Glycoconjugated polymer 6. Synthesis of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(styrene-<Emphasis Type="Italic">graft</Emphasis>-amylose)] via potato phosphorylase-catalyzed polymerization

Summary The potato phosphorylase-catalyzed polymerization of α-D-glucose-1-phosphate (G-1-P) onto poly[styrene-block-(4-vinylbenzyl maltohexaoside)] (1) was performed at the molar ratios of [G-l-P]₀ and [maltohexaose]₀ of 35, 80, and 250. The product was found to be soluble in dimethyl sulfoxide, which was a good solvent for amylose, and showed the complex-formation with iodine, indicating that the product was assignable to poly[styrene-block-(styrene-graft-amylose)] (2). The quantitative analysis of the liberated phosphoric acid gave the average degree of polymerization o f the glucose unit (n) as 27, 5 1, and 180 for 2-I, 2-II, and 2-III, respectively. Received: 29 November 2002/Accepted: 22 December 2002 Correspondence to Toyoji Kakuchi     

Formation of Bromate Ion Through a Radical Pathway in a Continuous Flow Reactor

The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ～ 3.8 mgL), pH (6.5 ～ 8.5), and t-butanol concentration (0 ～ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k _HO,Br^? of 1.7 × 10⁹ (M^?1s^?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor.     

Synthesis of Hard Materials by Field Activation: The Synthesis of Solid Solutions and Composites in the TiB2–WB2–CrB2 System

The synthesis of solid solutions of (Ti,W,Cr)B₂ from elemental reactants using the field-activated, pressure-assisted synthesis method and employing the SPS apparatus was investigated. The nature of the products depended on temperature; they were nearly pure solid solutions at 1900°C with minor amounts of β-WB. The product density and microhardness depended on the temperature of synthesis for the same value of applied pressure (64 MPa). Samples with the highest density (94%) corresponded to a hardness of 22.7 GPa. When annealed at 1500°C, the solid solutions decomposed, precipitating a (W,Ti,Cr)B₂ phase in a spinodal form. In addition, β-WB precipitates in the form of thin (0.4–5.3 nm) layers were observed. They existed in a 60°/120° orientation to the (Ti,W,Cr)B₂ matrix, in agreement with previous observations. Highly faceted, small (nanosized) pores associated with the β-WB precipitates were also observed.     

Raman spectra of high‐density,low‐density,and linear low‐density polyethylene pellets and prediction of their physical properties by multivariate data analysis

Raman spectra have been measured for pellets of five samples of high‐density polyethylene (HDPE), seven samples of low‐density polyethylene (LDPE), and six samples of linear low‐density polyethylene (LLDPE). The obtained Raman spectra have been compared to find out characteristic Raman bands of HDPE, LDPE, and LLDPE. Principal component analysis (PCA) was applied to the Raman spectra in the 1600–650 cm^?1 region after multiplicative scatter correction (MSC) to discriminate the Raman spectra of the three different PE species. They are classified into three groups by a score plot of PCA factor 1 vs. 2. HDPE with high density and high crystallinity gives high scores on the factor 1 axis, while LDPE with low density and low crystallinity yields negative scores on the same axis. It seems that factor 1 reflects the density or crystallinity. A PC weight loadings plot for factor 1 shows six upward peaks corresponding to the bands arising from the crystalline parts or all‐trans ? (CH₂)_n? groups and seven downward peaks ascribed to the bands of the amorphous or anisotropic regions and those arising from the short branches. Partial least‐squares (PLS‐1) regression was applied to the Raman spectra after MSC to propose calibration models that predict the density, crystallinity, and melting points of the polyethylenes. The correlation coefficient was calculated to be 0.9941, 0.9800, and 0.9709 for the density, crystallinity, and melting point, respectively, and their root‐mean‐square error of cross validation (RMSECV) was found to be 0.0015, 3.3707, and 2.3745, respectively. The loadings plot of factor 2 for the prediction of melting point is largely different from those for the prediction of density and crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 443–448, 2002     

Anomalous oxide scale formation under exposure of sodium containing gases for solid oxide fuel cell alloy interconnects

Reactivity of oxide scale on Fe-Cr alloy with Na-containing gases was examined to estimate the stability against sodium (Na): vapors of NaCl and Na₂SO₄ exposures with air flow at 1073 K. The identified reaction phases were Cr-Mn spinel, Cr₂O₃, and alloy from the X-ray diffraction of surface with no Na-reaction products. However, the protective oxide scales (Mn-Cr spinel and Cr₂O₃ layers) on the Fe-Cr alloy were partially decomposed by reacting with Na to form Na-compounds inside the oxide scale/alloy interfaces. In some parts, anomalous oxide scales were found around the oxide scale/Fe-Cr alloy interfaces, with forming Na-rich compounds: the compounds were distributed inner parts of oxide scales around oxide scale/alloy interfaces. The stability of oxide scales and degradation were discussed based on the observed distribution of elements.     

