Axially chiral dicarboxylic acid catalyzed asymmetric semipinacol rearrangement of cyclic β-hydroxy-α-diazo esters

The development of axially chiral dicarboxylic acid catalyzed desymmetrizing asymmetric semipinacol rearrangement of symmetrically substituted six-membered cyclic β-hydroxy-α-diazo esters is reported as a means to give chiral cycloheptanones with good enantioselectivities.     

Piezo electric sensor for endocrine-disrupting chemicals using receptor-co-factor interaction.

In vitro screening assays are useful techniques for the determination of receptor-mediated activities in environmental samples. In order to define whether environmental chemicals act as an agonist or antagonist to the human estrogen receptor (hER), we have constructed a biosensor based on ligand-inducible interactions between hER and relative proteins on a quartz crystal microbalance (QCM). The his-tagged proteins, which were expressed in E. coli by recombinant DNA technology, were immobilized on an Au-electrode with Ni(II)-mediated chemisorption using the histidine tag and thiol-modified iminodiacetic acid. The resonance-frequency change of the protein-modified electrode was caused by association or dissociation with the hER relative proteins on the surface in the presence of estrogen. These results suggest that this sensor is applicable as a large-scale screening tool for estrogenic compounds.     

Eine neue Probe auf Kohlenoxydh?moglobin

Ohne Zusammenfassung     

Formation of a ripple pattern at a water/silicon interface using an oscillating bubble

A single femtosecond laser pulse was irradiated at a water/silicon interface, and the processed surface was investigated. Rings surrounded by ripples were found within the irradiated spot. The diameter of the rings ranged from 500 nm to 10 μm. It is proposed that acoustic waves, caused by the oscillating motion of bubbles near the water/silicon interface, deformed the melting silicon surface. In the present work, a pulse (pulse width: 150 fs) was tightly focused in water to induce optical breakdown, and a bubble was generated at an arbitrary spot. When the power density was below the ablation threshold and above the melting threshold at the silicon surface and set above the breakdown threshold at the focus in water, a pattern was generated at a specific place and with a specific size. PACS 79.20.Ds; 42.62.Cf     

Analysis of liquid structure without construction of any structure models by the X-ray scattering method.

A simple approach for determining a liquid structure using X-ray scattering data, in which a liquid structure is uniquely evaluated without construction of any plausible structure models, has been applied to liquid acetonitrile, acetone and cyclohexane. For a pair of molecules, a given point within a molecule is located at the origin with a given molecular orientation. The site of the given point of another molecule is defined by the polar coordinates and the molecular orientation is treated by three Eulerian angles. These parameters are optimized by a non-linear least-squares calculation applied to X-ray scattering data. The reliability of the method was examined by determining the liquid structure of polar acetonitrile and the obtained intermolecular interatomic distances are in good agreement with the previously reported values. The method was then successfully applied to the determination of the liquid structure of acetone and cyclohexane. Especially for nonpolar cyclohexane, the construction of a variety of plausible structural models is very difficult. It was revealed that acetone has an ordered liquid arrangement similar to that found in its crystal, although the intermolecular distances in liquid acetone are different from those in the crystal. On the other hand, the liquid structure of cyclohexane is disordered.     

Sojourn time analysis for a cyclic-service tandem queueing model with general decrementing service

A sojourn time analysis is provided for a cyclic-service tandem queue with general decrementing service which operates as follows: starting once a service of queue 1 in the first stage, a single server continues serving messages in queue 1 until either queue 1 becomes empty, or the number of messages decreases to k less than that found upon the server's last arrival at queue 1, whichever occurs first, where 1 ≤ k ≤ ∞. After service completion in queue 1, the server switches over to queue 2 in the second stage and serves all messages in queue 2 until it becomes empty. It is assumed that an arrival stream is Poissonian, message service times at each stage are generally distributed and switch-over times are zero. This paper analyzes joint queue-length distributions and message sojourn time distributions.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Function of vinyl copolymers with pendant porphyrin or metalloporphyrin dimers as photoredox catalyst

Photoredox catalytic functions of water-soluble vinyl copolymers with pendant porphyrin or metalloporphyrin dimers were investigated. With FRA-L-ascorbic acid in aqueous solution, a vinyl copolymer bearing Mg-porphyrin dimer linked with the shortest N,N′-methylenebisamide bridge was found to have a remarkable accelerating effect under illumination of visible light as compared with that bearing Mg-porphyrin monomer and other copolymers with longer dimer bridges as well as vinyl copolymers bearing porphyrin dimers and monomer. A copolymer bearing Zn-porphyrin dimer was much inferior to that bearing monomer. Copolymers with other metals such as Co(II), Ni(II), and Cu(II) were almost inert.