Determination of triazine pesticides and related compounds in environmental water by liquid chromatography-mass spectrometry.

A method for the determination of 5 triazine herbicides and 12 degradation products in environmental water samples using liquid chromatography-electrospray ionization mass spectrometry (LC/ESI/MS) has been developed. The pesticides in water were extracted with two types of solid phase: a styrene-divinylbenzene copolymer and a graphitized carbon black. Desorption solvents for the extracted compounds were acetone for the styrene-divinylbenzene copolymer and methanol for the graphitized carbon black. Overall recoveries from ground water and river water ranged from 73% to 111%. The limits of detection (LODs) were 0.2 to 28 ng l(-1). This method was applied to several ground water samples.     

Phase rotation scheme of laser-produced ions for reduction of the energy spread

In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented.     

Discrimination of poly(vinyl chloride) samples with different plasticizers and prediction of plasticizer contents in poly(vinyl chloride) using near-infrared spectroscopy and neural-network analysis.

In the recycling of poly(vinyl chloride) (PVC), it is required to discriminate every plasticizer for quality control. For this purpose, the near-infrared spectra were measured for 41 kinds of PVC samples with different plasticizers (DINP, DOP, DOA, TOTM and Polyester) and different plasticizer contents (0-49%). A neural-network analysis was applied to the near-infrared spectra pretreated by second-derivative processing. They were discriminated from one another. The neural-network analysis also allowed us to propose a calibration model which predicts the contents of plasticizers in PVC. The correlation coefficient (R) and the root-mean-square error of prediction (RMSEP) for the DINP calibration model were found to be 0.999 and 0.41 wt%, respectively. In comparison, a partial least-squares regression analysis was carried out. The R and RMSEP of the DINP calibration model were calculated to be 0.993 and 1.27 wt%, respectively. It is found that a near-infrared spectra measurement combined with a neural-network analysis is useful for plastic recycling.     

Synthesis of 5-heteroarylazulenes: first selective electrophilic substitution at the 5-position of azulene

1,3-Di-tert-butylazulene reacted with highly electrophilic trifluoromethanesulfonate of N-containing heterocycles to give 5-(dihydroheteroaryl)azulene derivatives in good yield and treatment of the 5-(dihydroheteroaryl)azulene derivatives with KOH afforded 5-(heteroaryl)azulenes in excellent yield.     

Improved method for measurement of rhodanese activity using methanethiosulfonate as sulfur donor substrate and its application to human serum.

We have developed a sensitive method for the measurement of rhodanese activity in human serum which is based on the colorimetric method for the determination of thiocyanate produced from methanethiosulfonate and cyanide as substrates. Thiocyanate gives a red complex with ferric ion in an acidic condition. The present method is about 70-fold more sensitive than the conventional method using cyanide and thiosulfate as substrates and correlates well (r = 0.997) with the conventional method in bovine liver rhodanese. Within-run precision of the method is 0.91% for 420 units/l serum and the calibration curve is linear up to 1850 units/l. The normal value for human serum, determined by the present method on 31 healthy persons, was 20.9 +/- 20.0 units/l (mean +/- 2S.D.). Rhodanese activity was clearly elevated in some serum samples which were observed at abnormal values in some biochemical diagnostic tests and showed significant positive correlations with guanase activity (r = 0.728, p less than 0.01) and glutamic-oxalacetic transaminase activity (r = 0.625, p less than 0.01).     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

Electronic effect on the regioselectivity in the ring opening of para-substituted phenyloxiranes by acetylides

The electronic effect on the regioselectivity in the alkynylation of phenyloxiranes was investigated using three kinds of metal acetylides. BF₃ mediated lithium acetylide provided either the α- or β-alkynylated products by controlling the effect of the para-substituents of the phenyloxiranes. LiClO₄ mediated lithium acetylide and titanium acetylide, on the other hand, afforded predominantly the β- and α-products, respectively.     

Heteroatom-guided torquoselective olefination of alpha-oxy and alpha-amino ketones via ynolates

Ynolates were found to react with alpha-alkoxy-, alpha-siloxy-, and alpha-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the beta-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, alpha-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and gamma-butyrolactams in good yield.     

Amino acid end-group in commercial heparin. III. Determination of the number of amino groups of amino acid and hexosamine residues per heparin molecule

The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.