Stable-isotope dilution activation analysis,and determination of Ca,Zn and Ce by means of photon activation

As a new method, stable-isotope dilution activation analysis has been developed. When an element consists of at least two stable isotopes which are converted easily to the radioactive nuclides through nuclear reactions, the total amount of the element (xg) can be determined by irradiating simultaneously the duplicated sample containing small amounts of either enriched isotope (y g), and by using the following equation. $${{x = y\left( {{M \mathord{\left/ {\vphantom {M {M*}}} \right. \kern-\nulldelimiterspace} {M*}}} \right)\left[ {\left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)\left( {{{\theta _2^* } \mathord{\left/ {\vphantom {{\theta _2^* } {\theta _2 }}} \right. \kern-\nulldelimiterspace} {\theta _2 }}} \right) - \left( {{{\theta _1^* } \mathord{\left/ {\vphantom {{\theta _1^* } {\theta _1 }}} \right. \kern-\nulldelimiterspace} {\theta _1 }}} \right)} \right]} \mathord{\left/ {\vphantom {{x = y\left( {{M \mathord{\left/ {\vphantom {M {M*}}} \right. \kern-\nulldelimiterspace} {M*}}} \right)\left[ {\left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)\left( {{{\theta _2^* } \mathord{\left/ {\vphantom {{\theta _2^* } {\theta _2 }}} \right. \kern-\nulldelimiterspace} {\theta _2 }}} \right) - \left( {{{\theta _1^* } \mathord{\left/ {\vphantom {{\theta _1^* } {\theta _1 }}} \right. \kern-\nulldelimiterspace} {\theta _1 }}} \right)} \right]} {\left[ {1 - \left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)} \right]}}} \right. \kern-\nulldelimiterspace} {\left[ {1 - \left( {{{R*} \mathord{\left/ {\vphantom {{R*} R}} \right. \kern-\nulldelimiterspace} R}} \right)} \right]}}$$ Where M and M^* are atomic weights of the element to be determined and the enriched isotope used as a spike,θ ₁ andθ ₂ are natural abundances of two stable isotopes in the element,θ ₁ ^* andθ ₂ ^* are isotopic compositions of the above isotopes in the enriched isotope, and R and R^* are counting ratios of gamma-rays emitted by two radionuclides produced in the sample and the isotopic mixture. Neither calibration standard nor correction of irradiation conditions are necessary for this method. Usefulness of the present method was verified by photon activations of Ca, Zn and Ce using isotopically enriched⁴⁸ca,⁶⁸Zn and¹⁴²Ce.     

Mössbauer study of hydrogenated Fe-Zr amorphous alloys

The effect of electrochemical hydrogenation was investigated in Fe₉₀Zr₁₀ and Fe₈₉Zr₁₁ amorphous alloys by means of⁵⁷Fe Mössbauer spectroscopy. Significant changes in the Mössbauer spectra as well as in the hyperfine field distribution of hydrogenated samples were found with increasing hydrogen concentration. It was established that the dependence of Curie temperature on hydrogen content had a maximum, and the hydrogen had two mean localization sites. By comparing the Mössbauer spectra of hydrogenated samples as-quenched and annealed before hydrogenation it was shown that low-temperature relaxation processes were going on at aging temperature as low as 150°C in this amorphous alloy and the low-temperature relaxation processes modify the localization of hydrogen. The combination of the hydrogenation and Mössbauer techniques gives a very sensitive method for detecting structural changes.     

Application of chemical P450 model systems to studies on drug metabolism. I. Phencyclidine: a multi-functional model substrate

Cytochrome P450 model and liver microsomal oxidations of drugs were compared using phencyclidine. In general, the chemical reaction systems produced many oxidation products. Besides the formation of the cyclohexane-4-hydroxyl compound (2), hydroxylation of the aromatic ring was favored in the Fenton reaction system (Fe2+ + H2O2). Formation of an m-hydroxylated product (m-5) was the main aromatic oxidation pathway in the Udenfriend reaction (Fe2+-ascorbic acid-O2), and 2, the piperidine-3-hydroxyl compound (3), and the piperidine-4-hydroxyl compound (4) were also formed. In the system using meso-tetraphenylporphinatoiron chloride (Fe(III)TPPC1) with an oxidant, the main product was the piperidine-3-oxo compound (8). In the liver microsomes system, 2, 4, 8, and m-5, which were all generated by the chemical oxidation reactions, were detected as metabolites of phencyclidine. They were formed by cytochrome P450-dependent reactions. Chemical oxidation systems can be used to study drug metabolism; they can reveal some tendencies of the real metabolic reactions, are easy to operate, and yield sufficient amounts of product.     

In situ chemical aminoacylation with amino acid thioesters linked to a peptide nucleic acid

tRNA-specific chemical aminoacylation was achieved with nonnatural amino acids. A nonnatural amino acid was activated as a thioester derivative, and the latter was linked through a spacer to the N-terminal of a 9-mer peptide nucleic acid that is complementary to the 3'-terminal region of yeast phenylalanine tRNA. Efficient aminoacylation was observed when the amino acid thioester-spacer-PNA conjugate was mixed with the tRNA. The PNA-assisted aminoacylation was also successful in an Escherichia coli in vitro protein synthesizing system that contained an orthogonalized tRNA. The in situ aminoacylation/in vitro translation gave a mutant protein in which the nonnatural amino acid was incorporated into the position directed by a CGGG 4-base codon/anticodon pair.     

