Asymmetric Dearomative Fluorination of 2‐Naphthols with a Dicarboxylate Phase‐Transfer Catalyst

A linked dicarboxylate phase‐transfer catalyst enables smooth asymmetric dearomative fluorination of 2‐naphthols with Selectfluor under mild conditions to give the corresponding 1‐fluoronaphthalenone derivatives in a highly enantioselective manner. This reaction, which is compatible with a range of functional groups, is the first example of catalytic asymmetric fluorination of 2‐naphthols, and is expected to be useful in the synthesis of bioactive molecules.     

Molecular Interaction of Baicalein and Phosphatidylcholine in Liposomal Membrane

Baicalein is the flavonoid contained in the root of Scutellaria baicalensis Georgi. X-ray diffraction patterns of the dried baicalein-intermixed phosphatidylcholine films and ¹H NMR spectra in d₆-acetone solutions were investigated to clarify the interaction of the flavonoid and phosphatidylcholine molecules in the liposomal membranes. It was found that baicalein molecules were entrapped in liposomal membranes by hydrogen bonding of the polar headgroups of phosphatidylcholine molecules with C₅- and C₆-hydroxyl groups of baicalein.     

Isolation and structure of citreopyrone,a metabolite of penicillium citreo-viride biourge

Citreopyrone isolated from the mycelium of $\text{Penicillium citreo-viride}$ B. has been found to be 5-crotonoyl-4-methoxy-6-methyl-2-pyrone. This is the first naturally occurring pyrone with an acyl group at C₅-position.     

Laurencenyne,a plausible precursor of various nonterpenoid C15-compounds,and neolaurencenyne from the red alga laurencia okamurai

Structural elucidation of two new acetylenic polyenes, laurencenyne $\text{5}$ and neolaurencenyne $\text{6}$ isolated from $\text{Laurencia okamurai}$, together with their syntheses, was achieved, suggesting that laurencenyne $\text{5}$ was a possible precursor of various nonterpenoid C₁₅-compounds in the marine red algae of the genus $\text{Laurencia}$.     

Time-resolved observation of structural change of copper induced by laser shock using synchrotron radiation with dispersive XAFS

ABSTRACT

We report a single-shot nanosecond time-resolved dispersive XAFS measurement of copper foil under laser-induced shock compression. Obtained EXAFS results indicated clearly the structural evolution, though XANES spectra showed that the laser irradiation does not affect the copper electronic state. The nearest (ca. 0.22 nm) and longer (ca. 0.44 nm) Cu–Cu distances are changed at 4 and 200 ns, respectively, in the radial structure functions (RSFs). It was revealed that an average compression of 2% occurs at 4 ns and is released within 200?ns. It was found that the fragmentation of the copper begins at around 200 ns according to the increase in distance of the RSF.     

A nanocarbon film electrode as a platform for exploring DNA methylation

We describe the quantitative nonlabel electrochemical detection of both cytosine (C) and methylcytosine (mC) in oligonucleotides using newly developed nanocarbon film electrodes. The film consists of nanocrystalline sp2 and sp3 mixed bonds formed by employing the electron cyclotron resonance (ECR) sputtering method. We successfully used this film to develop a simple electrochemical DNA methylation analysis technique based on the measurement of the differences between the oxidation currents of C and mC since our ECR nanocarbon film electrode can directly measure all DNA bases more quantitatively than conventional glassy carbon or boron-doped diamond electrodes. The excellent properties of ECR nanocarbon film electrodes result from the fact that they have a wide potential window while maintaining the high electrode activity needed to oxidize oligonucleotides electrochemically. Proof-of-concept experiments were performed with synthetic oligonucleotides including different numbers of C and mC. This film allowed us to perform both C- and mC-positive assays solely by using the electrochemical oxidation of oligonucleotides without bisulfite or labeling processes.     

Newly developed chemical probes and nano-devices for cellular analysis.

A cellular analyzing system including a "real-time cellular imaging system" and a "comprehensive analyzing system for cellular responses" was developed. A "real-time cellular imaging system" is a system used to measure real-time imaging of multiple phenomena of a single cell with high special and temporal resolutions for the purpose to understand the pathology and physiology in a single cell and realize to single cell level diagnosis. A "real-time cellular imaging system" includes multi-probe imaging with AFM (atomic force microscopy), optical and SECM (scanning electrochemical microscopy) modes, which provides us with topological information and biochemical reactions at the local area of the interior and exterior of a cell. Scanning electrochemical/optical microscopy was applied to image PC12 cells. On the other hand, cells respond to their specific substances via their ligands. Therefore, the comprehensive analysis of protein-protein interaction is the important issue to determine the functions of cells. For this purpose, a "comprehensive analysis system for cellular responses" was developed. This system is based on SPR (surface plasmon resonance) and MS (mass spectrometry) using a nano-fabricated substrate. The interaction between IL-1 beta and anti-IL-1 beta antibodies was detected.     

Comparison of Electrochemical and Surface Plasmon Resonance Immunosensor Responses on Single Thin Film

This paper reports results obtained when comparing an electrochemical enzyme immunosensor and a surface plasmon resonance (SPR) based immunosensor on the same gold surface installed in an electrochemical SPR flow cell. Simultaneous electrochemical and SPR measurements were performed on a gold surface modified with multilayers of poly‐L ‐lysine and poly‐styrenesulfonate assembled with the layer‐by‐layer method. First, we obtained the SPR response induced by the formation of an immunocomplex from the shift in the SPR angle by injecting an anti tumor necrosis factor‐α antibody solution labeled with alkaline phosphatase into the flow cell containing the multilayer modified with tumor necrosis factor‐α. Then we compared this SPR result with that obtained for the electrochemical oxidation current of p‐aminophenol catalyzed by alkaline phosphatase from p‐aminophenolphosphate on the same gold film. We compared the two immunosensor responses obtained using the different measurement principles and found that there was a high correlation efficient of 0.973 between them. This was because we were able to immobilize the immunoreagents with good stability and without losing the transport of the enzyme product in the multilayer whose thickness we easily controlled with nanometer scale accuracy. We also report that the detection limit of our electrochemical immunosensor after optimization was around 100 pg/mL (0.4 pM), which is one of the lowest values yet reported for an electrochemical immunosensor.