Effect of chemical compositional distribution on solid-state structures and properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Solid-state structures and crystallization kinetics were compared between poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [PHB-HV] and PHB/PHB-HV blends exhibiting the cocrystallization. As cocrystallizable blends, both the blends showing complete cocrystallization, i.e. the PHB content in the crystalline phase is the same as that of the whole blends, and the blends forming a PHB-rich crystalline phase were used. The PHB and HV content in the cocrystalline phase were determined by high-resolution solid-state ¹³C NMR spectroscopy. In order to determine these contents with a minimum experimental error, site-specific ¹³C-labeled PHB/PHB-HV blends and PHB-HV copolymers were used. The crystallinity, lamellar structures, spherulite growth rate, and melting behavior were analyzed by wide-angle X-ray diffraction, small-angle X-ray scattering, polarized microscope, and differential scanning calorimetry, respectively. In these data, no difference was observed between the complete-cocrystallizable PHB/PHB-HV blends and the PHB-HV copolymers with the same overall HV content. On the other hand, the PHB/PHB-HV blends forming a PHB-rich crystalline phase has the amorphous layers thicker than that of the PHB-HV copolymers with the same overall HV content. Based on the collected data, the similarity and differences in the solid-state structures and properties between PHB-HV copolymers and cocrystallizable PHB/PHB-HV blends were discussed.     

Optical absorption matrix elements in single-wall carbon nanotubes

The optical absorption matrix element as a function of one-dimensional (1D) wave vector k, and subband index μ of a single wall carbon nanotube is given analytically for linearly polarized light with polarization parallel to the nanotube axis. For armchair nanotubes, it is found that the optical transitions for non-degenerate A symmetry bands are forbidden over the whole 1D k region and the transitions for all other bands are also forbidden at the k = 0 point. Near the Fermi level, the absorption for all metallic nanotubes is found to be approximately zero. For both metallic and semiconducting nanotubes, it is found that the absorption matrix element has a maximum absolute value at the van Hove singularity (vHS) k point around the Fermi energy for each band. The absorption dependence on diameter and chiral angle is also presented for semiconducting nanotubes. For light polarization perpendicular to the nanotube axis, on the other hand, the absorption for nanotubes is generally weak near a vHS.     

Evaluation of a palladinized Nafion™ for direct methanol fuel cell application

Palladinized Nafion™ was prepared via ion-exchange and chemical reduction method. Palladium precursors and solvent systems determined the efficiency of the incorporation and distribution of nanoparticles. The tortuous thin Pd film was formed on the surface of membrane when Na⁺-Nafion™ and water were used. Pd nanoparticles enhanced the water uptake of Nafion™ and reduced its methanol uptake. And dispersed Pd nanoparticles in Nafion™ disturbed the proton conduction and methanol permeation simultaneously in Nafion™ cluster. In order to reduce methanol permeation of Nafion™ and keep its high conductivity, it was more efficient for Pd nanoparticles to distribute near the surface of membrane. Palladinized Nafion™ improved the performance of DMFC single cell operation by reducing the methanol permeation.     

Crystallographic Texture Development in Bismuth Sodium Titanate Prepared by Reactive-Templated Grain Growth Method

Bi_0.5Na_0.5TiO₃ (BNT) and 0.94Bi_0.5Na_0.5TiO₃·0.06BaTiO₃ (BNT–BT) bulk ceramics with extensive 〈100〉 texture were prepared by the reactive-templated grain growth method, using platelike Bi₄Ti₃O₁₂ (BIT) particles as templates for BNT. Calcined compacts were composed of matrix grains with random orientation and 〈100〉-oriented grains transformed from aligned BIT particles, and the texture developed by the growth of oriented grains during sintering. Ceramics with extensive texture were obtained by using the starting mixture containing the maximum concentration of platelike BIT to form the maximum volume fraction of oriented grains.     

Effects of aging on poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet radiation for gas separation

In this study, we investigated the effects of physical aging on the surface and gas‐transport properties of highly gas permeable poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet (VUV) radiation. VUV excimer lamp irradiation was performed on one side of the membrane for 6 or 60 min. The gas permeabilities for carbon dioxide (CO₂) and nitrogen (N₂) were determined through a volumetric measurement method at 23 °C. The gas permeabilities for CO₂ and N₂ increased temporarily at 7 days after 6 and 60 min of VUV irradiation of the membranes. The change in the gas permeability for N₂ was more remarkable than that for CO₂. These changes were related to the C?O or SiO_x ratio. The C?O ratio was related to the gas permeability of the membranes VUV‐irradiated for 6 min, whereas the SiO_x ratio was related to the gas permeability of the membranes VUV‐irradiated for 60 min. These changes affected the gas selectivities of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45973.     

