Reactions between ammonium sulphate and metal oxides (metal=Cr,Mn and Fe) and thermal decomposition of the products

The reactions between ammonium sulphate and three metal oxides (Cr₂O₃, MnO₂ and Fe₂O₃) were studied. It was confirmed by X-ray diffraction and chemical analysis that stable reaction intermediates were formed consecutively in the course of the reactions.These were (NH₄)₃M(SO₄)₃ and NH₄M(SO₄)₂ for Cr₂O₃ and Fe₂O₃ and (NH₄)₂Mn₂(SO₄)₃ for MnO₂. The thermal decompositions of these intermediates and of the metal sulphates were carried out. The contracting-volume equation was valid for the decomposition of all the intermediates. The Arrhenius parameters were determined.

---

Zusammenfassung Es wurden die Reaktionen zwischen Ammoniumsulfat und drei Metalloxiden (Cr₂O₃, MnO₂ und Fe₂O₃) untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, dass im Verlaufe der Reaktion stabile Zwischenprodukte gebildet werden. Es handelt sich dabei um (NH₄)₃M(SO₄)₃ und NH₄M(SO₄)₂ im Falle von Cr₂O₃ und Fe₂O₃ und um (NH₄)₂Mn₂(SO₄)₃ im Falle von MnO₂. Diese Zwischenprodukte und die Metallsulfate wurden thermisch zersetzt. Die Volumenkontraktionsgleichung war für die Zersetzung all dieser Zwischenprodukte gültig. Die Arrheniusparameter wurden bestimmt.

---

Cr₂O₃, MnO₂ Fe₂O₃. , . , (NH₄)₃M(SO₄)₃ NH₄M(SO₄)₂, (NH₄)₂Mn₂(SO₄)₃. . . .

     

Prospective study to assess the clinical efficacy of bone scintigraphy--some analyses of clinical data

The value of preoperative bone scans in patients with primary breast and prostate cancer was evaluated prospectively. Of 414 patients with breast cancer, clinical stage I is 14, II is 219, IIIA is 59, IIIB is 39 and IV is 14. Of 88 patients with prostate cancer, clinical stage I is 14, II is 15, III is 18 and IV is 41. 11 percent of patients with breast cancer and 54 percent of patients with prostate cancer had bone metastases. Clavicle, ribs, thoracic spine, lumbar spine and pelvis metastasized most frequently. The incidences of bone metastases were 18.4% with Scirrhous carcinoma, 15.4% with Medullary tubular carcinoma and 3.8% with Papillotubular carcinoma. The methodology and results of ROC analysis were described in our other papers. Some results of data analysis were described in this paper.     

π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage

Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction.     

Analysis of free fatty acids by a micro-liquid chromatograph directly coupled with a mass spectrometer through a vacuum nebulizing interface

A liquid chromatograph directly coupled with a quadrupole mass spectrometer through a vacuum nebulizing interface was applied to the analysis of various free fatty acids. Chemical ionization mass spectra of the C₇? C₂₂ free fatty acids were first examined using either methanol or benzene as the reagents. Then the practical compositional analysis of the fatty acids were performed with various biological samples such as bean oil, rape oil, palm oil and milk fat where most of the fatty acids are included as their triglycerides.     

Kinetics of the interconversion of parahydrogen and orthohydrogen catalyzed by paramagnetic complex ions

The rate constants of para-/orthohydrogen (p-/o-H2) nuclear spin isomerization have been measured by means of 1H NMR in deuterated solvents at 298.2 K. The indicated reaction is catalyzed by paramagnetic complex ions giving rate constants that are proportional to the concentrations of the catalysts. The second-order rate constants are directly proportional to the squares of the magnetic moments for the solvated metal complexes for two classifications: M(solv)m2+, M = 3d transition metals; Ln(solv)n3+, where in 1:9 D2O-CD3CN the aqua complexes are the predominant species, Ln = lanthanides. The other 3d transition metal complexes with different ligands show rate constants that also depend on the sizes of ligands. Whereas the correlation between the second-order rate constants and magnetic moments is consistent with Wigner's theory, the size of catalyst shows a more modest effect on the rate constants than expected. The effective collision radii of the complexes, calculated from the rate constants, proved to be approximately constant for each series of solvated metal complexes.     

Synthesis of substituted polymethylenes by radical polymerization of alkyl N,N-dialkylfumaramates and maleamates: Relative reactivity of the isomers

Bulk polymerization of alkyl N,N-dialkylfumaramates (FAE) and maleamates (MAE) was performed in the presence of a radical initiator. It has been found that FAE is more reactive than MAE when the reactivity of the two geometrical isomers was compared for their homo- and copolymerizations. From investigation on the effect of ester and N-substituents of these monomers, it has been found that the isopropyl ester shows a higher reactivity than the methyl ester and that N-ethyl and n-butyl substitution gives polymers with high molecular weight of more than several thousands. The resulting substituted polymethylenes from FAE and MAE were characterized and compared with each other. The isomerization of MAE to FAE with morpholine as an isomerization catalyst and monomer-isomerization radical polymerization were also investigated.     

Radiation-induced emission from golden hamster embryo cells

Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H₂O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H₂O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy.     

Polymerization of tetraallyl ammonium chloride

The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion.