Chiral Transfer of Linear Polysiloxane with Preferred-Handed Helical Conformation.

We report the preparation of chiral silica using a linear polysiloxane main chain with a preferred-handed helical structure as the template. Poly(methylvinyl siloxane) (PMVS) with a cysteine derivative side chain designated as PMVS-Cys was prepared using anionic polymerization and an ene-thiol reaction. PMVS-Cys forms a helical conformation in both solution and film via hydrogen bonding between amide groups at side chains. The helical structure remains during the calcination process, resulting in silica with helical structure. The silica with a helical structure shows optical activity.

All-Perfluorosulfonated-Ionomer Composite Membranes Containing Blow-Spun Fibers: Effect of a Thin Fiber Framework on Proton Conductivity and Mechanical Properties.

In this study, thin fiber composite polymer electrolyte membranes (PEMs) were prepared using short side-chain perfluorosulfonic acid (PFSA) ionomers, Aquivion, to create composite PEMs with improved proton conductivity and improved mechanical properties. PFSA thin fiber webs prepared by blow spinning and successive hot pressing were used as the porous substrate. Herein, PFSA ionomers were used for both the substrate and the matrix of the composite PEMs, and their structures, properties, and fuel cell performance were characterized. By adding the PFSA thin fiber webs to the matrix, the proton conductivity was enhanced and the mechanical properties were slightly improved. The prepared PFSA thin fiber composite PEM showed better FC performance than that of the pristine PFSA one for the high-temperature low-humidity condition in addition to the low-temperature high-humidity one. To the best of our knowledge, this is the first report on the all PFSA composite membranes containing a PFSA thin fiber framework.

Structures of Nanoconfined Liquids Determined by Synchrotron X-ray Diffraction.

We have successfully performed X-ray diffraction measurements of the liquids octamethylcyclotetrasiloxane (OMCTS, a quasi-spherical-shaped molecule) and n-hexadecane (a normal alkane) confined between mica surfaces at surface separation distances (D's) from 500 nm to the hard-wall thickness (1.9 nm for OMCTS and 1.0 nm for hexadecane). At all of the studied D's, we observed diffraction peaks corresponding to their mean intermolecular spacing at q = 8.6 nm-1 (d = 0.73 nm) for OMCTS and q = 13.6 nm-1 (d = 0.45 nm) for n-hexadecane. The peak intensity increased at D < ca. 50 nm for OMCTS even with the decreasing distance and exhibited a local maximum at D = 17-13 nm, indicating the sharp increase in the molecular order in this distance range. The peak intensities normalized by the D and Inormalized values of OMCTS and n-hexadecane were nearly constant at D's greater than 100 nm, though they appeared to increase slightly. The increase then became more significant with decreasing D below 100 nm, and finally the Inormalized values became 120 (for OMCTS) and 160 (for n-hexadecane) at the hard wall. These results clearly demonstrated the significant increase in the structural order of OMCTS and n-hexadecane under nanoconfinement, especially below 100 nm. The fwhm values of the peaks of OMCTS and n-hexadecane showed no significant change until small distances when the confinement effect was significant. These results indicated that the increase in the structural order should be mainly ascribed to the ordering of the molecules in the parallel plane in the enhanced layered structure formed under the confinement. The viscous parameters (b2) of OMCTS and n-hexadecane obtained from the resonance shear measurement showed no increase at D's down to ca. 7 nm. This indicated that a certain ordering of the confined molecules was required for the observable increase in the viscosity.

Chiral Silica with Preferred-Handed Helical Structure via Chiral Transfer.

A strategy to obtain chiral silica using an achiral stereoregular polymer with polyhedral oligomeric silsesquioxane (POSS) side chains is described herein. The preferred helical conformation of the POSS-containing polymer could be achieved by mixing isotactic polymethacrylate-functionalized POSS (it-PMAPOSS) and a chiral dopant. The array structure of POSS molecules, which are placed along the helical conformation, is memorized even after removing the chiral dopant at high temperatures, leading to a chiral silica compound with exclusive optical activity after calcination.

Analysis of the sol and gel structures of potato starch over a wide spatial scale.

We analyzed edible potato starch and observed the interaction between its granular structure and water molecules. We studied the changes caused by gelatinization during heating and stirring using microscopy, micro-FT-IR spectroscopy, and X-ray scattering techniques. A wide range of spatial scales was revealed using these various techniques. The rate of gelatinization varied significantly and was dependent on the starch concentration. The process of adsorption of water on starch molecules was studied using the humidity-controlled FT-IR spectroscopy technique. Furthermore, by comparing the X-ray scattering profiles of dry and wet granules, the 9-nm repeat "cluster" structure was studied. A gradual collapse of the granules occurred during the processes of heating and stirring. A clustered smectic structure and a smectic-like structure were observed in the opaque gel after gelatinization. Upon further heating, a transparent gel was obtained after the melting of the cluster.

