonic all along the measured temperature range (100-310K) and mean-square displacements (MSDs) exhibited no temperature transition up to 310K. In contrast, MSDs of hydrated stripped RBCs (h ≈ 0.38g D2O/g dry powder) exhibited a pronounced transition near 260K, with the sharp rise of anharmonic diffusive motions of hydrogen atoms. This transition at ~260K was correlated with both the onset of nonvibrational (harmonic and nonharmonic) motions and the melting of crystallized hydration water. GENERAL SIGNIFICANCE: In conclusion, we have shown that MSDs in human RBC vesicles are temperature-and hydration-dependent. These results provide insight into biomembrane internal dynamics at picosecond timescale and nanometer length scale. Such motions have been shown to act as the "lubricant" of larger conformational changes on a slower, millisecond timescale that are necessary for important biological processes.

Heterogeneous Microscopic Dynamics of Intruded Water in a Superhydrophobic Nanoconfinement: Neutron Scattering and Molecular Modeling.

With their strong confining porosity and versatile surface chemistry, zeolitic imidazolate frameworks-including the prototypical ZIF-8-display exceptional properties for various applications. In particular, the forced intrusion of water at high pressure (∼25 MPa) into ZIF-8 nanopores is of interest for energy storage. Such a system reveals also ideal to study experimentally water dynamics and thermodynamics in an ultrahydrophobic confinement. Here, we report on neutron scattering experiments to probe the molecular dynamics of water within ZIF-8 nanopores under high pressure up to 38 MPa. In addition to an overall confinement-induced slowing down, we provide evidence for strong dynamical heterogeneities with different underlying molecular dynamics. Using complementary molecular simulations, these heterogeneities are found to correspond to different microscopic mechanisms inherent to vicinal molecules located in strongly adsorbing sites (ligands) and other molecules nanoconfined in the cavity center. These findings unveil a complex microscopic dynamics, which results from the combination of surface residence times and exchanges between the cavity surface and center.

Consequence of excess configurational entropy on fragility: the case of a polymer-oligomer blend.

By taking advantage of the molecular weight dependence of the glass transition of polymers and their ability to form perfectly miscible blends, we propose a way to modify the fragility of a system, from fragile to strong, keeping the same glass properties, i.e., vibrational density of states, mean-square displacement, and local structure. Both slow and fast dynamics are investigated by calorimetry and neutron scattering in an athermal polystyrene-oligomer blend, and compared to those of a pure 17-mer polystyrene considered to be a reference, of the same Tg. Whereas the blend and the pure 17-mer have the same heat capacity in the glass and in the liquid, their fragilities differ strongly. Thus, the difference in fragility is related to an extra configurational entropy created by the mixing process and acting at a scale much larger than the interchain distance, without affecting the fast dynamics and the structure of the glass.

Picosecond dynamics of T and R forms of aspartate transcarbamylase: a neutron scattering study.

E. coli aspartate transcarbamylase (ATCase) is a 310 kDa allosteric enzyme which catalyses the first committed step in pyrimidine biosynthesis. The binding of its substrates, carbamylphosphate and aspartate, induces significant conformational changes. This enzyme shows homotropic cooperative interactions between the catalytic sites for the binding of aspartate. This property is explained by a quaternary structure transition from T state (aspartate low affinity) to R state (aspartate high affinity) accompanied by a 5% increase of radius of gyration of ATCase. The same quaternary structure change is observed upon binding of the bisubstrate analogue PALA (N-(phosphonacetyl)-L-aspartate. Owing to the large incoherent neutron scattering cross-section of the hydrogen atom and the abundance of this element in proteins, inelastic neutron scattering gives a global view of protein dynamics as sensed via the individual motions of its hydrogen atoms. We present neutron scattering results of the local dynamics (few angstroms), at short time (few tens of picoseconds), of ATCase in T and R forms. Compared to the T form, we observe an increased mobility of the protein in the R form that we associate to an increase of accessible surface area to the solvent. Beyond this specific result, this highlights the key role of the accessible surface area (ASA) in dynamic contribution to inelastic neutron data in the picosecond time scale. In particular, we want to stress out (i) that a difference at the picosecond time scale does not allow to conclude to a difference in the dynamics at a longer time scale and to address whether the T state is looser than the R state (ii) how challenging is, any comparison in terms of general dynamics (tense or relaxed) between dynamic values deduced from experimental neutron data on proteins with different sequences and therefore ASA. This caveat holds particularly when comparing dynamics of a mesophile with the corresponding extremophile.

