Anionic surfactants: lauric products

Lauryl sulfate and lauryl ether sulfate obtained by the sulfation of lauryl alcohol and lauryl alcohol ethoxylate are representative of anionic surfactants and are used as a formable detergent or an emulsifier. For the sulfation of lauryl alcohol and lauryl alcohol ethoxylate, SO₃ gas, it was found that the quality of products was significantly influenced by the reaction conditions. In order to obtain good quality products we developed a new technology by using a new type of reactor called a “climbing film reactor,” in which SO₃ gas and liquid raw material flow ascendingly.     

STD‐NMR‐Based Protein Engineering of the Unique Arylpropionate‐Racemase AMDase G74C

Structure‐guided protein engineering achieved a variant of the unique racemase AMDase G74C, with 40‐fold increased activity in the racemisation of several arylaliphatic carboxylic acids. Substrate binding during catalysis was investigated by saturation‐transfer‐difference NMR (STD‐NMR) spectroscopy. All atoms of the substrate showed interactions with the enzyme. STD‐NMR measurements revealed distinct nuclear Overhauser effects in experiments with and without molecular conversion. The spectroscopic analysis led to the identification of several amino acid residues whose substitutions increased the activity of G74C. Single amino acid exchanges increased the activity moderately; structure‐guided saturation mutagenesis yielded a quadruple mutant with a 40 times higher reaction rate. This study presents STD‐NMR as versatile tool for the analysis of enzyme–substrate interactions in catalytically competent systems and for the guidance of protein engineering.     

Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.

     

燃烧合成AlN粉体的放电等离子烧结及其导热性能

利用放电等离子烧结(spark plasma sintering,SPS)工艺研究了燃烧合成法制备的2种具有不同形貌的AlN粉以及1种碳热还原氮化法制备的市售亚微米级AlN粉的烧结性能、致密化机理以及导热性能。结果表明:燃烧合成法制备的AlN纳米晶须状粉末具有与亚微米级标准市售AlN粉末同样优异的烧结性能,都能够在无烧结助剂情况下在1600℃的较低温度下烧结致密。在烧结过程中,由于燃烧合成AlN粉自身的高化学活性和SPS产生的等离子体活化作用,使得AlN粉以自身的分解-再结晶-凝聚机制进行致密化,导致晶界强度很高,断裂时以穿晶断裂为主;而在市售AlN粉末烧结过程中以表面扩散机制致密化,在晶界处形成了AlON相,降低了晶界强度,因此以沿晶断裂为主。AlN原料的氧含量对热导率的影响很大。由于燃烧合成AlN粉体的氧含量较碳热还原法制备的市售AlN粉体略高,导致其烧结试样热导率略低。     

Anisotropic corrosion of iron in pH 1 sulphuric acid

Anisotropic corrosion behaviour of a single grain of pure iron in 0.05 mol dm⁻³ sulphuric acid (pH 1) was investigated by a simple polarization technique. Both corrosion potential and corrosion current were found to be dependent on crystallographic orientation of the iron grain. A high corrosion current flowed on a grain showing a relatively noble corrosion potential, although both cathodic and anodic Tafel slopes were independent of the orientation. It was shown that cathodic hydrogen evolution reaction (HER) governed the corrosion reaction on the iron grain. Covalent bonding of Fe and H and coverage of H on Fe seem to play important roles in the HER and anisotropic corrosion behaviour of pure iron.     

