Multifunctional Initiator with Platinum-Acetylide Dendritic Core for Living Polymerization of Isocyanides

A novel multifunctional initiator has been developed by peripheral modification of a Pt-acetylide dendrimer. Pd–Pt μ-ethynediyl units were introduced to the first-generation dendrimer by a divergent method. The dendritic initiator was applicable to the living polymerization of aryl isocyanides, producing high molecular weight polymers with a narrow polydispersity index in quantitative yields. The ³¹P NMR spectrum of the resulting polymer suggested that all Pd–Pt μ-ethynediyl units in the dendritic molecule actually functioned as an initiator.     

Potato and soy peptides alter caecal fermentation and reduce serum non‐HDL cholesterol in rats fed cholesterol

We examined the effect of potato peptides (PPC) in rats fed a cholesterol‐enriched diet, in comparison with two cholesterol‐enriched diets containing soy peptides (SPC) or casein (CNC), and a cholesterol‐free diet containing casein (CN) for 4 weeks. The serum non‐high‐density lipoprotein (HDL) cholesterol level was lower in the PPC‐ (–18.39%) and SPC‐fed (–32.76%) groups (p <0.05) than in the CNC‐fed group at the end of the feeding period. The low‐density lipoprotein receptor mRNA level in the PPC‐fed group, and cholesterol 7α‐hydroxylase and scavenger receptor class B type 1 mRNA levels in the SPC‐fed group, were higher (p <0.05) than in the CN‐ and CNC‐fed groups. Faecal neutral sterol and caecal short‐chain fatty acid concentrations in the PPC‐ and SPC‐fed groups were higher (p <0.05) than in the CN‐ and CNC‐fed groups. The faecal total acidic sterol concentration was higher in the SPC‐fed group than in the CN‐ and PPC‐fed groups. Caecal anaerobe and Bifidobacterium populations were higher (p <0.05) in the PPC‐ and SPC‐fed groups than in the CN‐fed group. This study suggests that potato peptides, as soy peptides, alter caecal fermentation and steroid absorption and reduce the serum non‐HDL cholesterol level in rats fed cholesterol.     

Production of dihomo-γ-linolenic acid byMortierella alpina 1S-4

The mycelial dihomo-γ-linolenic acid content of an arachidonic acid-producing fungus,Mortierella alpina 1S-4, was found to increase, with an accompanying marked decrease in its arachidonic acid content, on cultivation with sesame oil. The resultant mycelia were found to be a rich source of dihomo-γ-linolenic acid. This unique phenomenon was suggested to be due to specific repression of the conversion of dihomo-γ-linolenic acid to arachidonic acid by the oil. After fractionation of the oil with acetone into oil and non-oil fractions, it was found that the effective factor(s) was present in the non-oil fraction. In a study on optimization of the culture conditions for the production of dihomo-γ-linolenic acid byM. alpina 1S-4, a medium containing glucose, yeast extract and the non-oil fraction was found to be suitable for the production. Under the optimal conditions in a 50-1 fermentor, the fungus produced 107 mg of dihomo-γ-linolenic acid/g dry mycelia (2.17 g/l of culture broth). This value accounted for 23.1% of the total fatty acids in the lipids extracted from the mycelia. The mycelia were also rich in arachidonic acid (53.5 mg/g dry mycelia, 11.2%). Other major fatty acids in the lipids were palmitic acid (24.1%), stearic acid (7.0), oleic acid (20.1), linoleic acid (6.6) and γ-linolenic acid (4.1). On leave from Suntory Ltd.     

Ionic transport in amorphous anodic titania stabilised by incorporation of silicon species

Incorporation of silicon species from an alloy substrate into anodic titania is shown to stabilise the structure of the film, facilitating investigation of the ionic transport processes in amorphous titania grown at high efficiency. Thus, an amorphous anodic film developed on a sputtering-deposited Ti-6 at.%Si alloy formed to 100 V in phosphoric acid electrolyte in contrast to a partially crystalline film developed on relatively pure titanium at <20 V. Silicon species, which are immobile and act as marker species in the growing film, are present in the inner 58% of the film thickness. Evidently, the film material forms simultaneously at the film/electrolyte and alloy/film interfaces by co-operative transport of cations and anions, as is usual in amorphous anodic oxides. The phosphate anions incorporated from the electrolyte migrate inward at 0.34 times the rate of O²⁻ ions and hence are present in the outer 62% of the film thickness.     

The micro-nanoformability of Pt-based metallic glass and the nanoforming of three-dimensional structures

Pt_48.75Pd_9.75Cu_19.5P₂₂ amorphous alloy exhibits obvious glass transition behavior at a temperature of T_g=502 K, which is below the crystallization temperature T_x=588 K, and develops a supercooled liquid state in a wide temperature range of ΔT_x (=T_x−T_g)=86 K. The present paper investigates the macroscopic and microscopic deformation behavior of the material and the possibility of micro-nano forming as a fabrication method and material for nano-devices. On a macroscopic scale, the material exhibits a Newtonian viscous flow in a supercooled liquid state. An index of the microformability is also evaluated by the geometrical transferability of a die shape to the material. For this study, we fabricated V-grooved micro dies of (100) Si by a silicon process. The V-groove dies are from 100 nm to 1 μm wide. The material exhibits superior formability on micrometer and nanometer scales and may possibly be applied to micro-nanomaterials for micro-nano devices.     

