Construction of positively-charged layered assemblies assisted by cyclodextrin complexation

A beta-cyclodextrin dimer is found to be effective in preparing a layer-by-layer architecture of positively charged ferrocene-appended poly(allylamine) presumably on the basis of strong beta-cyclodextrin-ferrocene host-guest interaction.     

New partially oxidized 1-D platinum chain complexes consisting of carboxylate-bridged cis-diammineplatinum dimer cations

The first/second examples of partially oxidized 1-D platinum chain compounds consisting of cationic dimer units have been obtained from electro-oxidation of an aqueous solution containing cis-[Pt(NH3)2(OH2)2]2+ and acetate/propionate. The analytical and crystallographic studies reveal the mixed-valency of Pt(2.2+)infinity. The XPS confirms the presence of both Pt(II) and Pt(III). The solid-state physical measurements reveal that they are diamagnetic semiconductors and display a fairly broad, low-energy absorption band in the range of 500-3200 nm.     

Tritium in a Pine Forest Ecosystem: Relation between Fresh Pine Needles, Organic Materials on a Forest Floor and Atmosphere

Tritium concentrations were analyzed in organic and water fractions of fresh pine needles, dead and degraded pine needles accumulating on a pine forest floor to examine tritium cycle in a forest ecosystem. Tritium concentration was higher in the organic fraction of dead and degraded pine needles compared to others, suggesting two tritium sources. Rain is responsible for water fractions in the samples, while atmospheric hydrogen and methane are speculated to be responsible for high tritium level in the organic fraction of dead and degraded pine needles.     

Fundamental photoluminescence properties of pyrene carbonyl compounds through absolute fluorescence quantum yield measurement and density functional theory

We reviewed the photophysical properties of carbonyl-functionalized pyrene derivatives [i.e., pyrene with aldehyde (PA: 1-formylpyrene), ketone (PK: 1-acetylpyrene), carboxylic acid (PCA: 1-pyrenecarboxylic acid), and ester groups (PE: 1-methoxycarbonylpyrene)] using a measurement of absolute fluorescence quantum yield in various solvents and time-dependent density functional theory (TD-DFT) calculations. Here, we obtained new important data that fill in the gaps in existing datasets on these properties and help identify photoluminescence mechanisms. The results of the TD-DFT calculations were in agreement with the experimental results, and indicated that the low fluorescence of PA and PK is derived not only from intersystem crossing but also from internal conversion due to the proximity effect; this inference was also supported by the measurements of the photoluminescence spectra at low temperatures. In addition, factors leading efficiently to non-radiative processes were shown to be absent in PCA and PE. Thus, we successfully revised and systematized the photophysical properties of pyrene modified by carbonyl substitutes, including carboxamide groups, which were previously reported by us. Moreover, we showed that the photoluminescence properties of such compounds might be predictable by using TD-DFT calculations.     

Adenosine-1,3-diazaphenoxazine derivative for selective base pair formation with 8-oxo-2'-deoxyguanosine in DNA

The selective detection of 8-oxo-2'-deoxyguanosine (8-oxo-dG) in DNA without chemical or enzymatic treatment is an attractive tool for genomic research. We designed and synthesized the non-natural nucleoside analogue, the adenosine-1,3-diazaphenoxazine (Adap) derivative, for selective recognition of 8-oxo-dG in DNA. This study clearly showed that Adap has a highly selective stabilizing effect on the duplex containing the Adap-8-oxo-dG base pair. Furthermore, the fluorescent property of Adap was shown to be useful for the selective detection of 8-oxo-dG in the duplex DNA. To the best of our knowledge, this is the first successful demonstration of a non-natural nucleoside with a high selectivity for 8-oxo-dG in DNA.     

Biomimetic one-pot preparation of a black tea polyphenol theasinensin A from epigallocatechin gallate by treatment with copper(II) chloride and ascorbic acid

Chromatographic separation of black tea polyphenols is too difficult to supply sufficient quantities of pure compounds for biological experiments. Thus, facile methods to prepare black tea constituents were desired. Treatment of epigallocatechin gallate with copper(II) chloride efficiently afforded an unstable quinone dimer, dehydrotheasinensin A, and subsequent treatment with ascorbic acid stereoselectively yielded theasinensin A. The latter is a dimer with an R-biphenyl bond, one of the major polyphenols found in black tea. The method is simpler and more effective than enzymatic preparation.