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With the increasing importance of light-responsive materials, it is vital to analyze the relationship between function and structural changes induced by light irradiation. Small-angle scattering (SAS) is effective for such structural analysis. However, quantitatively capturing local molecular structure formation and molecular reactions at a scale of less than 1 nm via SAS is difficult. In this study, to analyze the structure of non-equilibrium phenomena in light-responsive materials, a new sample environment has been developed for a time-of-flight small- and wide-angle neutron scattering instrument (TAIKAN), comprising a UV–Vis irradiation system, UV–Vis absorption measurement equipment and photodetector. Simultaneous measurement of small-angle neutron scattering and UV–Vis absorption was achieved. This system was used to demonstrate the in situ observation of UV–Vis irradiation-induced structural change of micelles formed by 4-butylazobenzene-4′-(oxyethyl)trimethylammonium bromide, which is a light-responsive surfactant, in an aqueous solution. The results showed that the present measuring system provides direct information on the interplay between changes in micelle structure and changes in molecular configuration.

The conformation and structure of methyl cellulose (MC) ether samples dissolved in pure water under dilute conditions were carefully reconsidered based on the results obtained using small-to-wide-angle neutron scattering (S-WANS), static light scattering (SLS), dynamic light scattering (DLS), and viscometric techniques. The examined MC samples possessed an average degree of substitution by methyl groups per glucose unit of ca 1.8 and weight average molar masses (

Cryogenic electron microscopy is one of the fastest and most robust methods for capturing high-resolution images of proteins, but stringent sample preparation, imaging conditions, and in situ radiation damage inflicted during data acquisition directly affect the resolution and ability to capture dynamic details, thereby limiting its broader utilization and adoption for protein studies. We addressed these drawbacks by introducing synthesized giant carbon nano-test tubes (GCNTTs) as radiation-insulating materials that lessen the irradiation impact on the protein during data acquisition, physical molecular concentrators that localize the proteins within a nanoscale field of view, and vessels that create a microenvironment for solution-phase imaging. High-resolution electron microscopy images of single and aggregated hemoglobin molecules within GCNTTs in both solid and solution states were acquired. Subsequent scanning transmission electron microscopy, small-angle neutron scattering, and fluorescence studies demonstrated that the GCNTT vessel protected the hemoglobin molecules from electron irradiation-, light-, or heat-induced denaturation. To demonstrate the robustness of GCNTT as an imaging platform that could potentially augment the study of proteins, we demonstrated the robustness of the GCNTT technique to image an alternative protein, d-fructose dehydrogenase, after cyclic voltammetry experiments to review encapsulation and binding insights. Given the simplicity of the material synthesis, sample preparation, and imaging technique, GCNTT is a promising imaging companion for high-resolution, single, and dynamic protein studies under electron microscopy.

Polyethyleneglycol 12 mol / polydimethylsiloxane co-polymer (PEG-12 dimethicone) is a type of polyether modified silicone (PEMS), which can form a lamellar liquid crystalline phase, and is widely used in cosmetics. The structural changes of PEG-12 dimethicone caused by water contents as well as shear flow were evaluated using simultaneous measurements of rheology and small angle neutron scattering (Rheo-SANS) and neutron reflectometry (NR). At high PEG-12 dimethicone concentrations (≥ 36 wt%), a reorientation of plate-like lamellar structures were observed and the neutral orientation was the most favorable. However, lamella-to-vesicle transitions were hardly observed. PEG-12 dimethicone turned out to form a bi-layer on a hydrophilized Si-wafer in a similar manner to that in bulk though the structure had a certain level of roughness.

In this study, we used small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) to investigate the formation process of silver (Ag) nanoparticles (NPs) in water-in-oil (w/o) reverse microemulsions comprising sodium bis(2-ethylhexyl) sulfosuccinate (AOT), water, and organic solvents (such as benzene, octane, and decane) by the photoreduction of silver perchlorate (AgClO4). Combining SANS and SAXS, the structural changes in the w/o microemulsions before and after the formation of Ag NPs via photoreduction were quantitatively evaluated. From the SANS experiments performed using the contrast-variation method, the size of water cores containing Ag NPs and the thickness of the AOT shells were calculated using the core-shell hard-sphere model. The size of the Ag NPs and their aggregates was calculated via SAXS analysis based on the polydisperse sphere model with a Schulz-Zimm distribution. We found that aggregates of three or four primary Ag NPs are formed by, first, the aggregation of water droplets through the entanglement of the tails of the AOT shell, followed by the self-assembly of Ag NPs into their aggregates because of particle-particle attractive interactions.

