Morphological Study of hydroxypropyl cellulose films prepared from thermotropic melt under shear

A strain-induced crystallization behavior of hydroxypropyl cellulose (HPC) from the thermotropic liquid-crystalline state is described based on morphological observations by electron microscopy. It is shown that originally round-shaped particles behave as a structure unit in formation of a variety of supermolecular architectures of HPC films prepared from the thermotropic melt under shear. In an oriented HPC film obtained under weak shear, many round particles are elongated and aligned in the direction of shear (SD), but with their bodies bent to some degree. As deformation increases further, fibrillation occurs on the surface of the elongated particles, and then the resulting fibrils are arranged in a zigzag fashion along the SD to form a banded structure. In some cases, a pleated arrangement of fibrils is noticeable between bands. The structural transformation mechanism of thermotropic HPC under shear is discussed in detail on the basis of the morphological evidence.     

Time-resolved Fourier-transform infrared reflection study on photoinduced phase transition of tetrathiafulvalene-p-chloranil crystal

We have measured temporal change of infrared reflection spectrum of ionic phase oftetrathiafulvalene-p-chloranil (TTF-CA) crystal induced by 10 ns pulsedlaser excitation at 2.35 eV with using a step-scan Fourier-transform infraredspectrometer. The excitation reduced the magnitude of thea _g -mode bands around 980 cm^-1and 1380 cm^-1 and enhanced reflection intensity at 1630 cm^-1. Thetime evolution of both the a _g -mode changes and the enhancementat 1630 cm^-1 are described by the sum of two decay components: one decayedwithin 2 μs and the other showed very gradual decay within the timerange used in the present study. The fractional changes of reflectivity for the fast decaycomponents were almost identical for all a _g modes.The 1630 cm^-1 enhancement can be ascribed to the carbonyl stretchingvibration of CA. The position of this peak shifts slightly to low-wavenumber side from theCA peak of the neutral phase in thermal equilibrium. Consequently, the fast decaycomponent is ascribed to the photoinduced phase. The slow decay component is conceivablydue to the metastable center formed by the excitation, because we could not resolve thespectral change corresponding to the slow component in the range between 1595and 1660 cm^-1, where the carbonyl stretching vibration of TTF-CA is observed.The degree of charge transfer of the photoinduced phase is evaluated to 0.52 ± 0.08 bycomparing the peak position of the transient enhancement with those of the carbonylstretching vibration modes in ionic and neutral phases in thermal equilibrium.     

Structural phase transitions at clean and metal-covered Si(111) surfaces investigated by RHEED spot analysis

Structural phase transitions between various kinds of superlattice structures formed on a Si(111) surface have been investigated by spot analysis of reflection high-energy electron diffraction (RHEED). Reversible transitions induced by temperature changes and irreversible ones induced by metal depositions were observed. Detailed discussions on the dynamics of the phase transitions are made by quantitative analyses of integrated spot intensity and profile. For a phase transition of 7′7  1′1 structures on a clean Si(111) surface, a hysteresis with temperature difference of 5°C. between in heating and cooling processes was found in the spot intensity change, indicating a first-order transition. Hysteresis was hardly recognized, on the other hand, for transitions of Au-induced superstructures (5×2-Au or ×-Au)  1×1-Au. The spot profiles were found to be broadened during the transition of Si(111)-×-Au  1×1-Au, which was a signature of a continuous transition, while the profiles remained unchanged during the transitions of the 7×7  1×1 and 5×2-Au  1×1-Au phases. Structural conversions induced by In adsorption on the Si(111) surface kept at constant temperatures were also analyzed. The conversions at room temperature were totally dependent on the initial substrate surface structures; the 7×7 surface did not show any structural conversion with In adsorption, while the ×-In surface successively converted to a 2×2 and a × phase with coverage increase. The structural transitions at elevated temperatures were sensitively dependent on the temperatures. Sequences of transitions among the 7×7, 4×1, ×, 1×, and ×4 were quantitatively revealed as changes in RHEED spot intensity.     

