"Invisible" Detergents Enable a Reliable Determination of Solution Structures of Native Photosystems by Small-Angle Neutron Scattering.

Photosystems I (PSI) and II (PSII) are pigment-protein complexes capable of performing the light-induced charge separation necessary to convert solar energy into a biochemically storable form, an essential step in photosynthesis. Small-angle neutron scattering (SANS) is unique in providing structural information on PSI and PSII in solution under nearly physiological conditions without the need for crystallization or temperature decrease. We show that the reliability of the solution structure critically depends on proper contrast matching of the detergent belt surrounding the protein. Especially, specifically deuterated ("invisible") detergents are shown to be properly matched out in SANS experiments by a direct, quantitative comparison with conventional matching strategies. In contrast, protonated detergents necessarily exhibit incomplete matching so that related SANS results systematically overestimate the size of the membrane protein under study. While the solution structures obtained are close to corresponding high-resolution structures, we show that temperature and solution state lead to individual structural differences compared with high-resolution structures. We attribute these differences to the presence of a manifold of conformational substates accessible by protein dynamics under physiological conditions.

Dynamic properties of different liquid states in systems with competing interactions studied with lysozyme solutions.

Recent studies of colloidal systems with a short-range attraction and long-range repulsion (SALR) have been demonstrated to have a generalized phase diagram with multiple liquid states defined by their structures. In this paper, we identify the different liquid states of previous experimentally studied lysozyme samples within this proposed generalized state diagram and explore the dynamic properties of each liquid state. We show that most lysozyme samples studied here and previously at low and intermediate concentrations are dispersed fluids while a few high concentration samples are randomly percolated liquids. In the dispersed fluid region, the short-time diffusion coefficient measured by neutron spin echo agrees well with the long time diffusion coefficient estimated with the solution viscosity. This dynamic feature is maintained even for some samples in the random percolated region. However, the short-time and long-time diffusion coefficients of random percolated fluids deviate at larger concentration and attraction strength. At high enough concentrations, the mean square displacement can be as slow as those of many glassy colloidal systems at time scales near the characteristic diffusion time even though these lysozyme samples remain in liquid states at the long-time limit. We thus identify the region in the generalized phase diagram where these equilibrium states with extremely slow local dynamics exist relative to bulk percolation and kinetic arrest (gel and glassy) transitions.

Small-angle neutron scattering and molecular dynamics structural study of gelling DNA nanostars.

DNA oligomers with properly designed sequences self-assemble into well defined constructs. Here, we exploit this methodology to produce bulk quantities of tetravalent DNA nanostars (each one composed of 196 nucleotides) and to explore the structural signatures of their aggregation process. We report small-angle neutron scattering experiments focused on the evaluation of both the form factor and the temperature evolution of the scattered intensity at a nanostar concentration where the system forms a tetravalent equilibrium gel. We also perform molecular dynamics simulations of one isolated tetramer to evaluate the form factor numerically, without resorting to any approximate shape. The numerical form factor is found to be in very good agreement with the experimental one. Simulations predict an essentially temperature-independent form factor, offering the possibility to extract the effective structure factor and its evolution during the equilibrium gelation.

Characterization of a Biomimetic Mesophase Composed of Nonionic Surfactants and an Aqueous Solvent.