Lewis Acid‐Catalyzed or Base‐Promoted Regioselective Cycloisomerization of N‐Imidoyl‐o‐alkynylanilines for Synthesis of N‐Imidoyl‐(1 H)‐indoles and 4‐Alkylidene‐3,4‐dihydroquinazolines

Product selectivity control for the synthesis of imidoylindoles and 4‐alkylidenedihydroquinazolines from N‐imidoyl‐o‐alkynylanilines via silver triflate‐catalyzed cycloisomerization or tetrabutylammonium fluoride‐promoted cyclization is described. The product selectivity depends mainly on the catalyst/promoter used, and on the substituents on the alkyne and amidine functions of the substrates.

     

Capability of Utilizing CYP3A5 Polymorphisms to Predict Therapeutic Dosage of Tacrolimus at Early Stage Post-Renal Transplantation

While CYP3A5 polymorphisms are used to predict the initial dosage of tacrolimus therapy, the predictive capability of genetic information for dosing at early stage post-renal transplantation is unknown. We investigated the influence of polymorphisms over time. An initial oral dose of modified-release once-daily tacrolimus formulation (0.20 mg/kg) was administered to 50 Japanese renal transplant patients every 24 h. Stepwise multiple linear regression analysis for tacrolimus dosing was performed each week to determine the effect of patient clinical characteristics. The dose-adjusted trough concentration was approximately 70% higher for patients with the CYP3A5*3/*3 than patients with the CYP3A5*1 allele before the second pre-transplantation tacrolimus dose (0.97 (0.78–1.17) vs. 0.59 (0.45–0.87) ng/mL/mg; p < 0.001). The contribution of genetic factors (CYP3A5*1 or *3) for tacrolimus dosing showed increased variation from Day 14 to Day 28 after transplantation: 7.2%, 18.4% and 19.5% on Days 14, 21 and 28, respectively. The influence of CYP3A5 polymorphisms on the tacrolimus maintenance dosage became evident after Day 14 post-transplantation, although the tacrolimus dosage was determined based only on patient body weight for the first three days after surgery. Tacrolimus dosage starting with the initial administration should be individualized using the CYP3A5 genotype information.     

Morphological evolution and mechanical property enhancement of natural rubber/polypropylene blend through compatibilization by nanoclay

Nanocomposites of natural rubber (NR)/polypropylene (PP) (80/20 wt %) blends filled with 5 phr pristine clay were prepared by melt‐mixing process. Effects of clay incorporation technique via conventional melt‐mixing (CV) and masterbatch mixing (MB) methods on nanostructure and properties of the blend nanocomposites were investigated. The XRD, SAXS, WAXD, and TEM results showed that the clays in the NR/PP blend nanocomposites were presented in different states of dispersion and were locally existed at the interface between NR and PP as well as dispersed in the NR matrix. The presence of clay caused unique morphological evolution such as fine fibrillar PP domains. The tensile strength was improved over the unfilled NR/PP blends by 53% and 224%, and the storage modulus at 25 °C was increased by 78% and 120% for the NR/PP/clay nanocomposites prepared by CV and MB methods, respectively. Significant improvement in both properties was particularly obtained from the MB method due to finer dispersion fibrillar PP phase in the NR matrix and stronger interfacial adhesion between NR and PP fibers, as suggested from DMA. The oil resistance of blend nanocomposites was also improved over that of the unfilled NR/PP blend, and this property was further progressed by the masterbatch mixing method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44574.     

Rolling Motion of a Ball on Pressure Sensitive Adhesives

Rolling motion of a ball on pressure sensitive adhesives was carefully observed under well-controlled conditions. Rolling distance was measured as a function of time by means of stroboscopic photography, and rollout distance was measured as a function of initial height of a ball. Both rolling distances and rollout distances were analysed according to a unified theory, where rolling friction coefficient (f) of a pressure sensitive adhesive is involved. It is suggested that f depends on viscoelastic properties of the adhesives.     

Estimation of the Surface Energy of Polymer Solids

The methods to estimate the surface tension of polymer solids using contact angles have been reviewed in the first part. They are classified into the following three groups depending on the theories or the equations applied: (1) the methods using the Young's equation alone, (2) the methods using the combined equation of Young and Good-Girifalco, and (3) the methods using the equations of work of adhesion. Some notes and comments are given for each method and results are compared with each other. The two-liquids method for rather high energy surface is also introduced.

Next, some new possibilities to evaluate the surface tension of polymer solids are presented by our new contact angle theory in consideration of the friction between a liquid drop and a solid surface. The advancing and receding angles of contact (θ _a and θ _r ) are explained by the frictional tension γ_F and accordingly two kinds of the critical surface tension γ_C (γ_Ca and γ_Cr ) are given.

This work has shown that one of the recommendable ways to evaluate γ_S is either the maximum γ_LV cos θ_a or the maximum γ_C using the advancing contact angle θ_a alone, and another way is the arithmetic or the harmonic mean of the γ_Ca and γ_Cr . A depiction to determine the γ_C such as ln(1 + cos θ₀ ) vs. γ_LV with cos θ₀ = (cos θ₀ + cos θ_r )/2 has also been proposed.