Living ring-opening polymerization of ɛ-caprolactone with combinations of tert-butyllithium and bilky aluminium phenoxides

Summary The polymerization of ɛ-caprolactone (ɛ-CL) with a combination of tert-butyllithium (t-BuLi) and bis(2,6-di-t-butylphenoxy)methylaluminum [MeAl(ODBP)₂] in toluene at 0°C proceeded in a living manner to give polymers with narrow molecular weight distributions (MWD) within a few minutes, while the polymerization with t-BuLi alone gave a polymer with much broader MWD. The yield of the polymer did not reach 100 % at the Al/Li ratio of 5, because the excess MeAl(ODBP)₂ coordinates with ɛ-CL to protect it from the attack by the propagating species. The polymerization with t-BuLi/EtAl(ODBP)₂ gave polymers in quantitative yields regardless of Al/Li ratio, and also narrower MWD even for higher molecular weight polymers. Received: 1 August 2000/Accepted: 11 August 2000     

General Nature of Luminous Body Transition Produced by Pulsed Discharge on an Electrolyte Solution in the Atmosphere

A luminous body (LB) was produced by a pulsed electric discharge that initiated at the tip of the cathode and widely propagated on the surface of an electrolyte in the atmosphere. Entire images of the LB transition taken by a high-speed camera are visually demonstrated for the first time. It is indicated that the entire phenomenon of the LB transition can be classified into three sequential processes, regardless of the experimental conditions. It is estimated that the bright and octopus-like discharge, which may act as a source of high-energy ions and atoms, plays an essential role to make the mechanism of LB phenomena clear. Copyright © 2009 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Measurement of tritium concentration in water by imaging plate

Concentration of tritium in water (4–400 kBq cm^?3) was measured by exposing an imaging plate without protection layer (Fujifilm, BAS-IP TR) to vapor for 2–48 h. It was found that tritium gradually penetrated into Eu-doped BaFBr phosphor and induced sufficiently intense photostimulated luminescence (PSL) even at the concentration of 4 kBq cm^?3. The intensity of PSL was proportional to tritium concentration in water. In addition, tritium absorbed in phosphor was reversibly released by keeping IP in air, and IP was able to be used repeatedly if total duration of exposure was ca. 24 h or less. The contamination of IP with tritium was not serious. It was concluded that IP technique has potential to measure tritium concentration in water without direct handling of tritiated water and with a minimum amount of radioactive waste.     

(Z,E,E)-dodecatrien-1-ol: A minor component of trail pheromone of termite,Coptotermes formosanus Shiraki

In the course of the elucidation of the primary structure of an isolated trail pheromone fromC. formosanus, a minor component that had the same molecular weight as the major trail pheromone, (Z,Z,E)-3,6,8-dodecatrien-1-ol [(Z,Z,E)-DTE-OH], was detected in the mass chromatogram ofm/z 180 of capillary GC-MS. The mass spectrum of the minor component showed a prominent pattern of dodecatrien-1-ol. Chemical analysis demonstrated that the complete structure was (Z,E,E)-DTE-OH. Furthermore, capillary GC-MS-HR-SIM analysis indicated that the component existed only in the workers ofCoptotermes formosanus Shiraki and was not present in workers ofReticulitermes speratus (Kolbe). This minor component may be a species-specific factor ofC. formosanus, although this was not suggested by a two-choice bioassay.     

Bhc-cNMPs as either water-soluble or membrane-permeant photoreleasable cyclic nucleotides for both one- and two-photon excitation

Cyclic nucleoside monophosphates (cNMPs) play key roles in many cellular regulatory processes, such as growth, differentiation, motility, and gene expression. Caged derivatives that can be activated by irradiation could be powerful tools for studying such diverse functions of intracellular second messengers, since the spatiotemporal dynamics of these molecules can be controlled by irradiation with appropriately focused light. Here we report the synthesis, photochemistry, and biological testing of 6-bromo-7-hydroxycoumarin-4-ylmethyl esters of cNMP (Bhc-cNMP) and their acetyl derivatives (Bhc-cNMP/Ac) as new caged second messengers. Irradiation of Bhc-cNMPs quantitatively produced the parent cNMPs with one-photon uncaging efficiencies (Phiepsilon) of up to one order of magnitude better than those of 2-nitrophenethyl (NPE) cNMPs. In addition, two-photon induced photochemical release of cNMP from Bhc-cNMPs (7 and 8) can be observed with the two-photon uncaging action cross-sections (delta(u)) of up to 2.28 GM (1 GM=10(-50) cm(4) s photon(-1)), which is the largest value among those of the reported Bhc-caged compounds. The wavelength dependence of the delta(u) values of 7 revealed that the peak wavelength was twice that of the one-photon absorption maximum. Bhc-cNMPs showed practically useful water solubility (nearly 500 microM), whereas 7-acetylated derivatives (Bhc-cNMPs/Ac) were expected to have a certain membrane permeability. Their advantages were demonstrated in two types of biological systems: the opening of cAMP-mediated transduction channels in newt olfactory receptor cells and cAMP-mediated motility responses in epidermal melanophores in scales from medaka fish. Both examples showed that Bhc and Bhc/Ac caged compounds have great potential for use in many cell biological applications.     