We have investigated the physical and biomimetic properties of a sponge (L3) phase composed of pentaethylene glycol monododecyl ether (C12E5), a nonionic surfactant, an aqueous solvent, and a cosurfactant. The following cosurfactants, commonly used for solubilizing membrane proteins, were incorporated: n-octyl-ß-d-glucopyranoside (ß-OG), n-dodecyl-ß-d-maltopyranoside (DDM), 4-cyclohexyl-1-butyl-ß-d-maltoside (CYMAL-4), and 5-cyclohexyl-1-pentyl-ß-d-maltoside (CYMAL-5). Partial phase diagrams of these systems were created. The L3 phase was characterized using crossed polarizers, diffusion of a fluorescent probe by fluorescence recovery after pattern photobleaching (FRAPP), and freeze fracture electron microscopy (FFEM). By varying the hydration of the phase, we were able to tune the distance between adjacent bilayers. The characteristic distance (db) of the phase was obtained from small angle scattering (SAXS/SANS) as well as from FFEM, which yielded complementary db values. These db values were neither affected by the nature of the cosurfactant nor by the addition of membrane proteins. These findings illustrate that a biomimetic surfactant sponge phase can be created in the presence of several common membrane protein-solubilizing detergents, thus making it a versatile medium for membrane protein studies.

Static and dynamic behaviour of responsive graphene oxide-poly(N-isopropyl acrylamide) composite gels.

Thermoresponsive hydrogels have enormous potential e.g., as sensors, actuators, and pollution control remedies or in drug delivery systems. Nevertheless, their application is often restricted by physical limitations (poor mechanical strength and uncontrolled thermal response). Composite systems may offer a means of overcoming these limitations. This paper presents a systematic study of the structure and dynamics of graphene oxide-poly-(N-isopropylacrylamide) composite systems, and investigates the effect of the nanoparticle filler content on the mechanical and swelling properties of the systems. A combination of macroscopic (swelling and elastic modulus) and microscopic (differential scanning microcalorimetry, small angle neutron scattering and neutron spin-echo spectroscopy) investigations reveals that the architecture of the polymer network is modified by chain nucleation at the surface of the GO platelets, and these form a percolating network inside the gel. Our results show that the elastic modulus of the gels is reinforced by the filler, but the mobility of the polymer chains in the swollen state is practically unaffected. The macroscopic deswelling of the composites, however, is slowed by the kinetics of ordering in the GO network.

Micelle structure in a deep eutectic solvent: a small-angle scattering study.

In recent years many studies into green solvents have been undertaken and deep eutectic solvents (DES) have emerged as sustainable and green alternatives to conventional solvents since they may be formed from cheap non-toxic organic precursors. In this study we examine amphiphile behaviour in these novel media to test our understanding of amphiphile self-assembly within environments that have an intermediate polarity between polar and non-polar extremes. We have built on our recently published results to present a more detailed structural characterisation of micelles of sodium dodecylsulfate (SDS) within the eutectic mixture of choline chloride and urea. Here we show that SDS adopts an unusual cylindrical aggregate morphology, unlike that seen in water and other polar solvents. A new morphology transition to shorter aggregates was found with increasing concentration. The self-assembly of SDS was also investigated in the presence of water; which promotes the formation of shorter aggregates.

Custom AFM for X-ray beamlines: in situ biological investigations under physiological conditions.

A fast atomic force microscope (AFM) has been developed that can be installed as a sample holder for grazing-incidence X-ray experiments at solid/gas or solid/liquid interfaces. It allows a wide range of possible investigations, including soft and biological samples under physiological conditions (hydrated specimens). The structural information obtained using the X-rays is combined with the data gathered with the AFM (morphology and mechanical properties), providing a unique characterization of the specimen and its dynamics in situ during an experiment. In this work, lipid monolayers and bilayers in air or liquid environment have been investigated by means of AFM, both with imaging and force spectroscopy, and X-ray reflectivity. In addition, this combination allows the radiation damage induced by the beam on the sample to be studied, as has been observed on DOPC and DPPC supported lipid bilayers under physiological conditions.

Structure of a liquid/liquid interface during solvent extraction combining X-ray and neutron reflectivity measurements.

We have resolved the molecular structure of a bulk oil/water interface that contains amphiphilic ligand molecules using a combination of X-ray and neutron reflectivity measurements for the first time. This new capability can greatly impact future work in the field of ion separation by phase transfer, i.e. liquid/liquid extraction.