Rapid detection of enterotoxigenic Escherichia coli O6 in water by using monoclonal antibody and a photon-counting television camera

Monoclonal antibodies (MAbs) raised against Escherichia coli O6:H16 were screened against 15 strains of E. coli and 19 non-E. coli bacteria. A MAb-luminescence assay using MAb-5.8, which shows no cross-reactions with non-E. coli bacteria, and a photon-counting television camera were developed for rapid enumeration of E. coli O6:H16 in water. The membrane filter that retained bacteria was boiled for 5 min in a buffer and incubated with biotinylated MAb-5.8. After incubation with streptavidin-peroxidase conjugate, it was reacted with luminol-based reaction mixture. Luminous image and light intensity of the filter was recorded with a Biocell Counter. Levels of E. coli O6 higher than 7 x 10(3) CFU were detected by the MAb-luminescence assay when E. coli O6 was spotted onto the membrane filter. The sample that contained E. coli O6:H16 was filtered through a membrane filter, and the filter that retained bacteria was incubated on a filter paper soaked with nutrient broth supplemented with 0.5% NaCl at 37 degrees C for 6 h. The number of light emission points on the filter correlated well with initial E. coli O6:H16 counts within the range of 1 to 3 x 10(2) CFU. The correlation coefficient was 0.89.     

Monte Carlo simulation of diffusive-to-ballistic transition in phonon transport

Heat conduction properties in Si nanostructures are analyzed using a Monte Carlo method developed for solving the phonon Boltzmann transport equation. The thermal resistances are evaluated for the systems with various sizes, and the transition from the diffusive to the ballistic heat conduction are investigated. We compare the two different phonon dispersion models (the realistic dispersion relation based on the adiabatic bond charge model and the analytically approximated model), and it is shown that the correct implementation of the phonon dispersion relation is essential to accurately simulate the quasi-ballistic heat conduction properties, which becomes obvious in the structures smaller than the phonon mean free path.     

Structural Investigation of 95(0.6Li2S0.4SiS2)5Li4SiO4 Oxysulfide Glass by Using X-ray Photoelectron Spectroscopy

S2 p and O1 s photoelectron spectra were obtained for the 95(0.6Li₂S0.4SiS₂)5Li₄SiO₄ oxysulfide glass prepared by twin-roller quenching. A four-peak deconvolution technique was used to separate the S2 p peak of the glass into the components of bridging and nonbridging sulfur atoms. As a result of the deconvolution of the S2 p peak, we found that ∼92% of the sulfur atoms were present as nonbridging atoms. The O1 s peak of the glass was separated into two components: bridging and nonbridging oxygen atoms. This separation of the O1 s peak indicated that ∼85% of the oxygen atoms were present as bridging oxygen atoms.     

Phase transition of thermosensitive amphiphilic cellulose esters bearing olig(oxyethylene)s

Summary A series of cellulose esters bearing olig(oxyethylene)s with different degree of substitution (DS) and different length of the oxyethylene chain were synthesized by a homogeneous reaction of cellulose with corresponding monofunctional acid chloride in a 10% LiCl-dimethyl acetoamide (DMAc) solution. The effect of total DS value on the solubility of the derivatives in aqueous solution was investigated. It was found that the lower limit DS value for both water-soluble and amphiphilic derivatives decreases with increasing length of oxyethylene chains. The amphiphilic derivatives, which are soluble in both water and chloroform, precipitate out of aqueous solution on heating without gel forming, such a phase transition behavior was studied in terms of DS value, length of oxyethylene and concentration. The precipitation temperature (T_p) of the amphiphilic derivatives is range from 54°C to 96°C. It decreases with increasing the total DS value, and increases with an increase in the length of oxyethylene chains. The T_p value of the derivatives was found to be almost independent in the concentration range of 1–15 wt %, however the T_p value increases sharply with decreasing polymer concentration when the concentration is lower than 1 wt%. Received: 29 August 2000/Revised version: 16 October 2000/Accepted: 31 October 2000     

Analysis of mark-formation process for phase-change media

The objective of this study was to determine the mechanism of a phenomenon peculiar to phase-change recording regarding the mark shape or mark-forming process. The following results were obtained from our simulation of mark shapes, transparency electron microscope observations, and analysis of reproduced signals. A method of calculating a mark shape by calculating the holding-time profile was devised and its appropriateness was confirmed. We found there were close relationships between the cooling pulse shape, the effective erase ratio, the reproduced signal amplitude, and the noise level, and that the temperature change when the mark edge was cooled has a great influence on the stability of the mark shape and crystallized regions