Organic Crystalline Solid Electrolytes with High Mg-Ion Conductivity Composed of Nonflammable Ionic Liquid Analogs and Mg(TFSA)2.

The development of solid electrolytes with Mg-ion conductivity at room temperature is an important issue to achieve all-solid magnesium batteries. We focus on organic ionic crystals with Mg-ion conduction paths in addition to nonflammable and nonvolatile features as an innovative candidate of solid electrolytes with Mg-ion conductivity. Herein, we show the development of novel organic ionic crystals, [N(CH3)4-n(CH2CH3)n][Mg{N(SO2CF3)2}3] (n = 0 or 2), using analogs of ionic liquids, [N(CH3)4][N(SO2CF3)2] (N1111TFSA) and [N(CH3)2(CH2CH3)2][N(SO2CF3)2] (N1122TFSA), and magnesium salt, Mg{N(SO2CF3)2}2 (Mg(TFSA)2). We also report the crystal structures of the obtained crystals and the high Mg-ion conductivity of 10-4 S cm-1 under mild conditions of 80 °C in the solid state. These results indicate that organic ionic crystals with ion conduction paths have significant potential as safe solid electrolytes and provide insights into developing innovative Mg-ion conductors.

High Li-Ion Conductivity in Li{N(SO2F)2}(NCCH2CH2CN)2 Molecular Crystal.

There is an urgent need to develop solid electrolytes based on organic molecular crystals for application in energy devices. However, the quest for molecular crystals with high Li-ion conductivity is still in its infancy. In this study, the high Li-ion conductivity of a Li{N(SO2F)2}(NCCH2CH2CN)2 molecular crystal is reported. The crystal shows a Li-ion conductivity of 1 × 10-4 S cm-1 at 30 °C and 1 × 10-5 S cm-1 at -20 °C, with a low activation energy of 28 kJ mol-1. The conductivity at 30 °C is one of the highest values attainable by molecular crystals, whereas that at -20 °C is approximately 2 orders of magnitude higher than previously reported values. Furthermore, the all-solid-state Li-battery fabricated using this solid electrolyte demonstrates stable cycling, thereby maintaining 90% of the initial capacity after 100 charge-discharge cycles. The finding of high Li-ion conductivity in molecular crystals paves the way for their application in all-solid-state Li-batteries.

Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids.

In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

One-pot gram-scale rapid synthesis of MN4 complexes with 14-membered ring macrocyclic ligand as a precursor for carbon-based ORR and CO2RR catalysts.

Herein, CoN4, CuN4, and NiN4 complexes with a 14-membered ring hexaazamacrocycle ligand H2HAM were synthesised as precursors for ORR and CO2RR catalysts via a one-pot, gram-scale synthesis procedure, which involved microwave heating for only 10 min. Detailed structures of the obtained 14MR-MN4 complex were revealed by single-crystal X-ray diffraction measurements.

Stable hydrogen evolution from CdS-modified CuGaSe2 photoelectrode under visible-light irradiation.

The photoelectrochemical properties of CuGaSe2 modified by deposition of a thin CdS layer were investigated. The CdS layer formed a p-n junction on the surface of the electrode, improving its photoelectrochemical properties. There was an optimal CdS thickness because of the balance between the charge separation effect and light absorption by CdS. CdS-deposited CuGaSe2 showed high stability under the observed reaction conditions and evolved hydrogen continuously for more than 10 days.

Structural design of ionic conduction paths in molecular crystals for selective and enhanced lithium ion conduction.

The molecular crystals [Li{N(SO2CF3)2}{C6H4(OCH3)2}2] and [Li{N(SO2CF3)2}{C6F2H2(OCH3)2}2] with solid-state lithium ion conductivity have been synthesized by the addition of two equivalents of 1,2-dimethoxybenzene or 1,2-difluoro-4,5-dimethoxybenzene to Li{N(SO2CF3)2}, respectively. Single-crystal X-ray diffraction analysis revealed the formation of ionic conduction paths with an ordered arrangement of lithium ions in these crystal structures, afforded by the self- assembled stacking of molecular-based channels consisting of N(SO2CF3)2 anion and 1,2-dimethoxybenzene frameworks as a result of intermolecular aromatic and hydrogen interactions. These compounds show selective lithium ion conductivity as the anions behave as a component unit of the conduction paths. The relationship between the crystal structure and ionic conductivity of the molecular crystals provides a clue to the development of novel solid electrolytes based on molecular crystals showing fast and selective lithium ion conduction.

