Influence of water on the microscopic dynamics of 1-butyl-3-methylimidazolium tetrafluoroborate studied by means of quasielastic neutron scattering.

We present a systematic study on the effect of water on the microscopic dynamics of 1-butyl-3-methylimidazolium tetrafluoroborate by means of quasielastic neutron scattering. By mixing the ionic liquid with either heavy or light water, the different contributions to the quasielastic broadening could be identified and treated separately. This study was performed at room temperature, which is more than 15 °C above the demixing line. Our results show that even small amounts of water accelerate the diffusion mechanisms considerably. While samples with small water percentage reveal a diffusion process confined within ionic liquid nanodomains, an admixture of more than 15 wt. % water relieves the confinement. Furthermore, the presence of two water species was identified: one behaving as free water, whereas the other was interpreted as a component bound to the ionic liquid motion. Based on the fact that water preferentially binds to the BF4 anion, which itself has a negligible contribution to the scattered intensity, our experiments reveal unprecedented information about the microscopic anion dynamics.

A practical method to account for random phase approximation effects on the dynamic scattering of multi-component polymer systems.

Investigations of polymer systems that rely on the interpretation of dynamical scattering results as, e.g., the structure factor S(Q, t) of single chains or chain sections may require the inclusion of effects, as described within the framework of the random phase approximation (RPA) for polymers. To do this in practice for the dynamic part of S(Q, t) beyond the initial slope is a challenge. Here, we present a method (and software) that allows a straightforward assessment of dynamical RPA effects and inclusion of these in the process/procedures of model fitting. Examples of applications to the interpretation of neutron spin-echo data multi-component polymer melts are shown.

Protein dynamics as seen by (quasi) elastic neutron scattering.

BACKGROUND: Elastic and quasielastic neutron scattering studies proved to be efficient probes of the atomic mean square displacement (MSD), a fundamental parameter for the characterization of the motion of individual atoms in proteins and its evolution with temperature and compositional environment. SCOPE OF REVIEW: We present a technical overview of the different types of experimental situations and the information quasi-elastic neutron scattering approaches can make available. In particular, MSD can crucially depend on the time scale over which the averaging (building of the "mean") takes place, being defined by the instrumental resolution. Due to their high neutron scattering cross section, hydrogen atoms can be particularly sensitively observed with little interference by the other atoms in the sample. A few examples, including new data, are presented for illustration. MAJOR CONCLUSIONS: The incoherent character of neutron scattering on hydrogen atoms restricts the information obtained to the self-correlations in the motion of individual atoms, simplifying at the same time the data analysis. On the other hand, the (often overlooked) exploration of the averaging time dependent character of MSD is crucial for unambiguous interpretation and can provide a wealth of information on micro- and nanoscale atomic motion in proteins. GENERAL SIGNIFICANCE: By properly exploiting the broad range capabilities of (quasi)elastic neutron scattering techniques to deliver time dependent characterization of atomic displacements, they offer a sensitive, direct and simple to interpret approach to exploration of the functional activity of hydrogen atoms in proteins. Partial deuteration can add most valuable selectivity by groups of hydrogen atoms. "This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo".

Molecular View on Supramolecular Chain and Association Dynamics.

The chain and association dynamics of supramolecular polymer ensembles decisively determines their properties. Using neutron spin echo (NSE) spectroscopy we present molecular insight into the space and time evolution of this dynamics. Studying a well characterized ensemble of linearly associating telechelic poly(ethylene glycol) melts carrying triple H-bonding end groups, we show that H-bond breaking significantly impacts the mode spectrum of the associates. The breaking affects the mode contributions and not the relaxation times as was assumed previously. NSE spectra directly reveal the so far intangible H-bond lifetimes in the supramolecular melt and demonstrate that for both the microscopic and the macroscopic dynamics of the supramolecular ensemble the instantaneous average of the M_{w} distribution governs the system response at least as long as the Rouse picture applies.

