Overlapping spheres multiple scattering Xα calculations of the ionization potentials and electron affinities of nitrogen oxides

The ionization potentials and electron affinities of a series of nitrogen oxygen compounds have been calculated by the overlapping spheres MS Xα method to assess its applicability on a series for which good experimental data is available. The results for the ionization potentials were satisfactory although a straightforward matching of calculated and experimental IP's without consideration of other criterion would have led to some misassignments. The results for the electron affinities are in excellent agreement with experiment.     

Determination of the spin sublevel origin of radiative and non-radiative decay routes of phosphorescing benzene derived from precision lifetime measurements

The increase in the phosphorescence lifetime as temperature is lowered has been quantitatively determined in the 2–30 K range. Applying the Boltzmann population expression yields the information that virtually none of the radiative decay originates from the lowest spin sublevel (A_2g).     

Random peptide synthesis using immobilized enzymes in high concentrations of organic solvents

Trypsin, leucine aminopeptidase, and carboxypeptidase B were separately immobilized on controlled pore glass and reacted with a dipeptide substrate in high concentrations of either acetone or 1-propanol. Hydrolytic activity was demonstrated and evidence for the possible synthesis of peptide polymer is presented. Directed synthesis using amino acids and blocked amino acids as substrates was not successful.     

A study of the process of lignification of one-year willow wood

Conclusions 1. The content of lignin in the wood ofSalix viminalis andSalix acutifolia increases with the growth of the shoots during shortened days and also in drier climatic periods.2. The monosaccharides, glucose, fructose, and arabinose take part in the synthesis of the lignin of young wood ofSalix viminalis andSalix acutifolia. The formation of lignin of one-year willow wood takes place from May to January (with a maximum in June–July). The content of methoxyl groups in it gradually rises.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 6, pp. 546–550, 1969     

The molecular structure of the N-chloroimine product of rearrangement of N,N-dichloroperfluoroaniline: A study by gas-phase electron diffraction

A gas-phase electron-diffraction study of the product of rearrangement of N,N-dichloro-perfluoroaniline has assisted in establishing it to be the N-chloroimine, I, rather than the azepine, II. The molecule is found to be planar apart from atoms Cl13 and F14. The detailed dimensions shown in Fig. 2 were obtained by least-squares refinements in which several structural constraints were applied to reduce the total number of independent parameters. Of particular interest is the evidence for overcrowding around the CN bond: ∠N7C1C2 = 128°, ∠C18N7C1 = 126°, ∠N7C1C6 = 118° ; the distance C18 β F9 is 2.73 Å.     

Favorskii rearrangements—I: One electron transfer from α′-enolate intermediates to 3O2 in aprotic,polar- protic and mixed media

Evidene for the trapping of α′-enolate intermediates in Favorskii rearrangements by one-electron transfer (ET) to ³O₂ is presented. The mechanism of the ET reaction has been elucidated from studied of the extent of ET trapping, compared to H/D exchange. The trapping efficiency (alkene/esters) was found tobe dependent on the reaction medium, the pK_a of the α′-C-acid, (a larger pK_a favouring greater ET) and the substrate concentration. Conclusions from this work of relevance to the mechanism of the Favorskii rearrangement are outlined.     

Free energies of electron ejection of aromatic hydrocarbon negative ions in ethers at room temperature

The free energies of electron ejection of some aromatic hydrocarbon mono- and di-negative ions in DME and 2-MTHF at room temperature are estimated from existing experimental data. The formation of free solvated electrons requires about the same amount of free energy whether the negative ion is present as a loosely bound or a tightly bound associate with the sodium counter ion. When the ejected electrons are trapped by a solvent cavity in the vicinity of the sodium ion the reaction requires appreciably less energy for the tightly bound than for the loosely bound associates. The data are essential for the study of the photo-ionization of aromatic hydrocarbon negative ions in ethers.     

Activation a l'aide de polyamines tertiaires de la polymerisation anionique du styrene amorcee par les composes organolithiens

A study of the influence of tertiary polyamines on the reactivity of polystyryllithium ion-pairs in hydrocarbon solvents has been performed. The stability of active centres has been studied and allows the processing of kinetic data as for living systems. Rate constants of propagation have been measured in terms of the structure of the polyamine, its relative concentration, the concentration in organometallic species, the temperature and the nature of solvent; in all cases, they are absolute rate constants. The values show the important effect of the number of nitrogen atoms in the additive and especially the strong influence of its geometry: the cyclic polyamine studied leads to an activation of the reaction much greater than that of the corresponding linear substance. These results may be interpreted in terms of different solvation states for the polystyryllithium ion-pairs.     

Thermal properties of flame retardant viscose fibers

This paper discusses the problem of the thermal properties of flame retarding additives based on phosphazene derivatives and of the commercial agents TomflamB, FlammexT23P and StockhausenW-20949, as well as of flame resistant viscose fibers containing the above agents. Results of this investigation showed the action of FlammexT23P, StockhausenW-20949 and phosphazene derivatives at lower temperature. TomflamB acted within a much wider range of temperatures. The flame retardant additives applied to viscose fibers change the thermal properties of the fiber material.     

Thermal analysis and synthesis of pentazinc hexahydroxide dicarbonate: Investigations by thermogravimetry,thermo molecular beam analysis and x-ray measurements

A combination of thermobalance and X-ray camera is described which allows simultaneous thermogravimetric (TG) and X-ray measurements under high vacuum. During these measurements the sample is positioned in the sample holder of the camera in the usual fashion and is X-raved while the temperature is varied. The molecular beam of the gaseous decomposition products flows through a connecting tube which acts as a molecular beam former between camera and thermobalance. The molecular beam is directed towards the empty balance pan. The orifice through which the beam exits as well as the pan have special shapes that allow transfer of the angular momentum of the decomposition beam to the balance. The exerted force is a function of time and corresponds to the first derivative of the TG curve. i.e. to the DTG curve. The integrated curve is directly proportional to the change in mass of the probe. A quantitative evaluation is possible if the molecular composition of the beam is known. The calibration of the molecular beam and the evaluation of the measurements will be discussed. The results show that simultaneous detection of X-ray scattering and indirect TG curves allows a better interpretation of decomposition reactions.An additional investigation shows that thermal synthesis of chemical com- pounds can also be studied by thermogravimetry. Based on the same compound as described in the analysis. the pyrosynthesis is demonstrated. The special instrumentation and the test conditions are discussed.