Detection of a tryptophan radical as an intermediate species in the reaction of horseradish peroxidase mutant (Phe-221 --> Trp) and hydrogen peroxide

The crucial reaction intermediate in the reaction of peroxidase with hydrogen peroxide (H2O2), compound I, contains a porphyrin pi-cation radical in horseradish peroxidase (HRP), which catalyzes oxidation of small organic and inorganic compounds, whereas cytochrome c peroxidase (CcP) has a radical center on the tryptophan residue (Trp-191) and oxidizes the redox partner, cytochrome c. To investigate the roles of the amino acid residue near the heme active center in discriminating the function of the peroxidases in these two enzymes, we prepared a CcP-like HRP mutant, F221W (Phe-221 --> Trp). Although the rapid spectral scanning and stopped-flow experiments confirmed that the F221W mutant reacts with H2O2 to form the porphyrin pi-cation radical at the same rate as for the wild-type enzyme, the characteristic spectral features of the porphyrin pi-cation radical disappeared rapidly, and were converted to the compound II-type spectrum. The EPR spectrum of the resultant species produced by reduction of the porphyrin pi-cation radical, however, was quite different from that of compound II in HRP, showing typical signals from a Trp radical as found for CcP. The sequential radical formation from the porphyrin ring to the Trp residue implies that the proximal Trp is a key residue in the process of the radical transfer from the porphyrin ring, which differentiates the function of peroxidases.     

Three diabetic cases of acute dizziness due to initial administration of voglibose

We observed 3 diabetic patients with intolerable dizziness followed by nausea and vomiting immediately after an initial administration of the alpha-glucosidase inhibitor, voglibose. These symptoms did not recur after discontinuation of the drug. Adverse effects as observed in these cases have not been reported previously. Since the 3 patients were relatively old (average age, 72 years old) and had various degrees of micro- and macroangiopathies, these side effects may have been associated with increased micro- and macrocirculatory disturbances in their central nervous systems through alpha-glucosidase inhibition of this agent.     

Preparation of multiple oxide BaTiO3 fibres by the sol-gel method

Multiple oxide BaTiO₃ gel fibres were prepared by the sol-gel method from Ba(OC₂H₅)₂-Ti(O-isoC₃H₇)₄-H₂O-C₂H₅OH-CH₃COOH and Ba(CH₃COO)₂-Ti(O-isoC₃H₇)₄-H₂O-CH₃COOH solutions. Relatively long gel fibres of 10cm length were obtained from both solutions in the limited composition region. The latter solution in particular showed a spinnability even when it contained no water. Therefore, the occurrence of spinnability of the solution was considered to be due to the formation of linear polymers composed of bridging acetate groups such as TiO-C(CH₃)-O-Ti rather than metalloxane bonding as Ti-O-Ti. Addition of water to the solutions seems to break the bridging acetate bonds and replace some of them by bridging oxygen bonds. The as-drawn gel fibres which were X-ray amorphous crystallized into BaTiO₃ ceramic fibres of 5mm average length upon heating above 600 ° C. However, the gel fibres drawn from the sols without water became powdery on heating because of the lack of Ti-O-Ti metalloxane bonds. The crystallization behaviour of the BaTiO₃ gel fibres is discussed based on the infrared spectroscopy, X-ray diffraction analysis and thermogravimetric-differential thermal analysis.     

Microstructural investigation and indentation response of pressureless-sintered α- and β-SiC

The microstructure and indentation response of pressureless-sintered - and -SiC were studied using a high-resolution electron microscope and analytical electron microscopy. The materials were manufactured with boron and carbon as sintering aids. It was found that the overall porosity of the materials was very low but a large number of carbon inclusions were present. X-ray diffraction revealed the fabricated -SiC material was of the same 3C polytype as the initial starting powder; however, electron microscope observations indicated that the material contained a high density of faulting of the -forms. High-resolution imaging of grain boundaries in these materials indicated that the boundaries were very clean, and when they contained an amorphous intergranular film it was at most 0.5 to 1 nm thick. The presence of boron was not detected. Deformation due to identation took several forms. Firstly, radial cracks extending from the corners of the indent suffered little hindrance from the matrix microstructure, such that transgranular fracture was the dominant mode. Secondly, the deformation zone beneath the indentations showed copious lattice microcracks with some preferred orientation during crack formation and propagation.     

