Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Proton conductivity of phosphoric acid derivative of fullerene

The proton conductive property of methano [60] fullerene diphosphoric acid has been investigated under various humidity conditions at the temperature range between 15 and 45 °C. It shows proton conductivity as high as 10⁻² S cm⁻¹ at 25 °C under relative humidity of 95%. Thermal analyses including TG–DTA and thermal desorption mass spectroscopy (TDS) confirm that the compound is thermally stable up to 200 °C. Proton conduction of the compound depends very much on humidity or water content. The logarithmic conductivity at 25 °C is increased linearly with increasing relative humidity. The activation energy (E_a) estimated from the slope of log(σT) vs. 1/T is decreased from 1.08 to 0.52 eV, as the relative humidity is increased from 40% to 75%. The humidity dependence of conductivity is discussed in the light of the observed hydration isotherm.     

Measurement on Spot Size Dependence of Dense WDM Dielectric Multilayer Filters

We present the spot size dependence of dielectric multilayer filters for use in dense WDM systems. We found large dependences of filter performances on the spot size and the incident angle of input light, which should be important for miniaturizing multi-channel add/drop filters.     

A compact optical heterodyne interferometer by optical integration and its application

A compact high-resolution optical heterodyne interferometer combining a two-frequency light module and a minute optical system is described. The light module, which generates two independent frequencies of light, is fabricated by proton exchange method on LiNbO₃ substrate. We report an experiment evaluating measurement accuracy using a micro-displacement measurement system which incorporates this interferometer. Results of the experiment with a standard thickness sample show high thermal stability with maximum measurement error of 1.8 nm at a temperature from 19°C to 33°C. The system was used to measure the hysteresis of a piezoelectric element for displacements of several nm, thereby making it possible to analyze the system quantitatively in practice.     

Magneto-Optical Measurement of Organic Conductor Using Rotational Cavity System

We have developed a new magneto-optical measurement system using a rotational cavity system equipped with a millimeter vector network analyzer and a 14 T solenoid type super conducting magnet. The measurement can be performed in the transmission configuration down to 1.6 K. The results of the precise angular dependence measurement of quasi-one-dimensional organic conductor (DMET)₂I₃ using the new system are shown, and its Fermi surface will be discussed in connection with the previous reports.     

Oxidation of alcohols with oxoperoxobis(N-phenylbenzohydroxamato)molybdenum(VI)

The title complex oxidizes primary and secondary alcohols to the corresponding carbonyl compounds. Stereoselective epoxidation of allylic alcohols is also described.     

An efficient conversion of 1-abietic acid to (+)−3-deoxyaphidicolin

The first total synthesis of (+)?3-deoxyaphidicolin, a selective inhibitor of eukaryotic DNA polymerase α, has been completed efficiently and stereoselectively starting from 1-abietic acid.