Spatial Distribution of the Network Structure in Epoxy Resin via the MAXS-CT Method.

We have succeeded in visualizing the spatial heterogeneity of the reaction ratio in epoxy resins by combining medium-angle X-ray scattering (MAXS) and computed tomography (CT). The reaction ratio is proportional to the degree of cross-linking between epoxy and amine in epoxy resins. The reaction ratio and its spatial inhomogeneity affect the toughness of epoxy resins. However, there has been no non-destructive method to measure the spatial inhomogeneity of the reaction ratio, although we can measure only the spatially averaged reaction ratio by Fourier-transform infrared spectroscopy (FT-IR). We found that the scattering peak reflected the cross-linking structures in the q region of MAXS and that the peak intensity is proportional to the reaction ratio. By reconstructing CT images from this peak intensity, we visualized the spatial heterogeneity of the reaction ratio. The application of this method may not be limited to epoxy resins but may extend to studying the heterogeneity of cross-linked structures in other materials.

Avoidance of four-wave mixing in optical fiber bundle for coherent anti-Stokes Raman scattering endomicroscopy.

We propose and demonstrate a method of suppressing four-wave mixing (FWM) in an optical fiber bundle to realize coherent anti-Stokes Raman scattering (CARS) endomicroscopy, which is the leading candidate for a definitive diagnosis of gastrointestinal cancer. Two excitation laser beams with different wavelengths are delivered via different cores to suppress FWM and are then combined with a polarization prism and a dual-wavelength wave plate and are focused to a spot. The background emission from the optical fiber bundle was suppressed to 1/3289, and we demonstrated CARS imaging of a polystyrene bead using the proposed method.

Neutron Reflectometry Tomography for Imaging and Depth Structure Analysis of Thin Films with In-Plane Inhomogeneity.

Neutron reflectometry (NR) has been used for the depth structure analysis of materials at the surface and interface with a sub-nanometric resolution. Conventional NR provides averaged information for an area larger than several square centimeters; therefore, it cannot be applied to an interface with an in-plane inhomogeneity. In this study, the NR imaging of the in-plane structure of polymer thin films was achieved. The tomographic reconstruction of the spatially resolved NR profiles obtained by a sheet-shaped neutron beam provided a two-dimensional image of the in-plane interface morphology. The depth distribution of the neutron scattering length density was obtained by analyzing the position-dependent NR profile at a local area less than 0.1 mm2. The current NR tomography method enables NR measurements for an interface with an inhomogeneous structure. It also provides information on the three-dimensional distribution of the atomic composition near the surface and interfaces for various materials.

Investigation of Interfacial Water Accumulation between Polypropylene Thin Film and Si Substrate by Neutron Reflectivity.

We performed neutron reflectivity (NR) measurements of isotactic polypropylene (PP) thin films deposited on a Si substrate at the saturated vapor pressure of deuterated water to investigate interfacial water accumulation between the PP and metal surfaces in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. The PP thin films prepared on a Si substrate by a spin-coating technique were adequate as a model system for the PP/metal interface in these materials. A water-rich layer with a maximum water concentration of 0.5, which was considerably higher than those reported in previous studies of organic/inorganic interfaces, was observed within a width of approximately 3 nm at the interface under saturated vapor conditions. This could be attributed to the weak interaction between the PP thin film and the Si substrate. The pathway of moisture transport to the interfacial region was along the interface rather than through the PP film because the hydrophobic PP thin film does not entirely swell with water vapor.

USAXS analysis of concentration-dependent self-assembling of polymer-brush-modified nanoparticles in ionic liquid: [I] concentrated-brush regime.

