Lasting chemiluminescence of 3-indoleglyoxylyl chloride and its enhancement.

The chemiluminescence (CL) intensities of various indole derivatives substituted with a glyoxylyl group at the 3-position and a hydroxyl group at the 5-position of the indole ring were compared upon the addition of H2O2 in alkaline media. The CL intensities of 3-indoleglyoxylyl chloride, 3-indoleglyoxylic acid, 5-hydroxyindole and 5-benzyloxyindole in CH3CN were 5.9-, 48-, 5.9- and 3.3-fold stronger than that of 3-methylindole. A lasting CL of 3-indoleglyoxylyl chloride was found. Under appropriate conditions, the CL emission reached a maximum within 10 min after the addition of H2O2 in the presence of NaOH, and the intensity was retained for 25 min. One of the final products via the CL reaction of 3-indoleglyoxylyl chloride was indole-3-carboxylic acid. 3-Indoleglyoxylyl chloride emitted light by decompositions via both dioxetane and dioxetanedione. An enhancement effect of beta-cyclodextrin and bovine serum albumin on the CL of 3-indoleglyoxylyl chloride was also found.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.     

Collection of iron(III) from homogeneous aqueous solutions on membrane filters using Chromazurol B with Triton X-100.

A membrane filtration method was examined concerning the effective collection of iron(III) from a homogeneous aqueous solution with Chromazurol B (CAB), one of the triphenylmethane dyes, as a precipitating reagent in the presence of a non-ionic surfactant, polyethylene glycol mono[4-(1,1,3,3-tetramethylbutyl)phenyl]ether (Triton X-100). A formed blue Fe(III)-CAB complex was collected as a precipitate on a membrane filter by filtration under suction from a homogeneous aqueous solution in the pH range over about 2. The original solution was prepared at a concentration ratio of CAB to Fe(III) of to 10, and that of Triton X-100 to CAB of 10 to 100. It was then adjusted to a pH value of between 1.0 and 6.5. A linear relationship (r = 0.999) was obtained between the initial concentration and the found one of Fe(III) in the range of 2.0 x 10(-5) to 4.0 x 10(-4) mol dm(-3) at a fixed concentration ratio of CAB to Fe(III) of 3 and that of Triton X-100 to CAB of 20. This membrane filtration with CAB and Triton X-100 may be utilized for the separation of Fe(III) as a background species.     

Argon sorption and partial molar volume in poly(ethyl methacrylate) above and below the glass transition temperature

Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (T_g=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above T_g follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above T_g (about 40 cm³/mol), whereas the volumes below T_g are smaller and dependent on both temperature and concentration (19–26 cm³/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 ų, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm³ from the temperature dependence of the dual-mode parameters.     

Structure and enantioselective synthesis of polyamine toxin MG30 from the venom of the spider Macrothele gigas

A novel polyamine toxin, named MG30, was isolated from the venom of the spider, Macrothele gigas, and its structure was elucidated by two-dimensional NMR and mass analysis. In addition, the enantioselective synthesis of MG30 was achieved to assign its absolute stereochemistry.     

Synthesis of endogenous sperm-activating and attracting factor isolated from ascidian Ciona intestinalis

A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity.     

Enantioselective spiro ene-carbocyclization of 1,6-enynes catalyzed by tropos rhodium(I) complex with skewphos ligand

A tropos rhodium(I) complex having skewphos ligand is shown to be a highly enantioselective catalyst for asymmetric ene-type carbocyclization of 1,6-enynes with tri-substituted olefins to control quaternary stereogenic centers or spiro-rings.     

Approximate controllability for trajectories of semilinear control systems

We treat an abstract semilinear control system and study the controllability problem for its trajectories. Assuming a range condition of the control action operator and an inequality condition on the system parameters, we can show that the reachable trajectory set of the semilinear system is equivalent to that of its corresponding linear system.The author wishes to express his deep appreciation to Prof. T. I. Seidman for his many helpful suggestions and to Prof. W. Takahashi for many stimulating conversations.