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.     

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.     

Quantum degenerate mixtures of alkali and alkaline-earth-like atoms

We realize simultaneous quantum degeneracy in mixtures consisting of the alkali and alkaline-earth-like atoms Li and Yb. This is accomplished within an optical trap by sympathetic cooling of the fermionic isotope ?Li with evaporatively cooled bosonic 1??Yb and, separately, fermionic 1?3Yb. Using cross-thermalization studies, we also measure the elastic s-wave scattering lengths of both Li-Yb combinations, |a(?Li-1??Yb)| = 1.0 ± 0.2 nm and |a(?Li-1?3Yb)| = 0.9 ± 0.2 nm. The equality of these lengths is found to be consistent with mass-scaling analysis. The quantum degenerate mixtures of Li and Yb, as realized here, can be the basis for creation of ultracold molecules with electron spin degrees of freedom, studies of novel Efimov trimers, and impurity probes of superfluid systems.     

Multifunctional Core–Shell Silica Nanoparticles for Highly Sensitive 19F Magnetic Resonance Imaging

¹⁹F magnetic resonance imaging (¹⁹F MRI) is useful for monitoring particular signals from biological samples, cells, and target tissues, because background signals are missing in animal bodies. Therefore, highly sensitive ¹⁹F MRI contrast agents are in great demand for their practical applications. However, we have faced the following challenges: 1) increasing the number of fluorine atoms decreases the solubility of the molecular probes, and 2) the restriction of the molecular mobility attenuates the ¹⁹F MRI signals. Herein, we developed novel multifunctional core–shell nanoparticles to solve these issues. They are composed of a core micelle filled with liquid perfluorocarbon and a robust silica shell. These core–shell nanoparticles have superior properties such as high sensitivity, modifiability of the surface, biocompatibility, and sufficient in vivo stability. By the adequate surface modifications, gene expression in living cells and tumor tissue in living mice were successfully detected by ¹⁹F MRI.     

One‐Pot Synthesis of N‐Acetyl‐ and N‐Glycolylneuraminic Acid Capped Trisaccharides and Evaluation of Their Influenza A(H1 N1) Inhibition

Human lung epithelial cells natively offer terminal N‐acetylneuraminic acid (Neu5Ac) α(2→6)‐linked to galactose (Gal) as binding sites for influenza virus hemagglutinin. N‐Glycolylneuraminic acid (Neu5Gc) in place of Neu5Ac is known to affect hemagglutinin binding in other species. Not normally generated by humans, Neu5Gc may find its way to human cells from dietary sources. To compare their influence in influenza virus infection, six trisaccharides with Neu5Ac or Neu5Gc α(2→6) linked to Gal and with different reducing end sugar units were prepared using one‐pot assembly and divergent transformation. The sugar assembly made use of an N‐phthaloyl‐protected sialyl imidate for chemoselective activation and α‐stereoselective coupling with a thiogalactoside. Assessment of cytopathic effect showed that the Neu5Gc‐capped trisaccharides inhibited the viral infection better than their Neu5Ac counterparts.