Hydrogenation of 1,3-butadiene over magnesium oxide prepared by the decomposition of magnesium oxalate

In order to find the cause of the high activity for hydrogenation of 1,3-butadiene over a magnesium oxide catalyst prepared by thermal decomposition of magnesium oxalate, ESR and poisoning techniques were used. The cause of the high activity was attributed to large surface area and electron donating properties, which might be related to the surface basicity.

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, 1,3-, . - , .

     

Phason strains on growth, stability and structure of icosahedral phases

Growth, stability and structure of icosahedral (i-) phases have been studied by electron diffraction and X-ray diffraction in relation with the phason strains. Three alloy systems; AlPdCr, AlPdMn and AlCuV were chosen in this study. An i- Al₇₂Pd₂₅Cr₃ grain has been analysed to have a phason matrix toward to a tetragonal or orthorhombic structure. Stability of the i-phases correlated with the phason relaxation was discussed in Al-Pd-Mn system. A quenched i-Al₇₄Pd₁₇Mn₉ close to but containing significant phason strains, revealed that the phason relaxation induced by precipitation of crystalline phases upon annealing. Phason disorder dominated by the chemical composition was evidenced in a composition study in Al-Pd-Mn system. A high density random phasons characterized the icosahedral glass phase was observed in AlCuV alloys.     

Chemically driven structural change in quasicrystalline Al---Pd---Mn alloys

Quasicrystals, including face-centered icosahedral (FCI), simple icosahedral (SI) and decagonal (D) phases with periodicities of 1.6 nm and 1.2 nm along periodic axis, are found to form over a wide composition range in the Al---Pd---Mn system. A very strong composition dependence of the chemical order is seen in icosahedral Al_90−xPd_xMn₁₀ alloys alloys. A discontinuous change in the lattice parameter, a_R, with the Pd content of the i-phases suggests that the replacement of Al by Pd is selective. The predominant occupation site for the Pd atoms is icosahedral structure varies between the FCI and SI lattices. It is proposed that the FCI phase can be constructed as a two-cell structure, originating from the Al---Pd and Al---Mn binary systems.     

Internal friction and structural relaxation of amorphous Fe---Mn---P alloys

Measurements of internal friction and dynamic modulus have been carried out on amorphous Fe_83−xMn_xP₁₇(x=9,12, or 15) alloys in the temperature range 300–800 K, as a function of applied frequency, by a forced oscillation method. The characteristic transition temperatures and activation energies for crystallization were measured by differential scanning calorimetry (DSC). The viscous flow of the sample was measured using a thermomechanical analyzer (TMA) under continuous heating conditions. Internal friction increases rapidly with temperature starting from 450 K for 0.1 Hz, 474 K for 0.5 Hz, 486 K for 1.0 Hz, 511 K for 5 Hz, and 525 K for 10 Hz for the Fe₇₄Mn₉P₁₇ specimen. It was found that the internal friction peak temperature was very closely the same as the steady state viscous flow temperature from the TMA curves for Fe₇₄Mn₉P₁₇ and Fe₆₈Mn₁₅P₁₇ but not for Fe₇₁Mn₁₂P₁₇. It is assumed that the internal friction peak does not correspond to the glass transition temperature or crystallization temperature for these alloy systems. Two maxima in the free-volume fraction and two minima in the viscosity were also found for the samples which exhibit a ‘mid-contraction’ in their TMA displacement curves. The internal friction peak occurred at the steady state viscous flow temperature. This occurrence means that the origin of the internal friction peak is related to the viscous flow behavior and free-volume fluctuation for this alloy system.     

Young's modulus sound velocity and Young's modulus of Ti-, Zr- and Hf-based amorphous alloys

The Young's modulus sound velocity (V_E) and the Young's modulus of amorphous ribbons for (Ti, Zr, Hf)_100?x (Si, Ge)_x binary and (Ti, Zr, Hf)_85?xM_x(Si, Ge)₁₅ (M = V ? VIII group transition metal) ternary systems were measured as a function of alloy composition. V_E increases with increasing silicon or germanium content and with the replacement of titanium, zirconium or hafnium by M elements except tantalum or hafnium, and tends to increase with the Debye temperature of the constituent elements themselves. E increases linearly with increasing σ_f and H_v, and ratios of σ_f/E and H_v/3E show a nearly constant value (? 0.018) for Zr_100?xSi_x and Zr_85?xM_xSi₁₅(M = Ti, V, Nb, Ta or Mo) amorphous alloys. Considering the compositional dependence of these mechanical properties (E, σ_f and H_v) and the strong correlation among them, it is suggested that (1) the short-range ordering due to the strong interaction among constituent atoms causes an increase in E, σ_f and H_v, and (2) all the early transition metal-based amorphous alloys possess a common mechanism for plastic flow.