Stratum Corneum Function: A Structural Study with Dynamic Synchrotron X-ray Diffraction Experiments.

Studies on the effectiveness of substances such as drugs and cosmetics that act on the skin require structural evidence at the molecular level in the stratum corneum to clarify their interaction with intercellular lipid and soft keratin. For this purpose, when applying the substances to the stratum corneum X-ray diffraction experiment is one of the powerful tools. To detect minute structural changes in a stratum corneum sample, using a "solution cell", dynamic synchrotron X-ray diffraction measurements were performed when applying aqueous solution of the substances to the stratum corneum: (1) It was found that a surfactant, sodium dodecyl sulfate, significantly disrupted the long-period lamellar structure. (2) To study the effects of water, structural modifications of the short-period lamellar structure and the soft keratin in corneocytes were measured as a function of time. At the initial water content of 15 wt%, the spacings of the short-period lamellar structure and the soft keratin increased toward those at the water content of 25 wt%, that is a key water content in the stratum corneum. (3) Nanoparticles composed of assembly of amphiphilic molecules are one of the leading pharmaceutical formulations. When the nanoparticles were applied, a new assembly of amphiphilic molecules originated from the nanoparticle appeared. This phenomenon suggests that the formation of the new assembly at the surface of skin is concerned with the release of the drug from the nanoparticles. (4) When ethanol was applied to the stratum corneum, only the liquid state in the intercellular lipid matrix was dissolved. After the removal of ethanol from this stratum corneum, the ordered hydrocarbon-chain packing structures appeared. From this fact we would propose that the liquid state region is the main pathway for hydrophobic drugs with a small molecular weight in connection with the so-called 500 Da rule. Here, not only the technique but also the background to these studies and the characteristic results obtained from these studies are explained.

Microstructure Investigation of Polymer Electrolyte Fuel Cell Catalyst Layers Containing Perfluorosulfonated Ionomer.

Perfluorosulfonated ionomers are the most successful ion-exchange membranes at an industrial scale. One recent, cutting-edge application of perfluorosulfonated ionomers is in polymer electrolyte fuel cells (PEFCs). In PEFCs, the ionomers are used as a component of the catalyst layer (CL) in addition to functioning as a proton-exchange membrane. In this study, the microstructures in the CLs of PEFCs were characterized by combined synchrotron X-ray scattering and transmission electron microscopy (TEM) analyses. The CL comprised a catalyst, a support, and an ionomer. Fractal dimensional analysis of the combined ultrasmall- and small-angle X-ray scattering profiles indicated that the carbon-black-supported Pt catalyst (Pt/CB) surface was covered with the ionomer in the CL. Anomalous X-ray scattering revealed that the Pt catalyst nanoparticles on the carbon surfaces were aggregated in the CLs. These findings are consistent with the ionomer/catalyst microstructures and ionomer coverage on the Pt/CB surface obtained from TEM observations.

Impact of the Composition of Alcohol/Water Dispersion on the Proton Transport and Morphology of Cast Perfluorinated Sulfonic Acid Ionomer Thin Films.

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor that controls the performance of catalyst layers in membrane electrode assemblies of polymer electrolyte fuel cells. Herein, the effects of water/alcohol compositions on the morphological properties and proton transport are examined by grazing incidence small-angle X-ray scattering, grazing incidence wide-angle X-ray scattering, and electrochemical impedance spectroscopy. The thin films cast by a high water/alcohol ratio Nafion dispersion have high proton conductivity and well-defined hydrophilic/hydrophobic phase separation, which indicates that the proton conductivity and morphology of the Nafion thin films are strongly influenced by the state of dispersion. This finding is expected to further understand the morphology and proton transport properties of Nafion thin films with different water/alcohol ratios, which has implications for the performance of the Pt/Nafion interface.

Preparation of Perfluorosulfonated Ionomer Nanofibers by Solution Blow Spinning.

In this work, we report the preparation of high-purity perfluorosulfonated ionomer (Nafion) nanofibers (NFs) via solution blow spinning (SBS). Fiber formation in solution jet spinning is strongly dependent on the structure of the spinning solution. Upon adding a small amount of poly(ethyleneoxide) (PEO) as a spinning aid to Nafion dispersion, most of the highly ordered Nafion aggregate disappeared, allowing the stable production of bead-free and smooth high-purity NFs (Nafion/PEO = 99/1) by SBS. The microstructure of the blowspun Nafion NFs differed from that of electrospun NFs. In the blowspun NFs, incomplete microphase separation between hydrophilic (ionic) and hydrophobic domains was observed, but the crystallization of CF2-CF2 chains was enhanced owing to the high extensional strain rate and rapid solidification during SBS. These findings provide fundamental information for the preparation and characterization of blowspun Nafion NFs.

