Three-dimensionally arrayed and mutually connected 1.2-nm nanopores for high-performance electric double layer capacitor

Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140-190 F g(-1)) and volumetric (75-83 F cm(-3)) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g(-1). This extraordinary high performance is attributed to the unique pore structure.     

NO reduction by C3H6 over apatite-type A10(PO4)6(OH)2 (A?=?Ca and Sr)-supported Pt catalysts

A₁₀(PO₄)₆(OH)₂ (A = Ca and Sr)-supported Pt catalysts were prepared and their catalytic activity in NO reduction were investigated. The Sr₁₀(PO₄)₆(OH)₂-supported catalyst had high catalytic activity in the C₃H₆?CNO?CO₂ reaction; the activity was higher than that of the ??-Al₂O₃-supported catalyst at 300 °C. The basicity of the apatite supports would affect the chemical state of Pt on catalyst, resulting in promotion of NO reduction.     

Copolymerization of optically active N-bornylmaleimide with vinyl monomers

Optically active N-bornylmaleimide (NBMI) was copolymerized with styrene, methyl methacrylate, and vinylidene chloride with a free-radical catalyst to obtain optically active copolymers. The monomer reactivity ratios for the radical copolymerization of NBMI (M₂) with styrene, methyl methacrylate, and vinylidene chloride were: ST-NBMI, r₁ = 0.13, r₂ = 0.05; MMA-NBMI, r₁ = 2.02, r₂ = 0.16; VCl₂-NBMI, r₁ = 1.15, r₂ = 0.47. The Q-e values for NBMI were Q₂ = 0.48 and e₂ = +1.47. The specific rotation and optical rotatory dispersion of these copolymers were measured. The correlation between the specific rotation and composition of these copolymers was not linear. The value of λ_c for each copolymer was independent of the copolymer composition and the comonomer, being 260 mμ for the St-NBMI system, 262 mμ for the MMA-system, and 260 mμ for the VCl₂-NBMI system. The effects of solvents and temperature on the specific rotation of these copolymers were investigated.     

Optically active copolyamides by melt and solution condensation polymerization

The melt and solution condensation copolymerization of nylon salts which were prepared from d-camphoric acid and adipic acid with hexamethylenediamine were carried out, and optically active copolyamides were obtained. The copolyamides obtained had a positive specific rotation. The specific rotations for the copolyamides increased with increasing content of d-camphoryl units in the copolymers. The optical rotatory dispersion of the copolyamides had positive curves and were found to fit the simple Drude equation. The λ_c values of the polymers obtained by the melt and solution condensation polymerization were 241 mμ and 245 mμ, respectively.     

Metal-containing initiator systems. IV. Polymerization of methyl methacrylate by systems of some activated metals and organic halides

A study of the polymerization of methyl methacrylate initiated by the binary systems of some activated metals and organic halides has been made. It was found that the initiator activities of these systems were greatly dependent on the kind and the preparation or activation method of the metals (i.e., oxidation potential, surface area, and purity), and also on the kind of organic halides (i.e., bond-dissociation energy of their carbon–halogen bonds). From the kinetic studies of the polymerization at 60°C with the system reduced nickel–carbon tetrachloride, the rate of polymerization was found to be proportional to the monomer concentration and to the square root of concentration of both nickel and carbon tetrachloride at the lower concentration range of carbon tetrachloride, indicating that the system induced the radical polymerization. A similar conclusion was also obtained from the copolymerization with styrene with this system at 60°C, i.e., the resulting copolymer composition curve was in agreement with that obtained with azobisisobutyronitrile (AIBN). The apparent overall activation energy for the methyl methacrylate polymerization with this system was estimated to be 7.5 kcal/mole, which was considerably lower than that with AIBN. On the basis of the results obtained, an initiation mechanism for the polymerization with these initiator systems is presented and discussed.     

Novel water-soluble sedative-hypnotic agents: isoindolin-1-one derivatives

We developed new intravenous sedative-hypnotic compounds with the isoindolin-1-one skeleton focusing on the water-soluble property and in vivo safety. We synthesized approximately 170 derivatives and evaluated their hypnotic effects by intravenous administration of the compounds to mice. A series of the 2-phenyl-3-[2-(4-methyl-1-piperazinyl)-2-oxoethyl]isoindolin-1-one analogs, 3(-), 5(-), 27(-), and 47(-) [JM-1232(-)], showed potent sedative-hypnotic activity with good water solubility and a wide safety margin. The hypnotic doses (HD50s) of these 4 compounds when administered to mice were 2.35, 1.90, 2.17, and 3.12 mg/kg, respectively, and the lethal doses (LD50s) were 88.67, 64.69, >120, and >120 mg/kg, respectively. The therapeutic indexes (LD50/HD50) were 37.73, 34.05, >55.30, and >38.46, respectively. Among these compound, 47(-) [JM-1232(-)] is being considered as the most potential candidate for clinical trials in humans.     

Specific isolation of N-terminal fragments from proteins and their high-fidelity de novo sequencing

A new method to determine N-terminal amino acid sequences of multiple proteins at low pmol level by a parallel processing has been developed. The method contains the following five steps: (1) reduction, S-alkylation and guanidination for targeted proteins; (2) coupling with sulfosucccimidyl-2-(biotinamido)ethyl-1,3-dithiopropionate(sulfo-NHS-SS-biotin) to N(alpha)-amino groups of proteins; (3) digestion of the modified proteins by an appropriate protease; (4) specific isolation of N-terminal fragments of proteins by affinity capture using the biotin-avidin system; (5) de novo sequence analysis of peptides by MALDI-TOF-/MALDI-TOF-PSD mass spectrometry with effective utilization of the CAF (chemically assisted fragmentation) method.1 This method is also effective for N-terminal sequencing of each protein in a mixture of several proteins, and for sequencing components of a multiprotein complex. It is expected to become an essential proteomics tool for identifying proteins, especially when used in combination with a C-terminal sequencing method.     

Ba-catalyzed direct Mannich-type reactions of a beta,gamma-unsaturated ester providing beta-methyl aza-Morita-Baylis-Hillman-type products

Barium-catalyzed direct Mannich-type reactions of a beta,gamma-unsaturated ester are described. The Ba-catalyst not only promoted the Mannich-type reactions, but also isomerized Mannich adducts to afford beta-methyl aza-Morita-Baylis-Hillman-type products in 61-88% yield from various aryl, heteroaryl, and alkyl imines. Preliminary trials on enantioselective variants with a chiral biaryldiol ligand gave products in up to 80% ee.     

Tubular structures bearing channels in organic crystals composed of adamantane-based macrocycles

Five macrocyclic molecules (1–5) were efficiently synthesized from the dimerization and trimerization of di-substituted adamantane derivatives, which were composed of three different aromatic units and two different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with channels that assembled into three-dimensional networks through CH/π interactions.