Fast Water Diffusion and Long-Term Polymer Reorganization during Nafion Membrane Hydration Evidenced by Time-Resolved Small-Angle Neutron Scattering.

We report a small-angle neutron scattering study of liquid water sorption in Nafion membranes. The swelling of hydrophilic domains was measured on the nanoscale by combining in situ time-resolved and long-term static experiments, yielding kinetic curves recorded over an unprecedented time scale, from hundreds of milliseconds to several years. At low water content, typically below 5 water molecules per ionic group, a limited subdiffusive regime was observed and ascribed to nanoconfinement and local interactions between charged species and water molecules. Further ultrafast and thermally activated swelling due to massive liquid water sorption was observed and analyzed by using Fick's equation. The extracted mutual water diffusion coefficients are in good agreement with pulsed field gradient NMR self-diffusion coefficient values, evidencing a water diffusion-driven process due to concentration gradients within the Nafion membrane. Finally, after completion of the ultrafast regime, the kinetic swelling curves exhibit a remarkable long-term behavior scaling as the logarithm of time, showing that the polymer membrane can continuously accommodate additional water molecules upon hydration stress. The present nanoscale kinetics results provide insights into the vapor-versus-liquid sorption mechanisms, the nanostructure of Nafion, and the role of polymer reorganization modes, highlighting that the membrane can never reach a steady state.

Una revisión sobre la incontinencia urinaria de esfuerzo / No disponible

La incontinencia urinaria, contemplada como enfermedad por la OMS desde 1998, es considerada una consecuencia de la alteración de la fase de llenado vesical que ocurre en diversas enfermedades. En España se ha calculado una prevalencia cercana al 10% en mujeres de entre 25 y 64 años, siendo mayor del 50% en mujeres mayores de 65 años. Con este trabajo pretendemos realizar una revisión de las publicaciones enfermeras sobre la incontinencia urinaria en la mujer desde la perspectiva de una consulta externa de patología de suelo pélvico. Tipo de estudio: revisión de la literatura. Se sintetizó la información obtenida sobre la incontinencia urinaria en la mujer. Conclusiones: las mujeres viven de forma muy diferente la incontinencia urinaria, desde un proceso normal hasta algo que repercute seriamente en su calidad de vida, con repercusiones sociales, laborales, familiares y emocionales. Queda demostrada la eficacia de los programas de educación sanitaria (AU)

Urinary incontinence, as provided by WHO disease since 1998, is considered a consequence of the alteration of bladder filling phase that occurs in various diseases. In Spain it is estimated a prevalence of about 10% in women between 25 and 64 years, with more than 50%in women over 65 years. In this paper we conduct a literature review nurses on urinary incontinence in women from the perspective of an outpatient pelvic floor disorders. Type of study: literature review. We synthesized information obtained on urinary incontinence in women. Conclusions: Women live very differently urinary incontinence from a normal process to something that seriously affects their quality of life, social, work, family and emotional. It is demonstrated the effectiveness of health education programs (AU)

Uniaxial pressure setup for piezoresistance and magnetoresistance measurements in Heusler materials.

We report on a new uniaxial pressure experimental setup for electrical resistivity measurements working in a 77 K-500 K temperature range and in a magnetic field up to 8 T. Such a continuous uniaxial pressure device enables the study of the piezoresistance and the pressure induced change in electrical properties of bulk samples. Strong influence of uniaxial pressure on transport properties is shown for Ni-Co-Mn-In Heusler single crystal material. A shift of the martensite-austenite first order transformation temperature is measured with an applied uniaxial pressure leading to an electrical resistance changed by up to 120%.

Rheo-small-angle neutron scattering at the National Institute of Standards and Technology Center for Neutron Research.

