Bulletin of the Chemical Society of Japan

Pandian, Ganesh N; Sugiyama, Hiroshi

doi: 10.1246/bcsj.20160062pmid: N/A

In the natural cellular environment, nucleic acid biomolecules like DNA have biological implications via structural modifications and through precise coordination with other biomolecules in the local environment. Here, we detail the design of nature-inspired smart biomaterials that are based on the chemical biology of nucleic acids. N-Methylpyrrole (P) and N-methylimidazole (I) polyamides (PIPs), sequence-specific DNA-binding molecules have been, developed to image specific DNA sequences and to alter gene expression inside the living cells. The self-assembling feature of DNA was harnessed to achieve the programmed assembly of nanostructures with different dimensions. Also, the advanced DNA architectures with well-defined properties allowed the real-time visualization of the complicated single-molecule interactions, which in-turn provided vital intracellular mechanistic information. The molecular recognition properties of DNA were exploited to design biologically inspired hybrid catalysts for sustainable organic synthesis. Our review could serve as a guidebook for researchers who aim to develop nucleic acid-based synthetic biomaterials.

Jabbari, Morteza; Jabbari, Azam

doi: 10.1246/bcsj.20160095pmid: N/A

The antioxidant ability of bioactive agent hesperidin was assessed in terms of radical-scavenging activity (RSA) against the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical in aqueous colloidal media containing micelle using UV–vis spectrophotometry. The DPPH assay was carried out at 25.0 ± 0.1 °C and cationic surfactant CTAB and anionic surfactant SDS at various concentrations above the critical micelle concentration (CMC). The rates of the antioxidant reaction (Rs) of hesperidin were also measured in the micelle systems. The activity and rate of the DPPH radical scavenging by hesperidin were found to depend on concentration and nature of the surfactants used, so that both RSA and Rs values increase with increasing concentration of micelles CTAB and SDS. Finally, the micelle effects on the antioxidant efficiency were explained based on possible interaction modes between hesperidin and the micellar surfaces.

Honda, Takuya; Ishida, Yuka; Arai, Tatsuo

doi: 10.1246/bcsj.20160094pmid: N/A

Introduction of a formyl group greatly increased the fluorescence emission of the tautomer produced via intramolecular hydrogen-atom transfer reaction of 2-hydroxybenzazole (HBX) derivatives.

Fukaya, Yukinobu; Asai, Ryo-ichi; Kadotani, Shiho; Nokami, Toshiki; Itoh, Toshiyuki

doi: 10.1246/bcsj.20160073pmid: N/A

Extraction of polysaccharides from Japanese cedar using ionic liquids has been demonstrated. To this aim, eleven types of phosphonate ionic liquids have been synthesized, their properties investigated, and applied to biomass processing. All ionic liquids prepared display strong hydrogen-bonding characteristics of Kamlet–Taft parameters (β > 1.1) which enabled the effective extraction of polysaccharides from Japanese cedar. In particular, 15 wt % of polysaccharides was extracted from Japanese cedar powder using 1-(3-methoxypropyl)-3-methylimidazolium ethyl ethylphosphonate. Since the ionic liquid is easily prepared using conventional reagents and might be applicable to large-scale reactions, it is expected that practical polysaccharide extraction using the ionic liquid might be possible from a wide variety of biomass resources.

Modak, Arindam; Yamanaka, Ken-ichi; Goto, Yasutomo; Inagaki, Shinji

doi: 10.1246/bcsj.20160105pmid: N/A

Conjugated microporous polymers (CMPs) have recently been investigated as an alternative approach to light-to-chemical energy conversion. In a previous paper, we reported an easy, safe, and low-cost synthesis of a 9,9′-spirobifluorene-based conjugated microporous organic polymer (COP-3), which had a large surface area and large micropore volume. Herein, we report photocatalytic H2 evolution from water using Pt-loaded COP-3 (Pt/COP-3). H2 was successfully evolved under irradiation with visible light (>380 nm) on COP-3 dispersed in distilled water containing triethanolamine (TEOA, sacrificial agent) and a Pt source (H2PtCl6). The HOMO and LUMO energy levels for COP-3 were positive and negative enough to oxidize TEOA and reduce PtCl62− and H+, respectively. The stability of Pt/COP-3 further underlines the merit of COP-3 as a heterogeneous photosensitizer.

