Tensile behaviour of corroded and hydrogen embrittled 2024 T351 aluminum alloy specimen

The synergetic effect of corrosion and corrosion induced hydrogen embrittlement damage processes which occur at local scale has been found to result in a dramatic macroscopic tensile ductility loss of the 2024 aluminum alloy. In the present work, the tensile behaviour of corroded 2024 T351 specimens has been estimated on the basis of FE analysis by taking into account the local material properties in the damaged areas. A parametric study is involved to account for the effect of thickness in the results. Calculated tensile properties obtained with the analysis agree well with experimental data.     

1H and13C nuclear magnetic relaxation and local dynamics of lysozyme and synthetic polypeptides

The combined analysis of¹H and¹³C NMR relaxation data in solid lysozyme and some typical homopolypeptides was carried out by using “model-free” approach. Three types of relaxation transitions (γ’, γ and β) were revealed in the temperature range investigated. The microdynamical parameters of these motions were determined. From the comparison of these parameters with those of selected synthetic polymers it follows that the molecular motions in proteins and synthetic polymers are of the same nature. All these motions show pronounced anisotropic character. In the investigated temperature range no molecular motions corresponding to α-relaxation (liquid-like) transition were revealed. The hydration effects on parameters of the motions in proteins were considered. The most pronounced effect takes place for β-transition. The effect of Brownian rotation of protein molecule in solution on measured correlation function of local motions was also discussed.     

Positron annihilation studies in highT c superconductor YBa2Cu3Cd x O y (x=0, 0.05)

Positron lifetime and Doppler broadening of the annihilation line measurements were performed in highT _c superconducting samples YBa₂Cu₃Cd _x O _y ,x=0, 0.05 and 6.9<y<7, as a function of temperature in the region of 14–300 K. It was found that the positron lifetime and theS parameter values are lower in the Cd doped sample than those in the undoped one. It was also observed that the positron annihilation parameters show similar temperature dependence for the undoped and Cd doped samples. We conclude that the Cd doping in highT _c superconductor YBa₂Cu₃Cd _x O _y , 6.9<y<7 fills defects associated with oxygen vacancies probably in oxygen deficient regions which can trap positrons.     

CHROMOPHORE ROTATION IN 124-kD ALTON A vena sativa PHYTOCHROME AS MEASURED BY LIGHT-INDUCED CHANGES IN LINEAR DICHROISM

Abstract— From light-induced changes in linear dichroism, we have calculated the rotation of the long-wavelength-absorbing transition moment that occurs during phototransformation of 124-kilodalton Avena sativa phytochrome. Phytochrome was purified to homogeneity and immobilized onto Sepharose beads covalently coated with antibodies against A. sativa phytochrome. Changes in linear dichroism were induced by plane-polarized red or far-red light and measured by the absorbance differences at 660 and 730 nm using a dual-wavelength spectrophotometer equipped with polarizing filters in the measuring beams. From such measurements, we calculate a rotation angle of 31^o (or 149^o) during photoconversion of Pr to Pfr and 30^o (or 150^o) during photoconversion of Pfr to Pr. These values are similar to the value of 32^o (or 148^o) reported earlier for the rotation of the transition moment of "large" A. sativa phytochrome (∽ 120 kilodalton) isolated under conditions that did not preclude post homogenization proteolysis of the 124 kilodalton molecule.     

Exchange of halogen bonded on aromatic core. Heterogeneous catalysis—I : Reaction mechanism of iodine exchange in o-iodobenzoic acid

Reaction mechanism of halogen exchange between arylhalogenide and halogenide anion is studied in a case when the aromatic core is inactivated with respect to the S_NAr substitution by other substituents. The exchange of iodine between o-iodobenzoic acid and ¹³¹I labelled NaI serves as a modelling reaction. The reaction was found to proceed heterogeneously on a glass surface. In the case of a rapid course of the surface reaction the reaction mechanism is more complicated and the equation derived by McKay cannot be applied for expressing the time dependence of the degree of isotopic exchange. Reaction mechanism was proposed for this reaction and compared with experimental data.     

Partially selective semiconductor redox electrodes

Redox electrodes made of passivated metals of the subgroups IV to VI of the periodic system with a surface coating of n-conducting metal oxides, generated by oxidizing agents or anodic oxidation, are well suited for measuring the concentration of oxidizing agents. Neither oxygen nor reducing agents affect the measurements. There is a correlation between the mean conductivity of the passive layer and its selectivity. The aged n-conducting passive layers permit reproducible potential settings, and the occurring changes in potential are greater than what is to be expected according to the Nernst equation. The potentiometric measuring of nitrosyl ions and chlorine is used as an example to demonstrate the selectivity of these electrodes.     

A general Brownian dynamics simulation program for biopolymer dynamics and its implementation on a vector computer

A Brownian dynamics simulation program for the computation of transport properties of charged polarizable macromolecules is presented. The program contains routines for simulating polymer dynamics in a gel network as well as in a quiescent fluid or in a shear field. An electric field can also be included to simulate e.g., gel electrophoresis or electric dichroism. Vector algorithms have been used where possible to obtain maximum efficiency on a vector processor. The length of the vector registers and the effect of computer memory organization have also been considered. On an IBM 3090-150S VF, more than 1.5 · 10⁶ steps are executed in one cpu hour for a chain with 128 subunits diffusing in a rigid gel consisting of 8828 beads.     

Determination of uranium by XRF analysis following its preconcentration with some organic precipitants

The determination of uranium in natural waters by XRF analysis after its preconcentration with some organic precipitants is described.¹⁰⁹Cd source is used for the excitation of L-series X-rays of uranium. Separation yield, kinetics of coprecipitation and the possibility of preparing thin-layer samples for XRF analysis were studied in detail for uranium concentration with α-nitroso-β-naphtol, methylene blue with ammonium thiocyanate, tannin with urotropine and other precipitants. A procedure using coprecipitation of uranium with α-nitroso-β-naphtol from 500 ml samples of surface or waste, waters is proposed.     

Theoretical study on solvation effects in chemical reactions: A vibrational coupling model

A vibrational coupling model to treat the solvation effects in chemical reaction rate calculations is proposed and applied to the intramolecular hydrogen transfer reaction CH₃O· → ·CH₂OH in the condensed phase. The effect of solvation is taken into account in two ways: (1) the solvent effect on the activation energy of the reaction is simulated by including 39 surrounding water molecules, represented by fractional charges at the assumed atomic positions, in the potential energy surface calculation; and (2) the vibrational couplings between the 10 nearest solvent molecules and the molecules constituting the reaction system are explicitly included in a vibrational frequency calculation. RRKM theory with Miller's tunneling correction included is employed to calculate the rate constants. The effect of solvation causes a significant change in the chemical reaction rate, mainly through a lowering of the activation energy. The vibrational coupling causes a slight increase of the rate constant in the tunneling region by perturbing the vibrational frequencies of the reactant and transition states, which appear in the rate-constant expression, but has little effect at higher temperatures.     

Computerized separation of chromatographically unresolved peaks

A computerized peak deconvolution software and mass spectra were successfully applied for the deconvolution of overlapped peak cluster in the chromatogram obtained separating the complex mixture of pesticides by retention time locking gas chromatography-mass spectroscopy. The method based on the unique fragment ions in the spectra can be used for deconvolution of peak clusters if mass spectra of overlapped peaks differ. This method allows determining actual retention times of overlapped peaks. Peak areas found by this method however, cannot be used naturally for the quantitative purposes as the abundance of fragment ions used for this deconvolution procedure can dramatically differ. Computer assisted deconvolution of peaks in the peak clusters gives more realistic peak area ratios as at this method it is supposed equal response for all peaks overlapped in a cluster.