Liquid-Phase-Assisted Sintering of Calcium-Doped Lanthanum Chromites

Investigations have been made on the low-temperature sinterability of calcium-doped lanthanum chromites which are to be used as interconnectors in solid oxide fuel cells (SOFCs). Nominally chromium deficient lanthanum calcium chromites (La_0.7Ca_0.3Cr₁-_yO₃, y = 0.02) were found to be sinterable to 94% theoretical density at 1573 K in air, whereas no densification was observed for samples with y = 0. The two-step shrinkage process suggests a liquid phase sintering mechanism with calcium oxychromates playing an important role as the liquid phase. After sintering at 1573 K, calcium-rich substances remained at grain boundaries.     

Prolongation of ventricular action potential due to sympathetic stimulation

The changes of monophasic action potential durations due to stellate stimulation for the period of 3 sec were studied in dogs with suction electrodes from the anterior surface of the right ventricle and the posterior surface of the left ventricle. Prolongation of monophasic action potential duration was observed from the period of 2 to 3 sec during stimulation to that of 10 to 20 sec after the termination of stimulation. Prolongation of monophasic action potential duration due to right stellate stimulation was predominant in the right ventricle and that due to left stellate stimulation was predominant in the left ventricle. The transient T wave change in the surface electrocardiogram occurring immediately after the beginning of stellate stimulation could be explained by this local difference in prolongation of ventricle repolarization. Since the onset of prolongation of monophasic action potential duration preceded increase in blood pressure following stellate stimulation, this prolongation of monophasic action potential duration did not result from the hemodynamic changes and could be a primary effect of the sympathetic nerve stimulation.     

Carbonization of adamantane to a graphitizable carbon

Adamantane was carbonized in sealed tubes to 1073 K. Despite the non-planar molecular structure of adamantane, the resulting carbon was graphitizable. Using i.r. and u.v. spectrometry, mass spectrometry and X-ray diffraction, it was found that adamantane begins to decompose at ≈ 823 K to yield such planar molecules as phenanthrene, methyl-phenanthrene and pyrene. These molecules lead to a graphitizing carbon through a carbonization process which is similar to that of a pitch.     

Femtosecond Ti: Sa ultra short-pulse laser irradiation effects on the properties and morphology of the zirconia surface after ageing

Femtosecond pulses from a Ti:Sapphire laser were used to irradiate specimens of yttria-stabilised (35% mol) tetragonal zirconia (Y-TZP) with the purpose of studying the effects of the irradiations on their surface properties and morphology after ageing. Zirconia disks were divided into eight groups (n = 32) according to their surface treatment and subsequent ageing: Control: no treatment; sandblasting: Al₂O₃ sandblasting 50 μm; and ultrashort laser pulses irradiation with 25 μJ pulses, considering two different scanning steps based on the width between two grooves. These groups were duplicated and submitted to ageing. The surfaces were analysed using scanning electron microscopy (SEM), and X-ray diffraction. A finite element analysis, a biaxial flexure test, as well as fractographic and Weibull analyses, were performed. The strengths of the disks were statistically different for the treatment factor, and the principal stresses seemed to be concentrated at the centre of the specimens, as predicted by the computer simulations. Ageing decreased the strengths for all groups and increased the Weibull modulus for the laser group with the 40 μm-width between two grooves. The sandblasting group presented the highest monoclinic phase peak. Although the most significant strength was found within the sandblasting group, the phase transformation was favourable to the laser groups. The Weibull modulus was higher for the laser group with the 60 μm-width between two grooves, confirming the highest homogeneity of its failure distribution. Regardless of the surface treatment, strength was decreased with ageing in all groups. The femtosecond Ti:Sa ultra-short pulse laser irradiation can be suggested as an alternative to the gold standard sandblasting in long-term Y-TZP zirconia rehabilitations, such as crowns and veneers.