Perfume solubilization is an important process in the production of commercial products such as beverages, foods, and cosmetics. In the present study, small-angle neutron scattering (SANS) experiments were performed to investigate the solubilization behavior of perfumes in cetyltrimethylammonium bromide (CTAB) micelles. The solubilization of linalool (LL) and l-menthol (MT), which are relatively hydrophilic perfumes, did not change the size of the CTAB micelles although the perfumes were incorporated in the micelles, as indicated by a decrease in scattering length density. On the other hand, the solubilization of d-limonene (LN), a hydrophobic perfume, led to the swelling of CTAB micelles. An internal contrast variation SANS study was performed by the deuteration of CTAB molecules to directly observe the perfumes in the micelles. The radius of d-CTAB micelles solubilizing LL or MT corresponds to that of h-CTAB, which indicates that these perfumes are accommodated in the palisade layers of the micelles and are homogeneously distributed in the micelles. On the other hand, LN formed small droplets, as indicated by the SANS profile, which implies the solubilization of LN molecules in the core of the CTAB micelles. We found that the relatively hydrophilic perfumes (LL and MT) show less impact on the sizes of the cationic micelles in comparison to nonionic micelles. Thus, the internal contrast variation method of SANS allowed the direct observation of the solubilization sites of perfumes with different hydrophilicity-hydrophobicity balances. This method is a powerful tool to determine the solubilization states that affect the solubilization capacity, volatilization, or release speed of perfumes.

The condensation of globular myoglobin (Mb) at the pore entrances of mesoporous silica (MPS) with a series of pore diameters (4.2, 6.4, 7.7, and 9.0 nm) was examined by differential scanning calorimetry (DSC) and contrast-matching small-angle neutron scattering (CM-SANS) experiments. The DSC measurements were performed to estimate the amount of Mb adsorbed at two different adsorption sites, namely, the pore interior and the pore entrance regions. The CM-SANS measurements were conducted to observe condensation of Mb molecules at the pore entrance regions. Notably, the nanopore entrance with a diameter close to twice that of the Mb diameter was found to be the specific cavity to facilitate the condensation of globular Mb. The Mb condensation occurred at the entrances of the 6.4 nm pore during the adsorption uptake from concentrated Mb solutions, whereas the adsorption uptake from diluted Mb solutions induced the condensation of Mb at the entrances of the 7.7 nm pore.

The ionomers distributed on carbon particles in the catalyst layer of polymer electrolyte fuel cells (PEFCs) govern electrical power via proton transport and oxygen permeation to active platinum. Thus, ionomer distribution is a key to PEFC performance. This distribution is characterized by ionomer adsorption and deposition onto carbon during the catalyst-ink coating process; however, the adsorbed and deposited ionomers cannot easily be distinguished in the catalyst layer. Therefore, we identified these two types of ionomers based on the positional correlation between the ionomer and carbon particles. The cross-correlation function for the catalyst layer was obtained by small-angle neutron scattering measurements with varying contrast. From fitting with a model for a fractal aggregate of polydisperse core-shell spheres, we determined the adsorbed-ionomer thickness on the carbon particle to be 51 A and the deposited-ionomer amount for the total ionomer to be 50%. Our technique for ionomer differentiation can be used to optimally design PEFC catalyst layers.

A thixotropic characteristics of aqueous gels containing smectite clay minerals were used in various industrial applications such as paint additives, which have been affected by the clay types and clay particle sizes. A model called a house-of-card arrangement of clay particles and anisotropic arrangement in aqueous gels has been proposed. We prepared different sizes of synthetic hectorite and studied them by scanning electron-assisted dielectric microscopy (SE-ADM) and simultaneous small-angle neutron scattering and rheological measurements (Rheo-SANS). The Rheo-SANS results indicated that the clay particles with the cross-sectional radius of 30 nm were clearly oriented in the direction of shear-flow (1 × 103 s-1) direction, but the anisotropic change was not observed for an aqueous gel with clays whose average radius was 19.5 nm. The present study suggested the thixotropic characteristics of aqueous gels depend on the hectorite particle size and aggregation structure under shear conditions.

Neutron polarization analysis (NPA) for small-angle neutron scattering (SANS) experiments using a pulsed neutron source was successfully achieved by applying a 3He spin filter as a spin analyzer for the neutrons scattered from the sample. The cell of the 3He spin filter gives a weak small-angle scattering intensity (background) and covers a sufficient solid angle for performing SANS experiments. The relaxation time of the 3He polarization is sufficient for continuous use for approximately 2 days, thus reaching the typical duration required for a complete set of SANS experiments. Although accurate evaluation of the incoherent neutron scattering, which is predominantly attributable to the extremely large incoherent scattering cross section of hydrogen atoms in samples, is difficult using calculations based on the sample elemental composition, the developed NPA approach with consideration of the influence of multiple neutron scattering enabled reliable decomposition of the SANS intensity distribution into the coherent and incoherent scattering components. To date, NPA has not been well established as a standard technique for SANS experiments at pulsed neutron sources such as the Japan Proton Accelerator Research Complex (J-PARC) and the US Spallation Neutron Source. It is anticipated that this work will contribute significantly to the accurate determination of the coherent neutron scattering component for scatterers in various types of organic sample systems in SANS experiments at J-PARC, particularly for systems involving competition between the coherent and incoherent scattering intensity.

