Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

Light scattering of ideal random copolymers in bulk

Copolymerization is a useful way of modifying the physical properties of a material to meet specific needs, but it can result in a significant light scattering loss due to dielectric fluctuations in the material. Ideal random copolymers are known to be more transparent; however, the light-scattering properties of such copolymers in bulk have not been fully studied. In this paper, two representative ideal random copolymers were synthesized: methyl methacrylate (MMA)/benzyl methacrylate (BzMA) and MMA/2,2,2-trifluoroethyl methacrylate (TFEMA). The effects of copolymer composition and polymerization temperature on the light-scattering properties were investigated. Polarized light scattering (V_V) in copolymers was more sensitive to the polymerization temperature. Higher temperatures were necessary to homogenize the dielectric fluctuations and minimize excess light scattering. However, once the heterogeneous structures vanished, the copolymer bulk exhibited low scattering losses, which are comparable with homopolymers, over the entire range of copolymer compositions.     

Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C₀–C₂₂) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C₀), 1-hexanol (C₆), 1-dodecanol (C₁₂), and 1-docosanol (C₂₂) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having M_n of 6–7 × 10³ of 2 × 10⁴ g mol⁻¹, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having M_n of 6–7 × 10³ g mol⁻¹, but was not altered by the length of terminal n-alkyl group for PLLA having M_n of 2 × 10⁴ g mol⁻¹.     

Serum Amyloid A3 Promoter-Driven Luciferase Activity Enables Visualization of Diabetic Kidney Disease

The early detection of diabetic nephropathy (DN) in mice is necessary for the development of drugs and functional foods. The purpose of this study was to identify genes that are significantly upregulated in the early stage of DN progression and develop a novel model to non-invasively monitor disease progression within living animals using in vivo imaging technology. Streptozotocin (STZ) treatment has been widely used as a DN model; however, it also exhibits direct cytotoxicity to the kidneys. As it is important to distinguish between DN-related and STZ-induced nephropathy, in this study, we compared renal responses induced by the diabetic milieu with two types of STZ models: multiple low-dose STZ injections with a high-fat diet and two moderate-dose STZ injections to induce DN. We found 221 genes whose expression was significantly altered during DN development in both models and identified serum amyloid A3 (Saa3) as a candidate gene. Next, we applied the Saa3 promoter-driven luciferase reporter (Saa3-promoter luc mice) to these two STZ models and performed in vivo bioluminescent imaging to monitor the progression of renal pathology. In this study, to further exclude the possibility that the in vivo bioluminescence signal is related to renal cytotoxicity by STZ treatment, we injected insulin into Saa3-promoter luc mice and showed that insulin treatment could downregulate renal inflammatory responses with a decreased signal intensity of in vivo bioluminescence imaging. These results strongly suggest that Saa3 promoter activity is a potent non-invasive indicator that can be used to monitor DN progression and explore therapeutic agents and functional foods.     

Blood Pressure Elevation of Tubular Specific (P)RR Transgenic Mice and Lethal Tubular Degeneration due to Possible Intracellular Interactions between (P)RR and Alternative Renin Products

The prorenin/renin receptor ((P)RR) is a multifunctional protein that is widely distributed in various organs. Despite intensive research for more than 20 years, this receptor has not been fully characterized. In this study, we generated mice overexpressing the tubular epithelial (P)RR gene ((P)RR-TG mice) to test the previously reported functional role of (P)RR by Ramkumar et al. in 2015 using tubular specific (P)RR KO mice. (P)RR-TG mice were maintained and analyzed in individual metabolic cages and were administered angiotensin II blocker (ARB), direct renin inhibitor (DRI), and bafilomycin, that is, vacuolar ATPase (V-ATPase) antagonist. (P)RR-TG mice were hypertensive and had alkalized urine with lower osmolality and Na⁺ excretion. ARB and DRI, but not bafilomycin, concurrently decreased blood pressure. Bafilomycin acidized urine of (P)RR-TG mice, or equivalently this phenomenon restored the effect of overexpressed transgene, suggesting that (P)RR functioned as a V-ATPase in renal tubules. Afterall, (P)RR-TG mice were mated with alternative renin transgenic mice (ARen2-TG), which we identified as intracellular renin previously, to generate double transgenic mice (DT-TG). Lethal renal tubular damage was observed in DT-TG mice, suggesting that intracellular renin may be a ligand for (P)RR in tubules. In summary, (P)RR did not substantially affect the tissue renin-angiotensin system (RAS) in our model of tubular specific (P)RR gene over-expression, but alternative intracellular renin may be involved in (P)RR signaling in addition to conventional V-ATPase function. Further investigations are warranted.     