Three-dimensional analysis for explosions of a propane-air mixture in cylindrical vessels

A mathematically simple spatial difference method has been applied for analysing three-dimensionally, and for illustrating graphically, the process of the development of a flame after the propane-air stoichiometric mixture is ignited. The calculated results show that the mathematical simulation can well express the process of mixture explosion in cylindrical vessels, and can evaluate the effects of laminar swirl flow on the flame development. It is concluded that the swirl motion deforms the flame front and accelerates the flame enlargement. Described also is a comparison of swirl flame calculation, with and without the centripetal effect caused by the difference in densities between burnt and unburnt gases.List of symbols A, A _f , A _K , A _W area, flame surface area, flame element area, and wall area - b _e heat penetration coefficient - C _d coefficient - C _p molar specific heat at constant pressure - G mass of gas - H cylinder height - h enthalpy and molar enthalpy - L effective length - M _j molecular weight - n, N normal unit vector and normal vector to flame surface - p pressure - q heat input per unit mass - r _c flame center location - r, R radius and vessel radius - R universal gas constant - Re Reynolds number - s _b , s _u flame speed and burning velocity - t time measured from spark-ignition - U _c inward moving velocity of flame center - u _u compression velocity of the unburnt gas just ahead of the flame front - U(u, v, w) velocity vector - v _i , V _i specific volume and volume of region-i - x _j mole fraction of specie-_j - x mass fraction of burnt gas - X(x, Y, z), X(x, r, ) orthogonal and cylindrical coordinate systems - Y _j mass fraction of specie-_j - Y mass fraction of burnt gas - small amount of change - change from the initial state Suffixes ij flame element number - i region or state - j chemical species     

Optimum/adaptive incremental sequence in nonlinear analysis

An approach to improve the accuracy of the incremental solutions to a nonlinear problem, through a strategy to control the size of the increment, based on stationary of an argumented energy functional, is presented. The problem of control of an optimum step size in the incremental theory is formulated for a fixed number of increments. The variables in this argumented functional are: (i) the incremental displacement vector, (ii) the scalar parameters _i which characterize the size of each of the increments, i = 1,..., N, and (iii) a Lagrange multiplier which enforces the constraint that the sum of all the normalized increments, i. e., _i is equal to 1. The optimality condition provides us a rigorous approach which gives rise to an iterative procedure because of nonlinearity of the stationary condition. If the number of increments is not prescribed, a noniterative procedure can be obtained, where the incremental sequence is controlled adaptively with less computational effort. The extension of the proposed method to non-selfadjoint problems, where a potential energy function does not exist, is also discussed. Numerical examples demonstrate the remarkable improvement in the accuracy of the solution by optimizing the incremental sequence, as well as the effectiveness of the adaptive control procedure proposed.Paper presented at The 16th International Congress of Theoretical and Applied Mechanics, Lyngby, Denmark, August 19–25, 1984     

Activities of FexO in CaO + CaF2 + SiO2 + FexO quaternary slags by disposable electrochemical oxygen probes

The activities of Fe_xO in CaO + CaF₂ + SiO₂ + Fe_xO quaternary slags were measured by means of solid-oxide galvanic cell. The Fe_xO activities in the slags are influenced by CaF₂ as well as SiO₂. At constant Fe_xO mole fractions, e.g., , at low SiO₂ mole fractions i.e., , the substitution of CaF₂ for CaO has an effect of raising the Fe_xO activity. At higher SiO₂ mole fractions, e.g., , however, such an effect becomes insignificant.     

A new correlation for the viscosity of gaseous fluorocarbon refrigerants

A new generalized correlation is presented for the low-pressure gaseous viscosity of fluorocarbon refrigerants. The following empirical equation is obtained based on the most reliable experimental data for 16 fluorocarbons: $$\eta \xi = \left( {0.5124T_r - 0.0517} \right)^{0.82} Z_c ^{ - 0.81}$$ where η is the viscosity in μPa·s and ξ is the viscosity parameter defined using the critical temperature T _c in K, the critical pressure P _c in MPa, and the molar mass M in g·mol^?1 as follows: $$\xi = T_c ^{1/6} M^{ - 1/2} P_c ^{ - 2/3}$$ The applicable ranges are 0.6<T _r<1.8 and 0.253<Z _c<0.282. The availability of the correlating equation for both pure fluorocarbons and their mixtures has been investigated based on the experimental data of these authors and those in the literature. It is found that the present correlation is useful for the prediction of the viscosity of pure fluorocarbons and their binary mixtures at atmospheric pressure with mean deviations less than 1.6%.