The UCST of phase separation for imidazolium-based ionic liquids [Cnmim][TFSI] and formamide (FA) binary solutions increases with elongation of the alkyl chain lengthn. This is opposite to previous 1,4-dioxane solutions.

Polymer vesicles with intrinsic molecular permeability have attracted attention as structural components for nano/microreactors in the context of drug delivery and artificial cells. However, the mo...

Nafion is a fluorocarbon polymer, commonly used as a proton exchange membrane in fuel cells because of its excellent thermal and mechanical stabilities. However, the basic properties of Nafion, such as its nanostructures and rheological behavior, remain unclear because the morphology of this material is highly sensitive to its processing history. The present work involved a systematic analysis of both the structural and rheological properties of Nafion dispersions carefully prepared using a standard procedure, ranging from dilute (0.1 wt %) to highly concentrated (30 wt %) conditions. Small-angle X-ray scattering confirmed the cylindrical structure of Nafion in dispersion and the unique interactions of Nafion particles acting as polyelectrolytes. Three different scaling relationships involving the zero-shear viscosities of the Nafion dispersions were determined for specific concentration regimes. However, at the upper concentration limit of approximately 30 wt %, the viscosity greatly deviated from these ...

Liquid–liquid phase separation of binary systems for imidazolium-based ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Cnmim][TFSI], where n represents the alkyl chain length of the cation), with 1,4-dioxane (1,4-DIO) was observed as a function of temperature and 1,4-DIO mole fraction, x1,4-DIO. The phase diagrams obtained for [Cnmim][TFSI]–1,4-DIO systems showed that the miscible region becomes wider with an increase in the alkyl chain length, n. For n = 6 and 8, an upper critical solution temperature (UCST) was found. To clarify the mechanism of the UCST-type phase separation, small-angle neutron scattering (SANS) experiments were conducted on the [C8mim][TFSI]–1,4-DIO-d8 system at several x1,4-DIO. The critical exponents of γ and ν determined from the SANS experiments showed that phase separation of the system at the UCST mole fraction occurs via the 3D-Ising mechanism, while that on both sides of UCST occurs via the mean field mechanism. Thus, the crossover of mechanism was observed for this system. The microscopic interactions among the cation, anion, and 1,4-DIO were elucidated using 1H and 13C NMR and IR spectroscopic techniques, together with the theoretical method of molecular dynamics (MD) simulations. The results on the microscopic interactions suggest that 1,4-DIO molecules cannot strongly interact with H atoms on the imidazolium ring, while they interact with the octyl chain of the cation through dispersion force. With a decrease in temperature, 1,4-DIO molecules gradually aggregate to form 1,4-DIO clusters in the binary solutions. The strengthening of the C–H⋯O interaction between 1,4-DIO molecules by cooling is the key to the phase separation. Of course, the electrostatic interaction between the cations and anions results in the formation of IL clusters. When IL clusters are excluded from 1,4-DIO clusters, liquid–liquid phase separation occurs. Accordingly, the balance between the electrostatic force between the cations and anions and the C–H⋯O interaction between the 1,4-DIO determines the 3D-Ising or the mean field mechanism of phase separation.

Dynamically crosslinked gels are appealing materials for applications that require time-dependent mechanical responses. DNA duplexes are ideal crosslinkers for building such gels because of their excellent sequence addressability and flexible tunability in bond energy. However, the mechanical responses of most DNA gels are complicated and unpredictable despite the high potential of DNA. Here, we demonstrate a DNA gel with a highly homogeneous gel network and well-predictable mechanical behaviors by using a pair of star-polymer-DNA precursors with presimulated DNA sequences showing the two-state transition. The melting curve analysis of the DNA gels reveals the good correspondence between the thermodynamic potentials of the DNA crosslinkers and the presimulated values by DNA calculators. Stress-relaxation tests and dissociation kinetics measurements show that the macroscopic relaxation time of the DNA gels is approximately equal to the lifetime of the DNA crosslinkers over four orders of magnitude from 0.1-2,000 sec. Furthermore, a series of durability tests find the DNA gels are hysteresis-less and self-healable after the applications of repeated temperature and mechanical stimuli. These results demonstrate the great potential of star-polymer-DNA precursors for building gels with predictable and tunable viscoelastic properties, suitable for applications such as stress-response extracellular matrices, injectable solids, and soft robotics.