Effects of surface and shear forces on nano-confined smectic-A liquid crystals studied by X-ray diffraction.

The orientational behavior of a smectic-A liquid crystal (4-cyano-4'-octylbiphenyl, 8CB) confined between mica surfaces as well as between silica surfaces with a nanometer scale thickness was investigated by synchrotron X-ray diffraction measurement. The crystallographic axes of two confining mica sheets were adjusted parallel to each other to induce the preferential orientation of 8CB molecules along their crystallographic axis. The silica surfaces, which were hydrophilic and amorphous and had nanometer level smoothness, were prepared on mica surfaces using a sputtering technique. The X-ray diffraction measurement revealed that the 8CB molecules, confined between mica surfaces (DHW = 1.7 nm) and between silica surfaces (DHW = ca. 2 nm), took a planar orientation (oriented its long axis parallel to the surface) and formed a lamellar structure. However, the in-plane orientation of the confined 8CB changed depending on the confining surfaces. The lamellar axis of the 8CB confined between mica surfaces uniaxially oriented most probably due to the preferential alignment of its long axis along the principal crystallographic a-axis of the mica. On the other hand, 8CB between the silica surfaces formed lamellar domains in which the lamellar axis of 8CB omnidirectionally oriented in-plane. The effect of the shear on the orientation of the nano-confined 8CB was also investigated. The lamellar axis, corresponding to the long axis of the 8CB molecules confined between the mica surfaces, rotated only ca. 3 degrees within the plane parallel to the surface by perpendicularly applying shear to the axis. The lamellar axis of the 8CB molecules between the silica surfaces showed no noticeable change by applying the shear. These results indicated that the effect of shear to align the 8CB molecules was significantly suppressed due to the confinement effect which significantly reduces the mobility of molecules as well as the alignment effect along the crystallographic axis in the case of mica. We also observed a change in the orientation of nano-confined 8CB after shear treatment at large D (= 3.3 µm).

Polar-Nonpolar Interfaces of Normal Bicontinuous Cubic Phases in Nonionic Surfactant/Water Systems Are Parallel to the Gyroid Surface.

We investigated the structures of normal (type I) bicontinuous cubic phases in hexa-, hepta-, and octaethylene glycol dodecyl ether/water mixtures by small-angle X-ray crystallography of single-crystal domains. Reconstructed electron densities showed that the hydrophilic chains with high electron density are confined to a film centered on the surface of the Gyroid (a triply periodic minimal surface), while hydrophobic chains with low electron density are distributed within the pair of interwoven labyrinths carved out by the Gyroid. Further, the local minimum within the high electron density region, due to bulk water, coincides precisely with the Gyroid. This minimum is less pronounced in mixtures with longer ethylene glycol chains, consistent with their decreased water content. Our analysis clearly shows that the polar-nonpolar interfaces are parallel to the Gyroid surface in all mixtures. The repulsive hydration or overlapping force between the pair of facing monolayers of ethylene glycol chains on either side of the Gyroid surface is the likely origin of the parallel interfaces.

Microbeam X-ray diffraction study of lipid structure in stratum corneum of human skin.

Human skin, not previously frozen, was studied by small-angle X-ray diffraction. The samples were folded so that a 6µm X-ray beam passed through the top layer of skin, stratum corneum. Diffraction patterns recorded with this method consisted of peaks at about q = 0.5, 1.0 and 1.4 nm-1 in the direction perpendicular to the skin surface more clearly than in previous studies. These peaks are interpreted to arise from lipids between corneocytes. A simple unit of a linear electron density profile with three minima was used to account for the observed intensity profiles. Combinations of calculated diffraction from models with one, two and three units accounted for the major part of the observed diffraction pattern, showing the diversity in the structure of the intercellular lipids.

Morphology Changes in Perfluorosulfonated Ionomer from Thickness and Thermal Treatment Conditions.

The morphological changes of Nafion thin films with thicknesses from 10 to 200 nm on Pt substrate with various annealing histories (unannealed to 240 °C) were systematically investigated using grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS). The results revealed that the hydrophilic ionic domain and hydrophobic backbone in Nafion thin films changed significantly when the annealing treatment exceeded the cluster transition temperature, which decreased proton conductivity, due to the constrained hydrophilic/hydrophobic phase separation, and increased the crystalline-rich domain. This research contributed to the understanding of ionomer thermal stability in the catalyst layer, which is subjected to thermal annealing during the hot-pressing process.