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo.

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence on the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.

Microscopic dynamics of polyethylene glycol chains interacting with silica nanoparticles.

We present high resolution neutron spectroscopic investigations of polyethylene glycol matrices interacting attractively with neat SiO2 nanoparticles. We observe a very rich dynamical picture that significantly contradicts earlier conclusions on such systems. Investigating a short chain matrix we realized that a fraction of chains is attached at the nanoparticle surface suppressing completely its translational diffusion. Nevertheless these attached chains undergo an unchanged segmental dynamics seemingly forming a micellelike corona of chains attached with their OH end groups. Changing to methyl-terminated chains the picture changes drastically, now showing a tightly adsorbed layer that however is not glassy as often assumed but undergoes fast picosecond local dynamics. With the singular importance of end groups, mean field approaches are not applicable and future simulations should be redirected to model such unexpected phenomena.

Direct observation of nonaffine tube deformation in strained polymer networks.

We present a one-to-one comparison of polymer segmental fluctuations as measured by small angle neutron scattering in a network under deformation with those obtained by neutron spin echo spectroscopy. This allows an independent proof of the strain dependence of the chain entanglement length. The experimentally observed nonaffine square-root dependence of the tube channel on strain is in excellent agreement with theoretical predictions and permits us to exclude an often invoked nondeformed as well as affinely deformed tube.

Influence of charge density on bilayer bending rigidity in lipid vesicles: a combined dynamic light scattering and neutron spin-echo study.

We report a combined dynamic light scattering and neutron spin-echo study on vesicles composed of the uncharged stabilizing lipid 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) and the cationic lipid 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP). Mechanical properties of a model membrane and thus the corresponding bilayer undulation dynamics can be specifically tuned by changing its composition through lipid headgroup or acyl chain properties. We compare the undulation dynamics in lipid vesicles composed of DMPC/DOTAP to vesicles composed of a mixture of the uncharged helper lipid DMPC with the also uncharged reference lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). We have performed dynamic light scattering on the lipid mixtures to investigate changes in lipid vesicle size and the corresponding center-of-mass diffusion. We study lipid translational diffusion in the membrane plane and local bilayer undulations using neutron spin-echo spectroscopy, on two distinct time scales, namely around 25 ns and around 150 ns. Finally, we calculate the respective bilayer bending rigidities κ for both types of lipid vesicles. We find that on the local length scale inserting lipid headgroup charge into the membrane influences the bilayer undulation dynamics and bilayer bending rigidity κ less than inserting lipid acyl chain unsaturation: We observe a bilayer softening with increasing inhomogenity of the lipid mixture, which could be caused by a hydrophobic mismatch between the acyl chains of the respective lipid components, causing a lateral phase segregation (domain formation) in the membrane plane.

Large domain fluctuations on 50-ns timescale enable catalytic activity in phosphoglycerate kinase.

Large-scale domain motions of enzymes are often essential for their biological function. Phosphoglycerate kinase has a wide open domain structure with a hinge near the active center between the two domains. Applying neutron spin echo spectroscopy and small-angle neutron scattering we have investigated the internal domain dynamics. Structural analysis reveals that the holoprotein in solution seems to be more compact compared to the crystal structure but would not allow the functionally important phosphoryl transfer between the substrates if the protein were static. Brownian large-scale domain fluctuation dynamics on a timescale of 50 ns was revealed by neutron spin echo spectroscopy. The dynamics observed was compared to the displacement patterns of low-frequency normal modes. The displacements along the normal-mode coordinates describe our experimental results reasonably well. In particular, the domain movements facilitate a close encounter of the key residues in the active center to build the active configuration. The observed dynamics shows that the protein has the flexibility to allow fluctuations and displacements that seem to enable the function of the protein. Moreover, the presence of the substrates increases the rigidity, which is deduced from a faster dynamics with smaller amplitude.

Dynamics of the interfacial film in bicontinuous microemulsions based on a partly ionic surfactant mixture: A neutron spin-echo study.

In a microemulsion system based on a mixture of nonionic and ionic surfactants the addition of alcohol instead of changing the temperature was used to tune the curvature of the surfactant interface. The influence of the addition of the short-chain alcohol 2-propanol in the system water-perchloroethylene- Marlowet IHF-2-propanol is studied using neutron spin-echo spectroscopy. In contrast to alcohols with long alkyl chains 2-propanol is no strong co-surfactant, but changes the properties of the solvents. The present contribution focuses on the bicontinuous phase in this system and a quantitative analysis of the obtained neutron spin-echo data is proposed within the theoretical framework given by Zilman and Granek for amphiphilic membranes. It turns out that, in addition to the local movements of the surfactant film, also a collective diffusional mode of the bicontinuous structure has to be taken into account. The presented approach allows to calculate the bending elastic constant κ of the film. The approach is subsequently applied to follow changes of κ as induced by changes of the alcohol concentration.

Dissipative curvature fluctuations in bilayer vesicles: Coexistence of pure-bending and hybrid curvature-compression modes.

We have studied the relaxation dynamics of shape fluctuations in unilamellar lipid vesicles by neutron spin echo (NSE). The presence of a hybrid curvature-compression mode coexisting with the usual bending one has been revealed in the experimental relaxation functions at high q . Differently to the conventional relaxation approximately q (3) typical for bending modes, the hybrid mode was found to relax as approximately q (2) , which is compatible with a dissipation mechanism arising from intermonolayer friction. Complementary data obtained from flickering spectroscopy (FS) in giant unilamellar vesicles confirm the existence of both modes coexisting together. By combining NSE and FS data we have depicted the experimental bimodal dispersion diagram, which is found compatible with theoretical predictions for reliable values of the material parameters. From the present data two conventional dynamical methods (NSE and FS) have been shown to be suitable for measuring intermonolayer friction coefficients in bilayer vesicles.

Functional variants of interleukin-23 receptor gene confer risk for rheumatoid arthritis but not for systemic sclerosis.

OBJECTIVES: Recently, an association was found between Crohn's disease and the interleukin-23 receptor (IL-23R) gene. Since the IL-23/IL-17 pathway is known to associate with other autoimmune diseases, including rheumatoid arthritis (RA) and systemic sclerosis (SSc), we hypothesised that IL-23R could be a shared susceptibility gene. METHODS: Groups of patients with rheumatoid arthritis (n = 412), systemic sclerosis (n = 224), Crohn's disease (n = 190) and healthy controls (n = 220) were genotyped for rs10889677 (exon-3'UTR C2370A), rs2201841, and rs1884444 variants; the first two have been shown to confer risk for Crohn's disease. RESULTS: We observed an increased prevalence of the homozygous rs10889677 AA and homozygous rs2201841 CC genotypes both in the Crohn's disease and in the RA groups as compared to the controls (12.1%, 11.9% vs 5.91%, p<0.05; and 13.2%, 13.1% vs 5.91%, p<0.05), but not in the SSc patients. Logistic regression analysis revealed that bearing these alleles represent risk for the development of rheumatoid arthritis (chi(2) = 5.58, p = 0.018, OR = 2.15, 95% CI 1.14-4.06 for rs10889677; and chi(2) = 7.45, p = 0.006, OR = 2.40, 95% CI 1.28-4.51 for rs2201841). The rs1884444 allele, which has been previously reported as neutral for development of Crohn's disease, was also found neutral for all studied groups in the present study. CONCLUSIONS: The data reported here provide direct evidence that some allelic variants or haplogroups of IL-23R represent independent risk factors for rheumatoid arthritis as well as Crohn's disease, but not for scleroderma.

Cooperative dynamics in homopolymer melts: a comparison of theoretical predictions with neutron spin echo experiments.