Mukawa, Kei; Oyama, Naganobu; Shinmi, Toshitaka; Sekine, Yasushi

doi: 10.1246/bcsj.20160137pmid: N/A

We synthesized a characteristic graphene-layered carbon particle composite using pyrolysis of hydrocarbon in an electric field and consecutive activation treatment under CO2 atmosphere. TEM, N2 adsorption isotherm, Raman spectroscopy, and XPS revealed structural features of this unique composite. Graphenes and carbon particles in the resultant composite are combined homogeneously in nanoscale with a mesoscale structure and with high carbon purity. When Pt nanoparticles are loaded on the composite, they show high performance as an electrocatalyst because of their higher electrochemical active surface area and higher durability against the sintering of Pt nanoparticles. Resulting material is a multifunctional composite by virtue of its nanostructural features.

Umemoto, Hironobu; Miyata, Atsushi

doi: 10.1246/bcsj.20160074pmid: N/A

Efficient sustained release of B atoms, sufficient for doping to semiconductor substrates, was achieved when W wires boronized by NH3BH3/H2 were heated in the presence of H2. The B-atom density in the gas phase was on the order of 1011 cm−3 and could be kept constant more than 240 min.

Thomas, Arun; Kuttassery, Fazalurahman; Remello, Seabatian Nybin; Mathew, Siby; Yamamoto, Daisuke; Onuki, Satomi; Nabetani, Yu; Tachibana, Hiroshi; Inoue, Haruo

doi: 10.1246/bcsj.20160091pmid: N/A

Novel environment-benign one-pot syntheses of water-soluble porphyrins, trans-dihydroxy-5,10,15,20-tetra(N-methyl-4′-pyridiniumyl)porphyrinate tin(IV) (Sn(IV)TMPyP(OH)2) and water-insoluble trans-dihydroxy-5,10,15,20-tetra(4-pyridyl)porphyrinate tin(IV) (Sn(IV)TPyP(OH)2), were found to proceed in water as solvent at room temperature with high yield (90 and 93%).

Li, Jun; Liu, Sha; Lu, Xiaohua

doi: 10.1246/bcsj.20160084pmid: N/A

In this work, we study the hydrogenation of CO2 via the direct addition of hydride to CO2 on Ru(II) complexes to make clear the influences of two key factors, the nature of Ru–H bond and the effect of hydrogen bonding, on CO2 insertion into the Ru–H bond. The density functional theory calculation results show that: (1) There exist two types of Ru–H bonds. If the Ru–H bond is formed from the mixing of the sd3 hybrid orbital of Ru with the 1s orbital of H, the hydride cannot be directly added to CO2 even with the help of hydrogen bonding. The direct hydride addition to CO2 only can occur for the hydride involved in a Ru–H bond formed from the mixing of the sd2 hybrid orbital of Ru with the 1s orbital of H. (2) For active hydride, hydrogen bonding can facilitate the migration of hydride to CO2. (3) If less d orbital component is involved in the formation of the Ru–H bond on similar complexes, the hydride will be more active. In the light of these laws, the activity of the hydride on a Ru(II) complex might be adjusted by the change of the ligand trans to the hydride.

Sakurai, Hiroya; Arai, Tatsuo

doi: 10.1246/bcsj.20160113pmid: N/A

Newly synthesized 4,4′-distyrylbiphenyl-cored water-soluble dendrimers underwent trans-to-cis photoisomerization, while the core 4,4′-distyrylbiphenyl underwent cis-to-trans one-way photoisomerization.