Effect of Lipase Activity and Specificity on the DAG Content of Olive Oil from the Shodoshima-Produced Olive Fruits

Olive oils have a higher relative diacylglycerol (DAG) content than other plant oils. The lipase in olive fruits is involved in DAG production and is directly related to the acidity of the olive oil. However, the lipase activity and positional selectivity have not been clarified. To investigate the properties of olive fruit lipase, olive fruits of the Mission variety harvested during mid-December of 2005 on Shodoshima Island (Japan) were stored at 20, 30 or 40 °C for 4 weeks. Changes in the acidity and acylglycerol content of the oils extracted from the stored fruits were analyzed. The acidity and DAG content of the olive oils increased due to triacylglycerol (TAG) hydrolysis during storage. sn-1,2-DAGs preferentially increased during the early stages of storage, indicating that the olive fruit lipase is enantioselective for the sn-3 position, while non-enzymatic isomerization of sn-1,2-DAGs was observed throughout the entire duration of storage. Kinetic analysis revealed that the enantioselectivity of olive fruit lipase for the sn-3 position was approximately four times greater than for the sn-1 position. The lipase was gradually inactivated at temperatures of 30 °C or higher, and the ratios of the rate constant for inactivation to TAG hydrolysis at the sn-3 position was 0.2, 13, and 23 at 20, 30, and 40 °C, respectively.     

Removal of phosphate ions with a chemically modified chitosan/metal‐ion complex

The adsorption of metal ions (Mo⁶⁺, Cu²⁺, Fe²⁺, and Fe³⁺) was examined on chemically modified chitosans with a higher fatty acid glycidyl (CGCs), and the adsorption of Cu²⁺ was examined on ethylenediamine tetraacetic acid dianhydride modified CGCs (EDTA‐CGCs) synthesized by the reaction of the CGCs with ethylenediamine tetraacetic acid dianhydride. The adsorption of phosphate ions onto the resulting substrate/metal‐ion complex was measured. Mo⁶⁺ depicted remarkable adsorption toward the CGCs, although all the Mo⁶⁺ was desorbed under the adsorption conditions of the phosphate ions. The other metal ions were adsorbed to some extent on CGCs by chelating to the amino group in the substrate, except for CGC‐1, which had the highest degree of substitution (83.9%). Considerable amounts of Fe²⁺ were adsorbed onto CGCs; however, only a limited number of phosphate ions was adsorbed onto the substrate/metal‐ion complex. As a result, the following adsorbent/metal‐ion complexes gave higher adsorption ability toward phosphate ions: CGC‐4/Cu²⁺, CGC‐4/Fe³⁺, and EDTA‐CGC‐3/Fe³⁺. Where, CGC‐3 is a chemically modified chitosan with the degree of substitution of 26.5 percentage, and CGC‐4 is one with the degree of substitution of 16.0 percentage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Promotive effect of isopentane on cyclohexane isomerization catalyzed by sulfated zirconia

Cyclohexane isomerization to methylcyclopentane over sulfated zirconia is markedly enhanced in the presence of isopentane which acts as a hydride transfer agent to facilitate the slow step of hydride transfer from cyclohexane to isopropyl cation. This was revealed by deuterium tracer studies. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mixing in multiple-impeller stirred tank reactors with boiling liquids

Mixing in a boil-off mechanically stirred tank reactor with multiple impellers was examined. Power consumption and gas hold-up were measured in boiling water in a 0.2 m i.d. stirred tank reactor with three four-pitched blade downflow disk turbines. Vapour was generated from both the immersed ring heater and the impellers. At low vapour generation rates, vapour was mainly generated from the impellers rather than from the heater, whereas nucleation occurred at the heater instead of the impeller at higher vapour generation rates. The mechanical power consumption decreased due to vapour generation. The change in boiling-to-non-boiling mechanical power ratio with varying impeller rotational speed and boiling rate was complicated and not monotonous except at higher impeller speeds and boiling rates. The gas hold-ups increased with increasing vapour generation rate but were rather small as compared to those in cold gas dispersing systems. Empirical correlations for power consumption and gas hold-up in boiling liquids were developed using the present experimental data.     

Giant electric double-layer capacitance of heavily boron-doped diamond electrode

The physical and electrochemical properties of boron-doped polycrystalline diamond electrodes, prepared with various B/C ratio, i.e., 0.1%, 0.5% (BDD-A), 1% (BDD-B), and 5% (BDD-C), were investigated. Electrochemical measurements of the heavily boron-doped films (BDD-C) showed giant electric double-layer capacitance and activity which is significantly larger than BDD-A and BDD-B as well as glassy carbon electrodes. However, interestingly, actual boron concentration of BDD-C was observed to be almost the same as that of BDD-B by secondary ion mass spectroscopy (SIMS) and glow discharge optical emission spectroscopy (GDOES) analysis. It is suggested that the large capacitance is due to a few sp²-bonded carbon impurities, which was observed only in BDD-C, although the amount of the sp²-bonded nondiamond species are very small. In the present work, the reason for the interesting electrochemical properties of heavily boron-doped diamond electrodes is discussed. Furthermore, dimensional stability of the electrodes was also confirmed by conducting harsh anodic treatment.