We present a comparison between theoretical predictions of the generalized Langevin equation for cooperative dynamics (CDGLE) and neutron spin echo data of dynamic structure factors for polyethylene melts. Experiments cover an extended range of length and time scales, providing a compelling test for the theoretical approach. Samples investigated include chains with increasing molecular weights undergoing dynamics across the unentangled to entangled transition. Measured center-of-mass (com) mean-square displacements display a crossover from subdiffusive to diffusive dynamics. The generalized Langevin equation for cooperative dynamics relates this anomalous diffusion to the presence of the interpolymer potential, which correlates the dynamics of a group of slowly diffusing molecules in a dynamically heterogeneous liquid. Theoretical predictions of the subdiffusive behavior, of its crossover to free diffusion, and of the number of macromolecules undergoing cooperative motion are in quantitative agreement with experiments.

No influence of SLC22A4 C6607T and RUNX1 G24658C genotypic variants on the circulating carnitine ester profile in patients with rheumatoid arthritis.

OBJECTIVE: In a Japanese study, the C6607T SNP mapping to intron 1 of the SLC22A4 gene encoding the OCTN1 protein was found to be associated with rheumatoid arthritis. Similarly, a G24658C transversion in intron 6 of the gene encoding the RUNX1 transcription factor that regulates OCTN1 and also likely OCTN2 expression was also found to confer susceptibility to the disease. METHODS: We investigated the prevalence of these two SNPs by RFLP analysis in a cohort of 209 Hungarian rheumatoid arthritis patients, and 217 healthy controls. Since both the OCTN1 and OCTN2 play a central role in the transmembrane transport of carnitine, we also determined the quantitative serum carnitine ester profile by ESI tandem mass spectrometry. RESULTS: No statistically significant differences were found comparing the genotype prevalence rates between the patients and the controls for either the SLC22A4 genotypes or for the RUNX1 SNPs. There was no significant difference in the serum carnitine ester profile when the rheumatoid arthritis patients were compared with the controls; furthermore, no significant difference in the carnitine esters could be detected when genotype specific subgroups of the patients and the controls were studied. CONCLUSION: Data of the current study do not confirm the universal and population independent susceptibility role of the SLC22A4 C6607T and RUNX1 G24658C variants for rheumatoid arthritis; furthermore, the data presented here show, that there are no significant carnitine-metabolism associated functional consequences of the different genotypes evidenced by the lack of detectable differences in the carnitine ester profiles.

Prevalence of functional haplotypes of the peptidylarginine deiminase citrullinating enzyme gene in patients with rheumatoid arthritis: no influence of the presence of anti-citrullinated peptide antibodies.

OBJECTIVE: Citrullinated peptides produced by enzymatic deimination of arginine residues in proteins by peptidylarginine deiminases are of particular interest in the pathogenesis of rheumatoid arthritis (RA). One type of citrullinated protein - the cyclic citrullinated peptide - is the target of the anti-cyclic citrullinated peptide antibody, the most sensitive and specific autoantibody in RA. The peptidylarginine deiminase type 4 (PADI4) gene, which codes one of the PADI enzyme isotypes, has genetic variants that confer susceptibility to RA in Asian, but not in European populations. METHODS: Genetic associations were examined in 214 Hungarian RA patients characterized for the presence of anti-CCP and rheumatoid factor. The patients were characterized for the existing haplotypes of the PADI4 gene (defined by the combinations of 4 exonic padi4_89: 163G/A, padi4_90: 245T/C, padi4_92: 335C/G, padi4_104: 349T/C and 2 intronic padi4_94: 17535226C/T and padi4_102: 17546809C/T variants) by the PCR-RFLP method. RESULTS: None of the PADI4 haplotypes was accumulated in RA patients. One new finding was that we also did not detect the accumulation of any haplotypes either in the anti-CCP or in the RF-positive subgroups of patients. CONCLUSION: The data presented here show that none of the naturally occurring haplotypes of the PADI4 gene conferred susceptibility to RA in an average group of Hungarian patients; this is in agreement with findings for other European populations. In addition, none of the functional PADI4 haplotypes were associated with the pathologic immune response, which was evidenced by the absence of accumulation of anti-CCP-positive subjects in the specific PADI4 haplotypes.

