Organic Dicarboxylate Negative Electrode Materials with Remarkably Small Strain for High‐Voltage Bipolar Batteries

As advanced negative electrodes for powerful and useful high‐voltage bipolar batteries, an intercalated metal–organic framework (iMOF), 2,6‐naphthalene dicarboxylate dilithium, is described which has an organic‐inorganic layered structure of π‐stacked naphthalene and tetrahedral LiO₄ units. The material shows a reversible two‐electron‐transfer Li intercalation at a flat potential of 0.8 V with a small polarization. Detailed crystal structure analysis during Li intercalation shows the layered framework to be maintained and its volume change is only 0.33 %. The material possesses two‐dimensional pathways for efficient electron and Li⁺ transport formed by Li‐doped naphthalene packing and tetrahedral LiO₃C network. A cell with a high potential operating LiNi_0.5Mn_1.5O₄ spinel positive and the proposed negative electrodes exhibited favorable cycle performance (96 % capacity retention after 100 cycles), high specific energy (300 Wh kg^?1), and high specific power (5 kW kg^?1). An 8 V bipolar cell was also constructed by connecting only two cells in series.     

Mineral Composition of Seawater Bittern Nigari Products and Their Effects on Changing of Browning and Antioxidant Activity in the Glucose/Lysine Maillard Reaction

Seawater bittern (nigari) is a concentrated solution remaining after the crystallization process of salt that has been used as a coagulant for tofu. Recently, various nigari products are distributed in the East Asia. To clarify the properties of nigari products, major mineral composition of six nigari products was determined. Then, effects of the nigari on the browning and antioxidant activity during the glucose/lysine Maillard reaction were investigated. Though the predominant cation was Mg²⁺, the content was varied by each product (0.88–6.49 mol/L). The other major ion contents were also varied. Each 0.5 mol/L of d-glucose and l-lysine were incubated with the nigari (5–50 % (v/v)) or nigari-related salts (1 or 2 mol/L). The browning (OD at 465 nm) and antioxidant activity (1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging capacity and ferrous-reducing power) were increased remarkably by the nigari containing high Mg²⁺ content. The browning tended to be high with sulfates (Na₂SO₄, (NH₄)₂SO₄). On the other hand, high content of MgCl₂ decreased slightly the browning and antioxidant activity. These results suggest that the reaction and antioxidant activities were affected not only by salinity and cations but also by anions and other elements in the nigari.     

Mechanochromic Delayed Fluorescence Switching in Propeller‐Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli‐Responsive Intramolecular Charge‐Transfer Excited States

Herein, the universal design of high‐efficiency stimuli‐responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli‐triggered TADF switching for a series of carbazole–isophthalonitrile‐based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X‐ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited‐state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light‐emitting diodes using a single TADF emitter.     

Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation,Carboindation, Heterogallation,and Heteroindation

Organogallium and ‐indium compounds are useful reagents in organic synthesis because of their moderate stability, efficient reactivity and high chemoselectivity. Carbogallation and ‐indation of a carbon‐carbon multiple bond achieves the simultaneous formation of carbon‐carbon and carbon‐metal bonds. Heterogallation and ‐indation construct carbon‐heteroatom and carbon‐metal bonds. Therefore, these reaction systems represent a significant synthetic method for organogalliums and ‐indiums. Many chemists have attempted to apply various types of unsaturated compounds such as alkynes, alkenes, and allenes to these reaction systems. This minireview provides an overview of carboindation and ‐gallation as well as heteroindation and ‐gallation.     

