Study on ketalization reaction of poly(vinyl alcohol) by ketones. IV. Reaction between poly(vinyl alcohol) and aliphatic ketones and behavior of polyvinylketal in water

Ketalization reaction of poly(vinyl alcohol) (PVA) by aliphatic ketones, dimethylsulfoxide (DMSO) as solvent, under the presence of acidic catalyst, in homogeneous system was carried out and the synthesis of polyvinylketals were successfully performed. The equilibrium constant at 40°C is ca. 0.07 in the case of methyl n-propyl ketone (nPK) and methyl n-butyl ketone (nBK), but is ca. 0.05 in the case of methyl i-propyl ketone (iPK) and ca. 0.01 in the case of methyl i-butyl ketone (iBK) and methyl t-butyl ketone (tBK), respectively. Moreover, the ketalization degree of polyvinylketal by iBK and tBK reached to only ca. 35 mol % as the maximum. It seems that these were due to steric hindrance of bulky side chain of ketones. But the heat of reaction is 7.5 kcal/mol in all aliphatic ketones, it seems to proceed the same ketalization reaction mechanism. Films prepared from the polyvinylketals were soaked in water and degree of swelling, solubility, and hydrolysis of films were measured. The reaction of film with water, in acidic side, at first the film swells, and then, as the deketalization reaction proceeds, the film dissolves in water. The dissolution time is controlled by the kind of ketones, ketalization degree, and pH of water which reveals that deketalization reaction proceeds proportional to proton concentration. It is more difficult to dissolve highly ketalized polyvinylketals obtained by propyl ketones and butyl ketones than that by acetone. The hydrolysis of polyvinylketal film proceeds in the order as follows: acetone > MEK > nPK > iPK ≒ nBK > iBK > tBK. This phenomenon seems to be affected by hydrophobicity of the film surface which depends upon the kind of the original ketones.     

Stochastic Resonance in Recurrent Neural Network with Hopfield-Type Memory

Stochastic resonance (SR) is known as a phenomenon in which the presence of noise helps a nonlinear system in amplifying a weak (under barrier) signal. In this paper, we investigate how SR behavior can be observed in practical autoassociative neural networks with the Hopfield-type memory under the stochastic dynamics. We focus on SR responses in two systems which consist of three and 156 neurons. These cases are considered as effective double-well and multi-well models. It is demonstrated that the neural network can enhance weak subthreshold signals composed of the stored pattern trains and have higher coherence abilities between stimulus and response.     

Enhanced catalytic activity of nanoshell carbon co-doped with boron and nitrogen in the oxygen reduction reaction

The use of carbon cathode catalysts in polymer electrolyte fuel cells instead of the current platinum catalysts is attracting increasing attention. We claim that two factors are important for enhancing the activity of carbon cathode catalysts in the oxygen reduction reaction (ORR): the formation of a nanoshell structure and co-doping with boron and nitrogen. Herein, we investigate the preparation and characterization of active ORR carbon catalysts that combine the above factors. Boron and nitrogen (BN)-doped nanoshell-containing carbon (BN-NSCC) was prepared by carbonizing a mixture of poly(furfuryl alcohol), cobalt phthalocyanine, melamine, and a trifluoroborane–methanol complex at 1000 °C. Transmission electron microscopy and X-ray photoelectron spectroscopy revealed the formation of nanoshell structures with distorted graphitic layers and the introduction of boron and nitrogen atoms, respectively. The ORR activity was evaluated in oxygen-saturated 0.5 mol dm^?3 H₂SO₄ using Koutecky–Levich analysis. The BN-NSCC showed an eight to ten times higher ORR activity than undoped NSCC, with an increased number of electrons participating in the reaction. Tafel analysis revealed a change in the rate-determining step caused by BN-doping. Thus, the combination of a nanoshell structure and co-doping with boron and nitrogen was found to improve the ORR activity of carbon catalysts.     

Characteristics of neutralization of acids by newly isolated fungal cells

Soil microorganisms play an important role in maintaining soil pH at levels suitable for other soil organisms. To clarify the biological neutralization mechanism in soil, we isolated soil microorganisms showing a high ability to neutralize acids and studied their characteristics. From our taxonomic study, three isolated strains were identified as filamentous fungi, namely Mucor sp., Aspergillus fumigatus, and Aureobasidium pullulans. These strains could secrete basic materials, such as ammonia, for neutralization, grow in the medium at pH 4.0 and increase the pH of the medium to approximately 8.0. These microbial cells could neutralize not only nitric acid but also sulfuric and hydrochloric acids. The strains could also grow by utilizing nitric acid as a sole nitrogen source. In the soil containing these organisms, the pH was maintained in the neutral range by the buffering action of basic materials that they secrete. These results suggest that these fungal cells are useful for protecting the soil from acidification by acid rain.     