Origin of dynamic heterogeneities in miscible polymer blends: A quasielastic neutron scattering study

In order to investigate the origin of the often invoked nanoheterogeneities in miscible polymer blends, we have performed quasielastic neutron scattering experiments on the component dynamics within the miscible polymer blend polyisoprene/polyvinyl ether including the pure components as a reference. We find that the apparent local heterogeneities observed by spectroscopic techniques originate from the chain specific crossover properties between entropy driven and local chain dynamics and are, thus, a purely dynamical phenomenon.

Measurement of vortex motion in a type-II superconductor: A novel use of the neutron spin-echo technique

We have used the neutron spin-echo technique to measure the small energy change of neutrons which are diffracted by a moving vortex lattice in a low-pinning Nb-Ta superconducting sample. A transport current was passed in the mixed state to cause flux line movement. In the case of uniform motion, the flux velocity v(L) was given as expected by the values of electric and magnetic fields, via E = -v(L)wedgeB. We show that with a nonuniformly moving vortex lattice, one can measure the dispersion of the velocities, opening up new possibilities for investigating moving vortex lines.

Experimental evidence by neutron scattering of a crossover from Gaussian to non-Gaussian behavior in the alpha relaxation of polyisoprene.

We report incoherent quasielastic neutron scattering experiments exploring the alpha-relaxation range in polyisoprene over an unprecedented range in momentum transfer Q. The data corroborate and validate earlier molecular dynamics simulations and reveal the existence of a crossover from Gaussian to non-Gaussian character of the main chain protons self-correlation function in the alpha-relaxation regime. The real challenge of the experiment was to push the neutron techniques to cover a Q range as wide as possible. By combining two neutron spin echo spectrometers and a backscattering instrument, we have been able to study the dynamics in a Q range of 0.1 < or = Q < or = 4.7 A(-1). In the low-Q regime the shape of the relaxation function was found to be related to the dispersion of the relaxation times as predicted by the Gaussian assumption. At short distances or large Q, this relationship is strongly violated indicating a non-Gaussian regime. We have performed a detailed comparison between the experiments and simulations at different temperatures and found, apart from a temperature shift, complete agreement. Combining experiments and simulations led to a consistent interpretation in terms of a distribution of jumps underlying the diffusive motion of protons in the alpha process. This model leads to a time-dependent non-Gaussianity parameter that agrees nearly quantitatively with the simulations and exhibits all features resolved so far from various simulations.

Intermediate length scale dynamics of polyisobutylene.

We report on a neutron spin echo investigation of the intermediate scale dynamics of polyisobutylene studying both the self-motion and the collective motion. The momentum transfer (Q) dependences of the self-correlation times are found to follow a Q(-2/beta) law in agreement with the picture of Gaussian dynamics. In the full Q range of observation, their temperature dependence is weaker than the rheological shift factor. The same is true for the stress relaxation time as seen in sound wave absorption. The collective times show both temperature dependences; at the structure factor peak, they follow the temperature dependence of the viscosity, but below the peak, one finds the stress relaxation behavior.

Perfluorooctanoic acid rigidifies a model lipid membrane.

We report a combined dynamic light scattering and neutron spin-echo (NSE) study on vesicles composed of the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine under the influence of varying amounts of perfluorooctanoic acid. We study local lipid bilayer undulations using NSE on time scales up to 200 ns. Similar to the effect evoked by cholesterol, we attribute the observed lipid bilayer stiffening to a condensing effect of the perfluorinated compound on the membrane.