Solvent-Free Reaction for Unsymmetrical Organodisulfides with High Purity and Application as Cathode-Active Materials.

Unsymmetrical disulfides, in which different organic groups are bonded to disulfide bonds, have been synthesized by cross-coupling reactions using thiols as substrates. However, due to the low-binding energy of unsymmetrical disulfides, its disproportionation occurs based on the side reactions with nucleophilic thiols, resulting in the impurity of symmetric disulfides. In this study, we developed a solvent-free synthesis method for unsymmetrical disulfides using thiosulfonates, thiols, and a base. This synthetic method enabled us to obtain highly pure diaryl-substituted unsymmetrical disulfides with particularly low-binding energy without control over the nucleophilicity and elimination properties of the substrate. Furthermore, it was observed that the disproportionation of unsymmetrical disulfides occurred in the solvent. This means that solvent-free condition is one of the factors to obtain unsymmetrical disulfides. As a new application of unsymmetrical disulfides, we applied unsymmetrical disulfides to cathode active materials of lithium batteries based on the reversible multi-electron redox activity of S-S bonds. The batteries using unsymmetrical disulfide cathode-active materials with a carbon nanotube exhibited initial capacities of 127 and 158 Ah/kg, equal to 42 and 53% of their theoretical ones. We demonstrated that unsymmetrical disulfides could be used as cathode-active materials for rechargeable batteries.

Assessment of Dye-Absorbed Eggshell Membrane Composites as Solid Polymer Electrolyte of Fuel Cells.

Recently, polymer electrolytes have been developed for high-performance and eco-friendly fuel cells. Among the candidates, eggshell membrane (ESM) has been promising because of its abundance to assemble various energy devices with low cost and its absorption ability of organic materials. In this work, we investigated fuel cells that included ESM-absorbing xanthene-, triphenylmethane-, and azo-type tar dye, which contained abundant hydrophilic groups, as polymer electrolytes. We found out two points: (1) that the fuel cells that included ESM-absorbing xanthene-type dye generated the highest I-V performance, and (2) the basic molecular structures of the tar dyes determined the correlation of the maximum power and proton conductivities.

Ultra-High-Capacity Lithium Metal Batteries Based on Multi-Electron Redox Reaction of Organopolysulfides including Conductive Organic Moieties.

Recently, organic polysulfides have been synthesized as cathode active materials exceeding the battery performance of sulfur. However, the conventional organic polysulfides have exhibited capacities lower than the theoretical capacity of sulfur because the π-organic moieties do not conjugate with the sulfur chains. In this work, the organopolysulfides, synthesized via inverse vulcanization using disulfide compounds, exhibited higher capacities equal to the theoretical capacity of sulfur because of enhanced electronic conductivity based on the conjugation between organic moieties and sulfur chains. Furthermore, the organopolysulfide including 1,3-dhitiol-2-thione moiety exhibited the highest capacity because of the enhanced electronic conductivity. This finding will pave the way to develop next-generation rechargeable batteries.

Total Synthesis of Sophoraflavanone H and Confirmation of Its Absolute Configuration.

Sophoraflavanone H (1) is a polyphenol with a hybrid-type structure containing 2,3-diaryl-2,3-dihydrobenzofuran and flavanone ring moieties. This compound and related analogues are promising leads for antimicrobial and antitumor drug development. Here we describe a total synthesis of 1 and its diastereomer. The dihydrobenzofuran and flavanone rings were constructed by a Rh-catalyzed asymmetric C-H insertion reaction and selective oxy-Michael reaction. The absolute configuration of 1 was established by X-ray crystallographic analysis and CD spectral investigation of synthetic derivatives.

Physicochemical and biopharmaceutical characterization of amorphous solid dispersion of nobiletin, a citrus polymethoxylated flavone, with improved hepatoprotective effects.

The present study aimed to develop an amorphous solid dispersion (SD) of nobiletin (NOB), a citrus polymethoxylated flavone, with the aim of improving its biopharmaceutical and hepatoprotective properties. SD formulation of NOB (NOB/SD) was prepared by wet-milling and subsequent freeze drying, and its stability and dissolution properties were characterized. The hepatoprotective effects and pharmacokinetic behavior of orally dosed NOB/SD were evaluated in rats. During the storage of NOB/SD for 4 weeks under accelerated conditions, there were no significant transitions in the appearance, particle size, and amorphousity of wet-milled NOB. In comparison with crystalline NOB, the NOB/SD exhibited significant improvement in the dissolution with a 10-fold higher dissolution rate. In a rat model of acute liver injury, repeated treatment with NOB/SD (2 mg NOB/kg) every 4 h led to marked attenuation of hepatic damage as evidenced by decreased ALT and AST, surrogate biomarkers for hepatic injury; however, crystalline NOB was found to be less effective. After oral administration of NOB/SD (2 mg NOB/kg) in rats, compared with crystalline NOB, improved pharmacokinetic behavior was observed with increases of bioavailability and hepatic delivery by ca. 7- and 6-fold, respectively, possibly leading to better hepatoprotection. Given the improved physicochemical and biopharmaceutical properties, the SD formulation strategy might be efficacious for enhancing the therapeutic potential of NOB.