Enhanced ionic liquid mobility induced by confinement in 1D CNT membranes.

Water confined within carbon nanotubes (CNT) exhibits tremendous enhanced transport properties. Here, we extend this result to ionic liquids (IL) confined in vertically aligned CNT membranes. Under confinement, the IL self-diffusion coefficient is increased by a factor 3 compared to its bulk reference. This could lead to high power battery separators.

Electroproduction of the N*(1535) resonance at large momentum transfer.

We report on the first lattice calculation of light-cone distribution amplitudes of the N*(1535) resonance, which are used to calculate the transition form factors at large momentum transfers using light-cone sum rules. In the region Q2>2 GeV2, where the light-cone expansion is expected to converge, the results appear to be in good agreement with the experimental data.

Hydration water rotational motion as a source of configurational entropy driving protein dynamics. Crossovers at 150 and 220 K.

The existence of a protein dynamic transition around 220 K is widely known and the central role of the protein hydration shell is now largely recognized as the driving force for this transition. In this paper, we propose a mechanism, at the molecular level, for the contribution of hydration water. In particular, we identify the key importance of rotational motion of the hydration water as a source of configurational entropy triggering (i) the 220 K protein dynamic crossover (the so-called dynamic transition) but also (ii) a much less intense and scarcely reported protein dynamic crossover, associated to a calorimetric glass transition, at 150 K.

Signature of low-dimensional diffusion in complex systems.

We present a clear signature of the dimensionality of water diffusion in a powder sample of a synthetic hectorite (a model clay), by analyzing the corresponding neutron scattering functions. The data follow the theoretical predictions for a powder-averaged two-dimensional diffusion, with a two-dimensional diffusion coefficient of 0.75 x 10(-9) m2 s(-1). Neutron scattering data of bulk water are used as a reference, representing motion in three dimensions. The approach is based on analyzing the scattered intensity at zero energy transfers, along with the broadening of the scattering functions, collected at a wide range of energy resolutions. The mathematical relationship between these two quantities follows, for a given shape of the resolution function, a universal master curve, independent of the diffusion coefficient, but strongly dependent on the dimensionality of the motion, which can thus be determined with clarity.

Kl3 semileptonic form factor from (2+1)-flavor lattice QCD.

We present the first results for the K13 form factor from simulations with 2+1 flavors of dynamical domain wall quarks. Combining our result, namely, f+(0)=0.964(5) with the latest experimental results for Kl3 decays leads to |V us|=0.2249(14), reducing the uncertaintity in this important parameter. For the O(p6) term in the chiral expansion we obtain Delta f=-0.013(5).

Nucleon axial charge in (2+1)-flavor dynamical-lattice QCD with domain-wall fermions.

We present results for the nucleon axial charge g{A} at a fixed lattice spacing of 1/a=1.73(3) GeV using 2+1 flavors of domain wall fermions on size 16;{3} x 32 and 24;{3} x 64 lattices (L=1.8 and 2.7 fm) with length 16 in the fifth dimension. The length of the Monte Carlo trajectory at the lightest m_{pi} is 7360 units, including 900 for thermalization. We find finite volume effects are larger than the pion mass dependence at m{pi}=330 MeV. We also find a scaling with the single variable m{pi}L which can also be seen in previous two-flavor domain wall and Wilson fermion calculations. Using this scaling to eliminate the finite-volume effect, we obtain g{A}=1.20(6)(4) at the physical pion mass, m_{pi}=135 MeV, where the first and second errors are statistical and systematic. The observed finite-volume scaling also appears in similar quenched simulations, but disappear when V>or=(2.4 fm);{3}. We argue this is a dynamical quark effect.