Liquid-liquid phase separation of binary systems for imidazolium-based ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C

The solution properties of a water-soluble chemically modified cellulose ether, hydroxyethyl cellulose (HeC), were examined using static light scattering (SLS), dynamic light scattering (DLS), small-to-wide-angle neutron scattering (S-WANS), small-to-wide-angle X-ray scattering (S-WAXS) and viscometric techniques at 25 °C. The examined HeC samples had average molar substitution numbers ranging from 2.36 to 2.41 and weight average molar masses (Mw) that fell within a wide range from 87 to 1500 kg mol−1. Although the relationship between the determined radius of gyration (Rg) and Mw was described as Rg ∝ Mw~0.6, as is observed usually in flexible polymer solutions in good solvents, the observed scattering vector (q) dependencies of excess Rayleigh ratios were well interpreted using a rigid rod particle model, even in high-Mw samples. Moreover, the ratios of the formed particle length (L) evaluated assuming the model for rigid rods to the determined Rg showed the relationship LRg−1 ~ 3.5 irrespective of Mw and were close to those theoretically predicted for rigid rod particle systems, i.e., LRg−1 = 12. The observed SLS behavior suggested that HeC molecules behave just like rigid rods in aqueous solution. As the L values were not simply proportional to the average molecular contour length calculated from the Mw, the chain conformation or structure of the formed particles by HeC molecules in aqueous solution changed with increasing Mw. The q dependencies of excess scattering intensities observed using the S-WANS and S-WAXS experiments demonstrated that HeC molecules with Mw less than 200 kg mol−1 have a diameter of ~1.4 nm and possess an extended rigid rod-like local structure, the size of which increases gradually with increasing Mw. The observed Mw dependencies of the translational and rotational diffusion coefficients and the intrinsic viscosity of the particle suspensions strongly support the idea that the HeC molecules behave as rigid rod particles irrespective of their Mw.

Gemini-type amphiphilic dendrimers featuring two dodecyl chains and two poly(amidoamine) dendrons (2C12-2denGn, where n is the dendron (den) generation (G) number (1, 2, 3, 4, or 5)) were synthesized using ethylenediamine, alkyl bromide, and methyl acrylate. These gemini-type dendrimers were characterized by surface tension, pyrene fluorescence, static light scattering, and small-angle X-ray scattering. The results showed clear breakpoints in the surface tension versus concentration plots, which indicated adsorption at the air/water interface and micelle formation in solution despite the bulky dendron structure (e.g., generations 3 to 5), contrasting the behavior of conventional surfactants. The 2C12-2denGn dendrimers could be densely packed at the air/water interface owing to enhanced interaction between the dendrons and between the alkyl chains. Furthermore, these dendrimers formed spherical micelles at a concentration of 5.0 mmol dm-3 in solution (pH 9); the overall micelle size was not dependent on the generation number of the dendron, while as the generation number increased, the core radius of the micelle decreased, and the shell thickness of the micelle increased.

Herein, we characterized the micelle structure and hydration behavior of oleic acid-based gemini surfactants by small-angle neutron scattering. A larger counterion size (Li+ < Na+ < K+ < Cs+) resul...

The interior of living cells is a molecular-crowding environment, where large quantities of various molecules coexist. Investigations into the nature of this environment are essential for an understanding of both the elaborate biological reactions and the maintenance of homeostasis occurring therein. The equilibrium states of biological macromolecular systems are affected by molecular-crowding environments unmatched by in vitro diluted environments; knowledge about crowding effects is still insufficient due to lack of relevant experimental studies. Recent developments in the techniques of in-cell NMR and large-scale molecular dynamics simulation have provided new insights into the structure and dynamics of biological molecules inside the cells. This study focused on a new experimental technique to directly observe the structure of a specific protein or membrane in condensed crowder solutions using neutron scattering. Deuterated whole-cell debris was used to reproduce an environment that more closely mimics the interior of living cells than models used previously. By the reduction of the background scattering from large amounts of cell debris, we successfully extracted structure information for both small globular protein and small unilamellar vesicle (SUV) from the concentrated cell-debris solution up to a weight ratio of 1:60 for protein/crowder and 1:40 for SUV/crowder.

Hypothesis Gemini surfactant 12–2–12 (dimethylene-1,2-bis(dodecyl dimethylammonium bromide)) solutions are known to show shear thickening and thinning under salt-free conditions. Because the rheological behavior of the wormlike micelles formed by 12–2–12 in solution is related to their structure, we expected that changes to the precursor structure would affect their rheological behaviors. It is also important to understand the effect of the introduction of a spacer group in the 12–2–12 molecules on the rheological behavior and structure of the wormlike micelles under shear flow. Experiments Simultaneous small-angle neutron scattering and rheological measurements (Rheo-SANS) of the 12–2–12 solutions were performed. We exhaustively studied the structural changes in the wormlike micelles upon increasing shear rate. Findings We found that the wormlike micelles were oriented in the direction of the flow due to elongation and that changes to the precursor of the wormlike micelles did not affect the shear thickening. As a precursor structural change of shear thinning, the wormlike micelles elongated while maintaining their orientation. We found that an increase in the molecular curvature of the 12–2–12 due to the introduction of a spacer-group contributed to the unusual rheological behaviors of the wormlike micelles in a solution under shear flow.

