Nanosecond molecular relaxations in lipid bilayers studied by high energy resolution neutron scattering and in-situ diffraction

We report a high energy-resolution neutron backscattering study to investigate slow motions on nanosecond time scales in highly oriented solid supported phospholipid bilayers of the model system DMPC -d54 (deuterated 1,2-dimyristoyl-sn-glycero-3-phoshatidylcholine), hydrated with heavy water. Wave vector resolved quasi-elastic neutron scattering (QENS) is used to determine relaxation times $\tau$, which can be associated with different molecular components, i.e., the lipid acyl chains and the interstitial water molecules in the different phases of the model membrane system. The inelastic data are complemented both by energy resolved and energy integrated in-situ diffraction. From a combined analysis of the inelastic data in the energy and time domain, the respective character of the relaxation, i.e., the exponent of the exponential decay is also determined. From this analysis we quantify two relaxation processes. We associate the fast relaxation with translational diffusion of lipid and water molecules while the slow process likely stems from collective dynamics

Molecular Structural Dynamics in Water-Ethanol Mixtures: Spectroscopy with Polarized Neutrons Simultaneously Accessing Collective and Self-Diffusion

Binary mixtures of water with lower alcohols display non-linear phase behaviour upon mixing which are attributed to potential cluster formation at molecular level. Unravelling such elusive structures requires the investigation of hydrogen-bonding sub-nanosecond dynamics. We employ high-resolution neutron time-of-flight spectroscopy with polarization analysis in combination with selective deuteration to study the concentration-dependent structural dynamics, in the water rich part of the phase diagram of water-ethanol mixtures. This method enables the simultaneous access to atomic correlations in space and time, and allows us to separate spatially incoherent scattering probing self-diffusion of the ethanol fraction from the coherent scattering probing collective diffusion of the water network as a whole. Our observations indicate an enhanced rigidity of the hydrogen bond network at mesoscopic lengthscale compared to the intra-molecular scale as the ethanol fraction increases, which is consistent with the hypothesis of clusters

Effects of Flexibility in Coarse-Grained Models for Bovine Serum Albumin and Immunoglobulin G

We construct a coarse-grained, structure-based, low-resolution, 6-bead flexible model of bovine serum albumin (BSA, PDB: 4F5S), which is a popular example of a globular protein in biophysical research. The model is obtained via direct Boltzmann inversion using all-atom simulations of a single molecule, and its particular form is selected from a large pool of 6-bead coarse-grained models using two suitable metrics that quantify the agreement in the distribution of collective coordinates between all-atom and coarse-grained Brownian dynamics simulations of solutions in the dilute limit. For immunoglobulin G (IgG), a similar structure-based 12-bead model has been introduced in the literature [Chaudhri et al., J. Phys. Chem. B 116, 8045 (2012)] and is employed here to compare findings for the compact BSA molecule and the more anisotropic IgG molecule. We define several modified coarse-grained models of BSA and IgG, which differ in their internal constraints and thus account for a variation of flexibility. We study denser solutions of the coarse-grained models with purely repulsive molecules (achievable by suitable salt conditions) and address the effect of packing and flexibility on dynamic and static behavior. Translational and rotational self-diffusivity is enhanced for more elastic models. Finally, we discuss a number of effective sphere sizes for the BSA molecule, which can be defined from its static and dynamic properties. Here, it is found that the effective sphere diameters lie between 4.9 and 6.1 nm, corresponding to a relative spread of about ±10% around a mean of 5.5 nm

Motional Coherence in Fluid Phospholipid Membranes

URL:http://link.aps.org/doi/10.1103/PhysRevLett.101.248106 DOI:10.1103/PhysRevLett.101.248106We report a high energy-resolution neutron backscattering study, combined with in situ diffraction, to investigate slow molecular motions on nanosecond time scales in the fluid phase of phospholipid bilayers of 1,2-dimyristoyl-sn-glycero-3-phoshatidylcholine. A cooperative structural relaxation process was observed. From the in-plane scattering vector dependence of the relaxation rates in hydrogenated and deuterated samples, combined with results from a 0.1  μs long all-atom molecular dynamics simulation, it is concluded that correlated dynamics in lipid membranes occurs over several lipid distances, spanning a time interval from pico- to nanoseconds.We acknowledge financial support from the DFG through Project No. SA 772/8-2

The modifying effect of supramolecular gel fibres on the diffusion of paracetamol and ibuprofen sodium on the picosecond timescale

Employing neutron spectroscopy, we follow the tracer diffusion of two non-steroidal anti-inflammatory drug molecules, paracetamol (PCM) and ibuprofen sodium (IBU), in a supramolecular gel and the corresponding bulk solution. Both solutes show altered diffusion behaviour in the gel phase, deviating from each other and their bulk solution. Whilst picosecond diffusion of IBU is slightly quicker in the gel, this effect is significantly increased for PCM, which is up to 70% quicker in the gel than in solution.This effect is independent of changes in the solvent diffusion reported previously. An increased residence time of PCM in solution at lower temperatures points towards the onset of nucleation and crystallisation. This work reports one of the first experiments on the novel Backscattering and Time-of-Flight option (BATS) on the IN16B spectrometer at the Institut Laue-Langevin, France, which with its range and resolution in neutron energy and momentum transfer is ideally suited to observe this type of diffusion

How mobile are protons in the structure of dental glass ionomer cements?

The development of dental materials with improved properties and increased longevity can save costs and minimize discomfort for patients. Due to their good biocompatibility, glass ionomer cements are an interesting restorative option. However, these cements have limited mechanical strength to survive in the challenging oral environment. Therefore, a better understanding of the structure and hydration process of these cements can bring the necessary understanding to further developments. Neutrons and X-rays have been used to investigate the highly complex pore structure, as well as to assess the hydrogen mobility within these cements. Our findings suggest that the lower mechanical strength in glass ionomer cements results not only from the presence of pores, but also from the increased hydrogen mobility within the material. The relationship between microstructure, hydrogen mobility and strength brings insights into the material's durability, also demonstrating the need and opening the possibility for further research in these dental cements