Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Distributions of major-to-ultratrace elements among the particulate and dissolved fractions in natural water as studied by ICP-AES and ICP-MS after sequential fractionation.

In order to elucidate the distributions of the elements among the particulate and dissolved fractions in pond water, major-to-ultratrace elements in different sizes of particles as well as in the filtrate passed through the 0.05 microm filter were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The different sizes of particle samples (ca. 100-300 microg each) were collected on the membrane filters with pore sizes of 10, 3.0, 1.2, 0.4, 0.2 and 0.05 microm, respectively, by sequential fractionation. As a result, about 40 elements in different sizes of particles could be determined by ICP-AES and ICP-MS, after acid digestion using HNO3/HF/HClO4. Then, the fractional distribution factors of major-to-ultratrace elements among the particulate and dissolved fractions were estimated from the analytical results. The total contents of Al, Fe, Ti, REEs (rare earth elements), Bi, Pb and Ag in the particulate fractions (larger than 0.05 microm) were more than 80-90%, while those of Ca, Sr, Cs, W, Ba, Mn and Co in the dissolved fraction, which corresponded to the filtrate passed through the 0.05 microm membrane filter, were more than 80%. It was further found that the fractional distributions of Cu and Zn in the dissolved fraction were ca. 50%. In addition, the enrichment factors (EFs) of the elements in the particulate fractions with particle sizes of 3.0-10 microm and 0.05-0.2 microm were estimated to elucidate their geochemical characteristics in natural water.     

Electroneutrality coupling of electron transfer at an electrode surface and ion transfer across the interface between thin-layer of 1-octyl-3-methylimidazolium bis(perfluoroalkylsulfonyl)imide covering the electrode surface and an outer electrolyte solution.

The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram.     

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.     

High-quality InAlN/GaN heterostructures grown by metal–organic vapor phase epitaxy

We fabricated high-quality InAlN/GaN heterostructures by metal–organic vapor phase epitaxy (MOVPE). X-ray diffraction measurements revealed that InAlN/GaN heterostructures grown under optimal conditions have flat surfaces and abrupt heterointerfaces. Electron mobility from 1200 to 2000 cm²/V s was obtained at room temperature. To our knowledge, this mobility is the highest ever reported for InAlN/GaN heterostructures. We also investigated the relationship between the Al composition and sheet electron density (N_s) for the first time. N_s increased from 1.0×10¹² to 2.7×10¹³ cm⁻² when the Al composition increased from 0.78 to 0.89.     

Basic Properties of the (t, n)-Threshold Visual Secret Sharing Scheme with Perfect Reconstruction of Black Pixels

In this paper we consider the (t, n)-threshold visual secret sharing scheme (VSSS) in which black pixels in a secret black-white images is reproduced perfectly as black pixels when we stack arbitrary t shares. This paper provides a new characterization of the (t, n)-threshold visual secret sharing scheme with such a property (hereafter, we call such a VSSS the (t, n)-PBVSSS for short). We use an algebraic method to characterize basis matrices of the (t, n)-PBVSSS in a certain class of matrices. We show that the set of all homogeneous polynomials each element of which yields basis matrices of the (t, n)-PBVSSS becomes a set of lattice points in an (n−t+1)-dimensional linear space. In addition, we prove that the optimal basis matrices in the sense of maximizing the relative difference among all the basis matrices in the class coincides with the basis matrices given by Blundo, Bonis and De Santis [3] for all n≥ t ≥ 2.     

A new monitoring system of cultured myocardial cell motion: effect of pilose antler extract and cardioactive agents on spontaneous beating of myocardial cell sheets

Effects of various cardioactive agents and a water extract of the pilose antler of Cervus nippon var. mantchuricus on periodic beating of cultured myocardial cell sheets were examined by using an image analyzing system. Norepinephrine increased the beating rate and the beating amplitude, whereas digoxin and forskolin enlarged only the beating amplitude. Verapamil and propranolol decreased both the beating rate and the beating amplitude. The water extract of the pilose antler showed no remarkable effects in a standard medium (2.1 mM Ca2+). However, it significantly increased the beating amplitude when the beating was suppressed by replacement with a low calcium medium (0.5 mM Ca2+). A similar effect was found for 70% ethanol-soluble and -insoluble fractions of the extract.     

A new route for the construction of the AB-ring core of Taxol

A new method for the construction of the AB-ring core of Taxol was developed utilizing a new skeletal transformation protocol as a pivotal step. The acid-catalyzed rearrangement of the cyclopentenone-allene photoadduct gave a bridged seven-membered ketone, which was easily transformed, using the intramolecular Suzuki reaction and the oxidative cleavage of the vicinal diol, to the bicyclic diketone.     

Topological spectrum of locally compact Cantor minimal systems

We show that there exists a locally compact Cantor minimal system whose topological spectrum has a given Hausdorff dimension.

     

Enhancement effect of iron addition for the decomposition of organic mercury as studied by continuous flow analysis with cold vapor atomic absorption spectrometric detection

Summary A continuous flow analysis is described for the determination of total mercury by cold vapor atomic absorption spectrometry. Organic mercury compounds such as methylmercury(II) chloride, ethylmercury(II) chloride and phenylmercury(II) chloride were decomposed by potassium peroxodisulphate with addition of ferric chloride as catalytic reagent. The reducing reagent used was tin(II) chloride in sodium hydroxide solution. With 1,000 mg Fe/l added in the decomposition process, we found that methylmercury(II) chloride and ethylmercury(II) chloride gave response signals similar to those of mercury(II) chloride. The proposed method was applied to the analysis of total mercury in waste water. Permanent address: Department of Chemistry, Faculty of Mathematics and Natural Sciences, Andalas University, Padang, West Sumatra, Indonesia