Differentiation of chiral phosphorus enantiomers by P and H NMR spectroscopy using amino acid derivatives as chemical solvating agents

The ability of commercially available amino acid derivatives, especially Fmoc-Trp(Boc)-OH, to differentiate enantiomers of chiral phosphonates, phosphinates, phosphates, phosphine oxides, and phosphonamidates is demonstrated with (31)P, (13)C, and (1)H NMR spectroscopy. The chiral differentiation provided a rapid and convenient method for measuring the enantiomeric purity of these phosphorus compounds.     

Mechanism of phase transitions in the (NH4)2WO2F4 ferroelastic

Precision studies of the thermophysical properties and structure of an (NH₄)₂WO₂F₄ crystal have been performed. It was established reliably that there is a sequence of two phase transitions at T ₁ = 201 K and T ₂ = 160 K characterized by wedging out of an intermediate phase with an increase in pressure. The role of tetrahedral and octahedral ionic groups in the mechanism of the structural transitions was determined.     

Optical and photoelectric properties of pure and cadmium-and lead-doped neodymium sesquisulfide thin films

A technique for preparing γ-Nd₂S₃ crystalline thin films through discrete vacuum thermal evaporation of a presynthesized bulk material is developed. The films deposited are doped with cadmium and lead. The reflectance and transmittance spectra of the films are measured in the photon energy range 0.2–3.0 eV at a temperature of 300 K. The frequency analysis of the absorption coefficient demonstrates that the γ-Nd₂S₃ films are characterized by an exponential absorption edge. The photoconductivity spectra and temperature dependences of the photoconductivity for the γ-Nd₂S₃ films doped with cadmium and lead are measured in the photon energy range 0.2–3.3 eV at temperatures varying from 115 to 380 K. The experimental data obtained are interpreted under the assumption that the acceptor levels formed by vacancies in the cation sublattice and compensated for by cadmium and lead donor dopants play a crucial role in the photoconduction. The ionization energy at the lead donor level is determined.     

Theoretical analysis of the spectra of X-ray resonant magnetic reflectivity

We have developed the general computer code for the calculations of reflectivity with polarization analysis from an arbitrary anisotropic multilayer, which allows us to test different approaches for the Bragg reflectivity spectrum treatment. We have proved the validity of the usage of the Bragg peak position for the determination of the energy dependence of the diagonal component of resonant susceptibility tensor, but revealed the essential discrepancy of this procedure for the off-diagonal term determination. The explanation lies in the polarization mixture by multiple reflections at large glancing angles. By the model calculations we have shown that in L-MOKE geometry the observed difference of the integrated Bragg peak reflectivity for the (+) and (−) field direction is predominantly caused by the magnetization of the central part of resonant layer at the first-order Bragg peak, but it is very sensitive to the interface magnetization at the second-order Bragg peak.     

Self-inhibition or the lack of it in the pyrolyses of neopentane and n-hexane

Published data show that in its early stages (up to 3% decomposition), the pyrolysis of n-hexane in the ranges 723–823 K and 10–100 Torr is not inhibited by the olefin products, in contrast with neopentane pyrolysis which is very strongly inhibited in similar conditions. Detailed consideration of the chain mechanisms for the two pyrolyses shows that the reactivity of the chain terminating radical towards hydrogen abstraction from an allylic C? H bond in product olefin is the factor which determines whether or not observable self-inhibition occurs. Thus, n-hexane pyrolysis, whose chain decomposition is terminated by recombination and disproportionation of ethyl, is not significantly self-inhibited, whereas that of neopentane which is terminated by recombination of methyl is very strongly inhibited because methyl is 14× more reactive than ethyl. The implications for other alkanes are briefly discussed.     

HPLC studies of isomeric chromium-N-benzoylphenylhydroxylaminates

Summary N-Benzoylphenylhydroxylarnine complexes of some metals have been investigated by HPLC. The green chromium complex formed by this reagent shows conclusive evidence of the presence of geometrical isomers. It is photosensitive and changes to a brown modification when irradiated with ultra violet or visible light. Elution behaviour of the complexes has been studied with different solvent mixtures. Attempts have been made to characterize the complexes from different measurements.

---

Untersuchung von isomeren Chrom-N-benzoylphenylhydroxylaminaten durch HPLC

     

High reliability atomic absorption spectrometry of major and minor elements in biological materials

Summary Reliable analytical information is of fundamental importance for decisions of far-reaching impact in many regulatory, medical and scientific areas and disciplines. It is however at times elusive. Although the technique of atomic absorption spectrometry (AAS) as become widely established in analytical laboratories throughout the world for the determination of inorganic elements, only few AAS-based methods have reached official status and even fewer have attained reference method status. Research is underway to delineate impacts of a number of parameters on method performance to lead to protocols for standard and reference flame AAS (FAAS) methods for the reliable measurement of major and minor levels of elements of nutritional and toxicological pertinence in clinical and biological materials. Factors investigated include preparation of standards, calibration techniques, sampling and sample decomposition, solution preparation, instrumental parameters, and measurement protocols. Examples of some pronounced effects of sample decomposition and calibration techniques are presented as well as indications of the excellent performance of well-applied AAS procedures determined by use of standard reference materials and comparison with other techniques of analysis. Reference will be made to the determination of the major and minor nutrient elements Na, K, Mg, Ca, Mn, Fe, Cu and Zn in plant biological reference materials.Formerly at Plant Research Centre, Agriculture Canada, Ottawa, Ontario K1A OC6, CanadaContribution No. 1030 from Plant Research Centre