Simultaneous analysis of four kinds of emulsifiers in beverages by GC/MS

An analytical method using GC/MS for the detection of 4 kinds of dietary emulsifiers, glycerin, sucrose, sorbitan and propylene glycol monoesters of fatty acids (GE, SuE, SE, PGE), in beverages was developed. The emulsifiers were extracted from beverages with tetrahydrofuranethyl acetate (6:4) by homogenizing. The extract was cleaned up on a silica gel column and subsequently a C8 cartridge column, followed by acetylation. The derivatives were then detected by GC/MS. Our newly established method enabled to characterize 4 kinds of emulsifiers and also to identify their fatty acids without hydrolysis or de-esterification. When this method was applied to various beverages on the market, many GE and SuE with different fatty acids were detected. These results suggested that several dietary emulsifiers are used as food additives at the same time in beverages on the market.     

Inter-laboratory evaluation studies of notified ELISA methods for allergic substances (egg)

Inter-laboratory evaluation studies were conducted for the notified ELISA methods for allergic substances (Egg). Standard extracts of egg spiked in extracts of sausage, sauce, cookie, bread and cereal at a level of 5-20 ng/mL as the sample solution were analyzed in replicate in 10 laboratories. Coefficients of variation (CVs) of all three ELISA methods using an Egg Protein ovalbumin ELISA Kit (ovalbumin kit), an Egg Protein ovomucoid ELISA Kit (ovomucoid kit) and a FASTKIT Egg ELISA kit (Egg ELISA kit) were mostly less than 10%. Mean recoveries of the standard extract of egg were over 40% in the three ELISA methods. Repeatability relative standard deviations of egg standard solution in five food extracts were in the ranges of 18.7-25.5%, 18.6-41.8%, 21.3-43.3% for the ovalbumin kit, the ovomucoid kit and the Egg ELISA kit, respectively. Reproducibility relative standard deviations of egg standard solution in five food extracts were 16.8-35.1%, 19.6-35.8%, 24.7-51.1% for the ovalbumin kit, the ovomucoid kit and the Egg ELISA kit, respectively. The detection limits of all the ELISA methods were 4-5 ng/mL in sample solutions. These results suggested that the notified ELISA methods are reliable and reproducible for the inspection of egg protein levels in extracts of sausage, sauce, cookie, bread and cereal.     

Induction of type 2 deiodinase activity by cyclic guanosine 3',5'-monophosphate in cultured rat glial cells

We investigated the effects of cyclic guanosine 3',5'-monophosphate (cGMP) on type 2 iodothyronine deiodinase (D2) in cultured rat glial cells. Rat glial cells were cultured in Dulbecco's modified Eagle's medium supplemented with 15% fetal bovine serum. When cells were cultured in the presence of 8-bromo cGMP (8-Br cGMP), an analogue of cGMP, D2 activity was increased in a time- and concentration-dependent manner. Lineweaver-Burk plots revealed that the stimulation of D2 activity by 8-Br cGMP (10(-3) M) was associated with fivefold increase in maximum velocity but without a significant change in Michaelis-Menten constant, suggesting that cGMP increases D2 activity via new enzyme synthesis. Both atrial natriuretic peptide (ANP) and C-type natriuretic peptide (CNP) are well known to increase the intracellular cGMP level via their guanylate cyclase-linked receptors in rat glial cells. In the present study, ANP (10(-6) M) and CNP (10(-6) M) significantly increased the D2 activity in rat glial cells (1.9-fold [ANP] or 2.3-fold [CNP] compared with control activity, respectively). Northern blot analysis demonstrated that D2 mRNA level increased in the presence of 8-Br cGMP (10(-3) M), and reached a plateau (six-fold) after 4 hours of incubation. The increment of D2 mRNA level by 8-Br cGMP was comparable with the increase of the D2 activity by this agent. Our data suggest that cGMP induces rat D2 activity, at least in part, at the pretranslational level, and that ANP and CNP increase D2 activity most likely via their guanylate cyclase-linked receptors in rat glial cells.