An absolute requirement of fructose 1,6-bisphosphate for the Lactobacillus caseiL-lactate dehydrogenase activity induced by a single amino acid substitution

Lactobacillus casei allosteric L-lactate dehydrogenase (L-LDH)absolutely requires fructose 1,6-bisphosphate [Fru(1,6)P2] forits catalytic activity under neutral conditions, but exhibitsmarked catalytic activity in the absence of Fru(1,6)P₂ underacidic conditions through the homotropic activation effect ofsubstrate pyruvate. In this enzyme, a single amino acid replacement,i.e. that of His205 conserved in the Fru(1,6)P₂-binding siteof certain allosteric L-LDHs of lactic acid bacteria with Thr,did not induce a marked loss of the activation effect of Fru(1,6)P₂or divalent metal ions, which are potent activators that improvethe activation function of Fru(1,6)P₂ under neutral conditions.However, this replacement induced a great loss of the Fru(1,6)P₂-independentactivation effect of pyruvate or pyruvate analogs under acidicconditions, consequently indicating an absolute Fru(1,6)P₂ requirementfor the enzyme activity. The replacement also induced a significantreduction in the pH-dependent sensitivity of the enzyme to Fru(1,6)P₂,through a slight decrease and increase of the Fru(1,6)P₂ sensitivityunder acidic and neutral conditions, respectively, indicatingthat His205 is also largely involved in the pH-dependent sensitivityof L.casei L-LDH to Fru(1,6)P₂. The role of His205 in the allostericregulation of the enzyme is discussed on the basis of the knowncrystal structures of L-LDHs.     

Gibbs Energy Change of Carbothermal Nitridation Reaction of Al2O3 to Form AlN and Reassessment of Thermochemical Properties of AlN

The experimental method for the high-temperature reaction equilibria in the AlN-Al₂O₃ system has been established. The equilibrium N₂-CO gas compositions coexisting with AlN- Al₂O₃-graphite have been successfully measured by quadrupole mass spectrometry and gas chromatography. From the obtained results, the standard Gibbs energy change of the forming reaction of AlN by carbothermal nitridation is determined at temperatures ranging from 1723 to 1899 K:
From the obtained result, the standard Gibbs energy of formation of AlN and the third-law enthalpy of formation of AlN at 298.15 K are derived as
The disagreement between the present results and values in the NIST–JANAF thermodynamic table is discussed.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

采用MAMMOS技术的高密度光记录

MAMMOS(Magnetic Amplifying Magneto－ Optical System:磁畴扩大磁光系统 )是实现高密度磁光盘的有效方法。不仅能得到不依赖于磁畴长度的较大的读出信号振幅,而且还能实现超出光学系统衍射极限的分辨率。过去,为实现磁畴的复印与扩大,要对记录膜面施加垂直方向的外部磁场。而现在得知,同时施加垂直磁场和水平方向的磁场,可大幅度地提高微小磁畴的读出特性。确认采用施加水平磁场的方法,在λ =635 nm, NA=0.55的条件下, 0.15μ m的连续磁畴也能获得 BER=2× 10－ 4的读出效果。     

Study on the Anti-Coking Nature of Ni/SrTiO3 Catalysts by the CH4 Pyrolysis

A solid phase crystallization (spc) method was applied for the preparation of SrTiO₃-supported Ni catalysts and compared to the impregnation (imp) method. spc-Ni_0.2/SrTiO₃ has highly dispersed and stable Ni metal particles resulting in higher activity and higher sustainability against coking than imp-Ni_0.2/SrTiO₃ in the partial oxidation of CH₄. Both catalysts were tested for the CH₄ pyrolysis in order to elucidate the catalytic nature against coking of spc-Ni_0.2/SrTiO₃. The amount of carbon and the rate of H₂ formation were similar over both catalysts at both 773 and 1073 K. On both catalysts, CH₄ continuously decomposed at 773 K, while the rate of CH₄ pyrolysis quickly decreased at 1073 K. Fibrous carbons grew up with a Ni metal particle on the tip of the fiber at 773 K, while carbon balls and short carbon fibers with a Ni metal particle encapsulated inside formed and no sufficient growth of the fiber was observed at 1073 K. The carbon species formed at 773 K was hydrogenated completely to CH₄ around 873 K, while the hydrogenation of that formed at 1073 K needed higher temperature around 1073 K. However, the carbon species formed on both the catalysts at either 773 or 1073 K was completely oxidized around 773 K. Thus, judging from the anti-coking nature, the behaviors in the CH₄ pyrolysis are similar over both catalysts, nonetheless spc-Ni_0.2/SrTiO₃ was far superior to imp-Ni_0.2/SrTiO₃ in the CH₄ oxidation. It is likely that the high sustainability against coking of spc-Ni_0.2/SrTiO₃ is not due to its intrinsic nature suppressing the coking but due to its high activity of reforming which can quickly eliminate the carbon formed on the catalyst surface.     

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.     

EXPERIMENTAL STUDIES ON A NOVEL CHEMICAL HEAT PUMP DRYER USING A GAS-SOLID REACTION

The authors have been studying Chemical Heat Pumps (CHP) from the viewpoints of energy saving and environmental impact. The CHP can store thermal energy in the form of chemical energy by an endothermic reaction, and release it at various temperature levels during heat demand periods by exo/endothermic reactions. The authors have proposed in an earlier study a novel chemical heat pump (CHP) system for environmentally-friendly effective utilization of thermal energy in drying as a chemical heat pump dryer (CHPD). In this exploratory study, we test the effectiveness of operating the proposed CHPDs experimentally. Basic experiments on the CHPDs such as hot dry air production for convective drying are performed on lab-scale CHPD apparatuses using gas-solid reactions in calcium oxide/calcium hydroxide reactant beds. The proposed CHPDs are found to produce hot air by CHP operation for drying. The temperature levels of the produced hot air and the reaction rates/conversions are as good as in the case of hot water supply system using basically same CHP operation. The cold heat for air dehumidification is also found to be generated/recovered by the same CHPD system. The generated heat amounts can be increased by changing the operating conditions although the heat recovery must be enhanced for practical application of CHPDs.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

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.     

Preparation and Characterization of Chitosan‐Gellan Hybrid Capsules Formed by Self‐Assembly at an Aqueous Solution Interface

Summary: True spherical capsules are formed by electrostatic polysaccharide interaction between chitosan and gellan gum via polyion complex (PIC) formation in aqueous solutions. Dropwise addition of a chitosan solution into the gellan solution gave spherical capsules whose outside surface was gellan and whose inside was chitosan (chitosanⁱⁿ‐gellan^out capsule). Conversely, the addition of gellan into chitosan yields chitosan^out‐gellanⁱⁿ capsules. SEM observation revealed a fibrous network spreading along the capsule membrane of the chitosanⁱⁿ‐gellan^out capsule. The releasing properties of the capsules were examined using low molecular weight substances and high molecular weight proteins. For low molecular weight substances, the releasing kinetics were affected by the attractive and repulsive interactions between the substances and the inside component of the capsule. The molecular weight of the encapsulated substances also affects the releasing kinetics. These results, together with a simple preparation procedure, indicate the applicability of chitosan‐gellan capsules as drug‐carrier materials having a controlling release mechanism. As an application example, preparation of an actually eatable artificial roe was also described.

Illustrative drawing of PIC capsule formation.