Effects of pH and temperature on the deposition properties of stannate chemical conversion coatings formed by the potentiostatic technique on AZ91 D magnesium alloy

The effects of pH and temperature of a stannate bath on the quality of stannate chemical conversion coatings formed on AZ91 D magnesium alloy by using the potentiostatic polarization technique at E = −1.1 V were investigated in order to improve uniformity and corrosion protection performance of the coating films. It was found that the uniformity and corrosion resistance of coating films deposited by potentiostatic polarization were closely associated with pH and temperature of the coating bath. The pH and temperature to obtain the best coating film were investigated as a function of corrosion protection performance evaluated by curves of potentiodynamic anodic polarization conducted in borate buffer solution. Scanning electron microscope observation and electrochemical corrosion tests of the stannate-coated samples confirmed significant improvement in uniformity and corrosion resistivity of coating films deposited by the potentiostatic technique by modifying the pH and temperature of the coating bath. It was also found that uniformity and corrosion resistivity of the coating films deposited by the potentiostatic technique were considerably improved compared to those of coatings deposited by the simple immersion method at the best conditions of pH and temperature of the coating bath.     

Dioxin-like and transthyretin-binding compounds in indoor dusts collected from Japan: average daily dose and possible implications for children

Many researchers are increasingly interested in human exposure to house dust containing household compounds such as polybrominated diphenylethers (PBDEs). Nevertheless, no investigations have addressed the endocrine-disrupting potencies of compounds contained in indoor dust. This study specifically addresses endocrine-disrupting potencies such as dioxin-like activity and human transthyretin (TTR)-binding potencies. Using in vitro bioassays, we investigated these activity levels in indoor dusts. We performed exposure assessments of active compounds that are contained in house dust for subsequent evaluation of house dusts' risks to humans. Dioxin-like and TTR-binding activities in sulfuric acid treatment extracts of house and office dust were investigated using Dioxin-Responsive Chemical-Activated LUciferase gene eXpression assay (DR-CALUX) and TTR-binding assay (in vitro competitive human TTR-binding assay). Dioxin-like activities in indoor dust were 38-1400 pg CALUX-TEQ (2,3,7,8-TCDD equivalent)/g (median 160 pg CALUX-TEQ/g) and TTR-binding potencies were 300-5000 pmol T4EQ (thyroxine (T4) equivalent)/g (median 1000 pmol T4EQ/g), which are higher values than those in other environmental samples, e.g., contaminated sediments. These exposure results suggest that children might be affected by both dioxin-like compounds and TTR-binding compounds via house dust. When the ingestion rate, CALUX-TEQ, and T4EQ for house dust are high, thyroid hormone homeostasis in children may be disrupted.     

Characterization and CO2 sorption properties of poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane‐ co‐3‐methacryloxypropyltris(trimethylsiloxy)silane]

Poly[methacryloxypropylheptacyclopentyl‐T8‐silsesquioxane (MAPOSS)‐co‐3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA)] was synthesized through free radical polymerization. The physical and carbon dioxide (CO₂) sorption properties of the copolymer membranes were investigated in terms of the MAPOSS content. As the MAPOSS content increases, the membrane density increased, suggesting a decrease in the fractional free volume. In addition, the thermal stability was improved with increasing the MAPOSS content. These are because of the polyhedraloligomericilsesquioxane (POSS) units that restrict the high mobility of poly(SiMA) segments. The glass transition temperature, T_g of the copolymers was single T_g based on the differential scanning calorimetry, suggesting that the copolymers were random and not phase separation. Based on the CO₂ sorption measurement, the POSS units play a role in reducing Henry's dissolution by suppressing the mobility of the poly(SiMA) component, while POSS units increase the nonequilibrium excess free volume, which contributes to the Langmuir dissolution. Based on these results, the introduction of MAPOSS unit is one of the effective ways to improved the thermal stability and CO₂ sorption property due to the enhancement of the polymer rigidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structural features of anodic oxide films formed on aluminum substrate coated with self-assembled microspheres

The structural features of anodic oxide films formed on an aluminum substrate coated with self-assembled microspheres were investigated by scanning electron microscopy and atomic force microscopy. In the first anodization in neutral solution, the growth of a barrier-type film was partially suppressed in the contact area between the spheres and the underlying aluminum substrate, resulting in the formation of ordered dimple arrays in an anodic oxide film. After the subsequent second anodization in acid solution at a voltage lower than that of the first anodization, nanopores were generated only within each dimple. The nanoporous region could be removed selectively by post-chemical etching using the difference in structural dimensions between the porous region and the surrounding barrier region. The mechanism of anodic oxide growth on the aluminum substrate coated with microspheres through multistep anodization is discussed.     

