Synthesis,crystal structures,spectral, electrochemical and magnetic properties of di-µ-phenoxido-bridged dinuclear copper(II) complexes with N-salicylidene-2-hydroxybenzylamine derivatives: axial coordination effect of dimethyl sulphoxide molecule

The template reaction of salicylaldehyde and its substituted derivatives and 2-hydroxy-5-bromobenzylamine or 2-hydroxy-5-chlorobenzylamine with copper(II) acetate in dimethyl sulphoxide (dmso) afforded eight dinuclear Cu(II) complexes, [Cu₂(L)₂(dmso)₂] (H₂ L = N-salicylidene-2-hydroxy-5-bromobenzylamine, N-salicylidene-2-hydroxy-5-chlorobenzylamine and their 5-bromo, 5-nitro and 5-methyl-substituted salicylidene derivatives). These Cu(II) complexes were characterised by IR and UV-VIS-NIR spectroscopy, electric conductivity, cyclic voltammetry, and temperature dependence of magnetic susceptibilities (4.5–300 K). In the THF solution, the complexes are nonelectrolytes and exhibit a characteristic CT band due to phenoxido-bridging at 360–384 nm. In the cyclic voltammograms, an irreversible reduction process was observed at ?1.18–1.54 V vs Fc/Fc⁺. Single-crystal X-ray crystallography revealed that two Cu(II) ions were bridged by the two phenoxido-oxygen atoms of the two Schiff-base ligands with axial coordination of dmso molecules forming a square pyramid with a Cu-Cu distance of 3.0628(8)–3.0931(6) °A. In accordance with the crystal structures, the magnetic interaction between the two Cu(II) ions is relatively anti-ferromagnetic with ?2J value of 386–575 cm^?1. The axial coordination effect of the dmso molecule was discussed in relation to the correlation between the Cu-O-Cu angle and the ?2J value.     

Antioxidant effects of photodegradation product of nifedipine

Recently, increasing evidence suggests that the antihypertensive drug nifedipine acts as a protective agent for endothelial cells, and that the activity is unrelated to its calcium channel blocking. Nifedipine is unstable under light and reportedly decomposes to a stable nitrosonifedipine (NO-NIF). NO-NIF has no antihypertensive effect, and it has been recognized as a contaminant of nifedipine. The present study for the first time demonstrated that NO-NIF changed to a NO-NIF radical in a time-dependent manner when it interacted with human umbilical vein endothelial cells (HUVECs). The electron paramagnetic resonance (EPR) signal of NO-NIF radicals in HUVECs showed an asymmetric pattern suggesting that the radicals were located in the membrane. The NO-NIF radicals had radical scavenging activity for 1,1-diphenyl-2-picrylhydrazyl, whereas neither NO-NIF nor nifedipine did. In addition, the NO-NIF radical more effectively quenched lipid peroxides than NO-NIF or nifedipine. Furthermore, NO-NIF attenuated the superoxide-derived free radicals in HUVECs stimulated with LY83583, and suppressed iron-nitrilotriacetic acid (Fe-NTA)-induced cytotoxicity in rat pheochromocytoma (PC12) cells. Our findings suggest that NO-NIF is a candidate for a new class of antioxidative drugs that protect cells against oxidative stress.     

Thin Films that Consist of CuO Mesocrystal Nanosheets: An Application of Microbial‐Mineralization‐Inspired Approaches to Thin‐Film Formation

Thin films of copper oxides can be synthesized on substrates by using approaches that are inspired by microbial mineralization processes. In nature, precipitates of manganese and iron oxides with controlled oxidation states and crystal phases are produced through biomineralization by microorganisms. We have previously reported microbial‐mineralization‐inspired approaches that are comprised of direct and intermediate routes for the controlled syntheses of transition‐metal oxides. Herein, these approaches are applied to the thin‐film formation and coating of copper oxides and a related compound with controlled crystal phases and morphologies. Thin films of CuO, Cu₂O, and Cu₂(OH)₃Cl were selectively synthesized by using direct or intermediate routes. Notably, CuO mesocrystal nanosheets formed a thin film over the whole of the substrate. The resultant CuO mesocrystal nanosheets showed enhanced properties for the electrochemical detection of dopamine. This study shows the potential applicability of microbial‐mineralization‐inspired approaches to thin‐film coatings.     

Formation of Nanostructured MnO/Co/Solid–Electrolyte Interphase Ternary Composites as a Durable Anode Material for Lithium‐Ion Batteries

Nanoporous MnO frameworks with highly dispersed Co nanoparticles were produced from MnCO₃ precursors prepared in a gel matrix. The MnO frameworks that contain 20 mol % Co exhibited excellent cycle performance as an anode material for Li‐ion batteries. The solid–electrolyte interphase (SEI) formed in the frameworks through the electrochemical reaction mediates the active materials, such as MnO, Mn, and Li₂O, during the conversion reaction in the charge–discharge cycle. The Co nanoparticles and SEI provide the electron and Li‐ion conductive networks, respectively. The ternary nanocomposites of the MnO framework, metallic Co nanoparticles, and embedded SEI are categorized as durable anode materials for Li‐ion batteries.     