Molecular ionics in supramolecular assemblies with channel structures containing lithium ions.

A novel trilithium compound, Li(3)[B(C(6)H(4)O(2)){O(CH(2)CH(2)O)(3)CH(3)}(2)][N(SO(2)CF(3))(2)](2) (1-2.0), with solid-state ionic conductivity was synthesized. The crystal structure of 1-2.0 consists of the one-dimensional ionic conduction paths. The paths were afforded as a result of the self-assembled stacking of the component molecules of 1-2.0 with channel structures containing lithium ions. In this supramolecule, one lithium ion holds the component molecules in specific positions to construct a supramolecular structure with thermally stable ionic conduction paths and the others behave as carrier ions exhibiting selective lithium-ion conductivity. Owing to the existence of both roles for the lithium ions, this electrolyte shows selective lithium-ion conductivity.

Non-centrosymmetric coordination polymer with a highly hindered octahedral copper center bridged by mandelate.

A novel chiral coordination polymer, [Cu(C(6)H(5)CH(OH)COO)(µ-C(6)H(5)CH(OH)COO)] (1-L and 1-D), was synthesized through a reaction of copper acetate with L-mandelic acid at room temperature. Although previously reported copper mandelate prepared by hydrothermal reaction was a centrosymmetric coordination polymer because of the racemization of mandelic acid, the current coordination polymer shows noncentrosymmetry and a completely different structure from that previously reported. The X-ray crystallography for 1-L revealed that the copper center of the compound showed a highly distorted octahedral structure bridged by a chiral mandelate ligand in the unusual coordination mode to construct a one-dimensional (1D) zigzag chain structure. These 1D chains interdigitated each other to give a layered structure as a result of the formation of multiple aromatic interactions and hydrogen bonds between hydroxyl and carboxylate moieties at mandelate ligands. The coordination polymer 1-L belongs to the noncentrosymmetric space group of C2 to show piezoelectric properties and second harmonic generation (SHG) activity.

High Durability of a 14-Membered Hexaaza Macrocyclic Fe Complex for an Acidic Oxygen Reduction Reaction Revealed by In Situ XAS Analysis.

Nonplatinum metal (NPM) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) have been developed; however, NPM catalysts still need to be improved in terms of both their catalytic activity and durability. To overcome these problems, an Fe active site contained within a more compact ligand than conventional, porphyrinic, 16-membered ring ligands, or more specifically, a hexaaza macrocyclic ligand with a 14-membered ring (14MR), was developed. In this study, the durability of the Fe-14MR complex was compared to that of Fe phthalocyanine (FePc), which has a 16-membered ring ligand, using in situ X-ray absorption spectroscopy; demetalation of the Fe complexes was directly observed during electrochemical experiments performed under acidic ORR conditions. It was found that Fe-14MR is significantly more resistant to demetalation than FePc during the ORR.

Electrosprayed synthesis of red-blood-cell-like particles with dual modality for magnetic resonance and fluorescence imaging.

Red blood cells (RBCs) are able to avoid filtration in the spleen to prolong their half-time in the body because of their flexibility and unique shape, or a concave disk with diameter of some 10 µm. In addition, they can flow through capillary blood vessels, which are smaller than the diameter of RBCs, by morphing into a parachute-like shape. In this study, flexible RBC-like polymer particles are synthesized by electrospraying based on electrospinning. Furthermore, magnetite nanoparticles and fluorescent dye are encapsulated in the particles via in situ hydrolysis of an iron-organic compound in the presence of celluloses. The superparamagnetic behavior of the particles is confirmed by low-temperature magnetic measurements. The particles exhibited not only a dark contrast in magnetic resonance imaging (MRI), but also effective fluorescence. The RBC-like particles with flexibility are demonstrated to have a dual-modality for MRI and fluorescence imaging.

Size-controlled submicrometer hollow spheres constituted of ZnO nanoplates from layered zinc hydroxide.

A layered zinc compound is afforded by the heating of zinc acetate dihydrate with mandelic acid in dibenzyl ether. Thermolysis of the layered compound results in the formation of hollow spheres constructed from plate-like ZnO nanocrystals (NCs) in high yield. Size-controlled hollow spheres with a 690 nm diameter (size variation = 6.0%) are obtained by thermal treatment at 300 degrees C for 15 h. In this reaction, the mandelate moiety plays important roles not only in morphology control of ZnO NCs but also for the formation of hollow structures constituted of ZnO nanoplates.