Distribution, characteristics, and worldwide inventory of dioxins in kaolin ball clays

Distribution, characteristics, and global inventory of dioxins (polychlorinated dibenzo-p-dioxins [PCDDs] and dibenzofurans [PCDFs] and dioxin like polychlorinated biphenyls) in kaolin clays collected from 10 countries were investigated. Dioxins were found in all kaolin clay samples analyzed, at total concentrations ranging from 1.2 pg/g (Brazil) to 520,000 pg/g (USA). Dioxin concentrations in kaolin clays from a few countries (e.g., Brazil and UK) were lower than those reported for background soils in Japan. Dioxin profiles in kaolin clays were characterized by the domination of the congener octachlorodibenzo-p-dioxin (OCDD), and the concentrations of other congeners decreased in the order of reduction in the levels of chlorination. Furthermore, specific distribution of congeners, with predominant proportions of 1,4,6,9-substituted PCDDs within each homologue group, was found in most clay samples. The ratios of concentrations of PCDD to PCDF and 1,2,3,7,8,9-HxCDD to 1,2,3,6,7,8-HxCDD indicated differences in the profiles found for anthropogenic sources (including pentachlorophenol) and kaolin clays. Concentrations of PCDD/Fs in kaolin clays, except for American ball clays, did not exceed the environmental criteria set by the Law Concerning Special Measures against Dioxins in Japan. Based on the average concentrations measured in our study, inventories of PCDD/Fs from the production/usage of ball clays on a global scale were estimated to be 650 kg/yr; the corresponding value on a TEQ basis is 2400 g-TEQ/yr. More than 480 kg of OCDD is estimated to be released annually from the production of kaolin clays worldwide, suggesting that kaolin clays can be a major contributor for additional source of dioxins, especially OCDD, in the environment.     

Profiling and Imaging of Phospholipids in Brains of Abcd1‐Deficient Mice

ABCD1 is a gene responsible for X‐linked adrenoleukodystrophy (X‐ALD), and is critical for the transport of very long‐chain fatty acids (VLCFA) into peroxisomes and subsequent β‐oxidation. VLCFA‐containing lipids accumulate in X‐ALD patients, although the effect of ABCD1‐deficiency on each lipid species in the central nervous system has not been fully characterized. In this study, each phospholipid and lysophospholipid species in Abcd1‐deficient mice brains were profiled by liquid chromatography‐mass spectrometry. Among the phospholipid and lysophospholipid species that are significantly more enriched in Abcd1‐deficient mice brains, VLCFA were present in 75, 15, 5, 4, and 1 species of phosphatidylcholine, phosphatidylethanolamine, sphingomyelin, lysophosphatidylcholine, and lysophosphatidylethanolamine, respectively. Most VLCFA were incorporated at the sn‐1 position of phosphatidylcholine and phosphatidylethanolamine. Among the phospholipid species that are significantly less enriched in Abcd1‐deficient mice brains, odd‐numbered saturated or mono‐unsaturated fatty acyl moieties are contained in all phosphatidylcholine species. In addition, a number of phosphatidylglycerol, phosphatidylinositol, and phosphatidylserine species contained highly unsaturated fatty acyl moieties. Intriguingly, 44:1 phosphatidylcholine with VLCFA was mainly distributed in the gray matter, such as the cortex, but not in the white matter in the cerebrum and cerebellum. These results show that ABCD1‐deficiency causes metabolic alternation of long‐chain fatty acids and VLCFA. Moreover, our results imply a molecular mechanism for the incorporation of saturated or monounsaturated VLCFA into the sn‐1 position of phospholipids, and also indicate that the distribution of phospholipids with VLCFA may correlate with the development of X‐ALD.     

Mechanical and physical properties of epoxy composites reinforced by vapor grown carbon nanofibers

Epoxy/vapor grown carbon nanofiber composites (VGCF) with different proportions of VGCF were fabricated by the in situ process.The VGCFs were well dispersed in both of the low and high viscosity epoxy matrices, although occasional small aggregates were observed in a high viscosity epoxy of 20 wt.%. The dynamic mechanical behavior of the nanocomposite sheets was studied. The storage modulus and the glass transition temperature (T_g) of the polymer were increased by the incorporation of VGCFs.The electrical and mechanical properties of the epoxy-VGCFs nanocomposite sheets with different weight percentages of VGCFs were discussed. The results were that both had maximum tensile strength and Young’s modulus at 5 wt.% for both materials and reduced the fracture strain with increasing filler content. The electrical resistivity was decreased with the addition of filler content. Mechanical, electrical and thermal properties of low viscosity epoxy composites were resulted better than that of the high viscosity composites.     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.