Mechanical Stabilization of Deoxyribonucleic Acid Solid Films Based on Hydrated Ionic Liquid.

Solid films of deoxyribonucleic acid (DNA) containing a hydrated ionic liquid, choline dihydrogen phosphate (CDP), were prepared by a solvent-casting method. Thermal properties, aggregation structure, thermal molecular motion, and tensile properties of CDP-containing DNA films were examined by thermogravimetry (TG), wide-angle X-ray diffraction (WAXD) measurement, dynamic mechanical analysis (DMA), and tensile tests, respectively. The water retentivity of the films at room temperature was much improved with CDP. The packing density of DNA helical chains clearly depended on the amount of CDP in the film. A small amount of CDP contributed to the suppression of the BI → BII conformational transition and the cooperative motion of the DNA duplex in the film. The tensile properties of the film drastically changed in the presence of CDP. When the amount of hydrated CDP in the film increased, the mechanical response of the film changed from glassy-like to rubbery-like via a semicrystalline-like state. The above results make it clear that CDP plays two major roles as a water absorber and plasticizer in the DNA film. Thus, it can be concluded that the use of an ionic liquid as an additive significantly increases the possibility of using a DNA solid film as a structural material.

Structure of Ultrafine Bubbles and Their Effects on Protein and Lipid Membrane Structures Studied by Small- and Wide-Angle X-ray Scattering.

Ultrafine bubbles (UFBs) are defined as small gas-filled bubbles with a diameter smaller than 1 µm. UFBs are stable for several weeks in aqueous solutions due to their small size. Although the mechanism of the stability of UFBs remains under intensive investigation, industrial applications of UFBs have recently arisen in various fields such as agricultural and fishery industries and medical therapy. The relevance of ions (protons and hydroxide anions) in UFB solutions has been discussed; however, the mechanism underlying the behavior of UFBs is still ambiguous and there is little direct evidence of the effect of UFBs on biological materials. This study deals with gaseous UFBs in aqueous solutions. Using small- and wide-angle X-ray scattering, we have investigated the structures of UFBs (air-UFBs, O2-UFBs, and N2-UFBs) and their effect on protein and lipid membrane structures. X-ray scattering and modeling data suggest that UFBs present a dynamic diffusive boundary (interface) due to the continuous release and absorption of gas. UFBs were found to not affect the structures of proteins at all hierarchal structure levels (from quaternary to tertiary, to internal, to secondary), whereas they did influence the packing and fluctuation of the hydrocarbon chains in the liposomes but not their shapes.

Fluorination and chlorination effects on quinoxalineimides as an electron-deficient building block for n-channel organic semiconductors.

The quinoxalineimide (QI) unit, containing the electron-withdrawing quinoxaline and imide groups, is an electron-deficient building block for organic semiconductor materials. In this study, three fluorinated or chlorinated QIs (QI-1F, QI-2F, and QI-2Cl), have been designed and developed. We report the impact of the fluorination or chlorination of the QI unit on the electronic structures and charge carrier transport properties as compared to unsubstituted QI (QI-2H) bearing the same n-hexyl side chains. The frontier molecular orbital energy levels downshifted with the incorporation of fluorine or chlorine atoms onto the π-framework of QI. Single-crystal structure analyses revealed that all QI-based molecules have an entirely planar backbone and are packed into two-dimensional slipped stacks with diagonal electronic coupling that enables two-dimensional charge carrier transport. Notably, the doubly fluorinated or chlorinated QIs formed compact molecular packing in the single-crystal structures through an infinite intermolecular network relative to unsubstituted QI (QI-2H). The field-effect transistor-based QI molecules exhibited typical n-channel transport properties. As compared to unsubstituted QI (QI-2H), the chlorinated QI exhibited improved electron mobilities up to 7.1 × 10-3 cm2 V-1 s-1. The threshold voltages of the fluorinated or chlorinated QI devices were clearly smaller than that of QI-2H, which reflects the lowest unoccupied molecular orbital levels of the molecules. This study demonstrates that the fluorinated or chlorinated QIs are versatile building blocks in creating n-channel organic semiconductor materials.

Diffracted X-ray Blinking Tracks Single Protein Motions.

