Distributing aminophospholipids asymmetrically across leaflets causes anomalous membrane stiffening.

We studied the mechanical leaflet coupling of prototypic mammalian plasma membranes using neutron spin-echo spectroscopy. In particular, we examined a series of asymmetric phospholipid vesicles with phosphatidylcholine and sphingomyelin enriched in the outer leaflet and inner leaflets composed of phosphatidylethanolamine/phosphatidylserine mixtures. The bending rigidities of most asymmetric membranes were anomalously high, exceeding even those of symmetric membranes formed from their cognate leaflets. Only asymmetric vesicles with outer leaflets enriched in sphingolipid displayed bending rigidities in conformity with these symmetric controls. We performed complementary small-angle neutron and x-ray experiments on the same vesicles to examine possible links to structural coupling mechanisms, which would show up in corresponding changes in membrane thickness. In addition, we estimated differential stress between leaflets originating either from a mismatch of their lateral areas or spontaneous curvatures. However, no correlation with asymmetry-induced membrane stiffening was observed. To reconcile our findings, we speculate that an asymmetric distribution of charged or H-bond forming lipids may induce an intraleaflet coupling, which increases the weight of hard undulatory modes of membrane fluctuations and hence the overall membrane stiffness.

Topological Dynamics of Micelles Formed by Geometrically Varied Surfactants.

The molecular architecture of sugar-based surfactants strongly affects their self-assembled structure, i.e., the type of micelles they form, which in turn controls both the dynamics and rheological properties of the system. Here, we report the segmental and mesoscopic structure and dynamics of a series of C16 maltosides with differences in the anomeric configuration and degree of tail unsaturation. Neutron spin-echo measurements showed that the segmental dynamics can be modeled as a one-dimensional array of segments where the dynamics increase with inefficient monomer packing. The network dynamics as characterized by dynamic light scattering show different relaxation modes that can be associated with the micelle structure. Hindered dynamics are observed for arrested networks of worm-like micelles, connected to their shear-thinning rheology, while nonentangled diffusing rods relate to Newtonian rheological behavior. While the design of novel surfactants with controlled properties poses a challenge for synthetic chemistry, we demonstrate how simple variations in the monomer structure can significantly influence the behavior of surfactants.

Molecular Flexibility of Antibodies Preserved Even in the Dense Phase after Macroscopic Phase Separation.

Antibody therapies are typically based on high-concentration formulations that need to be administered subcutaneously. These conditions induce several challenges, inter alia a viscosity suitable for injection, sufficient solution stability, and preservation of molecular function. To obtain systematic insights into the molecular factors, we study the dynamics on the molecular level under strongly varying solution conditions. In particular, we use solutions of antibodies with poly(ethylene glycol), in which simple cooling from room temperature to freezing temperatures induces a transition from a well-dispersed solution into a phase-separated and macroscopically arrested system. Using quasi-elastic neutron scattering during in situ cooling ramps and in prethermalized measurements, we observe a strong decrease in antibody diffusion, while internal flexibility persists to a significant degree, thus ensuring the movement necessary for the preservation of molecular function. These results are relevant for a more dynamic understanding of antibodies in high-concentration formulations, which affects the formation of transient clusters governing the solution viscosity.

Synthesis and physico-chemical properties of poly(N-vinyl pyrrolidone)-based hydrogels with titania nanoparticles.

Poly(N-vinyl pyrrolidone) (PVP)-based hydrogels with titania nanoparticles (TN) were synthesized by the sol-gel method for the first time and were characterized in different states (native, freeze-dried, air-dried to constant weight and ground to powder, or swollen to constant weight in H2O or D2O) by various methods such as wide-angle and small-angle X-ray and neutron scattering, neutron spin-echo (NSE) spectroscopy, and scanning electron microscopy. The static (static polymer-polymer correlation length (mesh size), associates of cross-links and PVP microchains) and dynamic (polymer chain relaxation rate, hydrodynamic polymer-polymer correlation length) structural elements were determined. The incorporation of titania nanoparticles into PVP hydrogel slightly increases the size of structural inhomogeneities (an increase in the static and dynamic polymer-polymer correlation length, the formation of associates of cross-links and PVP chains). Titania nanoparticles have an impact on the microstructure of the composite hydrogel and form associates with sizes from 0.5 to 2 µm attached to PVP hydrogel pore walls. The PVP and TN/PVP hydrogels show a high degree of water swelling. Moreover, the presence of titania nanoparticles in TN/PVP increases the number of water adsorption cycles compared to PVP hydrogel. The high swelling degree, bacteria-resistant and antimicrobial properties against Staphylococcus aureus allow considering NT/PVP hydrogels for medical applications as wound coatings.

Neutron spin echo monitoring of segmental-like diffusion of water confined in the cores of carbon nanotubes.

Following the stream of increasing scientific interest in condensed-matter systems under ultra-hydrophobic confinement, the present work reports the first incoherent neutron spin echo assessment of the dynamics of water axially confined inside single-wall carbon nanotubes of diameter d∼ 1.4 nm. At the time scale of nanoseconds, two water populations are retrieved, whose relative proportion matches the one expected for a concentric shell + chain arrangement with cylindrical symmetry. The time dependence of the mean square displacement related to the external component is found to be subdiffusive, with peculiar resemblance to segmental diffusion typical of entangled polymeric systems.

Crowding-Controlled Cluster Size in Concentrated Aqueous Protein Solutions: Structure, Self- and Collective Diffusion.

We investigate the concentration-controlled formation of clusters in ß-lactoglobulin (BLG) protein solutions combining structural and dynamical scattering techniques. The static structure factor from small-angle X-ray scattering as well as de-Gennes narrowing in the nanosecond diffusion function D(q) from neutron spin echo spectroscopy support a picture of cluster formation. Using neutron backscattering spectroscopy, a monotonous increase of the average hydrodynamic cluster radius is monitored over a broad protein concentration range, corresponding to oligomeric structures of BLG ranging from the native dimers up to roughly four dimers. The results suggest that BLG forms compact clusters that are static on the observation time scale of several nanoseconds. The presented analysis provides a general framework to access the structure and dynamics of macromolecular assemblies in solution.

Ionic Liquids: evidence of the viscosity scale-dependence.

Ionic Liquids (ILs) are a specific class of molecular electrolytes characterized by the total absence of co-solvent. Due to their remarkable chemical and electrochemical stability, they are prime candidates for the development of safe and sustainable energy storage systems. The competition between electrostatic and van der Waals interactions leads to a property original for pure liquids: they self-organize in fluctuating nanometric aggregates. So far, this transient structuration has escaped to direct clear-cut experimental assessment. Here, we focus on a imidazolium based IL and use particle-probe rheology to (i) catch this phenomenon and (ii) highlight an unexpected consequence: the self-diffusion coefficient of the cation shows a one order of magnitude difference depending whether it is inferred at the nanometric or at the microscopic scale. As this quantity partly drives the ionic conductivity, such a peculiar property represents a strong limiting factor to the performances of ILs-based batteries.

Nanostructuration of ionic liquids: impact on the cation mobility. A multi-scale study.

When probed at the macroscopic scale, Ionic Liquids (ILs) behave as highly dissociated (i.e. strong) electrolytes while, at the molecular scale, they show clear characteristics of weak ionic solutions. The multi-scale analysis we report in this paper reconciles these apparently at odds behaviors. We investigate by quasi-elastic neutron scattering (QENS) and neutron spin-echo (NSE), the nanometer/nanosecond dynamics of OMIM-BF4, an imidazolium-based IL showing strong nanostructuration. We also probe the same IL on the microscopic (µm and ms) scale by pulsed field gradient NMR. To interpret the neutron data, we introduce a new physical model to account for the dynamics of the side-chains and for the diffusion of the whole molecule. This model describes the observables over the whole and unprecedented investigated spatial ([0.15-1.65] Å-1) and time ([0.5-2000] ps) ranges. We arrive at a coherent and unified structural/dynamical description of the local cation dynamics: a localized motion within the IL nanometric domains is combined with a genuine long-range translational motion. The QENS, NSE and NMR experiments describe the same long-range translational process, but probed at different scales. The associated diffusion coefficients are more than one order of magnitude different. We show how this apparent discrepancy is a manifestation of the IL nanostructuration.

Effect of molybdenum on the structure formation of resorcinol-formaldehyde hydrogel studied by coherent x-ray scattering.

A detailed study on the effect of Mo on the gelation process of resorcinol-formaldehyde systems is presented. The evolution of the system was followed by x-ray photon correlation spectroscopy, which allows in situ investigation of the dynamics as well as of the structural evolution in non-equilibrium processes. The Mo was introduced into the system after a pre-polymerization period (PP), the effect of which was also examined. Our results show that the presence of Mo substantially modifies the gelation process by favoring the growth of large compact clusters with weak bonds between them. However, this effect can be reduced by increasing PP.

Cu-doped resorcinol-formaldehyde (RF) polymer and carbon aerogels.

Introduction of transition metal salt(s) onto the surface of porous carbons may increase the selectivity and/or efficiency of these adsorbents in catalysis or separation. Carbon aerogels with low pressure drop are particularly suited for these applications. Moreover the sol-gel process used in the synthesis of the resorcinol-formaldehyde polymer gel (RF) precursors offers an extra opportunity for introducing metal ions. Salts of different metals modify both the macroscopic texture and the porosity, depending on the synthesis protocol. In this paper we show, by means of low temperature nitrogen adsorption measurements and SEM, as well as small- and wide-angle X-ray scattering (SAXS and WAXS), how the addition of copper acetate at three different stages influences not only the specific surface area but also the resulting overall structure over a wide range of length scales. Posttreatment in either the polymer or the carbon aerogel stage provides a means of adjusting the copper content. While the Cu-containing carbon aerogels differ mainly in their micropore volume but not in the width of the distribution, their pore size window in the mesopore range can be tuned between 50 and 400 A by the protocol of Cu addition. The synthesis protocol also determines the chemical form of the copper.

Influence of surface chemistry on the SAXS response of polymer-based activated carbons.

Small-angle X-ray scattering (SAXS) measurements using contrast variation are reported for activated carbons prepared from poly(ethyleneterephthalate). The carbon surfaces are functionalized to different degrees by cold and hot nitric acid treatment. The latter treatment reduces the surface area by 75%, but the pore size distribution in the micropore range is hardly affected. Seven liquids, n-hexane, i-octane, i-propanol, cyclohexane, toluene, alpha-pinene, and nitrobenzene, in addition to water vapor, were used as contrast modifiers. Although the values of the specific surface area S(X) deduced from these measurements are relatively insensitive to the solvent, the detailed SAXS spectra reveal interactions occurring on different spatial scales that depend on the surface chemistry of the carbon and on the physicochemical properties of the solvent. In the most heavily oxidized sample, the amphiphilic molecule i-propanol stabilizes the surface structure, whereas nonpolar molecules make the rough surface smoother. In the untreated and the lightly functionalized carbons, water vapor at 50% relative humidity condenses only partially in the micropores at room temperature, whereas in the heavily treated sample condensation in the micropores is practically complete.