Evidence that Crystal Facet Orientation Dictates Oxygen Evolution Intermediates on Rutile Manganese Oxide

Elucidating the mechanism that differentiates the oxygen‐evolving center of photosystem II with its inorganic counterpart is crucial to develop efficient catalysts for the oxygen evolution reaction (OER). Previous studies have suggested that the larger overpotential for MnO₂ catalysts under neutral conditions may result from the instability of the Mn³⁺ intermediate to charge disproportionation. Here, by monitoring the surface intermediates of electrochemical OER on rutile MnO₂ with different facet orientations, a correlation between the stability of the intermediate species and crystal facets is confirmed explicitly for the first time. The coverage of the Mn³⁺ intermediate is found to be 11‐fold higher on the metastable (101) surfaces compared to (110) surfaces, leading to the superior OER activity of (101) surfaces. The difference in OER activity may result from the difference in surface electronic states of Mn³⁺, where interlayer charge comproportionation of Mn²⁺ and Mn⁴⁺ to generate two Mn³⁺ species is favored on (101) facets. Considering the fact that the OER enzyme accommodates Mn³⁺ stably during the Kok cycle, the enhanced OER activity of the rutile MnO₂ catalyst with a metastable surface highlights the importance of mimicking not only the crystal structure but also the electronic structure of the targeted natural enzyme.     

Pectin‐[(3‐acrylamidopropyl) trimethylammonium chloride‐co‐acrylic acid] hydrogel prepared by gamma radiation and selectively silver (Ag) metal adsorption

Pectin‐[(3‐acrylamidopropyl) trimethylammonium chloride‐co‐acrylic acid] hydrogel has been prepared from the aqueous blend solution of pectin, (3‐acrylamidopropyl) trimethylammonium chloride (APTAC), and acrylic acid (AAc) by applying gamma radiation of different doses (1–25 kGy) from ⁶⁰Co gamma source. The hydrogels were characterized by equilibrium swelling, Fourier transform infrared, differential scanning calorimetry, and scanning electron microscopy. The hydrogels were used in multielement adsorption and it was found that pectin‐(APTAC‐co‐AAc) gel is highly selective toward silver (I) ion among 27 metal ions. The data obtained from equilibrium adsorption studies were fitted in Langmuir and Freundlich adsorption isotherm models and model parameters evaluated. The maximum adsorption capacity of pectin‐(APTAC‐co‐AAc) gel was found to be 67.6413 mg/g of dry gel at sample volume of 25 mL. The kinetic data were tested using pseudo‐first order and pseudo‐second order kinetic models and different adsorption diffusion models such as film diffusion and intra‐particle diffusivity model. Thiourea solution was used for desorption of adsorbed metal ions from the hydrogel. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45906.     

Electronic states and cation distributions of MgAl2O4 and Mg0.4Al2.4O4 microwave dielectric ceramics

The electronic state and microwave dielectric properties of MgAl₂O₄ prepared using solid-state (MA-S) and molten salt (MA-M) methods and those of Mg_0.4Al_2.4O₄ (M04A24) were investigated. The λ values, which correspond to the fraction of Al³⁺ cations in tetrahedral sites, for MA-S, MA-M, and M04A24 were 0.23, 0.41, and 0.60, respectively. In molecular orbital calculations, a larger overlap was observed between Al-3s or Al-3p in tetrahedral sites and O-2p orbitals for M04A24, and the bond order for AlO at tetrahedral sites of M04A24 (0.241) was higher than those for MA-S (0.178) and MA-M (0.205). The dielectric constant, ε_r, for M04A24 (7.6) was lower than those for MA-S and MA-M (both 7.9), and the highest quality factor, Q·f, was obtained for M04A24 (235, 800 GHz). It was found that the covalency of the AlO bonds in the MO₄ tetrahedra is closely related to the Q?f values of the present ceramics.     

Stromal vascularization in the endometrium during adenomyosis

In adenomyosis, the two major frequent symptoms are hypermenorrhea and dysmenorrhea. The incidence of the former is said to be high, ranging from 36 to 70%. It has been found that vascular distribution of the endometrium in adenomyosis is diversely different from fertile patients without adenomyosis. For example, hysteroscopy revealed that approximately half of the patients have abnormal vascularization. In these patients, vascular distribution was generally irregular, and vessels were thick, dilated, and/or reticular in some patients. Moreover, morphometric analysis of the endometrium revealed that in the fertile women, the mean surface area, total surface area, and total number of capillaries, all increased significantly in the secretory phase compared to the proliferative phase. In contrast, the above parameters increased in the adenomyosis group in both the proliferative phase and secretory phase compared to the fertile women. In particular, the total surface area of capillaries per mm(2) markedly rose, by 11.6 times, compared to that of the proliferative phase in the fertile women. These findings suggest that regulatory factors involved in the vascular proliferation are diversely exaggerated, and that the abnormal vascularization of the endometrium is closely related with hypermenorrhea.     

Characterization of light extraction efficiency for WOLEDS with light‐out‐coupling layer

We studied the light extraction efficiencies of white organic light‐emitting diodes with a light‐out‐coupling layer by simulations and experiments. The light extraction efficiencies estimated by the simulation were confirmed to agree well with those measured by the experiments. Moreover, we successfully obtained the high light extraction efficiency (η_OC) of 69%.     