Using ultra-small angle X-ray scattering (USAXS), we analyzed the higher-order structures of nanoparticles with a concentrated brush of an ionic liquid (IL)-type polymer (concentrated-polymer-brush-modified silica particle; PSiP) in an IL and the structure of the swollen shell layer of PSiP. Homogeneous mixtures of PSiP and IL were successfully prepared by the solvent-casting method involving the slow evaporation of a volatile solvent, which enabled a systematic study over an exceptionally wide range of compositions. Different diffraction patterns as a function of PSiP concentration were observed in the USAXS images of the mixtures. At suitably low PSiP concentrations, the USAXS intensity profile was analyzed using the Percus-Yevick model by matching the contrast between the shell layer and IL, and the swollen structure of the shell and "effective diameter" of the PSiP were evaluated. This result confirms that under sufficiently low pressures below and near the liquid/crystal-threshold concentration, the studied PSiP can be well described using the "hard sphere" model in colloidal science. Above the threshold concentration, the PSiP forms higher-order structures. The analysis of diffraction patterns revealed structural changes from disorder to random hexagonal-closed-packing and then face-centered-cubic as the PSiP concentration increased. These results are discussed in terms of thermodynamically stable "hard" and/or "semi-soft" colloidal crystals, wherein the swollen layer of the concentrated polymer brush and its structure play an important role.

Visualization of Individual Images in Patterned Organic-Inorganic Multilayers Using GISAXS-CT.

Using grazing-incidence small-angle scattering (GISAXS) with computed tomography (CT), we have individually reconstructed the spatial distribution of a thin gold (Au) layer buried under a thin poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) layer. Owing to the difference between total reflection angles of Au and PS-b-P2VP, the scattering profiles for Au nanoparticles and self-assembled nanostructures of PS-b-P2VP could be independently obtained by changing the X-ray angle of incidence. Reconstruction of scattering profiles allows one to separately characterize spatial distributions in Au and PS-b-P2VP nanostructures.

Observation of an Orientation Change in Highly Oriented Layer-by-Layer Films of a Ruthenium Complex upon Oxidation Reaction.

Layer-by-layer films composed of redox-active ruthenium dimer and Zr(IV) ions were fabricated on an indium tin oxide electrode. The fabricating behavior was monitored by cyclic voltammetry and UV-vis absorption spectral measurements. The orientation of the film was also monitored by grazing-incidence small-angle and wide-angle X-ray scattering (GISAXS) measurements, and it has been clarified that this film has a crystalline structure. The peaks obtained by GISAXS were changed upon oxidation reaction, which indicates that a change in the orientation of the ruthenium dimer occurred in the film.

PyBidine-Cu(OTf)2 -catalyzed asymmetric [3+2] cycloaddition with imino esters: harmony of Cu-Lewis acid and imidazolidine-NH hydrogen bonding in concerto catalysis.

A bis(imidazolidine)pyridine (PyBidine)-Cu(OTf)2 complex catalyzing the endo-selective [3+2] cycloaddition of nitroalkenes with imino esters was applied to the reaction of methyleneindolinones with imino esters to afford spiro[pyrrolidin-3,3'-oxindole]s in up to 98 % ee. X-ray crystallographic analysis of the PyBidine-Cu(OTf)2 complex and DFT calculations suggested that an intermediate Cu enolate of the imino ester reacts with nitroalkenes or methyleneindolinones, which are activated by NH-hydrogen bonding with the PyBidine-Cu(OTf)2 catalyst.

Grazing-incidence small-angle X-ray scattering from Ge nanodots self-organized on Si(001) examined with soft X-rays.

Grazing-incidence small-angle X-ray scattering (GISAXS) measurements with soft X-rays have been applied to Ge nanodots capped with a Si layer. Spatially anisotropic distribution of nanodots resulted in strongly asymmetric GISAXS patterns in the qy direction in the soft X-ray region, which have not been observed with conventional hard X-rays. However, such apparent differences were explained by performing a GISAXS intensity calculation on the Ewald sphere, i.e. taking the curvature of Ewald sphere into account.

Mesoscopic structures of vermiculite and weathered biotite clays in suspension with and without cesium ions.

The effect of cesium (Cs) adsorption on the mesoscopic structure of the clay minerals vermiculite and weathered biotite (WB) in suspensions was elucidated by small-angle X-ray scattering (SAXS). The clay minerals form multilayered structures, and the Cs cations (Cs(+)) are strongly adsorbed in the interlayer space of the soil clays, in particular vermiculite and WB. SAXS was used to monitor the relationship between Cs(+) adsorption at the clay interlayers and the structural changes at length scales from 1 to 1000 Å. The variation in the distance between the neighboring clay sheets and the spatial arrangement of the clay sheets with and without Cs(+) were clarified. Our quantitative analyses revealed that the number of stacked layers of pure vermiculite was decreased by Cs(+) addition, whereas that of WB increased. Moreover, the average distance between the neighboring layers of vermiculite in suspension was larger than that of WB, which reflects the different conditions of Cs(+) intercalation. These findings provide fundamental insights that are important for predicting the environmental fate of radioactive Cs in contaminated regions and for developing methods for extracting Cs from soil.

Colorimetric microchip assay using our own whole blood collected by a painless needle for home medical care.

We have developed a colorimetric measurement chip that measures triglycerides, total cholesterol, and high-density lipoprotein in 6 µL of whole blood collected with a painless needle. The chip can be used by patients to self-monitor certain health conditions at home. This chip contains a sharp 150 µm diameter stainless steel (SUS) needle that collects blood painlessly. The chip consists of three layers of injection-molded poly(methyl methacrylate) bonded together with two double-sided tapes. Two commercial reagents are used, and the volume ratio of plasma to reagent is doubled from the reagent specification to reduce the optical absorption length (and chip mass) by half. Centrifugal force separates the plasma from the blood, and then weighs out and mixes the plasma and reagents. A zigzag channel allows mixing of the plasma with the reagents mainly by vortex motion due to the centrifugal force generated at the corners of the channel. The measured values correlated well with conventionally tested values.

Anisotropy of upper critical fields and interface superconductivity in FeSe/SrTiO3grown by PLD.

In this study, we grow FeSe/SrTiO3with thicknesses of 4-19 nm using pulsed laser deposition and investigate their magneto-transport properties. The thinnest film (4 nm) exhibit negative Hall effect, indicating electron transfer into FeSe from the SrTiO3substrate. This is in agreement with reports on ultrathin FeSe/SrTiO3grown by molecular beam epitaxy. The upper critical field is found to exhibit large anisotropy (γ>11.9), estimated from the data near the transition temperature (Tc). In particular, the estimated coherence lengths in the perpendicular direction are 0.15-0.27 nm, which are smaller than thec-axis length of FeSe, and are found to be almost independent of the total thicknesses of the films. These results indicate that superconductivity is confined at the interface of FeSe/SrTiO3.

Synthesis and Characterization of Cyclotri- and Tetrasiloxanes with Pyrenyl Groups.

Cyclosiloxanes directly bearing polyaromatic groups on silicon atoms have scarcely been reported. Herein, hexa(1-pyrenyl)cyclotrisiloxane (2) and octa(1-pyrenyl)cyclotetrasiloxane (3) were successfully prepared from di(1-pyrenyl)silanediol (1) in the presence of a weak base such as tetraethylammonium acetate and triethylamine in MeCN. The structure of the cyclosiloxanes bearing multiple pyrenyl groups in the solid and solution states was evaluated by NMR, X-ray crystallography, and density functional theory (DFT) calculations. All pyrenyl groups of 2 were oriented outward, and no π-π stacking of adjacent pyrenyl groups was observed. However, all pairs of adjacent pyrenyl groups at 1- and 3-positions in 3 are oriented in the same direction and were π-π stacked with respect to each other. The UV-vis spectra of 2 and 3 in organic solvents showed a slight broadening of the peaks, as observed for typical pyrene derivatives. Interestingly, the fluorescence spectra of 2 showed small monomer and strong excimer emissions; however, those of 3 showed only a strong excimer emission in all solvents. Partially pyrenylated cyclotri- and tetrasiloxanes (compounds 4 and 5) showed solvent-dependent monomer and excimer spectra as observed for di(1-pyrenyl)silane derivatives, implying that the excimer emissions of 2 and 3 arise from mainly geminal and vicinal pyrenyl groups, respectively.

Effects of change in walking speed on time-distance parameters in post-stroke hemiplegic gait.

Objectives: In stroke patients, the assessment of gait ability over time is important. For quantitative gait assessment using measuring devices, the walking speed condition for measurement is generally based on the patient's preferred walking speed or the maximum walking speed at the time of measurement. However, because walking speed often increases during the convalescent stage, understanding the effects of change in walking speed on gait when comparing the course of recovery is necessary. Although several previous studies have reported the effects of change in walking speed on gait in stroke patients, the time-distance parameters described in these reports may not be generalizable because of the small case numbers. Therefore, we measured treadmill gait at the preferred walking speed (PWS) and 1.3 times the PWS (130% PWS) in 43 post-stroke hemiplegic patients and analyzed the effects of change in walking speed on time-distance parameters. Methods: Forty-three patients with hemiplegia after a first stroke, who were able to walk on a treadmill under supervision, were recruited as subjects. Using a three-dimensional motion analysis system, treadmill gait was assessed under two conditions: PWS and 130% PWS. The primary outcome measures were the time-distance parameters, which were compared between the PWS and 130% PWS conditions. Results: Cadence, stride length, and step length of the affected and unaffected lower limbs increased significantly at 130% PWS compared with at PWS. In terms of actual time, single stance time and initial and terminal double stance time in both affected and unaffected limbs decreased significantly at 130% PWS. In terms of relative time (% of the gait cycle), compared with PWS, relative single stance time increased significantly, whereas relative initial and terminal double stance times decreased significantly at 130% PWS in both the affected and unaffected limbs. Conclusions: This study on treadmill gait in patients with hemiplegia after a first stroke confirmed the effects of change in walking speed on time-distance parameters. Our results will help in the interpretation of time-distance parameters measured under different walking speed conditions.

Coupled versus decoupled visuomotor feedback: Differential frontoparietal activity during curved reach planning on simultaneous functional near-infrared spectroscopy and electroencephalography.

INTRODUCTION: Interacting with the environment requires the planning and execution of reach-to-target movements along given reach trajectory paths. Human neural mechanisms for the motor planning of linear, or point-to-point, reaching movements are relatively well studied. However, the corresponding representations for curved and more complex reaching movements require further investigation. Additionally, the visual and proprioceptive feedback of hand positioning can be spatially and sequentially coupled in alignment (e.g., directly reaching for an object), termed coupled visuomotor feedback, or spatially decoupled (e.g., dragging the computer mouse forward to move the cursor upward), termed decoupled visuomotor feedback. During reach planning, visuomotor processing routes may differ across feedback types. METHODS: We investigated the involvement of the frontoparietal regions, including the superior parietal lobule (SPL), dorsal premotor cortex (PMd), and dorsolateral prefrontal cortex (dlPFC), in curved reach planning under different feedback conditions. Participants engaged in two delayed-response reaching tasks with identical starting and target position sets but different reach trajectory paths (linear or curved) under two feedback conditions (coupled or decoupled). Neural responses in frontoparietal regions were analyzed using a combination of functional near-infrared spectroscopy and electroencephalography. RESULTS: The results revealed that, regarding the cue period, curved reach planning had a higher hemodynamic response in the left SPL and bilateral PMd and a smaller high-beta power in the left parietal regions than linear reach planning. Regarding the delay period, higher hemodynamic responses during curved reach planning were observed in the right dlPFC for decoupled feedback than those for coupled feedback. CONCLUSION: These findings suggest the crucial involvement of both SPL and PMd activities in trajectory-path processing for curved reach planning. Moreover, the dlPFC may be especially involved in the planning of curved reaching movements under decoupled feedback conditions. Thus, this study provides insight into the neural mechanisms underlying reaching function via different feedback conditions.

Involvement of the Rostromedial Prefrontal Cortex in Human-Robot Interaction: fNIRS Evidence From a Robot-Assisted Motor Task.

Assistive exoskeleton robots are being widely applied in neurorehabilitation to improve upper-limb motor and somatosensory functions. During robot-assisted exercises, the central nervous system appears to highly attend to external information-processing (IP) to efficiently interact with robotic assistance. However, the neural mechanisms underlying this process remain unclear. The rostromedial prefrontal cortex (rmPFC) may be the core of the executive resource allocation that generates biases in the allocation of processing resources toward an external IP according to current behavioral demands. Here, we used functional near-infrared spectroscopy to investigate the cortical activation associated with executive resource allocation during a robot-assisted motor task. During data acquisition, participants performed a right-arm motor task using elbow flexion-extension movements in three different loading conditions: robotic assistive loading (ROB), resistive loading (RES), and non-loading (NON). Participants were asked to strive for kinematic consistency in their movements. A one-way repeated measures analysis of variance and general linear model-based methods were employed to examine task-related activity. We demonstrated that hemodynamic responses in the ventral and dorsal rmPFC were higher during ROB than during NON. Moreover, greater hemodynamic responses in the ventral rmPFC were observed during ROB than during RES. Increased activation in ventral and dorsal rmPFC subregions may be involved in the executive resource allocation that prioritizes external IP during human-robot interactions. In conclusion, these findings provide novel insights regarding the involvement of executive control during a robot-assisted motor task.

