Electrodeposition of amorphous gold alloy films

The process for electroplating amorphous gold-nickel-tungsten alloy that we developed previously based on the addition of a gold salt to a known amorphous Ni-W electroplating solution was investigated further using the X-ray diffraction (XRD) method for the purpose of quickly surveying the effects of various experimental variables on the microstructure of the alloy. In this system the gold concentration in the plating bath was found to be critical; i.e., when it is either very low or very high, the deposit becomes crystalline to XRD. The deposit composition varies linearly with the mole ratio of Au to Ni in solution, and the alloy deposit is amorphous to XRD when the atomic ratio of Au/Ni in the deposit is between 0.5 and 1.5. At suitable concentrations of the metal ions, the deposit contains essentially no tungsten. By extending the work on the Au-Ni-W system, an amorphous Au-Co alloy plating process was also developed.     

Poly(p‐phenylene sulfide) nanofibers prepared by CO2 laser supersonic drawing

Poly(p‐phenylene sulfide) (PPS) nanofibers are prepared by irradiating a PPS fiber with a carbon dioxide (CO₂) laser while drawing it at supersonic speeds. A supersonic jet is generated by blowing air into a vacuum chamber through the fiber injection orifice. Nanofibers obtained at a laser power of 30 W and chamber pressure of 10 kPa exhibit an average diameter of 600 nm and a draw ratio of 110,000. Scanning electron microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction analyses are employed to investigate the relationships among the chamber pressure, fiber morphology, and crystallization behavior. The nanofibers exhibit two melting temperatures (T_m): approximately 280°C and 320°C. The endothermic peak at T_m = 280°C is ascribable to lamellar crystals and that at T_m = 320°C to the highly complete crystals, since the polymer molecular chain is highly oriented. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40922.     

Categorical observers for metamerism

A method is proposed to generate categorical colour observer functions (individual colour matching functions) for any field size based on the CIE 2006 system of physiological observer functions. The method combines proposed categorical observer techniques of Sarkar et al with a physiologically-based individual observer model of Asano et al and a clustering technique to produce the optimal set of categorical observers. The number of required categorical observers varies depending on an application with as many as 50 required to predict individual observers' matches when a laser projector is viewed. However, 10 categorical observers are sufficient to represent colour-normal populations for personalized colour imaging. The proposed and recommended categorical observers represent a robust and inclusive technique to examine and quantify observer metamerism in any application of colorimetry.     

Improvement of the surface quality of foam injection molded products from a material property perspective

Microcellular injection molding is an attractive method. However, their surface imperfections have been a major problem hindering wide industrial applications. Several methods have been proposed to improve the surface appearance of foams. In this study, we proposed a method to improve the surface appearance of polypropylene (PP) foams from the material property perspective, especially with regard to crystallization and viscosity. The basic idea of the surface improvement is to reduce the size of bubbles generated at the flow front, delay the solidification behavior of the polymer at the mold interface, squeeze the bubbles existing at the mold–polymer interface, and redissolve the bubbles into the polymer by holding pressure. Blending a low-modulus PP delays the crystallization of the polymers at the skin layer and solidification, taking enough time to squeeze the bubbles smaller. A sorbitol-based gelling agent, bis-O-([4 methylphenyl]methylene)-D-Glucitol, was used to increase the viscosity at a low strain rate to reduce the size of the bubbles generated at the flow front during the filling stage. The foam injection molding experiments demonstrated that the proposed method effectively improved the surface appearance of the foams. In particular, the surface appearance of the foams became almost equivalent to that of solid samples using low-modulus PP.     

Disorders and oxygen vacancies in p-type Sn2B2O7 (B = Nb,Ta): Role of the B-site element

Sn₂Nb_2−xTa_xO₇ (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn₂Nb₂O₇) was an order of magnitude lower than that of the Ta end (Sn₂Ta₂O₇). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn₂Nb₂O₇ and Sn₂Ta₂O₇. In this study, the crystal structures of Sn₂B₂O₇ (B = Nb, Ta), composed of BO₆ octahedra and Sn₄O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn₄O tetrahedra in Sn₂Nb₂O₇ compared to Sn₂Ta₂O₇; disorder in the BO₆ octahedra occurred only in Sn₂Ta₂O₇. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn₄O tetrahedra and subsequently improving the hole–carrier–generation efficiency.     