Chemical compositions,fine structure and physicochemical properties of kudzu (Pueraria lobata) starches from different regions

Three commercial kudzu starches from Vietnam, Japan and Korea were used to determine chemical compositions, isoflavone compounds, fine structure and physicochemical properties. The kudzu starch from Vietnam had polygonal granules, whereas the kudzu starches from Japan and Korea contained both polygonal and spherical granules. Total protein, lipid, ash and phosphorus contents present in these kudzu starches were less than 1% (starch basis). The kudzu starch from Vietnam and Korea contained both daidzein and daidzin, whereas the kudzu starch from Japan had only daidzein. These starches had similar actual amylose contents (22.2–22.9%). However, λ_max, blue value and apparent amylose contents of the kudzu starch from Vietnam were lower than those from Japan and Korea. Amylose molecules of the kudzu starch from Vietnam had the largest average degree of polymerization (DP_n) and number of chains (NC), followed by the kudzu starches from Japan and Korea. Amylopectin molecules of the kudzu starch from Vietnam also had the largest DP_n and NC, followed by the kudzu starches from Korea and Japan. X-ray diffraction patterns of the kudzu starches from Vietnam, Japan and Korea were A-type, C-type and B-type, respectively. The kudzu starch from Vietnam was found to have the specific characteristics such as significantly high gelatinization temperature, transition enthalpy and degree of crystallinity as compared to the kudzu starch from Korea and Japan.     

Identification of phenolic compounds isolated from pigmented rices and their aldose reductase inhibitory activities

Two anthocyanins (cyanidin-3-O-β-glucoside and peonidin-3-O-β-glucoside) and other phenolic (ferulic acid) were, respectively isolated from black and pigmented brown rices (Oryza sativa L. japonica) and their complete structures were determined by spectroscopic analyses (H NMR, C NMR and MALDI MASS). The HPLC profile of anthocyanins extracted from black rice showed cyanidin-3-O-β-glucoside as the first peak (85%) and peonidin 3-O-β-d-glucoside as the second (15%), while that of pigmented brown rice showed ferulic acid as the first peak (85.7%) and tocols as the second (14.3%). Several tocols were isolated and identified from the unsaponifiable fractions of both rices having some difference on their structures and amounts. The aldose reductase inhibitory activity of isolated compounds was in the following decreasing order: cyanidin-3-glucoside > quercetin > ferulic acid > peonidin-3-glucoside > tocopherol.     

Changes in textural properties of Japanese tenobe somen noodles during storage

Tenobe somen (TS) noodles are traditional Japanese wheat-based noodles that are produced manually using a sophisticated method called tenobe (literally, "hand stretched"). In the tension test, both the tensile strength and extensibility of TS noodles were greater than those of machine-made (MS) noodles. In the biting test, the chewy texture of TS noodles was realized in the analysis of the force-deformation curves of each type of somen noodles. The creep test indicated a clear difference between the external and internal elasticity of TS noodles. The texture of TS noodles appeared to change dramatically during storage in the rainy season. In addition, firm and chewy textures of TS noodles stored for 20 mo were observed. Similar to the results from our previous study, TS noodles exhibited significantly higher dityrosine content than the flour used for their manufacture. However, the increase in the dityrosine content during the manufacturing process was not observed in the case of MS noodles. Although clear textural differences were observed between TS noodles stored for 0 and 20 mo, the dityrosine contents of TS noodles at each stage were not largely different.     

Synthesis and crystalline structure of polyethylene containing 1,3-cylopentane units in the main chain by ring-opening metathesis copolymerization of cycloolefins following hydrogenation reaction

Polyethylene containing 1,3-cyclopentane units in the main chain was synthesized by ring-opening metathesis copolymerization of cyclopentene (CPE) or cyclooctene with norbornene (NB) following hydrogenation reaction. The copolymer with cis-1,3-cyclopentane units was obtained in good yield. The resulting copolymers showed multiple melting points. Temperature-rising elution fractionation of the copolymers elucidated a broad distribution of the copolymer composition. WAXD and FT-IR analyses of the copolymers showed existence of hexagonal crystal in hydrogenated poly(CPE-co-NB).