Single molecule dynamics studies have begun to use quantum probes. Single particle analysis using cryo-transmission electron microscopy has dramatically improved the resolution when studying protein structures and is shifting towards molecular motion observations. X-ray free-electron lasers are also being explored as routes for determining single molecule structures of biological entities. Here, we propose a new X-ray single molecule technology that allows observation of molecular internal motion over long time scales, ranging from milliseconds up to 103 seconds. Our method uses both low-dose monochromatic X-rays and nanocrystal labelling technology. During monochromatic X-ray diffraction experiments, the intensity of X-ray diffraction from moving single nanocrystals appears to blink because of Brownian motion in aqueous solutions. X-ray diffraction spots from moving nanocrystals were observed to cycle in and out of the Bragg condition. Consequently, the internal motions of a protein molecule labelled with nanocrystals could be extracted from the time trajectory using this diffracted X-ray blinking (DXB) approach. Finally, we succeeded in distinguishing the degree of fluctuation motions of an individual acetylcholine-binding protein (AChBP) interacting with acetylcholine (ACh) using a laboratory X-ray source.

Polar-Nonpolar Interfaces of Inverse Bicontinuous Cubic Phases in Phytantriol/Water System are Parallel to Triply Periodic Minimal Surfaces.

We investigated two distinct lyotropic liquid crystal inverse bicontinuous cubic phases of phytantriol/water mixtures by small-angle X-ray crystallography of the single-crystal regions. Reconstructed electron density maps revealed hydrophilic head and hydrophobic tail regions of the phytantriol bilayer membranes and water regions. The bilayer membranes are shown to be located on the D and gyroid triply periodic minimal surfaces. To investigate the structures of the polar-nonpolar interfaces, we optimized two models: a parallel surface model and a constant mean curvature surface model. The parallel surface model agreed well with the X-ray data, and the R factors, which show the degree of agreement between those structural models and the data, were less than 0.04. In stark contrast, the constant mean curvature surface model deviated significantly from the data, and the R factors were around 0.15. We therefore conclude that the polar-nonpolar interface of the inverse bicontinuous cubic phase of the phytantriol/water system is close to a parallel surface to a triply periodic minimal surface.

Restoration of Myoglobin Native Fold from Its Initial State of Amyloid Formation by Trehalose.

Organisms having tolerances against extreme environments produce and accumulate stress proteins and/or sugars in cells against the extreme environment such as high or low temperature, drying, and so forth. Sugars and/or polyols are known to prevent protein denaturation and enzyme deactivation. In particular, trehalose has received considerable attention because of its association with cryptobiosis and anhydrobiosis. This study focuses on the restoration of acid-denatured amyloid transition of myoglobin by trehalose. Myoglobin is known to proceed amyloidogenic reaction under denaturation conditions. We found that acid-denatured myoglobin at an initial process of amyloidogenic reaction (helix-to-sheet transition followed by oligomerization) at 25 °C was substantially restored to its native structure by trehalose. This action was prominent during the early stage of amyloid formation. Recent results showed that sugars are preferentially excluded from the protein surface to preserve its hydration shell and stabilize the protein structure against chemical and thermal denaturation. Therefore, the present results suggest that trehalose will restore the tightly bound water molecules around the hotspot (G-helix) of myoglobin on the amyloid transition by its intrinsic preservative action of the native hydration shell against denaturation. The present finding on the restorative action by trehalose could provide new insights into protein folding and amyloidosis.

Preferential Intercalation of Human Amyloid-ß Peptide into Interbilayer Region of Lipid-Raft Membrane in Macromolecular Crowding Environment.

This study focuses on the interaction of human amyloid ß-peptide (Aß) with a lipid-raft model membrane under macromolecular crowding conditions that mimic the intracellular environment. Aß is central to the development of Alzheimer's disease (AD) and has been studied extensively to determine the molecular mechanisms of Aß-induced cellular dysfunctions underlying the pathogenesis of AD. According to evidence from spectroscopic studies, ganglioside clusters are key to the fibrillization process of Aß. Gangliosides are a major component of glycosphingolipids and are acidic lipids of the central nervous system known to form so-called lipid rafts. In this study, the small unilamellar vesicle (SUV) membrane, composed of monosialogangliosides, cholesterol, and 1,2-dipalmitoyl- sn-glycero-3-phosphocholine, did not show any structural changes after the addition of Aß under noncrowding conditions. However, the addition of Aß under crowding conditions induced shape deformation and aggregation to SUV resulting in multilamellar stacking. The time evolution of the lamellar peak suggested the preferential cohesion or intercalation of the Aß peptide into the interbilayer region. This phenomenon was only observed at the gel (Lß) phase. These results suggest that an intracellular crowding environment promotes Aß-membrane interaction and a selective accumulation of Aß peptides into the interbilayer regions.