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Elucidating the state of interfacial water, especially the hydrogen-bond configurations, is considered to be key for a better understanding of the functions of polymers that are exhibited in the presence of water. Here, an analysis in this direction is conducted for two water-insoluble biocompatible polymers, poly(2-methoxyethyl acrylate) and cyclic(poly(2-methoxyethyl acrylate)), and a non-biocompatible polymer, poly(

Movable cross-network elastomer with knitting polymers (KP elastomer) were obtained by bulk polymerization of main chain monomers in presence of host polymer. The two design strategies successfully improve the toughness and stiffness of the KP elastomers.

Polyurethane (PU) materials with movable crosslinking were prepared by a typical two-step synthetic process using an acetylated γ-cyclodextrin (TAcγCD) diol compound. The soft segment of PU is polytetrahydrofuran (PTHF), and the hard segment consists of hexamethylene diisocyanate (HDI) and 1,3-propylene glycol (POD). The synthesized PU materials exhibited the typical mechanical characteristics of a movable crosslinking network, and the presence of hydrogen bonds from the urethane bonds resulted in a synergistic effect. Two kinds of noncovalent bond crosslinking increased the Young's modulus of the material without affecting its toughness. Fourier transform infrared spectroscopy and X-ray scattering measurements were performed to analyze the effect of introducing movable crosslinking on the internal hydrogen bond and the microphase separation structure of PU, and the results showed that the carbonyl groups on TAcγCD could form hydrogen bonds with the PU chains and that the introduction of movable crosslinking weakened the hydrogen bonds between the hard segments of PU. When stretched, the movable crosslinking of the PU materials suppressed the orientation of polymer chains (shish-kebab orientation) in the tensile direction. The mechanical properties of the movable crosslinked PU materials show promise for future application in the industrial field.

Glyoxylic acid (GA) is widely used as a straight perming agent for hair care products, however, advanced GA penetration enhancing agents are desired due to the peculiar odor and hair color fading caused by the continuous use of GA products. Hence, it is important to develop a penetration enhancing agent that helps minimize the GA concentration. We have found that the combined use of GA and glycolic acid (GCA) has a strong hair straightening effect.Straightening hair test was carried out for the evaluation of the effect of additives. Liquid chromatography-mass spectrometry (LC/MS) was performed to quantify the GA penetration amount into human hair. Attenuated total reflection (ATR) Fourier transform infrared spectroscopy (FT-IR) and FT-IR microscope were implemented to estimate the localization of GA in the hair.Straightening hair tests indicated that the hair straightening effect by GA was enhanced by the presence of GCA. LC/MS results showed that the addition of GCA enhanced the amount of GA that penetrated into human hair by about 4 times. ATR FT-IR and FT-IR microscope measurements indicated that GA was localized more in the innermost region of hair (medulla) than the cortex and cuticle. The GA accumulated in the medulla disappeared after a hair straightener treatment at 180 °C due to the chemical reaction.The GA penetration enhancing effect of GCA is worth investigating to reduce the GA concentration in products for more comfortable use.

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., We analyzed edible potato starch and observed the interaction between its granular structure and water molecules. A wide range of spatial scales was revealed using various techniques such as X‐ray scattering and FT‐IR measurements. We could succeed gelatinization and gelation process with a wide spatial scale.

Low-frequency vibrations of crystalline molecules are very sensitive to the local environment in which the molecules, for example, hydrated ions captured in crystals, find themselves. We present low-temperature X-ray crystallographic measurements on the harvested thiamine crystal containing hydrated ions and its temperature-dependent terahertz spectra and synchrotron infrared microspectra. It is found from the X-ray structure that the hydrated ions and hydration water are in a similar environment to liquid, although those are captured in crystals. The vibrationally resolved THz spectra of two states in the present organic crystals containing hydrated ions are well explained by the difference in the hydrogen-bonded pattern. Peak assignments were performed based on highly accurate first-principles calculations incorporating relativistic effects and dispersion corrections. The temperature dependences are observed for the vibrations around the chloride ions and hydration water due to the loose binding of chloride ions, the bond elongation with increasing temperature, and the cleavage of weak hydrogen bonds.

Infrared (IR) absorption and Raman spectra of methane hydrate (MH) were measured at low temperatures and high pressures to reveal the dynamics and cage occupancy of CH4 molecules and the hydration ...