Effect of retinoic acid on gene expression profiles of bovine intramuscular preadipocytes during adipogenesis.

To investigate genes involved in intramuscular adipogenesis in ruminants, 16 genes with dramatic variable expression were selected. These were selected from the differentiation- and proliferation-phase libraries of our previous serial analysis of gene expression (SAGE) studies of a clonal bovine intramuscular preadipocyte (BIP) cell line. We harvested the BIP cells over 12 days after adipogenic stimulation with all-trans retinoic acid (ATRA). Quantitative real-time PCR confirmed the earlier SAGE study results of the expression patterns of 15 of the genes. On day 6, TG accumulation increased significantly in the BIP cells but was completely inhibited in the 3T3-L1 cells (the monogastric reference). ATRA enhanced expression levels of six genes whereas it suppressed expression of eight genes on day 3 of adipogenesis in the BIP cells. Forty-eight hours after transfection, the messenger RNA expression level of the adipose differentiation-related protein (ADFP), encoded by one of the upregulated genes, in the ADFP small interference RNA (siRNA)-transfected cells was 3.5% of that in negative control-transfected cells. Also, 6 days after induction the TG level in the ADFP siRNA-transfected cells was 21.8% lower than that in negative control-transfected cells. This analysis of gene expression profiles after ATRA treatment will contribute to our understanding of the molecular mechanisms involved in bovine intramuscular adipogenesis.

Plastic crystalline lithium salt with solid-state ionic conductivity and high lithium transport number.

Plastic crystallinity of lithium salt, [LiB(OCH(2)CH(2)OCH(3))(4)] (1), and its solid-state ionic conductivity are disclosed. The addition of small amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to borate 1 led to the drastic increase of the ionic conductivity and lithium transport number of the electrolyte.

High-frequency, magnetic-field-responsive drug release from magnetic nanoparticle/organic hybrid based on hyperthermic effect.

Magnetic nanoparticles (MNPs) generate heat when a high-frequency magnetic field (HFMF) is applied to them. Induction heat is useful not only for hyperthermia treatment but also as a driving force for drug-release. beta-Cyclodextrin (CD) can act as drug container because of its inclusion properties. Drugs incorporated in the CD can thus be released through the use of induction heating, or hyperthermic effects, by applying a HFMF. In this study, we have synthesized folic acid (FA) and CD-functionalized superparamagnetic iron oxide nanoparticles, FA-CD-SPIONs, by chemically modifying SPIONs derived from iron(III) allylacetylacetonate. FA is well-known as a targeting ligand for breast cancer tumor and endows the SPIONs with cancer-targeting capability. Immobilization of FA and CD on spinel iron oxide nanoparticles was confirmed by Fourier transform IR (FTIR) and X-ray photoelectron spectroscopy (XPS). The FA-CD-SPIONs have a hydrodynamic diameter of 12.4 nm and prolonged stability in water. They are superparamagnetic with a magnetization of 51 emu g(-1) at 16 kOe. They generate heat when an alternating current (AC) magnetic field is applied to them and have a specific absorption rate (SAR) of 132 W g(-1) at 230 kHz and 100 Oe. Induction heating triggers drug release from the CD cavity on the particle - a behavior that is controlled by switching the HFMF on and off. The FA-CD-SPIONs are noncytotoxic for cells. Thus, FA-CD-SPIONs can serve as a novel device for performing drug delivery and hyperthermia simultaneously.

Structural Features of [(CpPPh2AuCl)2ZrCl2]: exploring the limits of aurophilic interactions.

The reaction of [(CpPPh(2))(2)ZrCl(2)] (1 a) with two molar equivalents of (Me(2)S)AuCl gave the trimetallic complex [(CpPPh(2)AuCl)(2)ZrCl(2)] (6). Crystalline complex 6 shows a conformational structure that features both P--Au--Cl vectors oriented toward the open front side of the bent metallocene wedge. Quantum-chemical calculations rationalized the absence of an aurophilic AuAu interaction in 6 by showing that a combination of noncovalent forces overcompensates any possible attractive AuAu interaction.

Hyperzincemia with systemic inflammation: a heritable disorder of calprotectin metabolism with rheumatic manifestations?

A boy had infantile-onset systemic inflammation, growth failure, hepatosplenomegaly, anemia, leukocytopenia, progressive muscular dystrophy, and hypercalprotectinemia, resulting in marked hyperzincemia. His mother had a history of chronic arthritis since childhood and also showed hypercalprotectinemia/hyperzincemia. We postulate an inherent defect in calprotectin metabolism.