Accretion of titanium carbide by electrical discharge machining with powder suspended in working fluid

A surface modification method by electrical discharge machining (EDM) with a green compact electrode has been studied to make thick TiC or WC layer. Titanium alloy powder or tungsten powder is supplied from the green compact electrode and adheres on a workpiece by the heat caused by discharge. To avoid the production process of the green compact electrode, a surface modification method by EDM with powder suspended in working fluid is proposed in this paper. After considering flow of working fluid in EDM process, the use of a thin electrode and a rotating disk electrode are expected to keep powder concentration high in the gap between a workpiece and an electrode and to accrete powder material on the workpiece. The accretion machining is tried under various electrical conditions. Titanium powder is suspended in working oil like kerosene. TiC layer grows a thickness of 150 μm with a hardness of 1600 Hv on carbon steel with an electrode of 1 mm in diameter. When a disk placed near a plate rotates in viscous fluid, the disk drags the fluid into the gap between the disk and the plate. Therefore, the powder concentration in the gap between a workpiece and a rotational disk electrode can be kept high. A wider area of the accretion can be obtained by using the rotational electrode with a gear shape.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Fabrication of nano-sized oxide composite coatings and photo-electric conversion/electron storage characteristics

Titanium dioxide TiO₂ can be used as a photo-anode to give generated electrons to the metal substrate under illumination. The transition metal oxide such as iron oxide Fe₂O₃ can be used to store electrons generated by the photo-electric conversion function of TiO₂ under the illuminated situation while the electrons are discharged from the transition metal oxide to the metal substrate in the dark. In this paper, coatings of nano-sized composite of TiO₂ and Fe₂O₃ were fabricated by the Warm Spray process, in which the feedstock powder is accelerated by a supersonic gas jet with speed above 1.0 km s^- 1 and temperature between 800 and 2500 K, and then impacted onto the target substrate continuously to form coatings. The coatings of TiO₂ and Fe₂O₃ nano-composite fabricated by Warm Spray showed no thermal deterioration such as phase transformation and particle growth of the feedstock during the spray process. The coatings fabricated by the Warm Spray had larger photo-current and the electron charge/discharge capacity than that by a conventional HVOF process. In addition, these characteristics were improved by decreasing the primary particle size of TiO₂ and Fe₂O₃.     

Self‐Degradable Lipid‐Like Materials Based on “Hydrolysis accelerated by the intra‐Particle Enrichment of Reactant (HyPER)” for Messenger RNA Delivery

RNA‐based therapeutics is a promising approach for curing intractable diseases by manipulating various cellular functions. For eliciting RNA (i.e., mRNA and siRNA) functions successfully, the RNA in the extracellular space must be protected and it must be delivered to the cytoplasm. In this study, the development of a self‐degradable lipid‐like material that functions to accelerate the collapse of lipid nanoparticles (LNPs) and the release of RNA into cytoplasm is reported. The self‐degradability is based on a unique reaction “Hydrolysis accelerated by intra‐Particle Enrichment of Reactant (HyPER).” In this reaction, a disulfide bond and a phenyl ester are essential structural components: concentrated hydrophobic thiols that are produced by the cleavage of the disulfide bonds in the LNPs drive an intraparticle nucleophilic attack to the phenyl ester linker, which results in further degradation. An oleic acid‐scaffold lipid‐like material that mounts all of these units (ssPalmO‐Phe) shows superior transfection efficiency to nondegradable or conventional materials. The insertion of the aromatic ring is unexpectedly revealed to contribute to the enhancement of endosomal escape. Since the intracellular trafficking is a sequential process that includes cellular uptake, endosomal escape, the release of mRNA, and translation, the improvement in each process synergistically enhances the gene expression.     

Dimethyl Fumarate Promotes the Survival of Retinal Ganglion Cells after Optic Nerve Injury,Possibly through the Nrf2/HO-1 Pathway

This study aimed to verify whether dimethyl fumarate (DMF) promotes the survival of retinal ganglion cells (RGCs) after optic nerve crush (ONC) accompanied by activation of the NF-E2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) pathway. We examined changes in the densities of tubulin β3 (TUBB3)-positive RGCs and the amplitudes of the positive scotopic threshold response (pSTR), reflecting the functional activity of RGCs, recorded on an electroretinogram, with daily administration of DMF, on day 7 after ONC. Furthermore, immunohistochemical and immunoblotting analyses were performed to study the activation of the Nrf2/HO-1 pathway using retinas treated with daily administration of DMF. Daily administration of DMF increasedthe density of TUBB3-positive RGCs in a dose-dependent fashion and significantly increased the amplitude of the pSTR. Immunohistochemical analysis showed that DMF administration increased the immunoreactivity for Nrf2 and HO-1, a potent antioxidant enzyme, in RGCs immunolabeled with RNA-binding protein with multiple splicing (RBPMS). Immunoblotting analysis revealed an increase in the nuclear expression of Nrf2 and marked upregulation of HO-1 after DMF administration. These results suggest that DMF has survival-promoting effects in RGC after ONC, possibly via the Nrf2/HO-1 pathway.