Mitigation of the amounts of CO2 in the environment is one of the most urgent problems requiring a solution. To fulfil this demand, efficient adsorbents for CO2 are required that work at room temperature (RT) and in a lower pressure region of not more than 5000 ppm under ambient conditions. In the present work, specific and selective adsorption of CO2 onto NaCaA-85 (A-type zeolite with an ion-exchange capacity of 85%) was observed under the required conditions; the amounts of adsorbed CO2 on the NaCaA-85 sample were far larger than amounts reported for other materials in the pressure range from 400 to 5000 ppm. The characteristic adsorption mechanism induced by this material was verified directly through methods combining synchrotron-based far-infrared (far-IR) measurements with a computational technique. The resultant Ca2+-framework vibration modes for the NaCaA-85 sample were observed at 266 and 246 cm−1, which shifted toward the lower wave-numbers, i.e., 225 and 203 cm−1, after CO2 adsorption at RT, respectively. The observed characteristic property was explained by a model consisting of a CO2 molecule simultaneously pinned by two Ca2+ ions positioned on two types of exchangeable sites composed of 8- and 6-membered rings, which was well supported by the density functional theory calculation method. This characteristically adsorbed CO2 species was completely desorbed, and the original state easily recovered through evacuation around 400 K. In addition, the selective adsorption behaviour of CO2 from other gases, such as H2, CH4, O2 and N2, was found at RT. On the basis of these data, the separation properties of CO2 were examined by measuring the breakthrough curve using a model gas composed of 0.04% CO2, 20% O2 and 79.96% N2, which mimicked ambient air, indicating the superior separation feature. These findings may pave a new way for the use of the NaCaA-85 material as an efficient adsorbent for selective CO2 adsorption functioning at RT and in the lower pressure region of up to 5000 ppm.

Wide ranges of absorbance spectra were measured to elucidate a difference in the antiferro-electric (AF) ordering mechanisms below 50 and 168 K in Cs

Hydrogels are biocompatible polymer networks; however, they have the disadvantage of having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydrogels (p-αCD/p-AADA). However, when CAC was directly added to p-αCD/p-AADA to form biocomposite hydrogels (p-αCD/p-AADA/CAC), it showed weaker mechanical properties than p-αCD/p-AADA itself. This was caused by the strong intramolecular hydrogen bonding (H-bonding) within the CAC, which prevented the CAC reinforcing p-αCD/p-AADA in p-αCD/p-AADA/CAC. Then, calcium chloride solution (CaCl

We demonstrate the formation of grid-type (crossed perpendicular to each other) fibrous assemblies of low-molecular-weight gelators in aligned liquid-crystalline smectic templates. In the template of layered structures, a gelator forms oriented fibers with one directional and two orthogonal directional (grid-like) alignment depending on the order of layered structures.

A helical metallofoldamer forms a columnar phase with high thermal stability owing to its rigid helical mesogenic structure.

We report the electronic structure of a natural mineral calaverite AuTe2 under high pressure by means of the infrared spectroscopy. The optical conductivity at ambient pressure shows a Drude respon...

We have investigated the temperature- and field-variation of electronic state for the Dirac semimetal of ${\mathrm{EuMnBi}}_{2}$ by means of optical spectroscopy and theoretical calculation. The optical conductivity spectra show a clear Drude peak in the paramagnetic phase, which gradually diminishes in the Mn-$3d$ antiferromagnetic phase with decreasing temperature. Meanwhile, the absorption peaks due to the interband transition grow at low temperatures, resulting in a pseudogap feature with an energy scale of 0.07 eV. The analysis of Drude weight shows that the Drude response is nearly governed by the Dirac electrons at low temperatures. On the contrary, both the antiferromagnetic transition and spin reorientation of Eu-$4f$ moment do not significantly change the spectra except the moderate variation of Drude weight. As a comparison, we have also investigated the charge dynamics for ${\mathrm{EuZnBi}}_{2}$, which is an analog without the Mn-$3d$ antiferromagnetic ordering. In ${\mathrm{EuZnBi}}_{2}$, the optical conductivity spectra do not show the pseudogap structure, but show an intense Drude peak at all temperatures. Combined with the results of ab initio calculation, in ${\mathrm{EuMnBi}}_{2}$, it is likely that the reconstruction of electronic state driven by the Mn-$3d$ antiferromagnetic ordering causes the Dirac semimetallic state with tiny hole pockets, wherein electronic states other than the Dirac band are nearly gapped-out from the Fermi level.

