High-performance polymer alloys of polybenzoxazine and bismaleimide

Two series of high-performance polymer alloys were prepared by mixing typical benzoxine monomers, 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (P-a) or 6,6-(1-methylethyliden)-bis-(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) (B-a), with a typical bismaleimide, 4,4-bismaleimidodiphenyl methane by various ratios followed by thermal treatment up to 240 °C. DSC and IR of the alloys were examined to follow the curing reaction. These analyses showed that the obtained polymer alloys are AB co-cross-linked polymer networks through the formation of ether linkage between the hydroxyl group of polybenoxazine and the double bond of bismaleimide. Viscoelastic analysis and softening temperature measurement revealed that the polymer alloys have much higher glass transition temperatures than those of each homopolymer. The thermal stability also increased with the increase of bismaleimide content as evidenced by TGA.     

The effect of inorganic additives on the formation,composition, and combustion of cellulosic char

At temperature above 300°C the glycosyl units of cellulose are simultaneously depolymerized to a tar and decomposed to a char by evolution of H₂O, CO, and CO₂. When the glycosyl units are depleted, a stable char is formed containing about 30% aliphatic and 70% aromatic components. The aliphatic component is formed first, but on further heating is converted to polycyclic aromatic structures. The chars formed at lower temperatures are more combustible because the aliphatic component of the char is highly pyrophoric and is oxidized almost at the same temperature at which it is formed (～360°C). The aromatic component, however, is less reactive and is oxidized at ～520°C. Consequently, the chars formed at higher temperatures are less combustible. It has been shown that (NH₄)₂HPO₄, which is a well-known flame retardant and smoldering inhibitor, lowers the pyrolysis temperature and increases the char yield by accelerating the decomposition reactions. This affects the composition of the intermediate chars but the final products have about the same composition irrespective of additives. (NH₄)₂HPO₄ also lowers the rate of oxidation of the aromatic component and the corresponding heat release. NaCl, which is an enhancer of smoldering combustion, has a slight stabilizing effect on pyrolysis of cellulose. It lowers the oxidation temperature of the aromatic component and dramatically increases its rate. The corresponding heat release is also increased due to complete oxidation to CO₂. The rate of oxidation calculated from the dynamic thermal analysis data is more than tripled by NaCl and significantly reduced by (NH₄)₂HPO₄.     

Unkeito Suppresses RANKL-Mediated Osteoclastogenesis via the Blimp1–Bcl6 and NF-κB Signaling Pathways and Enhancing Osteoclast Apoptosis

Osteoporosis is a common bone disease, particularly in menopausal women. Herein, we screened four Kampo medicines (Unkeito (UKT), Kamishoyosan (KSS), Kamikihito (KKT), and Ninjinyoeito (NYT)), frequently used to treat menopausal syndromes, for their effects on receptor activator of nuclear factor-kappaB ligand (RANKL)-induced osteoclast differentiation in RAW 264 cells. Considering that UKT exhibited the most potent effect, we examined its effect on RANKL-induced osteoclastogenesis, the induction of osteoclast apoptosis, and the mechanisms underlying its effects. UKT inhibits RANKL-induced osteoclast differentiation in the early stage and decreases osteoclast-related genes, including tartrate-resistant acid phosphatase (Trap), dendritic cell-specific transmembrane protein (Dcstamp), matrix metalloproteinase-9 (Mmp9), and cathepsin K (Ctsk). Specifically, UKT inhibits the nuclear factor of activated T cells 1 (NFATc1), which is essential for osteoclastogenesis. UKT increases Bcl6, which antagonizes NFATc1 and Dc-stamp, thereby blocking the progression of osteoclasts to maturation. UKT also decreased nuclear translocation by downregulating the activity of p65/NF-κB. In addition, UKT enhances mononuclear osteoclast apoptosis via activation of caspase-3. Herein, we demonstrate that UKT suppresses RANKL-mediated osteoclastogenesis via the Blimp1–Bcl6 and NF-κB signaling pathways and enhances mononuclear osteoclast apoptosis. Furthermore, UKT prevents bone loss in OVX mice. Thus, UKT might be a potential therapeutic agent for postmenopausal osteoporosis.     

Functional and Structural Insights into Human PPARα/δ/γ Subtype Selectivity of Bezafibrate,Fenofibric Acid,and Pemafibrate

Among the agonists against three peroxisome proliferator-activated receptor (PPAR) subtypes, those against PPARα (fibrates) and PPARγ (glitazones) are currently used to treat dyslipidemia and type 2 diabetes, respectively, whereas PPARδ agonists are expected to be the next-generation metabolic disease drug. In addition, some dual/pan PPAR agonists are currently being investigated via clinical trials as one of the first curative drugs against nonalcoholic fatty liver disease (NAFLD). Because PPARα/δ/γ share considerable amino acid identity and three-dimensional structures, especially in ligand-binding domains (LBDs), clinically approved fibrates, such as bezafibrate, fenofibric acid, and pemafibrate, could also act on PPARδ/γ when used as anti-NAFLD drugs. Therefore, this study examined their PPARα/δ/γ selectivity using three independent assays—a dual luciferase-based GAL4 transactivation assay for COS-7 cells, time-resolved fluorescence resonance energy transfer-based coactivator recruitment assay, and circular dichroism spectroscopy-based thermostability assay. Although the efficacy and efficiency highly varied between agonists, assay types, and PPAR subtypes, the three fibrates, except fenofibric acid that did not affect PPARδ-mediated transactivation and coactivator recruitment, activated all PPAR subtypes in those assays. Furthermore, we aimed to obtain cocrystal structures of PPARδ/γ-LBD and the three fibrates via X-ray diffraction and versatile crystallization methods, which we recently used to obtain 34 structures of PPARα-LBD cocrystallized with 17 ligands, including the fibrates. We herein reveal five novel high-resolution structures of PPARδ/γ–bezafibrate, PPARγ–fenofibric acid, and PPARδ/γ–pemafibrate, thereby providing the molecular basis for their application beyond dyslipidemia treatment.     

Enhanced Hole‐Transporting Behavior of Discotic Liquid‐Crystalline Physical Gels

Discotic liquid‐crystalline (LC) physical gels have been prepared by combining the self‐assembled fibers of a low‐molecular‐weight gelator and semiconducting LC triphenylene derivatives. The hole mobilities of the discotic LC physical gels measured by a time‐of‐flight method become higher than those of LC triphenylenes alone. The introduction of the finely dispersed networks of the gelator in the hexagonal columnar phases may affect the molecular dynamics of the liquid crystals, resulting in the enhancement of hole transporting behavior in the LC gel state.     

Numerical Analysis of the Boundary Scattering Effect on Transport Properties in Bi-Sb Nanowires

In this study, we have numerically analyzed the transport properties of Bi-Sb nanowires, taking into account wire boundary scattering. Wire boundary scattering slightly decreased the Seebeck coefficient of Bi-Sb nanowires. This effect is due to the observation that boundary scattering and the mobility ratio of L-point electrons to T-point holes in the nanowires are smaller than those in bulk Bi-Sb because the wire boundary scattering suppresses the mobilities of L-point electrons and heavy holes. The largest Seebeck coefficient for all wire diameters was obtained when the Sb concentration was 5 at.%. The effective mass approached zero near 5 at.% Sb, and the small effective mass led to a large subband shift in each band. Thus, a small effective mass enhances the quantum effect at a fixed wire diameter, even if wire boundary scattering is taken into account.