Infrared spectra and ferro‐electricity of ultra‐thin films of vinylidene fluoride and trifluoroethylene copolymer

The structures of ultra‐thin films of vinylidene fluoride and trifluoroethylene copolymer were characterized using Fourier transform infrared reflection absorption spectroscopy (FTIR‐RAS), FTIR transmission spectroscopy (FTIR‐TRS), atomic force microscopy, and wide‐angle X‐ray diffraction. The ferro‐electricity was determined from polarization charge (a displacement (D)–electric field (E) hysteresis). FTIR‐RAS and FTIR‐TRS measurements showed that the molecular chains of polymers (crystal c‐axis) near the substrate tended to align parallel to the substrate. However, thermal annealing of the sample films at temperatures above 145 °C caused a marked change in molecular alignment of the polymer chains (crystal c‐axis) from parallel to normal to the substrate, and, further, caused a conformation change from trans to partially gauche forms. Copyright © 2007 Society of Chemical Industry     

Load dependence of soft actuators based on polypyrrole tubes

Isotonic load stress dependence of biomimetic soft actuators based on polypyrrole tubes has been studied to elucidate the work behaviour. Polypyrrole (PPy) tubes were electrochemically prepared on gold coated acryl resin in an aqueous solution of pyrrole and dodecylbenzensulfonic acid (DBS). The tubes were operated electrochemically in aqueous 1 M LiCl, and the change of tube length was measured under various load stresses. It was found that with increasing load stresses the response time slowed down and the contraction ratio reduced. Hence, the current decreased and lasted longer, indicating that the tube was sensing the load stress. During contraction of the tube, the conversion efficiency was estimated from the electrical input and mechanical output energies to be 0.12%. The maximum volumetric work was approximately 120 kJ/m³. The results were discussed taking the dynamics of ion migration into consideration.     

Carrier separation analysis for clarifying carrier conduction and degradation mechanisms in high-k stack gate dielectrics

The carrier conduction and the degradation mechanism in n⁺gate p-channel metal-insulator-semiconductor field-effect-transistors with HfAlO_X (Hf: 60 at.%, Al: 40 at.%)/SiO₂ dielectric layers have been investigated using carrier separation method. Since gate current depends on substrate bias and both electron and hole currents are independent of temperature over the range of 25–150 °C, the conduction mechanism for both currents is controlled by a tunneling process. As the interfacial SiO₂ layer (IL) thickness increases in a fixed high-k layer thickness (T_high-k), a dominant carrier in the leakage current changes from hole to electron around 2.2-nm-thick IL. This is due to an asymmetric barrier height for electrons and holes at the SiO₂/Si interface. On the contrary, in the case of a fixed IL thickness of 1.3 nm, the hole current is dominant in the leakage current, regardless of T_high-k. It is shown that the dominant carrier in the leakage current depends on the structure of the high-k stack. Both electron and hole currents for the stress-induced-leakage-current (SILC) state increase slightly relative to the initial currents, which means that the trap generation in the high-k stack occurs near both the conduction band edge of n⁺poly-Si gate and the valence band edge of Si substrate. The electron current at soft breakdown (SBD) state dramatically increases over that for the SILC state, while the hole currents for both the SILC state and SBD are almost the same. This indicates that the defect sites generated in the high-k stack after SBD are located at energies near the conduction band edge of n⁺poly-Si gate. Both the defect generation rate and the defect size in the HfAlO_X/SiO₂ stacks are large compared with those in SiO₂. It is inferred that, in high-k dielectric stack, the defect generation mainly occurs in the high-k side rather than the IL side, and the defect size larger than the case of SiO₂ could be related to a larger dielectric constant of the high-k layer.     

Domain-Swapping Design by Polyproline Rod Insertion

During domain swapping, proteins mutually interconvert structural elements to form a di-/oligomer. Engineering this process by design is important for creating a higher order protein assembly with minimal modification. Herein, a simple design strategy is shown for domain-swapping formation by loop deletion and insertion of a polyproline rod. Crystal structures revealed the formation of the domain-swapped dimers and polyproline portion formed a polyproline II (PPII) structure. Small-angle X-ray scattering demonstrated that an extended orientation of domain-swapped dimer was retained in solution. It is found that a multiple of three of inserting proline residue is favored for domain swapping because of the helical nature of PPII. The rigid nature of the polyproline rod enables precise control of the interdomain distance and orientation.     

Low‐Molecular‐Weight CXCR4 Ligands with Variable Spacers

Low‐molecular‐weight CXCR4 ligands based on known lead compounds including the 14‐mer peptide T140, the cyclic pentapeptide FC131, peptide mimetics, and dipicolylamine‐containing compounds were designed and synthesized. Three types of aromatic spacers, 1,4‐phenylenedimethanamine, naphthalene‐2,6‐diyldimethanamine, and [1,1′‐biphenyl]‐4,4′‐diyldimethanamine, were used to build four pharmacophore groups. As pharmacophore groups, 2‐pyridylmethyl and 1‐naphthylmethyl are present in all of the compounds, and several aromatic groups and a cationic group from 1‐propylguanidine and 1,1,3,3‐tetramethyl‐2‐propylguanidine were also used. Several compounds showed significant CXCR4 binding affinity, and zinc(II) complexation of bis(pyridin‐2‐ylmethyl)amine moieties resulted in a remarkable increase in CXCR4 binding affinity.     

Creep behavior of glass‐fiber‐reinforced nylon 6 products

The creep properties, that is, the velocity constant, activation energy, stress index, and time index, of a test piece (TP) cut from a glass‐fiber‐reinforced nylon 6 product were successfully determined by a compression creep test. In the determination of the creep properties, the experimental creep curves for the TP were fitted by finite element analysis (FEA). Fiber‐reinforced nylon 6 beams with different fiber orientations were also prepared, and their creep properties were successfully determined by a combination of the bending creep test and the corresponding analysis. The creep behavior of the press‐fit component composed of a metal collar and a fiber‐reinforced nylon 6 product was predicted by FEA with the determined creep properties of the TP. The predicted retention forces were in good agreement with the experimental ones. The effects of the fiber orientation on the long‐term reliability of the press‐fit component are also discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of nanoscale structural changes in isolated bamboo constituents using multiscale instrumental analyses

To reveal morphological changes in bamboo constituents induced by delignification and hemicelluloses removal processes, changes in chemical composition and dynamics were examined at molecular‐ to nano‐scales, using scanning electron microscopy images, attenuated total reflection infrared spectra, solid state nuclear magnetic resonance spectra, and relaxation time analysis at multiple hierarchical levels. Boiling removed spherical particles from the parenchymal cells of bamboo, leaving the cells containing water that had infiltrated into the nanostructure composed of carbohydrates and lignin. Treatment of the boiled bamboo with NaClO₂ solution removed most of lignin, leaving hemicellulose chains that made the parenchymal cells stretch. In contrast, treatment of the boiled bamboo with NaOH solution removed both hemicellulose and lignin, with the result that parenchymal cells shrank in the cross‐section direction. Furthermore, treatment of the delignified bamboo with NaOH solution demolished the parenchymal cells due to complete removal of hemicellulose and lignin. A nanostructural model proposed on the basis of molecular‐ to nano‐scale analyses was consistent with the changes of vascular bundles and parenchymal cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40243.