The cuticular lipid covering the integument of insects is exposed to the environment and involved in a variety of functions offered by insect body surfaces, ranging from protection against the environment, such as the control of water transpiration, the reduction of abrasive damage, and the prevention of pathogen intrusion, to the communication between insects from intraspecific to interspecific interactions. In comparison with the importance of their physiological functions, there is remarkably little information on the structure and physical property of cuticular lipids on insect body surfaces. The lipid layer on the outer exoskeleton is very thin, estimated on the order of 0.01-1 μm or less, and this has led to a lack of practical methodologies for detailed structural analyses. To fill this devoid, we have exploited the characteristics of Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy, which allows us to conduct a chemical analysis on insect body surfaces and also to investigate depth-dependent structural changes. We have applied a combination of FTIR ATR microspectroscopy with IR radiation provided by a synchrotron facility to obtain in situ two-dimensional (2D) information of the cuticular lipid layer on the surface of the integument. The 2D FTIR spectra measured on the two-spotted cricket and the American cockroach show that the IR bands due to the cuticular lipid, such as CH2 symmetric and antisymmetric stretch, νa(CH2) and νs(CH2), change in intensity significantly, depending on the location of measurements. As if to keep pace with this, the bands of the amide group for the underlying cuticular layer also change in intensity significantly, although the changes are in the opposite direction; as the lipid bands increase in intensity, the amide band decreases, and vice versa. The ATR spectral analysis, which takes into account the characteristics of the evanescent wave, points out that the lipid layer would vary tens of times in the range of 0.01-1 μm significantly. The νa(CH2) and νs(CH2) bands show frequency shifts, which correlate to some extent with their intensity changes, suggesting that the drastic uneven distribution of the cuticular lipid would be related to the solid-liquid phase separation and also the coarsening of the solid phase domains. The formation of such topological features, significant heterogeneity in the lipid layer thickness, and solid-liquid phase ratios would be accompanied by the partitioning of lipid components according to molecular structures and physicochemical properties. Considering that each lipid component in insect body surface lipids is involved in various physiological roles, the segregation of lipid components during the formation of such heterogeneous structures is thought to have a significant impact on the functionality of the insect body surface.

Accumulated charge measurement (ACM) is a new experimental technique for organic semiconductors to evaluate the charge injection barrier at the semiconductor–metal interface directly using a metal–insulator–semiconductor–metal (MISM) capacitor. In this technique, the precise estimation of the electrostatic capacity of the insulator layer (CI) is required for the analysis. The information of this parameter is, in principle, included in the ACM data; however, it is not directly evaluated because of the error resulting from the charge-spreading effect in an organic MISM capacitor with an unrestricted electrode structure. Therefore, the CI in previous ACM experiments has been independently estimated from the area of the electrode. In this study, a novel design of a substrate with a restricted-bottom-electrode structure is reported. Using the newly designed substrate, it was possible to suppress the charge-spreading effect and successfully estimate precise values of CI directly from the ACM data. Subsequently, it was possible to evaluate the injection barriers at the metal-free phthalocyanine (H2Pc)–Ag and pentacene–Au interfaces, which were 0.4 and 0.15 eV, respectively. The built-in potentials in the semiconductor layer were also determined for the samples used in the measurement.

The electronic structures of platinum-group metal pernitrides MN2 (M = Ru, Rh, Ir, and Pt) were investigated via synchrotron radiation infrared spectroscopy and first-principles calculations. Measured reflectance spectra of marcasite-type RuN2 and RhN2 showed Drude-like responses, approaching 1 as the photon energy was decreased, whereas reflectance of arsenopyrite-type IrN2 and pyrite-type PtN2 became ∼0.3 in the low photon energy region with a few features. These findings agreed well with the predictions of the metallic nature of marcasite-type RuN2 and RhN2 and the semiconducting properties of arsenopyrite-type IrN2 and pyrite-type PtN2, respectively. The measured reflectance spectra were also reasonably consistent with the calculated optical responses. The band gaps of IrN2 and PtN2 were estimated to be 0.8 and 2.1 eV, respectively, via first-principles calculation with a modified Becke–Johnson (MBJ) potential for the exchange potential., ファイル公開：2021-04-01

The excitonic insulator Ta$_2$NiSe$_5$ experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps = 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of 0.1-0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Ni-valence bands due to the lattice distortion, indicative of the importance of electron-lattice coupling. The transition is suppressed with increasing pressure to Pc = 8 GPa. Superconductivity with a maximum Tsc = 1.2 K emerges around Pc, likely mediated by strongly electron-coupled soft phonons. The electron-lattice coupling is as important ingredient as the excitonic instability in Ta2NiSe5., Comment: 6 pages, 4 figures

Lewy bodies (LBs) and glial cytoplasmic inclusions (GCIs) are specific aggregates found in Parkinson’s disease (PD) and multiple system atrophy (MSA), respectively. These aggregates mainly consist of α-synuclein (α-syn) and have been reported to propagate in the brain. In animal experiments, the fibrils of α-syn propagate similarly to prions but there is still insufficient evidence to establish this finding in humans. Here, we analysed the protein structure of these aggregates in the autopsy brains of patients by synchrotron Fourier-transform infrared micro-spectroscopy (FTIRM) analysis without extracting or artificially amplifying the aggregates. As a result, we found that the content of the β-sheet structure in LBs in patients with PD was significantly higher than that in GCIs in patients with MSA (52.6 ± 1.9% in PD vs. 38.1 ± 0.9% in MSA, P

We performed a comprehensive study on structural, electrical, magnetic, and optical properties for iron-based ladder materials ${\mathrm{BaFe}}_{2}{({\mathrm{S}}_{1\ensuremath{-}x}{\mathrm{Se}}_{x})}_{3}\phantom{\rule{4pt}{0ex}}(0\ensuremath{\le}x\ensuremath{\le}1)$, which shows pressure-induced superconductivity in the vicinity of the Mott transition at $x=0$ and 1. We obtain a complete electronic phase diagram in a temperature-composition plane, which reveals that the magnetic ground state switches from the stripe-type to the block-type phase without any intermediate phase at $x=0.23$ with increasing $x$. This behavior is in sharp contrast to the filling controlled system ${\mathrm{Ba}}_{1\ensuremath{-}x}\phantom{\rule{4pt}{0ex}}{\mathrm{Cs}}_{x}{\mathrm{Fe}}_{2}{\mathrm{Se}}_{3}$, in which a paramagnetic state down to the lowest temperature is realized between two magnetic ordered states. The structural transition, which is considered to be relevant to the orbital order, occurs far above the magnetic transition temperature. The magnetic and structural transition temperatures exhibit a similar composition dependence, indicating a close relationship between magnetic and orbital degrees of freedom. In addition, we found that charge dynamics are considerably influenced not only by the magnetic order but also by the structural change (orbital order) from the detailed measurements of electrical resistivity and optical conductivity spectra. We discuss the magnetism and orbital order by comparing the experimental results with the proposed theory based on the multiorbital Hubbard model. The relationship between the charge dynamics and the magnetic/orbital order is also discussed.

We investigated the self-assembly of surfactin (SFNa), a cyclic peptide amphiphile produced by Bacillus subtilis, in a nonpolar organic solvent, namely, cyclohexane (CHx). The CHx solution of SFNa formed a thermoreversible organogel. Transmission electron microscopy and small-angle X-ray scattering (SAXS) analyses showed that gelation of the CHx solution of SFNa was caused by physical cross-linking of SFNa nanofibers. Wide-angle X-ray diffraction and Fourier-transform infrared analyses showed that the SFNa nanofibers were formed by one-dimensional stacking of SFNa rings with a period of 0.48 nm corresponding to the length of inter-ring hydrogen bonds between amide groups. A combination of SAXS and small-angle neutron scattering investigations of CHx and deuterated CHx solutions of SFNa nanofibers containing H2O or D2O showed that the SFNa nanofibers had a hydrophilic interior and formed water channels by water incorporation in this region.