In the room-temperature ionic liquid (IL) of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)amide ([C8mim][TFSA]), the complex formation of Ni2+ with molecular liquids (MLs), dimethyl sulfoxide (DMSO), methanol (MeOH), and acetonitrile (AN), has been examined using ultraviolet (UV)-visible spectroscopy. The overall stability constants log βn, enthalpies , and entropies of the equilibria have been determined to elucidate the mechanism of complex formation. From a comparison of such thermodynamic parameters of the present [C8mim][TFSA] systems with those of the previous systems of 1-ethyl-3-methylimidazolium-based IL, [C2mim][TFSA], the effects of the octyl chain of the imidazolium cation, [C8mim]+, on the complex formation of Ni2+ with MLs have been demonstrated. In [C8mim][TFSA]–ML systems, more stable complexes are formed with MLs in the sequence of AN > DMSO ≫ MeOH. This sequence differs from that of DMSO ≫ AN > MeOH in [C2mim][TFSA]. For the AN systems, the stabilities of [Ni(an)n] in [C8mim][TFSA] are higher as compared to those in [C2mim][TFSA]. In contrast, for the DMSO systems, [Ni(dmso)n] is less stable in the IL with the longer alkyl chain than that in the IL with the shorter chain. The dependence of the alkyl chain length on the stabilities of [Ni(meoh)n] is the least significant among the three MLs. These varieties of the stabilities of Ni2+ complexes with the MLs have been interpreted from the thermodynamic parameters, together with the static interactions in the [C8mim][TFSA]–ML and [C2mim][TFSA]–ML solvents observed by means of 1H and 13C NMR, small-angle neutron scattering (SANS), and infrared (IR) with an ATR diamond prism.

The present study aimed to investigate the thermal- and pH-dependent gelation behavior of gelatin/HPMCP blends using ultraviolet (UV) spectrophotometry, viscoelasticity, and dynamic light scattering (DLS). We found that the release of lisinopril from gelatin/HPMCP gels can be inhibited at low pH. UV spectrophotometric analysis showed that pH had a significant effect on the transparency of aqueous HPMCP systems and gelatin/HPMCP gels. The viscoelastic patterns of gelatin/HPMCP at pH 4.6 considerably differed from those of gelatin/HPMCP at pH 5.2 and 6.0. DLS measurements showed that HPMCP molecules in low concentrations underwent strong aggregation below pH 4.8. Such HPMCP aggregation induces a physical barrier in the matrix structures of the gelatin/HPMCP gels, which inhibits the drug release at pH 1.2. This hydrogel delivery system using polymer blends of gelatin/HPMCP can be used in oral gel formulations with pH-responsive properties.

We recently developed a simultaneous measurement system combining a wide Q-range SANS instrument and a Fourier-transform infrared (FTIR) spectrometer equipped with an infrared polarizer. The information of high Q neutron scattering and FTIR spectra helps to increase the reliability of structural analysis by SANS on complicated systems. In this study, we applied this simultaneous measurement system to a cocrystal system of syndiotactic polystyrene (sPS) and methyl benzoate (MeBA). The neutron scattering provided the evidence that MeBA molecules were certainly incorporated into the crystalline region of sPS. The polarized FTIR measurements showed that the guest MeBA has a certain orientation against the sPS lattice. With the help of different kinds of structure information, the thermal behavior of sPS/MeBA cocrystal was able to be analyzed in detail.

Photo-induced rapid control of molecular assemblies, such as micelles and vesicles, enables effective and on-demand release of drugs or active components, with applications such as drug delivery systems (DDS) and cosmetics. Thus far, no attempts to optimize the responsiveness of photoresponsive molecular assemblies have been published. We previously reported photoresponsive surfactants bearing a lophine dimer moiety that exhibit fast photochromism in confined spaces, such as inside a molecular assembly. However, rapid control of the micelle structures and solubilization capacity have not yet been demonstrated. In the present work, photo-induced morphological changes in micelles were monitored using in-situ small-angle neutron scattering (SANS) and UV/Vis absorption spectroscopy. An amphiphilic lophine dimer (3TEG-LPD) formed elliptical micelles. These were rapidly elongated by ultraviolet light irradiation, which could be reversed by dark treatment, both within 60 s. For a solution of 3TEG-LPD micelles solubilizing calcein as a model drug molecule, fluorescence and SANS measurements indicated rapid release of the incorporated calcein into the bulk solvent under UV irradiation. Building on these results, we investigated rapid controlled release via hierarchical chemical processes: photoisomerization, morphological changes in the micelles, and drug release. This rapid controlled release system allows for effective and on-demand DDS.

The structure and conformation of methyl cellulose (MC) and hydroxypropyl methyl cellulose (HpMC) ether samples dissolved in dilute aqueous (D2O) solutions at a temperature of 25 °C were reconsidered in detail based on the experimental results obtained using small- and wide-angle neutron scattering (S-WANS) techniques in a range of scattering vectors (q) from 0.05 to 100 nm−1. MC samples exhibited an average degree of substitution (DS) by methyl groups per glucose unit of DS = 1.8 and the weight average molar mass of Mw = 37 × 103 and 79 × 103 g mol−1. On the other hand, HpMC samples possessed the average molar substitution number (MS) by hydroxypropyl groups per glucose unit of MS = 0.25, DS = 1.9, and Mw = 50 × 103 and 71 × 103 g mol−1. The concentration-reduced scattering intensity data gathered into a curve for the solutions of identical sample species clearly demonstrated the relationship I(q)c−1 ∝ q−1 in a q range from 0.05 to 2.0 nm−1, and small interference peaks were found at q ∼ 7 and 17 nm−1 for all examined sample solutions. These observations strongly revealed that form factors for both the MC and HpMC samples were perfectly described with that for long, rigid rod particles with average diameters of 0.8 and 0.9 nm, respectively, and with an inner structure with characteristic mean spacing distances of ca. 0.9 and 0.37 nm, respectively, regardless of the chemically modified conditions and molar masses. A rationally speculated structure model for the MC and HpMC samples dissolved in aqueous solution was proposed.

We studied the effects of temperature and shear flow on the structures of α-gel bilayers and domains. The α-gel samples were prepared by a carboxylate-type gemini surfactant synthesized from oleic acid and a long-chain alcohol (1-tetradecanol) with water. The structural change as a function of temperature was investigated using small- and wide-angle X-ray scattering (SWAXS) measurements, spin-spin relaxation time (T2) measurements, and optical microscopy observations. SWAXS measurements suggested that the decreased temperature yielded the α-gel phase from a lamellar liquid-crystal phase. We also found that the lamellar d-spacing drastically decreased at the phase transition temperature. The T2 measurements suggested that two kinds of protons with different mobilities coexisted in amphiphiles consisting of lamellar bilayers. The abundance of the protons with low mobility increased with decreasing temperature. Optical microscopy results indicated that the size of the α-gel domains increased with decreasing temperature. We assumed that the increased abundance of the low-mobility protons, indicating low flexibility of lamellar bilayers, led to a decreased lamellar d-spacing and increased size of the α-gel domains. Shear-induced structural changes in the α-gel were also studied using simultaneous small-angle neutron scattering and rheological measurements. The α-gel can maintain bilayer structures even at high shear rates. We also found that the lamellar d-spacing was independent of the shear rate.

Liquid-crystalline (LC) bio-inspired materials based on colloidal nanoparticles with anisotropic morphologies such as sheets, plates, rods and fibers were used as functional materials. They show stimuli-responsive behaviour under mechanical force and in electric and magnetic fields. Understanding the effects of external stimuli on the structures of anisotropic colloidal particles is important for the development of highly ordered structures. Recently, we have developed stimuli-responsive hydroxyapatite (HAP)-based colloidal LC nanorods that are environmentally-friendly functional materials. In the present study, the ordering behaviour of HAP nanorod dispersions, which show LC states, has been examined using in situ small-angle neutron scattering and rheological measurements (Rheo–SANS) under shearing force. The structural analyses and dynamic viscosity observations provided detailed information about the effects of shear force on the structural changes of HAP nanorods in D2O dispersion. The present Rheo–SANS measurements unraveled three kinds of main effects of the shear force: the enhancement of interactions between the HAP nanorods, the alignment of HAP nanorods to the shear flow direction, and the formation and disruption of HAP nanorod assemblies. Simultaneous analyses of dynamic viscosity and structural changes revealed that the HAP nanorod dispersions exhibited distinctive rheological properties accompanied by their ordered structural changes.

The interior of cell is crowded with various kinds of macromolecules, and proteins are designed to function under crowding environment. However, experimental studies showing the direct evidence of the effect of macromolecular crowding environment on the structures of proteins seems to be insufficient. Then, by the complementally use of both X-ray and neutron scattering methods, we have studied the effect of macromolecular crowding on both the structure and the hydration-shell of myoglobin. The neutral co-solute, polyvinylpyrrolidone (PVP, 40 k Dalton) was used to mimic the crowding environment of cell. The compression of the maximum dimension and the radius of gyration of myoglobin by the presence of PVP were observed. These changes are reasonably explained by the theoretical scattering function simulation based on the preferential exclusion model accompanying a collapse of hydration-shell of the protein. The present results suggest the possibility that the crowding environment by high molecular-weight neutral co-solutes would be non-ideal and different from small molecular crowding such as sugars and polyols.

The small and wide angle neutron scattering instrument (TAIKAN) installed at the Material and Life Science Experimental Facility (MLF), Japan Proton Accelerator Research Complex (J-PARC) can cover a Q-range from 5 × 10−3 to 17 A−1 simultaneously, where the magnitude of the scattering vector Q is defined by Q = 4πsin(θ/2)/λ (θ and λ represent the scattering angle and the wavelength, respectively). To extend the accessible low Q-limit (Qmin) to a value in the order of 10−4 A−1, we successfully installed an ultra-small-angle detector with a spatial resolution of approximately 0.41 mm × 0.41 mm in TAIKAN. This detector is a high-resolution position-sensitive detector (HR-PSD), comprising a cross-wired position-sensitive photomultiplier tube and a ZnS/6LiF scintillator. HR-PSDs of the same type have been installed on steady-state small-angle neutron scattering (SANS) instruments at the research reactor (JRR-3), Japan. Comparing with these previously installed the HR-PSDs, we improved most of the HR-PSD components such as the scintillator, preamplifier, and data acquisition systems to increase its maximum count rate. A maximum count rate of 46 kcps was achieved with 10% counting loss, which is 2.3 times for those installed in the steady-state SANS instruments at JRR-3. Using the ultra-small-angle detector with existing 3He detector banks, TAIKAN can simultaneously cover a Q-range from 8 × 10−4 A−1 to 17 A−1 (over four orders of magnitude in Q).

Sugars are well known to retain protein structures and to protect denaturation. Protective actions of sugars on protein structures have been discussed under issues of preferential hydration and/or interaction between sugar and protein. By using synchrotron radiation wide-angle X-ray scattering (SR-WAXS) and small-angle neutron scattering (SANS) methods, we have succeeded to obtain a direct evidence of the effect of trehalose and glucose on a protein structure and hydration. Myoglobin from horse-skeletal muscles was used as one of typical globular proteins. The sugars used were trehalose and glucose whose concentrations were varied from 0% w/w to 35% w/w. The experimental SR-WAXS and SANS data combined with theoretical scattering function simulation and fitting clearly show that both sugars are preferentially excluded from the hydration-shell region of the protein to preserve hydration-shell density. up to the sugar concentration of ∼25% w/w. Compared with that of glucose (monosaccharide), the preservation action of the protein hydration-shell is much evidently seen for the case of trehalose (disaccharide), which might relate to a role of the preferential production of trehalose by organisms against extreme environmental stress.

The protective action of sugars against the denaturation of myoglobin was clarified by X-ray and neutron scattering methods. Different types of sugars such as disaccharides (trehalose, sucrose) and monosaccharides (glucose, fructose) were used. Experimental data and theoretical simulation based on three different solvation models (preferential solvation model, nonpreferential solvation model, and preferential exclusion (hydration) model) indicated that sugar molecules were preferentially or weakly excluded from the protein surface and preserved the native protein hydration shell. This trend was more evident for disaccharides. The preferential exclusion shifted gradually to the nonpreferential solvation at higher sugar concentrations. On the protective actions of the sugars against the guanidinium-chloride-mediated denaturation, all sugars, starting from the low concentration of 5% w/v, showed the protective trend toward the protein native structure, especially for the secondary structure. The thermal structural transition temperature of myoglobin was raised by about 4-5 °C, accompanied by amyloid formation, for all hierarchical structural levels. In particular, the oligomer formation of the amyloid aggregates was more suppressed. The above protective action was sugar-dependent. The present results clearly suggest that sugars intrinsically protect the native structure of proteins against chemical and thermal denaturation through the preservative action of the hydration shell.

In the present study, we examined the secondary and tertiary structure of myoglobin (Mb) within folded sheets mesoporous material (FSM)- and Santa Barbara amorphous (SBA)-type mesoporous silicas. The Barrett–Joyner–Halenda pore diameters of SBA-type mesoporous silicas were 39, 70, and 75 A, and that of FSM-type mesoporous silica was 40 A. The secondary and tertiary structures of myoglobin were observed by Fourier transform infrared (FTIR) and small-angle neutron scattering (SANS), respectively. The FTIR and SANS results indicated preservation of the secondary and tertiary structures of myoglobin inside the pores of SBA-type mesoporous silicas. Adsorption of myoglobin within FSM-type mesoporous silica, however, resulted in perturbation of the tertiary structure, accompanied by partial unfolding of the secondary structure. Lower structural stability of myoglobin within the FSM-type mesoporous silica was also confirmed. These findings suggest that the Mb structure is more influenced by the inner pore surface...