Artifact removal in the contour areas of SAXS-CT images by Tikhonov-L1 minimization.

Small-angle X-ray scattering (SAXS) coupled with computed tomography (CT), denoted SAXS-CT, has enabled the spatial distribution of the characteristic parameters (e.g. size, shape, surface, length) of nanoscale structures inside samples to be visualized. In this work, a new scheme with Tikhonov regularization was developed to remove the effects of artifacts caused by streak scattering originating from the reflection of the incident beam in the contour regions of the sample. The noise due to streak scattering was successfully removed from the sinogram image and hence the CT image could be reconstructed free from artifacts in the contour regions.

Multilayered Lamellar Materials and Thin Films by Instant Self-Assembly of Amphiphilic Random Copolymers.

Making ordered nanostructures in polymers and their thin films is an important technique to produce functional materials. Herein, we report instant yet precise self-assembly systems of amphiphilic random copolymers to build multilayered lamellar structures in bulk materials and thin films. Random copolymers bearing octadecyl groups and hydroxyethyl groups induced crystallization-driven microphase separation via simple evaporation from the solutions to form lamellar structures in the solid state. The domain spacing was controlled in the range between 3.1 and 4.2 nm at the 0.1 nm level by tuning copolymer composition. Interestingly, just by spin-coating the polymer solutions onto silicon substrates, the copolymers autonomously formed thin films consisting of multilayered lamellar structures, where amorphous/hydrophilic parts and crystalline octadecyl domains are alternatingly layered from a silicon substrate to the air/polymer interface at regular intervals. The lamellar domain spacing was tunable by selecting hydrophilic pendants.

Encapsulation of a hydrophobic drug into a polymer-micelle core explored with synchrotron SAXS.

Synchrotron small-angle X-ray scattering (SAXS) at the SPring-8 40B2 and 45XU beamlines was carried out on aqueous solutions of (PEG-P(Asp(Bzl))): partially benzyl-esterified poly(ethylene glycol)-block-poly(aspartic acid) with LE540 loaded up to 8.3 wt %, where LE540 is a very hydrophobic retinoid antagonist drug. The scattering profiles showed characteristic features for core-shell spherical micelles, confirming that P(Asp(Bzl)) forms a hydrophobic core and PEG forms a hydrophilic shell. Before the addition of LE540, a diffraction peak was observed around q = 4 nm(-1), where q is the magnitude of the scattering vector. This peak can be attributed to ordering between alpha-helices made of P(Asp(Bzl)), the so-called nonspecific hexatic arrangement. The P(Asp(Bzl)) helices disappeared as LE540 was added. This result can be interpreted by assuming a uniform distribution of LE540 in the core. By use of a core-shell spherical micelle model, the SAXS data could be well fitted for all of the samples. The analysis indicated that the core radius increases sigmoidally from 5.9 to 6.9 nm upon addition of LE540 whereas the shell radius stayed at 12.5-12.8 nm. The aggregation number that is the average number of PEG-P(Asp(Bzl))'s consisting of one micelle slightly increased from 145 to 182.

[A case of advanced rectal cancer with liver and lung metastasis showing a complete response by neo-adjuvant FOLFOX4 chemotherapy].

A 56-year-old man with abnormal chest X-P and stool occult bleeding was admitted. Colonoscopy detected rectal cancer and sigmoid al polyps. The biopsy results suggested that the rectal lesion was well- to moderately-differentiated adenocarcinoma and the sigmoidal polyp contained well -differentiated adenocarcinoma. CT scan revealed multiple lung, liver and lymph node metastasis. We judged the case to be inoperable and decided to start systemic chemotherapy (FOLFOX4). After treatment with chemotherapy, the tumor shrank and metastatic lesions disappeared. Low anterior resection was done, and final pathological examination revealed a complete response of the main tumor by treating with FOLFOX4.