Oblique detonation waves stabilized in rectangular-cross-section bent tubes

Oblique detonation waves, which are generated by a fundamental detonation phenomenon occurring in bent tubes, may be applied to fuel combustion in high-efficiency engines such as a pulse detonation engine (PDE) and a rotating detonation engine (RDE). The present study has experimentally demonstrated that steady-state oblique detonation waves propagated stably through rectangular-cross-section bent tubes by visualizing these waves using a high-speed camera and the shadowgraph method. The oblique detonation waves were stabilized under the conditions of high initial pressure and a large curvature radius of the inside wall of the rectangular-cross-section bent tube. The geometrical shapes of the stabilized oblique detonation waves were calculated, and the results of the calculation were in good agreement with those of our experiment. Moreover, it was experimentally shown that the critical condition under which steady-state oblique detonation waves can stably propagate through the rectangular-cross-section bent tubes was the curvature radius of the inside wall of the rectangular-cross-section bent tube equivalent to 14–40 times the cell width.     

High-power direct green laser oscillation of 598 mW in Pr(3+)-doped waterproof fluoroaluminate glass fiber excited by two-polarization-combined GaN laser diodes

We demonstrated a high-power and highly efficient Pr-doped waterproof fluoride glass fiber laser at 522.2 nm excited by two-polarization-combined GaN laser diodes and achieved a subwatt output power of 598 mW and slope efficiency of 43.0%. This system will enable us to make a vivid laser display, a photocoagulation laser for eye surgery, a color confocal scanning laser microscope, and an effective laser for material processing. Direct visible ultrashort pulse generation is also expected.     

Supramolecular Phosphatases Formed by the Self‐Assembly of the Bis(Zn2+–Cyclen) Complex,Copper(II), and Barbital Derivatives in Water

In our previous paper, we reported that a dimeric Zn²⁺ complex with a 2,2′‐bipyridyl linker (Zn₂L¹), cyanuric acid (CA), and a Cu²⁺ ion automatically assemble in aqueous solution to form 4:4:4 complex 3 , which selectively catalyzes the hydrolysis of mono(4‐nitrophenyl)phosphate (MNP) at neutral pH. Herein, we report that the use of barbital (Bar) instead of CA for the self‐assembly with Zn₂L¹ and Cu²⁺ induces 2:2:2 complexation of these components, and not the 4:4:4 complex, to form supramolecular complex 6 a , the structure and equilibrium characteristics of which were studied by analytical and physical measurements. The finding show that 6 a also accelerates the hydrolysis of MNP, similarly to 3 . Moreover, inspired by the crystal structure of 6 a , we prepared barbital units that contain functional groups on their side chains in an attempt to produce supramolecular phosphatases that possess functional groups near the Cu₂(μ‐OH)₂ catalytic core so as to mimic the catalytic center of alkaline phosphatase (AP).     

Preparation of arsenic‐containing white rice grains as calibration standards for X‐ray fluorescence analysis of total arsenic in cereals

A preparation method of arsenic‐containing white rice grains as calibration standards was developed for the X‐ray fluorescence (XRF) analysis of arsenic in rice grains. Calibration standards were prepared by adding 10 g of white rice grains (from Japan) to 100 ml methanol‐containing dimethylarsinic acid corresponding to 2–100 µg arsenic. The mixture was heated, dried at 150 °C, cooled to room temperature, and then stored in a silica gel desiccator. A total of 5.0 g of each calibration standard was packed into a polyethylene cup (32 mm internal diameter and 23 mm height) covered with a 6‐µm‐thick polypropylene film and then analyzed by wavelength‐dispersive XRF spectrometry. The calibration curve for arsenic obtained from the white rice grains containing arsenic showed good linearity over a concentration range of 0.21–5.00 mg kg^?1 arsenic. The limit of detection of arsenic was 0.080 mg kg^?1. To check the reliability of the XRF method, the concentrations of arsenic in six samples of grain cereals and two samples of flour were compared with those obtained by atomic absorption spectrometry after acid decomposition. The values obtained by both analytical methods showed good agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

Mössbauer and XRD analysis of corrosion products on weathering steel treated by wet-dry cycles using various solutions

Weathering steels (COR-TEN) were corroded by wet-dry cycles using a splay of various solutions in a laboratory. Corrosion products on weathering steel were characterized by X-ray diffractometry and Mössbauer spectrometry at room and low temperatures. Fine α-FeOOH, γ-FeOOH and γ-Fe ₂ O ₃ are fundamentally formed in various atmospheric conditions. β-FeOOH is additionally formed under the existence of chloride ions, but not formed when sulfate ions are coexisting. Spraying a NaF solution prevents the progress of corrosion.