Investigating How Organic Solvents Affect Tissue Culture Polystyrene Surfaces through Responses of Mesenchymal Stem Cells

Polymer coating of tissue culture polystyrene (TCPS) surfaces promotes their biofunctionality, which can aid manipulation of cellular functions. However, the effect of the solvent used for polymer coating is yet to be elucidated. In this study, solvent‐treated TCPS surfaces using water, methanol, ethanol, 2‐propanol, and dimethyl sulfoxide are fabricated. Solvent treatment of TCPS surfaces is performed by spreading solvents onto the surfaces and allowing them to dry. Solvent treatment changes the surface roughness and wettability, depending on the kind of solvents. In addition, these surface property changes affected the extension, proliferation, and differentiation of human bone marrow–derived mesenchymal stem cells. These results suggest that solvent selection for polymer coating is crucial in the regulation of cell responses. Further, treatment with an appropriate solvent can result in a more suitable culture environment for modulating cellular functions.     

Transmission of terahertz radiation using a microstructured polymer optical fiber

A hollow-core microstructured polymer optical fiber was analyzed in the terahertz (THz) region. Spectral analysis of time domain data shows propagation of THz waves in both the hollow-core and the microstructured cladding with a time delay of approximately 20 ps. The frequency range and shift of the transmission bands between different sized waveguides suggested photonic bandgap or resonant guidance. Finite-difference time domain calculations agree relatively well to the experimental transmission results. Propagation losses were estimated to be as low as 0.9 dB/cm.     

Correlation of fluctuation field and temperature coefficient of coercivity in a CoCrPtB thin film

The effect of the ratio of fluctuation field (H_f) to coercivity (H_c) on the temperature coefficient of coercivity [α(H_c)] was investigated for Co₅₅Cr_15.5Pt₂₈B_1.5/Co₆₃Cr₃₇/Cr, Co₆₉Cr₁₉Pt₉Ta₃/Cr, and Co₈₆Cr₁₀Ta₄/Cr thin films (longitudinal recording media) with very small average grain volume (V_phy). α(H_c) increases markedly with increase in temperature between near 250 and 350 K for Co₅₅Cr_15.5Pt₂₈B_1.5/Co₆₃Cr₃₇/Cr thin films. α(H_c) is approximately proportional to the ratio H_f/H_c for all thin films, as in the case of advanced data backup tapes prepared from ultrafine particles. α(H_c) and the ratio H_f/H_c increase as V_phy decreases. Smaller H_f/H_c values are necessary for small α(H_c) values, which is very important for the thermal stability of high-density recording media with very small V_phy.     

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate-opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

Stimulation of Microvascular Networks on Sulfonated Polyrotaxane Surfaces with Immobilized Vascular Endothelial Growth Factor

Modulation of material properties and growth factor application are critical in constructing suitable cell culture environments to induce desired cellular functions. Sulfonated polyrotaxane (PRX) surfaces with immobilized vascular endothelial growth factors (VEGFs) are prepared to improve network formation in vascular endothelial cells. Sulfonated PRXs, whereby sulfonated α‐cyclodextrins (α‐CDs) are threaded onto a linear poly(ethylene glycol) chain capped with bulky groups at both terminals, are coated onto surfaces. The molecular mobility of sulfonated PRX surfaces is modulated by tuning the number of threading α‐CDs. VEGF is immobilized onto surfaces with varying mobility. Low mobility and VEGF‐immobilization reinforce cell proliferation, yes‐associated protein activity, and rhoA, pdgf, ang‐1, and pecam‐1 gene expression. Highly mobile surfaces and soluble VEGF weakly affect these cell responses. Network formation is strongly stimulated in vascular endothelial cells only on low‐mobility VEGF‐immobilized surfaces, suggesting that molecular mobility and VEGF immobilization synergistically control cell function.