Hexaphyrin as a Potential Theranostic Dye for Photothermal Therapy and 19F Magnetic Resonance Imaging

Two features of meso‐Aryl‐substituted expanded porphyrins suggest suitability as theranostic agents. They have excellent absorption in near infrared (NIR) region, and they offer the possibility of introduction of multiple fluorine atoms at structurally equivalent positions. Here, hexaphyrin (hexa) was synthesized from 2,6‐bis(trifluoromethyl)‐4‐formyl benzoate and pyrrole and evaluated as a novel expanded porphyrin with the above features. Under NIR illumination hexa showed intense photothermal and weak photodynamic effects, which were most likely due to its low excited states, close to singlet oxygen. The sustained photothermal effect caused ablation of cancer cells more effectively than the photodynamic effect of indocyanine green (a clinical dye). In addition, hexa showed potential for use in the visualization of tumors by ¹⁹F magnetic resonance imaging (MRI), because of the multiple fluorine atoms. Our results strongly support the utility of expanded porphyrins as theranostic agents in both photothermal therapy and ¹⁹F MRI.     

Foam processing and cellular structure of polypropylene/clay nanocomposites

Polypropylene (PP)/clay nanocomposites (PPCNs) were autoclave‐foamed in a batch process. Foaming was performed using supercritical CO₂ at 10 MPa, within the temperature range from 130.6°C to 143.4°C, i.e., below the melting temperature of either PPCNs or maleic anhydride‐modified PP (PP‐MA) matrix without clay. The foamed PP‐MA and PPCN2 (prepared at 130.6°C and containing 2 wt% clay) show closed cell structures with pentagonal and/or hexagonal faces, while foams of PPCN4 and PPCN7.5 (prepared at 143.4°C, 4 and 7.5 wt% clay) had spherical cells. Scanning electron microscopy confirmed that foamed PPCNs had high cell density of 10⁷–10⁸ cells/mL, cell sizes in the range of 30–120 μm, cell wall thicknesses of 5–15 μm, and low densities of 0.05–0.3 g/mL. Interestingly, transmission electron microscopic observations of the PPCNs' cell structure showed biaxial flow‐induced alignment of clay particles along the cell boundary. In this paper, the correlation between foam structure and rheological properties of the PPCNs is also discussed.     

Effect of surface structure on cell growth prepared by the terminal immobilization method

Substrate effects of surface morphology and chemical structure for cell cultures prepared by molecular terminal immobilization method were studied. When we focused attention on a phenyl group as a functional moiety, the cell growth on the surface prepared by the immobilization method showed a better proliferation rate than that of a substrate prepared by the casting method. Further, from the results of mouse fibroblast L929 cell (L‐cell) growth on poly(amino acid)‐immobilized surfaces in Dulbecco's minimal essential medium containing 10% FBS, it was indicated that the amino group was more effective than the phenyl group, and that a slight difference of chemical structure had a substantial influence on cell growth. In addition, mouse bone marrow–derived Sp2/0‐Ag14 cell (Sp2/0 cell) culture in ASF‐104 serum‐free medium, poly(amino acid)‐immobilized substrates showed an almost equal proliferation rate to that in a serum‐containing medium. These results showed that effective cell growth can occur on immobilized surfaces, and that detection of a weak interaction depends on the functional groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3001–3008, 2004     

Prediction of Bending Fatigue Life of Cracked Out-of-Plane Gusset Joint Repaired by CFRP Plates

Carbon fiber reinforced polymer (CFRP), plates bonding repair method is one of the simple repair methods for cracked steel structures. In this study, the influence of width of CFRP plates on bending fatigue life of out-of-plane gusset joint strengthened with CFRP plates was investigated from the experimental and numerical point of view. In the bending fatigue test of cracked out-of-plane gusset joint strengthened with CFRP plates, the effect of width of CFRP plates on crack growth life was clarified experimentally. Namely, it was revealed that the crack growth life becomes larger with increasing the width of CFRP plates. In the numerical approach, the stress intensity factor (SIF) at the surface point of a semi-elliptical surface crack was estimated based on the linear fracture mechanics. Furthermore, the extended fatigue life of cracked out-of-plane gusset joint strengthened with CFRP plates was evaluated by using the estimated SIF at the surface point and the empirical formula of the aspect ratio of semi-elliptical crack. As the results of numerical analysis, the estimated fatigue life of the specimen strengthened with CFRP plates showed the good agreement with the test results.     

Poly(N‐isopropylacrylamide) grafting on aluminium to actively switch its surface drag in water

Active control of flow over object surfaces achieved by means of mechanical and/or electrical methods has recently been studied. However, there has been no report on actively switching the surface drag of an object by chemical modification of the object's surface. Poly(N‐isopropylacrylamide) (PNIPA) was grafted onto the surface of an aluminium (Al) substrate via (A) surface‐initiated atom transfer radical polymerization and (B) radical polymerization with an azo‐group surface initiator. The grafting density was 0.19 and 0.15 chains nm^?2, respectively. The water contact angle of the PNIPA‐grafted Al surface reversibly changed between 55° and 82° for (A) and between 42° and 65° for (B) at temperatures of 25 and 40 °C, which was ascribed to the temperature‐responsive, hydrophilic–hydrophobic switching of the grafted PNIPA surface. The PNIPA grafting was applied on the surface of an ogive‐shaped Al model. The normalized dropping speed of the model in water increased 1.1 times at 42 °C in comparison to that at 22 °C. Switching of the surface drag of PNIPA‐grafted Al in water was demonstrated on the basis of the hydrophilicity and hydrophobicity of the grafted Al surface, the switching occurring with a change in temperature. Copyright © 2010 Society of Chemical Industry