Adamantane is difficult to dissolve in water owing to its bulky steric hydrocarbon structure. We designed a novel amphiphilic molecule by introducing an alkyl chain and a cation group into an adamantyl group. N,N-dimethyl-N-alkyladamantylammonium bromide (CnAdAB; n is the alkyl chain length, where n = 10, 12, and 14) dissolves easily in water by forming micelles above the critical micelle concentration. Aggregates of this surfactant series form small nonspherical micelles several nanometers in size with relative small aggregation number; 53 (n = 10), 59 (n = 12), and 63 (n = 14) at the typical concentration. Small-angle X-ray scattering measurement showed that the micellar structure of C12AdAB was changed slightly by solubilization of naphthalene and stearic acid. Moreover, the solubilization ability of the aggregates was studied using naphthalene and long-alkyl-chain fatty acids (myristic, palmitic, and stearic acids). The same solubilization experiments were performed using typical cationic surfactants (dodecyltrimethylammonium bromide and a gemini surfactant) for comparison. The molar solubilization ratios indicate that the CnAdAB series can solubilize the aromatic compound naphthalene as well as the other surfactants, whereas they can barely solubilize the long-alkyl-chain fatty acids. The solubilization stability can be analyzed by estimating the Gibbs free energy change (ΔG0) for the transfer of solubilizate molecules to the aggregate phase. The gemini surfactant system showed the largest negative value of ΔG0 for both naphthalene and the fatty acids. On the other hand, solubilization of fatty acids into CnAdAB micelles was not advantageous energetically. These results indicate that the solubilization ability of CnAdAB surfactants is not generally suitable for solubilization of long-alkyl-chain fatty acids owing to the smallness of the micelles.

The microstructure of synthetic hectorite aqueous suspensions was investigated by scanning electron-assisted dielectric microscopy (SE-ADM) and small angle neutron scattering (SANS) coupled with rheological measurements (Rheo-SANS). The direct observations of the aqueous suspensions by SE-ADM confirmed the array structure of the hectorite discs with ~100–300 nm scale periodic length. The suspensions demonstrated a typical thixotropic flow curve with hysteresis. No change in the SANS profiles at high shear rate (1000 s−1) was observed by the Rheo-SANS. These results suggested that the array was destroyed by the shear rate but the microstructure in the arrays was preserved in flow condition.

The hydrogen bonds of the imidazolium-ring H atoms of ionic liquids (ILs), 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amides ([Cnmim][TFSA], n = 2 to 12 where n represents the alkyl chain length), with the O atom of dimethyl sulfoxide (DMSO) have been elucidated using 1H, 13C, and 15N NMR spectroscopy and soft X-ray absorption and emission spectroscopy (XAS and XES). Density functional theory (DFT) calculations have been performed on an isolated DMSO molecule and two cluster models of [Cnmim]+-DMSO by hydrogen bonding to interpret the XES spectra for the [Cnmim][TFSA]-DMSO solutions. The 1H and 13C NMR chemical shifts of the imidazolium ring showed that deshielding of the ring H and C atoms is moderate as the DMSO mole fraction xDMSO increases to ∼0.8; however, it becomes more significant with further increase of xDMSO. This finding suggests that the hydrogen bonds of the three ring H atoms with the DMSO O atoms are saturated in solutions with xDMSO increased to ∼0.8. The 1H and 13C chemical shifts of the alkyl chains revealed that the electron densities of the chain H and C atoms gradually decrease with increasing xDMSO, except for the N1-bound carbon atom C7 of the chain. The 15N NMR chemical shifts showed that the imidazolium-ring N1 atom which is bound to the alkyl chain is shielded with increasing xDMSO in the range from 0 to 0.8 and is then deshielded with further increase of xDMSO. In contrast, the imidazolium ring N3 atom is simply deshielded with increasing xDMSO. Thus, the electron densities of the alkyl chain may be condensed at the C7 and N1 atoms of [Cnmim]+ by the hydrogen bonding of the ring H atoms with DMSO. The hydrogen bonding of DMSO with the ring results in low-energy shifts of the XES peaks of the O K-edge of DMSO. Small-angle neutron scattering experiments showed that [Cnmim][TFSA] and DMSO are homogeneously mixed with each other on the mesoscopic scale. This results from the strong hydrogen bonds of DMSO with the imidazolium-ring H atoms.

Physical gels have attracted considerable attention due to the remoldability deriving from the reversible cross-linking points made of noncovalent bonds. In this study, we report a facile method to realize a mechanically tough syndiotactic polypropylene (sPP) gel, one of the physical gels made of semicrystalline polymers. The sPP/decahydronaphthalene gel quenched using liquid nitrogen (GEL LN) presented the fracture stress of over 2 MPa with the fracture strain as high as ∼0.7, while the sPP gel prepared at room temperature (GEL 25) presented the fracture stress of only 315 kPa and the fracture strain of ∼0.3. The fracture stress was found to increase with the increase in the sPP concentration. Furthermore, the structural analyses of the sPP gels revealed that the quenching of the sPP gel suppressed the phase separation, eventually forming homogeneous nanocrystalline cross-linking network structures to produce a mechanically tough sPP gel.