Spin structure of the pion.

We present the first calculation of the transverse spin structure of the pion in lattice QCD. Our simulations are based on two flavors of nonperturbatively improved Wilson fermions, with pion masses as low as 400 MeV in volumes up to (2.1 fm)(3) and lattice spacings below 0.1 fm. We find a characteristic asymmetry in the spatial distribution of transversely polarized quarks. This asymmetry is very similar in magnitude to the analogous asymmetry we previously obtained for quarks in the nucleon. Our results support the hypothesis that all Boer-Mulders functions are alike.

Molecular dynamics of a short-range ordered smectic phase nanoconfined in porous silicon.

4-n-octyl-4-cyanobiphenyl has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, the authors present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confined liquid phase, as a direct consequence of the boundary conditions imposed by the confinement. Temperature fixed window scans reveal a continuous glasslike reduction of the molecular dynamics of the confined liquid and SRS phases on cooling down to 250 K, where a solidlike behavior is finally reached by a two-step crystallization process.

Transverse spin structure of the nucleon from lattice-QCD simulations.

We present the first calculation in lattice QCD of the lowest two moments of transverse spin densities of quarks in the nucleon. They encode correlations between quark spin and orbital angular momentum. Our dynamical simulations are based on two flavors of clover-improved Wilson fermions and Wilson gluons. We find significant contributions from certain quark helicity flip generalized parton distributions, leading to strongly distorted densities of transversely polarized quarks in the nucleon. In particular, based on our results and recent arguments by Burkardt [Phys. Rev. D 72, 094020 (2005)], we predict that the Boer-Mulders function h(1/1), describing correlations of transverse quark spin and intrinsic transverse momentum of quarks, is large and negative for both up and down quarks.

Strange electric form factor of the proton.

By combining the constraints of charge symmetry with new chiral extrapolation techniques and recent low-mass quenched lattice QCD simulations of the individual quark contributions to the electric charge radii of the baryon octet, we obtain an accurate determination of the strange electric charge radius of the proton. While this analysis provides a value for G(E)(s)(Q(2) = 0.1 GeV(2)) in agreement with the best current data, the theoretical error is comparable with that expected from future HAPPEX results from JLab. Together with the earlier determination of G(M)(s), this result considerably constrains the role of hidden flavor in the structure of the nucleon.

Precise determination of the strangeness magnetic moment of the nucleon.

By combining the constraints of charge symmetry with new chiral extrapolation techniques and recent low mass quenched lattice-QCD simulations of the individual quark contributions to the magnetic moments of the nucleon octet, we obtain a precise determination of the strange magnetic moment of the proton. The result, namely, G(s)(M)=(-0.046 +/- 0.019)mu(N) is consistent with the latest experimental measurements but an order of magnitude more precise. This poses a tremendous challenge for future experiments.

Hydration-coupled dynamics in proteins studied by neutron scattering and NMR: the case of the typical EF-hand calcium-binding parvalbumin.

The influence of hydration on the internal dynamics of a typical EF-hand calciprotein, parvalbumin, was investigated by incoherent quasi-elastic neutron scattering (IQNS) and solid-state 13C-NMR spectroscopy using the powdered protein at different hydration levels. Both approaches establish an increase in protein dynamics upon progressive hydration above a threshold that only corresponds to partial coverage of the protein surface by the water molecules. Selective motions are apparent by NMR in the 10-ns time scale at the level of the polar lysyl side chains (externally located), as well as of more internally located side chains (from Ala and Ile), whereas IQNS monitors diffusive motions of hydrogen atoms in the protein at time scales up to 20 ps. Hydration-induced dynamics at the level of the abundant lysyl residues mainly involve the ammonium extremity of the side chain, as shown by NMR. The combined results suggest that peripheral water-protein interactions influence the protein dynamics in a global manner. There is a progressive induction of mobility at increasing hydration from the periphery toward the protein interior. This study gives a microscopic view of the structural and dynamic events following the hydration of a globular protein.