Radical copolymerization of alkyl 2‐norbornene‐2‐carboxylate with alkyl acrylates: Facile incorporation of norbornane framework into poly(alkyl acrylate)s

Radical copolymerization of alkyl 2‐norbornene‐2‐carboxylates (alkyl = Me 1a , nBu 1b ) with alkyl acrylates (alkyl = ethyl, methyl, and n‐butyl) was investigated. Copolymerization of 1a,b with the alkyl acrylates initiated by 1,1′‐azobis (cyclohexane‐1‐carbonitrile) at 85 °C proceeded to give random copolymers, although the homopolymerization of 1a,b did not proceed efficiently under the same conditions. Typically, bulk copolymerization of 1a with ethyl acrylate in a feed ratio of 1:3 ([ 1a ]:[EA]) afforded a copolymer with M_n = 33,300 containing 19.4 mol % of 1a unit in the composition. An increase of T_g derived from the incorporation of the rigid norbornane framework was observed, although the extent of the temperature rise was rather moderate. The ternary radical copolymerization of 1a,b /alkyl acrylate/N‐phenylmaleimide proceeded to give copolymers with the three repeating units in the main chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4597–4605, 2007     

Stereochemical recognition of doubly functional aminotransferase in 2-deoxystreptamine biosynthesis

The doubly functional aminotransferase BtrS in the 2-deoxystreptamine (DOS) biosynthesis, in which two transaminations are involved, was characterized by a genetic as well as a chemical approach with the heterologously expressed enzyme. The gene disruption study clearly showed that BtrS is involved, in addition to the previously confirmed first transamination, in the second transamination as well. This dual function of BtrS for the DOS biosynthesis was further confirmed by the structural determination of the reverse reaction product from DOS. Enantiospecific formation of the reverse reaction product from DOS clearly showed that BtrS distinguishes the enantiotopic amino groups of DOS, but in contrast, both enantiomers of 2-deoxy-scyllo-inosose (DOI) were efficiently accepted by BtrS to give a racemic product. This unique stereochemical recognition of DOI chirality and DOS prochirality by BtrS is mechanistically explained by a specific hydrogen-bond donating force in the enzyme active site as a particular feature of this doubly functional enzyme.     

Inhalation MR lymphography: A new method for selective enhancement of the lung hilar and mediastinal lymph nodes

On MR lymphography, a new approach to the lung hilar and mediastinal nodes was developed in an animal model. Five rabbits were made to inhale iron colloid (cideferron) that was nebulized to aerosol. Two days after inhalation of the agent, the mediastinal lymph nodes decreased in signal on SE 2000/30 and SE 2000/60 images and proved to have iron on histological evaluation, whereas the popliteal nodes did not have any iron. Experimental results indicate that inhalational administration can deliver the agent to the pulmonary lymphatic system and has the potential of lung hilar and mediastinal MR lymphography.     

Emission from charge recombination during the pulse radiolysis of arylethynylpyrenes

Emission from several 1-(arylethynyl)pyrenes with a substituent on the aryl group (REPy, R = phenyl (PEPy), 4-dimethylaminophenyl (NPEPy), 4-isopropoxyphenyl (OPEPy), 2-quinonyl (QEPy), and 9-(10-cyanoanthracenyl) (AEPy)) was studied with time-resolved fluorescence measurements during pulse radiolysis in benzene. NPEPy and AEPy showed only monomer emission, while PEPy, OPEPy, and QEPy showed both monomer and excimer emissions during pulse radiolysis. In addition, REPy's also showed long-lived emissions with very weak intensities in the absence of oxygen, which were assigned to the "P-type" delayed fluorescence derived from the triplet-triplet annihilation. The formation of REPy's in the singlet excited state (1REPy*) can be interpreted as the charge recombination between the REPy radical cation and anion (REPy*+ and REPy*-, respectively), which are initially generated from the radiolytic reaction in benzene. Both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of PEPy are localized on the 1-pyrenyl (Py) moiety, while the HOMO of REPy's with an electron donating or withdrawing substituent on the benzene ring (R(D)EPy such as NPEPy and OPEPy or R(A)EPy such as QEPy and AEPy) is mainly localized on the donor moieties (R(D) or Py) and the LUMO on the acceptor ones (Py or R(A), respectively). Therefore, it is suggested that the one-electron oxidation and reduction of REPy's can occur from the donor and acceptor moieties, respectively. This scheme reasonably explains the relationship between the annihilation enthalpy changes (-Delta H' degrees) for the charge recombination of REPy*+ and REPy*- and the singlet excitation energies (E'(S1) of the REPy's. The results are compared with those in electrogenerated chemiluminescence.     

Nearly free electrons in the layered oxide superconductor Ag5Pb2O6

We present first measurements of quantum oscillations in the layered oxide superconductor Ag5Pb2O6. From a detailed angular and temperature dependent study of the de Haas-van Alphen effect we determine the electronic structure and demonstrate that the electron masses are very light, m* approximately 1.2me. The Fermi surface we observe is essentially that expected of nearly free electrons--establishing Ag5Pb2O6 as the first known example of a monovalent, nearly free electron superconductor at ambient pressure.     

Electrostatic potential screened by a two-dimensional electron system: a real-space observation by scanning-tunneling spectroscopy

Scanning-tunneling spectroscopy at 5 K was used to investigate the electrostatic potential profile on the Si(111)-square root of 3 x square root of 3 Ag surface at subnanometer spatial resolution. The potential was measured from an energy-level shift of electronic states on the surface. The potential images obtained reveal that the potential drops around the steps and Ag adsorbates, upon which positive charges are presumably accumulated. The profiles of the reduced potentials are explained with the screening of potential due to the charges by two-dimensional electron gas (2DEG) existing on the surface. The Friedel oscillation, which results from the screening and has a period of the half Fermi wavelength of the 2DEG, was also observed in the potential images.     

Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies

We have demonstrated that one-dimensional supramolecular dye assemblies with a uniform diameter can be created by utilizing schizophyllan (SPG) as a one-dimensional host. In the supramolecular nanofibers, the dye molecules are assembled into the different aggregation modes depending on the preparation procedures. The findings establish that SPG is useful for creating the supramolecular nanofibers, where temporal superstructures can be stabilized by the SPG-specific helical higher-order structure. [structure: see text].     

Use of laser drilling in the manufacture of organic inverter circuits

Inverter circuits have been made by connecting two high-quality pentacene field-effect transistors. A uniform and pinhole-free 900 nm thick polyimide gate-insulating layer was formed on a flexible polyimide film with gold gate electrodes and partially removed by using a CO₂ laser drilling machine to make via holes and contact holes. Subsequent evaporation of the gold layer results in good electrical connection with a gold gate layer underneath the gate-insulating layer. By optimization of the settings of the CO₂ laser drilling machine, contact resistance can be reduced to as low as 3 Ω for 180 μm square electrodes. No degradation of the transport properties of the organic transistors was observed after the laser-drilling process. This study demonstrates the feasibility of using the laser drilling process for implementation of organic transistors in integrated circuits on flexible polymer films.     

Global stability of a generalized epidemic model

The competitive exclusion principle is one of the most interesting and important phenomena in both theoretical epidemiology and biology. We show that the equilibrium in which only the strain with the maximum basic reproductive number exists is globally asymptotically stable by using an average Lyapunov function theorem and some dynamical system theory. This result is anticipated by H.J. Bremermann and H.R. Thieme (1989) [6] where they showed that the equilibrium is locally stable — the global result has not been established previously.