Dietary CLA and DHA modify skin properties in mice

This study investigated the influence of PUFA on the properties of mouse skin. Mice (3 wk old) were given free access to oils high in linoleic acid, CLA, or DHA for 4 wk. At the end of the experiment, their skins were compared by both biochemical and histological methods. No significant differences in lipid and collagen contents were detected among treatments, although the FA composition in the skin was altered depending upon the FA composition of the supplemented oils. Electron microscopy revealed that the subcutaneous tissue layers in the CLA and DHA groups were significantly thinner than that in the high linoleic acid group, whereas no differences in the thickness of dermis layers were observed among the three groups. These results suggest that skin properties in mice are readily modified by dietary FA sources within 4 wk of dietary oil supplementation.     

Simple,Mild, and Practical Esterification,Thioesterification, and Amide Formation Utilizing p‐Toluenesulfonyl Chloride and N‐Methylimidazole

We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p‐toluenesulfonyl chloride (TsCl) together with N‐methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N‐methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N‐Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β‐methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful ¹H NMR monitoring study.     

Size Measurement of Polystyrene Latex Particles Larger than 1 Micrometer using a Long Differential Mobility Analyzer

We describe a newly constructed annular-type differential mobility analyzer (DMA) with an effective electrode length of 60 cm, which is longer than that of our original DMA (40 cm length). This long DMA was developed to extend the classification size of particles measuring up to 1.5 μm. As an application of this DMA, the mean diameters and standard deviations were determined for six samples of monodisperse polystyrene latex (PSL) particles ranging from 0.94 to 1.27 μm in nominal diameter. These PSL particles suspended in double-distilled water were aerosolized by a glass nebulizer and then introduced into the DMA. The mean diameters and standard deviations of these PSL particles were calculated by Ehara's method and compared with the nominal diameters and uncertainties. There was good correlation between the nominal diameters of these samples—particularly for recently certified samples—and the measured diameters. Classification of aerosol particles more than 1 micrometer in diameter using this DMA will be useful for many purposes.     

An experimental study of flow and heat transfer of supercritical carbon dioxide in multi-port mini channels under cooling conditions

This paper presents the fluid flow and heat transfer characteristics of supercritical CO₂ in a horizontal multi-port extruded aluminum test section consisting of 10 circular channels with an inner diameter of 1.31 mm. Both local and average pressure drop and heat transfer coefficients were measured as CO₂ was cooled in the multi-port circular channels with pressures ranging from 7.4 to 8.5 MPa, inlet fluid temperatures ranging from 22 to , and mass velocity ranging from 113.7 to 418.6 kg/m² s. The results indicate that the operating pressure, the mass velocity and the temperature of CO₂ had significant effects on fluid flow and heat transfer characteristics. The pressure drop and the average heat transfer coefficient increased greatly with increasing the average temperatures of CO₂ in the near-critical region; the average heat transfer coefficient attained a peak value near the corresponding pseudocritical temperature; and the maximum heat transfer coefficient decreased as the pressure increased. Both the pressure drop and the heat transfer coefficient increased with the mass velocity, but decreased with the operating pressure. The measured average heat transfer coefficients were compared with the experimental data reported in the literatures and a large discrepancy was observed. Based on the experimental data collected in the present work, a new correlation was developed for forced convection of supercritical CO₂ in horizontal multi-port mini channels under cooling conditions.     

Theoretical model for flash generation

Reduction of flash generated in a gas vent is of great concern for manufacturers of electronic parts. The present study proposes a theoretical model for flash generation through consideration of flow characteristics in a gas vent. The model predicts the factors controlling flash, i.e., material parameters such as zero‐shear viscosity, crystallization temperature, thermal conductivity, and heat capacity, and process parameters such as injection and mold wall temperatures, packing pressure, and the clearance of a gas vent. On the other hand, we measure the amount of flash generated in the molding of poly(phenylene sulfide) (PPS) composites containing glass fiber and spherical fillers (CaCO₃ or Al₂O₃). Flash reduces with decreasing size of spherical fillers. These experimental data are successfully interpreted using the flash model. Polym. Eng. Sci., 45:198–206, 2005. © 2005 Society of Plastics Engineers     

Processing and 3D printing of SiCN polymer-derived ceramics

Preceramic polymer resins are attractive for the 3D printing of net-shaped ceramic components. Recently various processes have been demonstrated for 3D printing of polymer-derived ceramics (PDCs). Ultimately in these processes, the process outcomes strongly depend on the process parameters. In particular, for PDCs the ceramic density, and ceramic yield are affected by the catalyst concentration and cross-linking duration. Here, we use thermal analysis and FTIR to quantify the interrelation of the process parameters on the process outcome for polysilazanes and demonstrate 3D printing of PDC components based on the best-identified process parameters. The results of this work can be used as guidelines for future additive manufacturing of PDCs.     

A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt)₃, Ge(OEt)₄ and Ti(OEt)₄ are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)₄. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.     

Energy value and digestibility of dietary oil containing mainly 1,3-diacylglycerol are similar to those of triacylglycerol

Diacylglycerol (DAG) is a component of various vegetable oils. Approximately 70% of the DAG in edible oils are in the configuration of 1,3-DAG. We recently showed that long-term ingestion of dietary oil containing mainly 1,3-DAG reduces body fat accumulation in humans as compared to triacylglycerol (TAG) oil with a similar fatty acid composition. As the first step to elucidate the mechanism for this result, we examined the difference in the bioavailabilities of both oils by measuring food energy values and digestibilities in rats. Energy values of the DAG oil and the TAG oil, measured by bomb calorimeter, were 38.9 and 39.6 kJ/g, respectively. Apparent digestibility expressed according to the formula: (absorbed) x (ingested)⁻¹x100=(ingested—excreted in feces)x(ingested)⁻¹x100 for the DAG oil and the TAG oil were 96.3±0.4 and 96.3±0.3% (mean±SEM), respectively. The similarity in the bioavailabilities of both oils supports the hypothesis that the reduced fat accumulation by dietary DAG is caused by the different metabolic fates after the absorption into the gastrointestinal epithelial cells.     

Preparation of sharp-melting hard palm midfraction and its use as hard butter in chocolate

Preparation of hard palm midfractions (PMF) and its use as a cocoa butter equivalent ingredient were studied. Hard PMF is obtained by multistep fractionation of palm oil involving dry fractionation (DF) and/or solvent fractionation (SF), usually using hexane or acetone. From our experience, in acetone, a polar solvent, symmetrical 1,3-disaturated triacylglycerols tend to selectively crystallize more than nonsymmetrical 1,2- or 2,3-disaturated triacylglycerols, making it suitable for obtaining the solid midfraction. Unfortunately, triacylglycerols are very soluble in hexane, and temperatures at least 15 degrees lower than those required for acetone must be used for equivalent crystal yields. On the other hand, DF is a less expensive and safer process. Thus, multistep fractionation combining DF and SF using acetone was developed to achieve sufficient removal of high-melting components, and further enrichment of 1,3-dipalmitoyl-2-oleoylglycerol and the hard PMF was obtained by triple-step fractionation of palm olein or double-step fractionation of soft PMF. Compared to conventional hard PMF, this hard PMF had a steeper melting curve and better snapping and sharp-melting qualities when used in chocolate. Heat resistance of the hard PMF chocolate was similar to the conventional hard PMF chocolate, and its bloom resistance could be improved by adding polyglycerol fatty acid esters.