Direct conversion mechanism of fluorine-GIC into poly(carbon monofluoride), (CF)n

The reaction mechanisms of a stage-1 fluorine-graphite intercalation compound (GIC), C_2.5F, with 0.10 MPa of fluorine gas have been studied at 573-773 K. The original stage-1 structure of C_2.5F with semi-ionic C-F bonds and planar sp² carbon sheets is maintained in most part of the compound after the reaction at 573 K, although a large number of covalent C-F bonds are formed on the surface. This compound is partially or completely converted to poly(carbon monofluoride), (CF)_n, with covalent C-F bonds and puckered sp³ carbon sheets at 673 or 773 K, respectively. Single-phase (CF)_n obtained at 773 K possesses remarkably small BET specific surface area, 61 m²/g carbon, almost unchanged from the value of the precursor C_2.5F (69 m²/g carbon). In this reaction, the accommodation of fluorine atoms supplied from the atmosphere into the galleries of C_2.5F is facilitated by the rearrangement of originally intercalated fluorine atoms in the GIC, forming (CF)_n with fewer defects compared to those by the conventional direct fluorination of graphite.     

Thermal and mechanical properties of bio-based polymer networks by thiol-ene photopolymerizations of gallic acid and pyrogallol derivatives

Allylated pyrogallol (A3PG) and acrylated pyrogallol (Ac3PG) as bio-based trienes, and allylated gallic acid (A4GA) and acrylated allyl gallate (Ac3A1GA) as bio-based tetraenes were synthesized from pyrogallol and gallic acid, respectively. Thiol-ene photopolymerizations of the bio-based polyenes and a pentaerythritol-based primary tetrathiol (pS4P) at the allyl/SH ratio of 1/1 produced photo-cured resins (A3PG-pS4P, Ac3PG-pS4P, A4GA-pS4P and Ac3A1GA-pS4P). The FT-IR spectral analysis revealed that thiol-ene reactions of thiol/allyl and thiol/acryloyl groups smoothly proceeded. Gel fractions of acryl-based cured resins were a little higher than those of allyl-based cured resins. The swelling test and dynamic mechanical analysis revealed that GA- and acryl-based cured resins exhibited higher crosslinking densities than PG- and allyl-based cured resins, respectively. A higher order of tan δ peak temperature was Ac3PG-pS4P (48.3 ° C) > Ac3A1GA-pS4P (24.1 ° C) > A4GA-pS4P (22.1 ° C) > A3PG-pS4P (?7.8 ° C). Ac3PG-pS4P displayed the highest 5 % weight loss temperature, tensile strength and tensile modulus among all of the cured resins.     

Effect of glass transition temperature on heat‐responsive gas bubbles formation from polymers containing tert‐butoxycarbonyl moiety

Various types of polymers containing tert‐butoxycarbonyl (BOC) moiety as the typical protecting group of functional moieties have been used for the design of stimuli‐responsive polymer materials. In this study, we investigated the heat‐responsive deprotection behavior of BOC‐containing polymers obtained by radical polymerization of 4‐(tert‐butoxycarbonyloxy)styrene (BSt) and copolymerizations of BSt with styrene and methyl acrylate. The deprotection of BOC groups accompanying the evolution of isobutene and carbon dioxide as gaseous products was monitored by thermogravimetric analyses at different temperature circumstances; that is, on heating at a rate of 10 °C/min and under isothermal conditions at various temperatures. The deprotection resulted in a significant decrease in the transmittance of visible light due to the formation of a large number of gas bubbles, that is, foaming, in the polymer films when a heating temperature was close to the glass transition temperature of the used polymer. The potential of BOC‐containing polymers was also evaluated as the heat‐responsive adhesive polymers for dismantlable adhesion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46252.     

“Click Peptide“: pH‐Triggered in Situ Production and Aggregation of Monomer Aβ1–42

Into neutral : We demonstrate the unique features of a pH click peptide based on an O‐acyl isopeptide method. Under acidic conditions, the click peptide remains in a monomeric form. Upon increase of the pH to 7.4, the click peptide is quickly able to convert into Aβ1–42 through an O‐to‐N intramolecular acyl migration. Further study using this pH click peptide would elucidate the pathological role of Aβ1–42 in Alzheimer's disease.

     

Development of Selective TGR5 Ligands Based on the 5,6,7,8-Tetrahydro-5,5,8,8-tetramethylnaphthalene Skeleton

TGR5, a G-protein-coupled receptor (GPCR), plays an important role in several physiological functions. TGR5 activation through bile acids induces an increase in energy expenditure. Therefore, synthetic TGR5 ligands could be useful for the treatment of obesity or dyslipidemia. In this study, we designed and synthesized a set of TGR5 ligands with a 5,6,7,8-tetrahydro-5,5,8,8-tetramethylnaphthalene (TMN) skeleton, and evaluated their TGR5 agonistic activity. We also investigated the selectivity of the synthesized compounds for TGR5 relative to the farnesoid X receptor (FXR) and retinoic acid receptor (RAR). Our results show that compound 4 b [N-(2-chlorophenyl)-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenecarboxamide] exhibited potent TGR5 agonist activity with an IC₅₀ value of 8.4 nM without significant cytotoxicity. In addition, compound 4 b showed only slight agonistic activity toward FXR and RAR at 1 μM treatment. These data indicate that compound 4 b is a selective TGR5 agonist, and could be a promising therapeutic agent for dyslipidemia.