Thermotropic cellulose derivatives with flexible substituents. III. Temperature dependence of cholesteric pitches exhibiting a cholesteric sense inversion

For the thermotropic cholesteric mesophase of tri-o-(β-methoxyethoxy)ethyl cellulose (DP = 11), cholesteric pitches larger than 2 μm were precisely determined by microscopic observation and their temperature dependence was examined in the temperature range from 80°C to 140°C. In the initial temperature region of 80°C to 106°C, the pitch increases with increasing temperature. After the pitch diverges at 106°C, it decreases as temperature is raised further. This anomalous temperature dependence of pitch was associated with a thermally-induced inversion from right- to left-handed helicoidal structure which was first observed in this kind of cellulose derivatives.     

Conceptual Design Study of a Novel Gyrotron for NMR/DNP Spectroscopy

In this paper we present some initial results from a conceptual design study focused on the development of a novel frequency tunable gyrotron for nuclear magnetic resonance (NMR) spectroscopy with signal enhancement based on the utilization of high field radiation and dynamic nuclear polarization (DNP) technique. The first variants of both the electron optical system and the resonant cavity which have been designed aiming continuous frequency tunability in a broad frequency band are presented and discussed. The selected method for frequency tunability is based on the excitation of higher order axial modes and smooth transition between them. It was selected after a critical examination of the known theoretical and practical results related to the frequency control in gyrotrons. It is believed that the current conceptual design is an appropriate basis for development of the next (optimized) design which will include also a detailed design of other components (mode converter, output window etc.) and magnetic circuit (superconducting magnet and supplementary solenoids) as well as for the overall mechanical design and fabrication of the prospective gyrotron.     

Methods of analysis for chemicals that promote/disrupt cellular signaling.

Methods of analysis were presented for chemicals that promote or disrupt cellular signaling pathways. The developed analytical methods are based not only on receptor binding, but also on the following known molecular-level processes involved in signal transduction along signaling pathways, reconstituted in vitro or taken in part in living cells. The methods were discussed in relation to receptor binding assay and/or bioassay. Examples include: (1) Insulin signaling pathways; (1-i) Chemical selectivity of agonists for insulin signaling pathways based on agonist-induced phosphorylation of a target peptide; (1-ii) An SPR-based screening method for agonist selectivity for insulin signaling pathways based on the binding of phosphotyrosine to its specific binding protein; (1-iii) A fluorescent indicator for tyrosine phosphorylation-based insulin signaling pathways; (2) An optical method for evaluating ion selectivity for calcium signaling pathways in the cell; (3) Assay and screening of chemicals that disrupt cellular signaling pathways, potential endocrine disruptors in particular; (4) Protein conformational changes, and (5) A screening method for antigen-specific IgE using mast cells, based on intracellular calcium signaling.     

Observation of Mode Patterns for High Purity Mode Operation in the Submillimeter Wave Gyrotron FU VA

Operation tests of a cavity designed for high purity mode operation of the submillimeter wave gyrotron FU VA has been carried out successfully. The observed emission patterns of several cavity modes appear very pure and are compared with calculated results. High purity mode operation has the advantage of making the conversion to Gaussian-like beams more efficient.     

Identification of arsenobetaine and a tetramethylarsonium salt in the clam Meretrix lusoria

Chemical forms of arsenic were examined in six tissues (gill, mid-gut gland, siphon, foot, mantle and adductor muscle) of the clam Meretrix lusoria. The gill was found to contain higher levels of arsenic than the other tissues. Regardless of the nature of the tissues, the presence of arsenobetaine was established by HPLC0ICP; it was a minor arsenic compound in gill but a major one in the other tissues. The major arsenic compound in gill, which was more cationic than arsenobetaine, was obtained in a relatively pure state by ion-exchange chromatography, gel filtration and HPLC. It was positive to the Dragendorff reagent and iodine vapor but negative to ninhydrin reagent. Its ¹HNMR spectrum exhibited only one signal at δ 1.7 (singlet) and its FAB mass spectrum gave a base peak at m/e 135 [(CH₃)₄As⁺] and two significant peaks at m/e 120 [(CH₃)₃As] and 106 [(CH₃)₂AsH]. These results suggested that the major arsenic compound in gill exists as a tetramethylarsonium salt (CH₃)₄As⁺ · X^?. The tetramethylarsonium salt was also found as a minor component in the tissues other than the gill.     

Total synthesis of (-)-martinellic acid via radical addition-cyclization-elimination reaction

The asymmetric total synthesis of martinellic acid, the first pyrrolo[3,2-c]quinoline alkaloid found in nature, is described. Three key steps in our synthesis of (-)-martinellic acid are the Bu(3)SnH-promoted radical addition-cyclization-elimination (RACE) reaction of an oxime ether with an alpha,beta-unsaturated ester to generate the pyrrolo[3,2-c]quinoline core, a chemoselective lactam carbonyl reduction, and guanidinylation under Mitsunobu reaction conditions. The key radical cyclization has also been investigated by using SmI(2). (-)-Martinellic acid was synthesized from commercially available methyl 4-bromo-3-methylbenzoate in fewer steps than previous syntheses and in an improved overall yield.     

A Remark on Support of the Principal Function for Class A Operators

Let be an invertible class A operator such that . Then we show that , where gT is the principal function of T. Moreover, we show that if T is pure, then .     

Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond

Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield.     

Synthesis and oxidative polymerization of dialkyl fluorene-9,9-dicarboxylates

Novel long-chain dialkyl fluorene-9,9-dicarboxylates were synthesized by treating fluorene with lithium diisopropylamide followed by alkyl chloroformates. The fluorene derivatives were readily electro-oxidized to form electroactive films on the surface of a glassy carbon electrode. From the viewpoint of suitable potential window (from −2.5 to 1.5 V vs Ag/Ag⁺), cyclic voltammograms of the films indicated the electroactive properties of the fluorene derivatives that make them good candidates for electrochemical capacitor materials.