In phases III and IV of Cs

While polyelectrolyte brushes have received extensive attention due to their particular surface properties, the ion-specific hydration states remain largely unknown. Here, we report the counteranion-specific hydration states of cationic poly[2-(methacryloyloxy)ethyltrimethylammonium] (PMTA) brushes in salt-free water. The water droplet contact angle on the PMTA brushes depends on the counteranion species, and the order is consistent with the Hofmeister series. Weakly hydrated chaotropic counteranions are strongly bound to weakly hydrated quaternary ammonium (QA+) cations in the PMTA brush chains, which induces a reduction in the ζ-potential, dehydration, and collapse of the PMTA brushes. The PMTA brushes with strongly hydrated chloride counteranions produce a more diffuse tail and less swollen bound layer under salt-free deuterium oxide than brushes with weakly hydrated thiocyanate counteranions. Ion pairing disturbs the ordering of hydrated water in the PMTA brushes. Our work enhances the understanding o...

We have investigated a newly found α′′-phase bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) molecular arrangement system, namely, α′′-(BEDT-TTF)2Rb2xCo(SCN)4 (α′′-Rb2xCo), with localized S = 3/2 ...

Phytic acid ( myo -inositol 1,2,3,4,5,6-hexa kis phosphate; IP 6 ) is the storage substance for phosphorus and many metals in plant seeds. Based on Synchrotron-based Fourier-transform infrared (FT-IR) spectra in the mid-infrared range from 1300 to 700 cm −1 , nine synthesized metal-IP 6 salts, with monovalent to trivalent coordination, were classified into four groups: trivalent metal-IP 6 salts, second-group divalent metal-IP 6 salts, d-block and p-block divalent metal-IP 6 salts, and monovalent metal-IP 6 salts. Synchrotron FT-IR analysis in the far-infrared range, from 650 to 100 cm −1 , contained clear, broad bands specific to each metal-IP 6 salt, including monovalent and divalent metal-IP 6 salts. These broad bands are likely derived from vibrations of bonds between the metal and the oxygen of IP 6 . These unique far-infrared spectra may provide useful information for identifying metal-IP 6 salts in biochemical fine-image analyses of seed tissues using synchrotron-based FT-IR microspectroscopy.

Effect of alkyl chain spacer length between the charged groups (CSL) in zwitterionic poly(sulfobetaine) (PSB) brushes on the hydration state was investigated. PSB brushes with ethyl (PMAES), propyl (PMAPS), or butyl (PMABS) CSL were prepared by surface-initiated atom transfer radical polymerization on silicon wafers. Hydration states of the PSB brushes in aqueous solutions and/or humid vapor were investigated by contact angle measurement, infrared spectroscopy, AFM observation, and neutron reflectivity. The PSB brushes are swollen in humid air and deionized water due to the hydration of the charged groups leading to the reduction of hydrated PSB brushes/water interfacial free energy. The hydrated PSB brushes exhibit clear interface with low interfacial roughness due to networking of the PSB brush chains through association of the SBs. The hydrated PSB brushes produce diffusive swollen layer in the presence of NaCl because of the charge screening followed by SB dissociation by the bound ions. The ionic strength sensitivity in the hydration got more significant with increasing the CSL in SBs because of the augmentation in partial charge by charged group separation.

We have measured the absorption and Raman spectral change induced by the irradiation of e-beam. By the irradiation of e-beam on SWNTs thin films, the intensity of defect related Raman band increase, and the peak energy of IR absorption bands shift to the higher energy side. These results indicate that the origin of infrared band is due to the plasmon resonance of finite-length SWNT. We have estimated the effective tube length and defect density from IR absorption peak energy.

Optical conductivity [σ (ω)] of CeRhIn5 and YbNi3Ga9 have been measured at external pressures to 10 GPa and at low temperatures to 6 K. Regarding CeRhIn5, at ambient pressure the main feature in σ (ω) is a Drude peak due to free carriers. With increasing pressure, however, a characteristic midinfrared (mIR) peak rapidly develops in σ (ω), and its peak energy and width increase with pressure. These features are consistent with an increased conduction (c)- f electron hybridization at high pressure and show that pressure has tuned the electronic state of CeRhIn5 from very weakly to strongly hybridized ones. As for YbNi3Ga9, in contrast, a marked mIR peak is observed already at ambient pressure, indicating a strong c- f hybridization. At high pressures, however, the mIR peak shifts to lower energy and becomes diminished and seems to merge with the Drude component at 10 GPa. Namely, CeRhIn5 and YbNi3Ga9 exhibit some opposite tendencies in the pressure evolution of σ (ω) and electronic structure. These results are discussed in terms of the pressure evolution of c- f hybridized electronic states in Ce and Yb compounds, in particular in terms of the electron-hole symmetry often considered between Ce and Yb.