We describe the design and operation of a modified commercial rheometer to simultaneously perform rheological measurements and structural studies by small angle neutron scattering (SANS). The apparatus uses a Couette geometry shear cell allowing two of the three scattering planes to be observed by performing experiments in either the radial or tangential geometries. The device enables small angle neutron scattering patterns to be obtained simultaneously with a wide variety of rheological measurements such as stress/strain flow curves, oscillatory deformations, and creep, recovery and relaxation tests, from -20 °C to 150 °C, for samples with viscosities varying by several orders of magnitude. We give a brief report of recent experiments performed on a dispersion of acicular nanoparticles and biopolymer network under stress demonstrating the utility of such measurements. This device has been developed at the National Institute of Standards and Technology's Center for Neutron Research (NCNR) and made available to the complex fluids community as part of the standard sample environment equipment.

Noninvasive neutron scattering measurements reveal slower cholesterol transport in model lipid membranes.

Proper cholesterol transport is essential to healthy cellular activity and any abnormality can lead to several fatal diseases. However, complete understandings of cholesterol homeostasis in the cell remains elusive, partly due to the wide variability in reported values for intra- and intermembrane cholesterol transport rates. Here, we used time-resolved small-angle neutron scattering to measure cholesterol intermembrane exchange and intramembrane flipping rates, in situ, without recourse to any external fields or compounds. We found significantly slower transport kinetics than reported by previous studies, particularly for intramembrane flipping where our measured rates are several orders of magnitude slower. We unambiguously demonstrate that the presence of chemical tags and extraneous compounds employed in traditional kinetic measurements dramatically affect the system thermodynamics, accelerating cholesterol transport rates by an order of magnitude. To our knowledge, this work provides new insights into cholesterol transport process disorders, and challenges many of the underlying assumptions used in most cholesterol transport studies to date.

Orientational distributions and nematic order of rodlike magnetic nanoparticles in dispersions.

Using small-angle neutron scattering (SANS), we have investigated the orientational order of iron nanoparticles dispersed in cyclohexanone. The particles have rodlike shape and size distributions with an average length of 200 nm and an average diameter of 25 nm. SANS shows an anisotropy, which is a measure of orientational order, in magnetic dispersions with a volume fraction of 3.2% and 3.9% iron particles in shear flow and/or magnetic field. The scattering anisotropy can be fitted by a model assuming an Onsager distribution of the orientation of the particles in shear flow. The orientational distribution of particles oriented by a magnetic field can be described by a different model assuming the Maier-Saupe orientational distribution for uniaxial ferromagnetic particles. The orientational distribution parameter m for the Maier-Saupe distribution or alpha for the Onsager distribution and the orientational order parameter S have been determined at shear rates gamma[over ] of to 0-4000 s(-1) and in magnetic fields of 0-18 mT. The S values indicate that the particles start to orient either in a shear flow of 100 s(-1) or in a magnetic field of 6 mT. Applying only shear results in an orientational order, with the dispersion returning to the disordered state when the shear rate is decreased to zero. In sharp contrast, application of magnetic fields greater than 6 mT results in orientational order in the field-increasing cycle, and two-thirds of the orientational order remains when the field is decreased to zero. This shows that the order in a magnetic field is different from the order in a shear flow, the action of magnetizing the particles along a certain direction is irreversible, and the orientational order parameter exhibits hysteresis.

Magneto-optical setup for in situ strain and transport measurements on superconductors.

A recently developed magneto-optical (MO) imaging setup for investigations on superconductors is reported. The main originality of our setup is its ability to combine both strain and transport measurements in the temperature range of 6-300 K with magneto-optical observations. We give here some theoretical considerations on the cryostat conception, which is a key point of our setup. In particular, the thermal and mechanical aspects are discussed. A detailed description of the MO setup and of the associated strain apparatus is given. Additionally, an example of MO strain and transport study on DyBCO coated conductors is given. Evidence of Luders Bands formation under strain in the Hastelloy is revealed by the field penetration inside cracks in the DyBCO and MgO layers. A correlation between the damaging morphology and the critical current at 70 K versus strain has been established.

