The facile synthesis of a large ring lactone by acid-catalysed cyclisation of an (z)-ene-diyne hydroxy acid precursor.

A Large ring lactone is obtained in good yield by acid catalysed cyclisation of the w-hydroxy acid precursor.     

μSR Studies of 2-propanone and aqueous solutions of 2-propanone

The radical (CH₃)₂ COMu has been studied in pure (CH₃)₂ CO and in binary aqueous systems. The value of the muon-electron hyperfine coupling constant fell sharply from 25.4 MHz to ca 22.5 MHz on the addition of low concentration of water. It then fell gradually on going to dilute solutions in water. The coupling increased with increasing temperature as expected for a positive hyperfine interaction. The results are compared with esr data for (CH₃)₂ COH radicals, and the solvent dependence is considered in terms of hydrogen-bonding. The mechanism of formation of these radicals is discussed in the light of reaction rates. It is concluded that their precursor cannot be muonium.     

Radiative decays of unbound levels in 20Ne

Nine levels in the range 8.7 to 12.5 MeV in ²⁰Ne have been investigated with the ¹⁶O(α, γ)²⁰Ne and ¹⁶O(α, α')¹⁶O¹(6.13 MeV) reactions using a differentially pumped windowless gas target. Three of the levels have not been observed previously in these reactions, and new information has been obtained for most of the others. In particular, the 11.27 MeV 1^? level is shown to have T = 1, a result of relevance to a proposed parity violation experiment, and the analogue of the 1.97 MeV (3^?T = 1) level in ²⁰F is shown to lie at 12.25 MeV in ²⁰Ne rather than at 12.39 MeV as proposed previously. In addition, the 12.25 MeV level has a width Γ < 1 keV, in contrast to the value Γ ～ 5 keV reported in other work. The electromagnetic transition rates for positive parity T = 1 states in ²⁰Ne are compared with shell-model calculations.     

ESR studies on the structure of C6F−6 anions

Rigid solution spectra for C₆F^?₆ and C₄F^?₈ are compared, and it is concluded that C₆F^]t-₆ cannot have the planar, σ^* structure previously postulated. Instead, a puckered-ring structure with σ and pseudo π delocalisation is postulated.     

Paramagnetic transition metal carbonyls : IV. ESR study of anions derived from (CO)5MnPbPh3 and (CO)4CoPbPh3 by high energy radiation

Exposure of (CO)₅MnPbPh₃ to ⁶⁰Co γ-ray at 77 K gave one major paramagnetic species detectable by ESR spectroscopy. This exhibited an anisotropic hyperfine interaction with ⁵⁵Mn, near free-spin g-values, and a small, almost isotropic coupling to ²⁰⁷Pb. The form of the A(⁵⁵Mn) and g-tensor components suggest an orbital of d_z² symmetry on manganese for the unpaired electron, but this cannot be directed along the MnPb bond since the ²⁰⁷Pb hyperfine coupling indicates a very low spin-density on lead. We suggest that the centre is formed by electron addition to manganese to give a formal d⁷ centre, with concomitant loss of one equatorial carbonyl ligand. We defind z as the direction of the lost ligand. A second centre, detected at high gain, having a large hyperfine coupling to ²⁰⁷Pb and a 31 G coupling to ⁵⁵Mn is tentatively identified as the parent cation.In marked contrast, the molecule (CO)₄CoPbPh₃ gave a single centre having comparable ⁵⁹Co hyperfine and g-tensor components, but also a very large hyperfine coupling to ²⁰⁷Pb (ca. 3300 G). Thus, in this case, an electron gain centre (d⁹) has been formed, the electron being accomodated in the highest MO having a large d_z² component on cobalt (z being now the CoPb direction).Reasons for the adoption of these different structures are discussed.     

The relative biological effectiveness of a high energy neutron beam for micronuclei induction in T-lymphocytes of different individuals

In assessing the radiation risk of personnel exposed to cosmic radiation fields as it pertains to radiological damage during travel in civilian aircrafts, it is particularly important to know the relative biological effectiveness (RBE) for high energy neutrons. It has been the subject of numerous investigations in recent years using different neutron energies and cytogenetic examinations. Variations in the radiosensitivity of white blood cells for different individuals are likely to influence the estimate of the relative biological effectiveness for high energy neutrons. This as such observations have been noted in the response of different cancer cell lines with varying inherent sensitivities. In this work the radiosensitivities of T-lymphocytes of different individuals to the p(66)/Be neutron beam at iThemba LABS were measured using micronuclei formations and compared to that noted following exposure to ⁶⁰Co γ-rays. The principle objective of this investigation was to establish if a relationship between neutron RBE and variation in biological response to ⁶⁰Co γ-rays for lymphocytes from different individuals could be determined. Peripheral blood samples were collected from four healthy donors and isolated lymphocytes were exposed to different doses of ⁶⁰Co γ-rays (1–5 Gy) and p(66)/Be neutrons (0.5–2.5 Gy). One sample per donor was not exposed to radiation and served as a control. Lymphocytes were stimulated using PHA and cultured to induce micronuclei in cytokinesis-blocked cells. Micronuclei yields were numerated using fluorescent microscopy. Radiosensitivities and RBE values were calculated from the fitted parameters describing the micronuclei frequency dose response data. Dissimilar dose response curves for different donors were observed reflecting varying inherent sensitivities to both neutron and gamma radiation. A clear reduction in the dose limiting RBE_M is noted for donors with lymphocytes more sensitive to γ-rays (p = 0.032, R² = 0.94). Unlike observations made with different cancer cell lines exposed to the same clinical neutron beam, the variations in neutron RBE observed in T-lymphocytes of different individuals is related to the cellular radioresistance to photons.     

Studies on thermionic ionisation detection in comprehensive two-dimensional gas chromatography

This study explores the application of specific thermionic ionisation detection in comprehensive 2-D GC (GC x GC) and represents the first report of GC x GC with nitrogen phosphorus detection (GC x GC-NPD). Of particular interest is the performance of the NPD with respect to peak parameters of asymmetry and sensitivity. Since GC x GC produces much narrower peaks than obtained with fast GC (e.g. 100 ms vs. <1 s) the effect of detector response time and any lack of symmetry arising from the detection step is important if peak separation (resolution) is to be maintained. It was observed that detector gas flows had a significant impact on peak asymmetry and peak magnitude, and that optimisation of the detector was critical, particularly for complex sample analysis by GC x GC-NPD. Peak asymmetries ranging from As = 1.8 to 8.0 were observed under different conditions of detector gas flows. Comparison of GC x GC-NPD with GC x GC-flame ionisation detection (FID) showed the former to be approximately 20 times more sensitive for the detection of nitrogen-containing methoxypyrazines analytes, and GC x GC-NPD had a larger linear detection range compared to GC x GC-FID. Furthermore, comparison of GC x GC-NPD and GC x GC-TOFMS chromatograms for the analysis of coffee head-space demonstrated the benefits of selective detection, ultimately realised in a comparatively simplified contour plot.