Programmed‐Assembly System Using DNA Jigsaw Pieces

A novel method for assembling multiple DNA origami structures has been developed by using designed 2D DNA origami rectangles, so‐called “DNA jigsaw pieces” that have sequence‐programmed connectors. Shape and sequence complementarity were introduced to the concavity and convex connectors in the DNA rectangles for selective connection with the help of nonselective π‐stacking interactions between the side edges of the DNA jigsaw piece structures. Single DNA jigsaw piece units were assembled into unidirectional nanostructures with the correct alignment and uniform orientation. Three and five different DNA jigsaw pieces were assembled into predesigned and ordered nanostructures in a programmed fashion. Finally, three‐, four‐, and five‐letter words have been displayed by using this programmed DNA jigsaw piece system.     

A novel proximity effect between superconductor and magnetic manganese oxide

A novel proximity effect between superconductor and magnetic manganese oxide has been found. To investigate interactions between superconductor and magnetic materials, we have fabricated both trilayered-type and coplanar-type junctions and investigated their current-voltage characteristics. The magnetic material was La_1-x Ca _x MnO _z (LCMO) or La_1-x Sr _x MnO _z (LSMO) manganese oxide. In YBCO/LCMO/YBCO junctions, supercurrents were observed through a magnetic barrier as thick as 500 nm. This phenomenon was also confirmed by coplanar junctions. The effect of magnetism of the barrier material was investigated. It was found that this proximity effect occurred only in a limited region where spin fluctuations are considered to exist.     

Photoelectrochemical decomposition of water into H2 and O2 on porous BiVO4 thin-film electrodes under visible light and significant effect of Ag ion treatment

The photoelectrochemical properties of porous BiVO4 thin-film electrodes on conducting glass for H2 production from water under visible light were investigated. BiVO4 films were prepared by the metal-organic decomposition method, and particles were 90-150 nm in diameter. Under visible-light irradiation, H2 and O2 evolved in a stoichiometric ratio (H2/O2 = 2) from an aqueous solution of Na2SO4 with an external bias. The photocurrent increased with addition of methanol. The band structure of BiVO4 was investigated by open-circuit potential, flat-band potential, X-ray photoelectron spectroscopy, and calculations based on density functional theory. The top of the valence-band potential of BiVO4 was shifted negatively compared to the potentials of the conventional oxide semiconductors without Bi. We surmise that hybridization between the O-2p and Bi-6s orbitals might contribute to the negative shift of the BiVO4 valence band. Treatment with an aqueous solution of AgNO3 improved the photocurrent of the BiVO4 electrode significantly. The maximum incident photon-to-current conversion efficiency at 420 nm was 44%. This value was the highest among mixed-oxide semiconductor electrodes under visible light irradiation. AgNO3 treatment also improved the stability of the photocurrent. The Ag+ ion in/on the BiVO4 catalyzed the intrinsic photogeneration of oxygen with the holes.     

Elucidation of factors obstructing quality improvement of MOVPE-grown InN

A systematic study of the crystallographic and electrical/optical properties of MOVPE-grown InN was performed, and the factors that restrict the quality of MOVPE InN were elucidated. The quality of grown InN is highly dependant on the thermal decomposition of NH₃ as a nitrogen source. At a lower growth temperature (~550 °C) a shortage of active nitrogen, due to a lower decomposition rate of NH₃, causes the formation of N vacancies in the grown InN. With increasing growth temperature, a more stoichiometric crystal is grown and the electrical/optical properties improve. At temperatures above 600 °C, however, deterioration occurs at the N-face of In-polar InN near the substrate interface. This deterioration results in the formation of a porous layer during high temperature (~650 °C) growth. There are a few evidences that show that the hydrogen produced by NH₃ decomposition causes this degradation. Thus, improving the quality of MOVPE-grown InN by changing the growth temperature can be difficult. However, a short growth time at a high growth rate and a relatively high temperature is one effective way to solve this dilemma, and one can achieve carrier concentrations as low as 4×10¹⁸ cm⁻³ by growth at 650 °C for 30 min.     

Excited states of poly(vinyl cinnamate) studied by low-energy electron loss spectroscopy and inmdo/s computation

The low-energy electron loss spectrum of poly (vinyl cimiamate) film was measured as a function of impact energy. Excited states of the polymer were also investigated by an INDO/S MO calculation using cinnamic acid as a model. The calculated results agree well with the experimental results both for triplet and singlet excitations, indicating that the observed excitations (2.8, 4.5, 5.8 and 7 eV) are localized in the pendant group of the polymer.     

A novel synthetic procedure of vinylacetamide and its free radical polymerization

The pyrolysis of N-(α-methoxyethyl) acetamide, which was obtained by one-step reaction of acetamide, acetaldehyde, and methanol, gave N-vinylacetamide (NVA) in a good yield. The polymerizability and copolymerizability of NVA were studied. Free radical polymerization was carried out in the presence of radical initiator or by γ-ray irradiation. The monomer reactivity ratios of NVA were estimated in the copolymerization with acrylamide, vinyl acetate, and methyl methacrylate. The solvents were found to influence the monomer reactivity ratio. NVA showed a typical copolymerizability as nonconjugated vinyl monomer, and Q and e values were obtained in DMF as 0.16 and ?1.57, respectively.     

Iodine(V) reagents in organic synthesis. Part 1. Synthesis of polycyclic heterocycles via Dess-Martin periodinane-mediated cascade cyclization: generality, scope, and mechanism of the reaction

The scope, generality, and mechanism of the Dess-Martin periodinane-mediated cyclization reaction of unsaturated anilides discovered during the total synthesis of the CP-molecules (phomoidrides A and B) are delineated. A plethora of heterocyclic compounds are accessible by employing gamma,delta-unsaturated amides (derived from anilines and carboxylic acids), urethanes, or ureas (derived from isocyanates and allylic alcohols and amines) as substrates. Optimization of the reaction led to room-temperature conditions, while isotope labeling studies allowed a mechanistic rationale for this cascade reaction.     

The Catalysis of Vapor-Phase Beckmann Rearrangement for the Production of ε-Caprolactam

Recently, Sumitomo Chemical Co., Ltd. developed the vapor-phase Beckmann rearrangement process for the production of -caprolactam. In the process, cyclohexanone oxime is rearranged into -caprolactam using a zeolite as a catalyst instead of sulfuric acid. EniChem in Italy developed the ammoximation process that involves the direct production of cyclohexanone oxime without producing any ammonium sulfate. Sumitomo Chemical Co., Ltd. has commercialized the combined process of vapor-phase Beckmann rearrangement and ammoximation in 2003.In this paper, the authors focus on some aspects of the vapor-phase Beckmann rearrangement catalysis. A solid catalyst that is mainly composed of a high-silica MFI zeolite (Silicalite-1) has been developed for the vapor-phase Beckmann rearrangement. This catalyst does not possess acidity that can be detected by ammonia TPD. Methanol fed into the reactor with cyclohexanone oxime improves the yield of caprolactam. Methanol reacts with terminal silanols on the zeolite surface and converts them to methoxyl groups. The modification of the catalyst by methanol has an important role for the Beckmann rearrangement reaction.Nest silanols located just inside the pore mouth of the MFI zeolite are supposed to be the active sites of the catalyst. We propose that the coordination between the NOH group of cyclohexanone oxime molecule and the nest silanols through hydrogen bonding is responsible for the reaction. The reaction mechanism of Beckmann rearrangement under vapor-phase conditions is the same as in the liquid phase, namely, the alkyl group in anti-position against the hydroxyl group of the oxime migrates to the nitrogen atom's position.