Shear-induced collapse in a lyotropic lamellar phase.

An entropically stabilized cetylpyridinium chloride, hexanol, and heavy brine lyotropic lamellar phase subjected to shear flow has been observed here by small angle neutron scattering to undergo collapse of smectic order above a threshold shear rate. The results are compared with theories predicting that such a lamellar phase sheared above a critical rate should lose its stability by a loss of resistance to compression due to the suppression of membrane fluctuations.

Quantitative analysis of lyotropic lamellar phases SANS patterns in powder oriented samples.

We have developed a detailed numerical method based on the Caillé model to fit Small Angle Neutron Scattering profiles of powder-oriented lyotropic lamellar phases. We thus obtain quantitative values for the Caillé parameter and the smectic penetration length from which we can derive the smectic compression modulus and the membrane mean bending modulus. Our method, applied to a surfactant lamellar phase system decorated by amphiphilic copolymers, provides excellent fits for any intermembrane spacing or membrane concentration over the entire q-range of the SANS experiments. We compare our fits with those obtained from the model of Nallet et al. (J. Phys. II 3, 487 (1993)), which is reviewed. Good fits are obtained with both methods for samples exhibiting "hard" smectic order (sharp Bragg peak, moderate small angle scattering). Only our procedure, however, gives good fits in the case of "soft" smectic order (smooth Bragg peak, strong small angle scattering). A quantitative criterion to discriminate between these "soft" and "hard" samples is also proposed, based on a simple analogy with smectic-A liquid crystal in contact with an undulating solid surface. This allows us to anticipate the type of thermodynamic information that can be derived from the fits.

Topological relaxation of a shear-induced lamellar phase to sponge equilibrium and the energetics of membrane fusion.

We report time-resolved small angle neutron scattering (t-SANS) measurements of the topological relaxation of Couette shear-induced stacked L(alpha) lamellar states to their multiconnected isotropic L3 sponge equilibrium phases in a surfactant bilayer membrane system. Comparison of this structural relaxation time to the interval between diffusive membrane contacts, as determined from dynamic light scattering or estimated from the shear rates required for L(alpha) saturation, allows us to determine the activation energy barrier to the membrane fusion process reestablishing the solution channel handles that characterize the sponge phase.

Shear- and magnetic-field-induced ordering in magnetic nanoparticle dispersion from small-angle neutron scattering.

Small-angle neutron scattering experiments have been performed to investigate orientational ordering of a dispersion of rod-shaped ferromagnetic nanoparticles under the influence of shear flow and static magnetic field. In this experiment, the flow and flow gradient directions are perpendicular to the direction of the applied magnetic field. The scattering intensity is isotropic in zero-shear-rate or zero-applied-field conditions, indicating that the particles are randomly oriented. Anisotropic scattering is observed both in a shear flow and in a static magnetic field, showing that both flow and field induce orientational order in the dispersion. The anisotropy increases with the increase of field and with the increase of shear rate. Three states of order have been observed with the application of both shear flow and magnetic field. At low shear rates, the particles are aligned in the field direction. When increasing shear rate is applied, the particles revert to random orientations at a characteristic shear rate that depends on the strength of the applied magnetic field. Above the characteristic shear rate, the particles align along the flow direction. The experimental results agree qualitatively with the predictions of a mean field model.

Scaling of shear-induced transformations in membrane phases.

Surfactant sponges are complex-fluid phases made up of convolutions of bilayer sheets. Although isotropic and free flowing they exhibit transient birefringence when stirred, reminiscent of the birefringence of lamellar phases. Previous attempts to understand this effect have led to confusing and often conflicting results. We have used a novel approach to designing the chemical system that gives us control over the relevant parameters needed to study microstructural and macroscopic responses of these phases to shear. We find a remarkable universal scaling behavior for both sponge and shear-induced lamellar states, which resolves a number of long-standing questions about these systems.