Structure and dynamics of a complex of cellulose with EDA: insights into the action of amines on cellulose

The neutron structure of a complex of EDA with cellulose has been determined to reveal the location of hydrogen atoms involved in hydrogen-bonding. EDA disrupts the hydrogen-bonding pattern of naturally occurring cellulose by accepting a strong hydrogen-bond from the O6 hydroxymethyl group as the conformation of this group is rotated from tg to gt. The O3-H·O5 intrachain hydrogen-bond commonly found in cellulose allomorphs is observed to be disordered in the neutron structure, and quantum chemistry and molecular dynamics calculations show that O3 prefers to donate to EDA. The hydrogen-bonding arrangement is highly dynamic with bonds continually being formed and broken thus explaining the difficulty in locating all of the hydrogen atoms in the neutron scattering density maps. Comparison with other polysaccharide-amino complexes supports a common underlying mechanism for amine disruption of cellulose.     

Electrochemical monitoring of intracellular enzyme activity of single living mammalian cells by using a double-mediator system

We evaluated the intracellular NAD(P)H:quinone oxidoreductase (NQO) activity of single HeLa cells by using the menadione–ferrocyanide double-mediator system combined with scanning electrochemical microscopy (SECM). The double-mediator system was used to amplify the current response from the intracellular NQO activity and to reduce menadione-induced cell damage. The electron shuttle between the electrode and menadione was mediated by the ferrocyanide/ferricyanide redox couple. Generation of ferrocyanide was observed immediately after the addition of a lower concentration (10 μM) of menadione. The ferrocyanide generation rate was constant for 120 min. At a higher menadione concentration (100 μM), the ferrocyanide generation rate decreased within 30 min because of the cytotoxic effect of menadione. We also investigated the relationship between intracellular reactive oxygen species or glutathione levels and exposure to different menadione concentrations to determine the optimal condition for SECM with minimal invasiveness. The present study clearly demonstrates that SECM is useful for the analysis of intracellular enzymatic activities in single cells with a double-mediator system.     

Highly efficient, organocatalytic aerobic alcohol oxidation

5-Fluoro-2-azaadamantane N-oxyl (5-F-AZADO) realizes a simple, organocatalytic aerobic alcohol oxidation system that has a wide scope under mild conditions at ambient pressure and temperature and is weakly acidic and halogen- and transition-metal-free. The oxoammonium nitrate (5-F-AZADO(+)NO(3)(-)) works as a bifunctional catalyst of 5-F-AZADO and NO(x) that enables the catalytic aerobic oxidation of alcohols by itself (a metal-salt-free system).     

Photoreaction of Benzenecarbothioamide with Aldehydes. Facile Synthesis of Tetracyclic Imidazoles.1)

Photoreaction of benzenecarbothioamide with various aldehydes in benzene solution gave 2-substituted phenanthroimidazoles.     

Polymer gel films with simple organic electrochromics for single-film electrochromic devices

Polymer gel films [poly(1-vinyl-2-pyrrolidinone-co-N,N′-methylenebisacrylamide) (PVPD)] which contain simple organic electrochromics [p-diacetylbenzene (p-DAB), dimethyl- or diethyl terephthalate (p-DMP or p-DEP)] are prepared and their optical responses to applied voltage are investigated. p-DAP/PVPD film is colored in green by the application of 1.2 V vs. Pt wire (quasireference electrode) across the film, and p-DMP/PVPD and p-DEP/PVPD films are colored in red by the application of ?2.5 and ?1.5 V vs. Pt, respectively. Their coloring responses are about a few seconds and the bleaching process also occurs rapidly. The films have no optical memory effect. © 1992 John Wiley & Sons, Inc.     

Surface acetylation of bacterial cellulose

Bacterial cellulose was partially acetylated by the fibrous acetylationmethod to modify its physical properties, while preserving the microfibrillarmorphology. The overall degree of substitution was varied from 0.04 to 2.77 bychanging the amount of acetic anhydride added. X-ray diffraction of thepartially acetylated samples showed the crystalline pattern of unmodified celluloseI up to moderate degrees of acetylation, and the change in peak widthsindicatedthat acetylation proceeded from the surface of microfibrils, leaving the coreportion unreacted. Scanning electron microscopy revealed that even low levelsofacetylation were effective to maintain the original microfibrillar morphologyofbacterial cellulose on direct drying from water.     

Automated measuring system for sound power measurement

It is sometimes important to know the sound power radiated from a sound source so that, for example, the solution noise abatement can be carried out on the basis of the sound power radiated.Measurement of the sound power in general is carried out in a reverberant enclosure. This measuring method is classed as an indirect one in that the sound power is obtained via the sound pressure level. Consequently, in order to determine the sound power radiated as precisely as possible, some measurement procedures for obtaining the space-average sound pressure have been devised. However, the procedure, which involves moving the measuring microphone from point to point, is extremely tedious. Accordingly, if the system from data acquisition to data processing is automated, the work required for obtaining the space-average sound pressure will be considerably reduced, as will the time required for processing the data.The development of an automatic measuring system for sound power is discussed and it is shown that the sound power obtained with the system devised agrees well with that obtained by more familiar means.     

Structural stability in partially substituted lithium manganese spinel oxide cathode

LiMn₂O₄ is one of the most promising cathode materials for lithium secondary battery because of natural abundance of manganese in the crust and its low toxicity to environment. Lithium ion can almost reversibly intercalate into or deintercalate from lithium manganese spinel oxide LiMn₂O₄. A part of substitution of manganese with other transition metals brings the improvement of cycle life. We focused on the local structure of the spinels and considered the effect of the local distortion on the cycle life of the spinel cathodes. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Structure and properties of the δ‐form and mesophase of syndiotactic polystyrene membranes prepared from different organic solvents

Syndiotactic polystyrene (sPS) membranes were prepared with different organic solvent systems and compared to get the information about the δ‐form complexing behavior of sPS. Further, the guest molecules included in the clathrate δ form of sPS are removed by stepwise extraction method. The conformational changes during the TTGG helical formation of sPS/organic solvent systems have been identified by FTIR spectroscopy, and it was concluded that the TTGG helices were constructed in regular sequences, which depends on the nature of the respective solvents. The TTGG content in the mesophase is found to be increased by removing the guest molecules. The structural changes of sPS/organic solvent systems have been characterized by WAXD analysis. Moreover, the different clathrate structures were found and showed the different crystalline reflections in the WAXD profiles, which are significantly changed with the kind of guest solvent included in sPS. The content of solvents in the clathrated sPS and the desorption temperatures were determined by thermal analysis. The resulted mesophase of sPS membrane contains the nanoporous molecular cavities that depend on the size of the guest molecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1873–1880, 2005