Counter‐ion‐specific helix formation of poly(γ‐methyl L‐glutamate) derivatives containing sulfonate group in aqueous alcohols

Charged polypeptides containing sulfonate groups were prepared by transesterification of poly(γ‐methyl L ‐glutamate) with isethionic acid. The coil–helix transition of the sulfonated polypeptides was investigated in aqueous alcohols. Marked counter‐ion specificity was observed for helix formation: Li⁺ < Na⁺ < Cs⁺ ≦ Rb⁺ ≦ K⁺; this was different to that for poly(L ‐glutamate) (PLG): Cs⁺ ? K⁺ < Li⁺ < Na⁺. Specific helix stabilization by counter‐ion mixing, which has been found for the PLG system, was not observed for the sulfonated polypeptides. The counter‐ion‐ and solvent‐specific helix formation is discussed and compared with that in PLG. © 2001 Society of Chemical Industry     

Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides

The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H₂, Ar, and CO₂, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H₂ atmosphere was white, whereas that obtained from the CO₂ atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO₂ atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H₂ atmosphere increasingly approached near‐stoichiometric SiO₂–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO₂ atmosphere approached a composition of SiO₂–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO₂–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO₂. Estimating from the signal intensity, the residual spin concentrations were in the range 10¹⁸–10¹⁹ g^?1. Meanwhile, the spectra from the samples obtained in H₂ showed weak and sharp signals with estimated spin concentrations ranging from 10¹⁶–10¹⁷ g^?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis.     

Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers     

Effects of freezing pretreatment and hygroscopicity of fluidizing particles on drying characteristics of carrots in fluidized bed under reduced pressure

Abstract

A method for low-temperature drying with high drying rate was developed for heat-sensitive foods and agricultural products. A freezing pretreatment was combined with fluidized bed drying under reduced pressure. Cylindrical carrot samples were frozen and then placed without thawing in a fluidized bed of hygroscopic porous silica gel particles that adsorbed water from the sample during the drying process. The effects of the freezing pretreatment and hygroscopicity of fluidizing particles on the drying characteristics of carrots were examined. A higher drying rate was achieved when carrots samples were subjected to freezing pretreatment than without it. At 12?kPa, the volume change was smaller in carrots subjected to freezing pretreatment than in untreated samples. A larger amount of water was absorbed during rehydration by carrots dried at 12?kPa than at 101?kPa within 120?min. The properties of dried carrots were affected not only by freezing pretreatment but also by the pressure applied during the drying process.     

Effect of agglomeration of triacylglycerols on the stabilization of a model cream

This study has been carried out on solidification of a model cream using palm oil as a sole fat source. It was found that the addition of 1‐palmitoylglycerol to palm oil promoted the solidification of the model cream while the addition of 1‐oleoylglycerol had no such effect. Solid fat content of palm oil in the cream with 1‐palmitoylglycerol was found to be lower than those of palm oil and palm oil with 1‐oleoylglycerol after cooling from 60 to 5 °C. Crystallization behaviors of bulk palm oil and mixture of 1, 3‐dipalmitoyl‐ 2‐oleoyl‐glycerol (POP) and 1‐palmitoyl‐2, 3‐dioleoyl‐glycerol (POO) were then studied in the presence of monoacylglycerols. Formation of granular crystals was observed for palm oil and POP/POO mixture in the presence of 1‐palmitoylglycerol. HPLC of the granular crystals revealed that agglomeration of higher melting point triacylglycerols (TAGs) around 1‐palmitolyglycerol took place, which promoted the formation of granular crystals. It was suggested that the agglomeration of higher melting point TAGs around 1‐palmitoylglycerol which was preferentially adsorbed at the oil‐water interface of oil droplets in the model cream led to destabilization of oil‐in‐water emulsion and the solidification of the model cream. At the same time, it was suggested that the fatty acid moiety of emulsifiers played an important role in the agglomeration of TAGs and stabilization of o/w emulsions.     

Ethanol production from raw starch by a recombinant yeast having saccharification and fermentation activities

In order to develop a method for converting raw starch into ethanol efficiently, direct fermentation of ozonized raw starch using a recombinant yeast was investigated. Ozonolysis was carried out as a pretreatment to convert raw starch into ethanol rapidly and efficiently, and then the effect of the ozone degradation conditions on the degree of polymerization and the amount of amylose in a raw starch was determined. Since the degree of polymerization was low and the amount of amylose was high, raw starch treated with an ozone concentration of 40 gm^?3 and an ozonation time of 30 min was the material chosen for alcohol fermentation. Though the recombinant yeast could not convert the untreated raw starch, it converted the soluble starch and the ozonized raw starch at a comparatively high yield into ethanol. About 56% of the ozonized raw starch decomposed, and the ethanol concentration obtained from the ozonized raw starch was markedly greater than that obtained from untreated raw starch. The dynamic behavior of cell growth, substrate degradation, and ethanol production was examined in a continuous culture under various dilution rates, and the optimal dilution rate, ie 0.15 h^?1, was determined for maximizing the ethanol productivity (amount of ethanol produced per unit time). © 2002 Society of Chemical Industry     

Superstructure and mechanical properties of poly(L-lactic acid) microfibers prepared by CO2 laser-thinning

Poly(L-lactic acid) (PLLA) microfibers were obtained by a carbon dioxide (CO₂) laser-thinning method. A laser-thinning apparatus used to continuously prepare microfibers was developed in our laboratory; it consisted of spools supplying and winding the fibers, a continuous-wave CO₂-laser emitter, a system supplying the fibers, and a traverse. The laser-thinning apparatus produced PLLA microfibers in the range of 100-800 m min⁻¹. The diameter of the microfibers decreased as the winding speed increased, and the birefringence increased as the winding speed increased. When microfibers, obtained through the laser irradiation (at a laser power of 8.0 W cm⁻²) of the original fiber supplied at 0.4 m min⁻¹, were wound at 800 m min⁻¹, they had a diameter of 1.37 μm and a birefringence of 24.1×10⁻³. The draw ratio calculated from the supplying and winding speeds was 2000×. The degree of crystal orientation increased with increasing the winding speed. Scanning electron microscopy showed that the microfibers obtained with the laser-thinning apparatus had smooth surfaces not roughened by laser ablation that were uniform in diameter. The PLLA microfiber, which was obtained under an optimum condition, had a Young's modulus of 5.8 GPa and tensile strength of 0.75 GPa.     

New Approach for Macro Porous RB‐SiC Derived from SiC/Novolac‐type Phenolic Composite

A novel fabrication route to make macroporous silicon carbide (SiC) has been proposed in this study. The route is composed of the following two steps: the fabrication of porous α‐SiC/novolac‐type phenolic composite using hexamethylenetetramine (HMT) as a curing/blowing agent for the novolac monomer and a conventional reaction‐bonded (RB) sintering of the composite. The α‐SiC/novolac‐type phenolic composite was carbonized at 800°C for 2 h in N₂ gas and then reacted with the molten silicon at 1450°C for 30 min under vacuum, resulting in the macroporous RB‐SiC with an open porosity of 48% and relatively large pore size of ~110 μm. The compressive strength of the macroporous RB‐SiC was 113 MPa, which is relatively high compared to those reported for macroporous SiC of equivalent porosities and pore sizes.