On the synthesis of protopine alkaloids

For the synthesis of protopine alkaloids, we studied a reaction sequence based on a ring enlargement of indeno[2,1-a][3]benzazepines by a singlet oxygen oxygenation, followed by conversion of an amide carbonyl group of the resultant 10-membered keto-lactam to a methylene group, which is the last step for completion of the synthesis. The key substances, indeno[2,1-a][3]benzazepines, were prepared by Bischler-Napieralski cyclization of alkoxy-substituted 1-(2-bromobenzyl)-3-benzazepin-2-ones. Steric effects of the substituents in this synthesis were examined.     

Infrared Spectroscopy and X-Ray Diffraction Studies on the Structure and Thermal Behavior of Biodegradable Polyhydroxyalkanoates

The structure and thermal behavior of new types of bacterial copolyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate); P(HB-co-HHx) (HHx=2.5, 3.4, and 12 mol %) have been explored by means of wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), and infrared (IR) spectroscopy. The WAXD pattern of P(HB-co-HHx) (HHx=12 mol %) copolymer measured at room temperature has revealed that it has an orthorhombic system (α=β=γ=90°) with a=5.76Å, b=13.20Å, c=5.96Å (fiber repeat), which is identical to that of poly(3-hydroxybutyrate) (PHB). It has been found from the temperature-dependent variations of the WAXD pattern that only the a lattice parameter shows the thermal expansion, while the b lattice parameter changes little with temperature in the crystalline P(HB-co-HHx) (HHx=12 mol %). This observation suggests that there are inter and intramolecular interactions between C=O groups and alkyl groups along the a axis and that interactions are broken little by little with temperature. IR spectra were measured for the four kinds of polymers over a temperature range from 30°C to high temperatures (200°C; PHB, 180°C; P(HB-co-HHx) (HHx=2.5 mol %), 180°C; P(HB-co-HHx) (HHx=3.4 mol %), 150°C; P(HB-co-HHx) (HHx=12 mol %)). Temperature-dependent IR spectral variations were analyzed for the CH, C=O, and C-O-C stretching band regions, and bands characteristic of crystalline and amorphous parts were identified in each region. It has been found from the IR study that the strength of interaction between the C=O group and the CH₃ (or CH₂) group is similar among the four polymers and that the population of C=O groups that are not involved in the interaction becomes higher with the increase in HHx. Both WAXD and IR studies have revealed that the crystallinity of P(HB-co-HHx) (HHx=12 mol %) decreases gradually starting from relatively low temperature (about 60°C) while that of PHB remains high up to 170°C.     

Raman and Wide-Angle X-Ray Diffraction Studies on Molecular Structure,Crystallinity, and Morphology of Uncompatibilized and Compatibilized Blends of High Molecular Weight Polyethylene/Nylon 12

Molecular structure, crystallinity and morphology of uncompatibilized and compatibilized blends of high molecular weight polyethylene (HMWPE) and Nylon 12 were investigated by using Fourier-transform (FT) Raman spectroscopy, wide-angle x-ray diffraction (WAXD), and scanning electron microscopy (SEM). One of the important purposes of the present study is to compare the present results for HMWPE/Nylon 12 with the previously obtained results for high-density polyethylene (HDPE/Nylon 12). Uncompatibilized and compatibilized blends of HMWPE/Nylon 12 with a Nylon 12 content ranging from 10 to 90 wt% at increments of 10 wt% were prepared. The compatibilized polymer blends were prepared by adding a small amount of maleic anhydride (MAH), and SEM images show that the addition of the small amount of MAH (0.5 wt%) yields a marked improvement of dispersion of HMWPE and Nylon 12. To evaluate the crystallinity of HMWPE from Raman spectra, the relative intensities of bands at 1418 and 1129 cm⁻¹ to the intensity of a band at 1000 cm⁻¹ (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) were estimated for all the uncompatibilized and compatibilized blends of HMWPE/Nylon 12. From the comparison of the relative intensities (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) between the uncompatibilized and compatibilized blends of HMWPE/Nylon 12 it was found that when the Nylon 12 content reaches 40 wt% the crystallinity of HMWPE in the compatibilized blends becomes higher than that of HMWPE in the uncompatibilized blends. The uncompatibilized and compatibilized blends of HMWPE/Nylon 12 (50/50) show quite different x-ray diffraction patterns; the compatibilized blend shows a significantly larger orientational effect in the x-ray pattern of HMWPE. It seems that the increase of interaction of MAH-HMWPE with the Nylon 12 matrix leads to the additional crystallinity.     

Precision synthesis of (1→6)-α-D-glucopyranan by cationic ring-opening polymerization of 1,6-anhydro-2,3,4-tri-O-allyl-β-D-glucopyranose

The ring-opening polymerization of 1,6-anhydro-2,3,4-tri-O-allyl-β-D-glucopyranose ( 2 ) has been carried out using various cationic initiators. For the condition of [ 2 ]/[BF₃·OEt₂] = 20 at −15°C for 90 h, the polymer yield, M_w and M_w/M_n of the polymer obtained were 79%, 215,600 and 3.45, respectively. In order to study the living characteristic of the polymerization of 2 , the cationic ring-opening bulk polymerization initiated by trimethylsilyl trifluoromethanesulfonate (TMSOTf) was carried out under the condition of [ 2 ]/[TMSOTf] = 1000 at −15 °C. The M_w value increased in proportion to conversion until c.a. 30% and below. The M_w/M_ns of resulting polymers were very narrow, e.g., the M_w/M_n value was 1.2 and below, which was smaller than that for the solution polymerization using BF₃·OEt₂. These results indicated that the ring-opening bulk polymerization of 2 using TMSOTf was living-like.     

The Existence of Global Solutions to a Fluid Dynamic Model for Materials for Korteweg Type

We discuss the existence of global solutions to a fluid dynamic model for materials of Korteweg type, and discuss the three dimensional nonisothermal motion. The higher order derivatives of density in the constitutive relation makes it necessary to introduce an interstitial working term in the energy equation. This makes the energy estimate more involved. Nevertheless, it is possible to show the existence of global solutions by the euergy method.     

Direct characterization of phase behavior and compatibility in PET/HDPE polymer blends by confocal Raman mapping

Morphology, chemical distribution and domain size in poly(ethylene terephthalate)/high‐density poly(ethylene) (PET/HDPE) polymer blends of various ratios prepared with and without maleic anhydride have been analyzed with confocal Raman mapping and SEM. The ratioimage method introduced here allows us to obtain enhanced chemical images with higher contrast and reliability. Compatibility numbers (N_c) are calculated to evaluate the compatibility of the blends. The incompatible polymer blends show heterogeneous distribution with phase separation behavior, while the semicompatible blends prepared with maleic anhydride show much smaller subphase distributions with less distinct interphases. After the blending modification by maleic anhydride of only 0.5%, the viscosity status and dispersibility between PET and HDPE could be substantially improved, and the interactions that exist between the two phases have also been proved by ATR‐FT‐IR results. High‐spatial‐resolution confocal Raman mapping coupled with the ratioimage method provides a very attractive way to characterize the compatibility and phase behavior of the polymer blend through different blending methodologies. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparison of three post-column reaction methods for the analysis of bromate and nitrite in drinking water

Three post-column ion chromatographic methods (i.e., a sodium bromide–sodium nitrite method, an o-dianisidine method, and a potassium iodide–ammonium heptamolybdate method) were compared for bromate and nitrite analysis. Also, the effect of direct mixing of the reagents without ion suppressors for the sodium bromide–sodium nitrite method and the potassium iodide–ammonium heptamolybdate method was investigated. For the analysis of bromate, the three methods showed similar method detection limits (0.17–0.24 μg/l) with pneumatic reagent delivery systems. Direct reagent mixing achieved comparable detection limits to the suppressor configuration. The three methods are also compatible with conductivity detection. When used in combination with conductivity detection, this compatibility allows simultaneous analysis of bromate, nitrite, and other common ions in drinking water, such as bromide. It was found that the o-dianisidine method achieves μg/l-level detection of nitrite and bromate with a simpler configuration than the potassium iodide–ammonium heptamolybdate method, while the sodium bromide–sodium nitrite method was not sufficiently sensitive for nitrite analysis at the μg/l level.