Water barrier characteristics of plasma polymers of perfluorocarbons

Perfluorocarbon monomers such as C₂F₄, C₂F₆, C₄F₁₀, and mixtures thereof with H₂, were subjected to plasma polymerization and deposited onto low-density polyethylene (LDPE) substrates. The effect of plasma conditions, surface characteristics, and surface dynamics of plasma polymers on their ability to improve the resistance to water vapor permeation was investigated. An optimum discharge energy density was found for a monomer which provided the greatest reduction water vapor permeability. Although all of the plasma polymers show higher hydrophobicity than polyethylene, the reduction in water vapor permeability is not uniquely related to water contact angle. The surface-dynamic stability of a plasma polymer surface was found to be the key factor in determining the barrier performance of the plasma polymer. The extent of change of surface-configuration after water immersion strongly correlated with the improvement in the water vapor permeation resistance. Plasma polymers with the higher surface-dynamic stability provided the better water barrier coating applied on LDPE films. © 1996 John Wiley & Sons, Inc.     

Protecting structure analyses of organic molecule-protected nanoscopic noble metal clusters

The stabilizing structure of cationic surfactant-protected platinum clusters in water and tertiary amine-protected rhodium clusters in chloroform, prepared by photo- and hydrogen-reduction, respectively, was investigated. These nanoscopic noble metal clusters present a narrow size distribution and are stable. The structural information of protective organic molecules on the surface of metal clusters was studied by transmission electron microscopy and hydrodynamic radius measurements according to the Taylor dispersion method. The size of the entire cluster with the protective layer surrounding the metal surface, obtained as Stokes' radii by the Taylor dispersion method, is considered to be fairly consistent with the sum of the naked particle size, obtained by transmission electron micrographs, and the size of the adsorbed protective layer, supporting the conformational information.     

XAFS spectra from X-ray fluorescence Kβ line using conventional energy-discriminating detector

X-ray fluorescence spectra of copper (Cu) metal, copper monoxide (CuO), and potassium chromate (K₂CrO₄) were recorded as a function of incident X-ray energy near the Cu K-edge and chromium (Cr) K-edge, respectively, using a conventional silicon drift detector. The spectra contained components due to elastic, inelastic, and multiple scattering, in addition to the Kα and Kβ lines. Cu and Cr K-edge X-ray absorption fine structure (XAFS) spectra of Cu, CuO, and K₂CrO₄ were obtained by an intensity analysis of the Kα and Kβ lines. The intensity of the Kβ line for the different incident photon energies was obtained by numerically removing the additional scattering components using the MUSCAT program. These spectra exhibited a jump near the K absorption edges, which reproduced the spectral features obtained in transmission mode for both Cu, CuO, and K₂CrO₄. A chemical shift was also clearly identified in the X-ray absorption near edges structure using the X-ray fluorescence Kβ line. In addition, the Cr K-edge extended XAFS spectrum of K₂CrO₄ was clearly observed using the Cr Kβ fluorescent line. The XAFS measurements on the Kα and Kβ lines are possible, and they carry equally valuable information.     

Magnetically Enhanced 15 kHz Glow Discharge of Methane

This work deals with the luminous chemical vapour deposition (plasma polymerization) of hydrocarbon polymeric thin films in a magnetic field enhanced discharge of methane. The films were deposited on 4″ <111> single crystal silicon substrates. We investigated the influence of the different glow discharge parameters (e.g. pressure, flow rate, power input, etc.) on the deposition rate of methane and the refractive index of the resulting polymeric films, as well as the distribution of these parameters across the wafer. We used a Shinko Seiki Plasma Polymerization equipment with a bell jar reactor comprising two electrodes connected to a symmetric AC power supply of 15 kHz. Two magnetrons were formed by placing two circular shaped concentric magnetic poles behind each electrode. The substrates were attached on both sides of a rotating wheel held at a floating potential in the middle of the two electrodes. This equipment allowed us to vary a single parameter and keep the other parameters constant over the whole process. We measured the thickness and the refractive index and their distribution over the wafer. The effect of the system pressure, decoupled from the effect of flow rate, is explained by the characteristic nature of luminous gas phase and by the polymerization/deposition mechanism of luminous chemical vapour deposition.     

Microstructure of metallic copper nanoparticles/metallic disc interface in metal–metal bonding using them

This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu²⁺ (0.01 M (CH₃COO)₂Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10^?4 M citric acid and 5 × 10^?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H₂ gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd.