Novel Phenomenon of Oxygen-to-oxygen Silyl Migration in Directed Aldol Reaction

The phenomenon of migration of the silyl groups from α-oxygen to β-oxygen in sodium aldol reaction was observed for the first time in this paper.     

Determination of nitric acid concentration by using europium ion fluorescence

A method is presented for the determination of 2-10M nitric acid based on the fact that the presence of high nitric acid concentration causes an enhancement of the intensity of some bands in the fluorescence spectra of rare earth ions in solution. The 616-nm band of Eu(3+) shows the most dramatic intensity enhancement with increasing nitric acid concentration. The present method, based on the measurement of the ratio of Eu(3+) fluorescent band intensities is shown to be independent of Eu(3+) concentration and relatively free of interference. This robust method allows the presence of an interferent to be determined from the experimental data.     

Spectroscopic evidence for the intermediacy of a 6-R-2,4-diazabicyclo-[3.1.0]hex-2-(3)ene in the photoisomerization of 4-R-1,4-(3,4)-dihydropyrimidines

¹H- and ¹³C-nmr spectroscopy is presented showing that photolysis of 4-(p-trifluoromethylphenyl)-1,4-(3,4)-dihydropyrimidine yields 6-(p-trifluoromethylphenyl)-2,4-diazabicyclo[3.1.0]hex-2-(3)ene.     

Appareillage pour la mesure de variations rapides de l'emission d'un gaz radioactif par un solide soumis a un traitement thermique,sous atmosphere controlee

An apparatus is described that enabled us to carry out a quantitative kinetic investigation of rather quick physicochemical transformations of divided solids by means of an emission of radioactive gas, as in the emanation method. Especially the details of the reaction cells are given in which surface area measurements by the BET method are also performed, and of the low volume scintillation chamber. Its high efficiency does not depend on the nature of the gas. The diverse components of the device ensure a good quality of pure atmosphere or vacuum, rapid and precise temperature setting and control, and reproducible sweeping of the radioactive gas escaping from the sample.     

On the biological importance of the hydrogen bond breaking potency of fluorocarbons

Fluorocarbons containing higher halogens have the potency of breaking certain hydrogen bonds in solutions. The relative strength of this potency varies in the series F < Cl < Br < I and the presence of hydrogen atoms in the fluorocarbon increases it. There is a striking parallelism between the hydrogen bond breaking and the anaesthetic potency of these molecules. It is suggested that the breaking of hydrogen bonds is an important step in the mechanism of anaesthesia.     

Kinetics of grafting acrylonitrile onto starch

Acrylonitrile (AN) was graft copolymerized onto gelatinized and granular wheat starch in aqueous media in the presence of ceric ammonium nitrate initiator at 91-364 anhydroglucose units (AGU) per cerium (IV) and at 1.08-4.33 AN to AGU ratios. Molecular weights and dispersities of polyacrylonitrile side chains were determined by gel-permeation chromatography. Conversion-time plots of AN polymerizations in both gelatinized and granular starch systems show characteristics common to heterogeneous polymerizations that could be explained on the basis of buried polymer radicals. The rates of polymerizations were directly related to the square root of the corrected cerium(IV) concentration and to the 1.3 power of the AN concentration. Graft copolymerization of AN onto starch, at least during initial stages, is not suitably explained by a kinetic scheme involving termination by polymer radical with cerium(IV) ion.     

Kinetic study of anhydride formation during thermal degradation of isotactic and atactic polymethacrylic acid

A kinetic study of anhydride formation in isotactic and atactic polymethacrylic acids (PMA) has been performed at about 200° using a vacuum thermobalance. The results obey first order kinetics and show that the rate of water loss is about four times higher for the isotactic PMA than for the atactic isomer. The activation energies are almost identical (42 ± 1 kcal per mole); it is concluded that the arrangement of neighbouring carboxyl groups is more favourable for the formation of a cyclic anhydride by intramolecular reaction in the case of the isotactic PMA.     

Mass spectra of benzotriazinones and the first loss of 28 mass units

Mass spectra of five benzotriazinone derivatives are reported and the fragmentation mechanisms are discussed. That the first loss of 28 mass units is a nitrogen molecule appears to be characteristic of the molecules.     

The determination of all the platinum group elements and gold in rocks and ore by neutron activation analysis after preconcentration by a nickel sulphide fire-assay technique on large samples

The noble metals are inhomogeneously distributed in sulphide ores and their host rocks. It is therefore necessary to analyse large sample sizes to obtain representative analyses. A nickel sulphide fire assay technique has been adapted to extract the noble metals from a large sample size (50 g) into a nickel sulphide button. Subsequently the fire assay button is dissolved in hydrochloric acid and the solution is filtered. The noble metal residue retained on the filter paper is analysed quantitatively by i.n.a.a. techniques. This method is rapid, relatively inexpensive and has better sensitivities for all the noble metals than other analytical techniques.     

Fabrication and characterization of high-temperature microreactors with thin film heater and sensor patterns in silicon nitride tubes

In this paper the fabrication and electrical characterization of a silicon microreactor for high-temperature catalytic gas phase reactions, like Rh-catalyzed catalytic partial oxidation of methane into synthesis gas, is presented. The microreactor, realized with micromachining technologies, contains silicon nitride tubes that are suspended in a flow channel. These tubes contain metal thin films that heat the gas mixture in the channel and sense its temperature. The metal patterns are defined by using the channel geometry as a shadow mask. Furthermore, a new method to obtain Pt thin films with good adhesive properties, also at elevated temperatures, without adhesion metal is implemented in the fabrication process. Based on different experiments, it is concluded that the electrical behaviour at high temperatures of Pt thin films without adhesion layer is better than that of Pt/Ta films. Furthermore, it is found that the temperature coefficient of resistance (TCR) and the resistivity of the thin films are stable for up to tens of hours when the temperature-range during operation of the microreactor is below the so-called "burn-in" temperature. Experiments showed that the presented suspended-tube microreactors with heaters and temperature sensors of Pt thin films can be operated safely and in a stable way at temperatures up to 700 degrees C for over 20 h. This type of microreactor solves the electrical breakdown problem that was previously reported by us in flat-membrane microreactors that were operated at temperatures above 600 degrees C.