Syntheses and reactions of some fluorinated dienes,cyclobutenes and furans

There are many reports¹ of the pyrolysis of fluorinated organic compounds, including the defluorination of cyclic fluorocarbons over iron to give aromatic compounds. Extending this technique we have investigated the flow pyrolysis of some readily accessible unsaturated fluorocarbons, such as I, II, and III, and found these to be synthetically

useful routes to fluorinated dienes, cyclobutenes, and furans. Pyrolyses were carried out using a nitrogen flow over platinum, iron or caesium fluoride heated at 430–700°. The various products can all be rationalized in terms of intermediate allylic radicals, and the solid substrate influences which allylic radicals are formed.We are also investigating the chemistry of those now accessible compounds, such as IV, V, and VI, and some of the preliminary results are described.

For example the fluoride ion induced dimerisation of IV gave two major products VII and VIII via a particular interesting mechanism.

     

An evaluation of SAM1 calculated vibrational frequencies

SAM1 and AM1 calculations were carried out on 41 molecules for the purpose of comparing the ability of these semiempirical methods to compute vibrational frequencies. For 442 vibrational modes, the results show that SAM1 reproduces all frequencies with an unsigned average error of 9.0% compared with 9.6% for AM1. The average signed error for SAM1 is less than 1%, while that for AM1 is about 5%. Except in the case of non-H atom stretching modes, the signed errors were near zero, indicating that no special scaling adjustment is needed. However, non-H atom stretching frequencies have highly systematic errors for both methods. The average signed error for SAM1 is + 14% which is quite close to the unsigned error at 16%. In such an obvious case, a systematic correction can be applied with some confidence. It can be said that the SAM1 non-H stretching frequencies are predicted to be too high by 14%, and should thus be scaled by a multiplicative factor of 0.86. A similar multiplicative correction of 0.15 can be applied in the case of AM1 to vibrations of this type.     

Characteristics of trimuon events observed in high-energy neutrino interactions

The properties of 76 neutrino-initiated μ^?μ^?μ⁺ events observed in the CDHS detector in the 350 GeV and 400 GeV wide-band beams at CERN are discussed. For neutrino energies 30 GeV and muon momenta ?4.5 GeV, the average trimuon rate is (3.0 ± 0.4) × 10^?5 of the single-muon event rate. The experimental distributions are compared with predictions from various models. The data cannot be understood in terms of either heavy-lepton or heavy-quark cascades; no evidence is found for such processes and upper limits for the two possibilities are established. The data can be understood in terms of the normal charged-current process with the additional production of a muon pair by both hadronic and electromagnetic processes.     

Comparison of moments from the valence structure function with QCD predictions

We present moments (both ordinary and Nachtmann) of the nucleon valence structure function measured in high Q²_νFE scattering, supplemented by data from deep inelastic eD scattering. These data seem to agree with QCD predictions for vector gluons. The QCD parameter Λ is found to be of the order 0.5 GeV.     

Evidence for highly charged ion Coulomb crystallization in multicomponent strongly coupled plasmas

Multicomponent non-neutral ion plasmas in a Penning trap consisting of Be(+) and highly charged Xe ions, having different mass-to-charge ratios than Be(+), are cooled to form strongly coupled plasmas by applying a laser-based collisional cooling scheme. The temperature of the plasma was determined from a Doppler broadened transition in Be(+). For the Xe ions, which are centrifugally separated from the Be, the Coulomb coupling parameter was estimated to be approximately 1000. Molecular dynamics simulations of the ion mixture show ordered structures, indicating crystallization of the Xe.     

Magnetic resonance imaging with lateralized arterial spin labeling

We report the development of a new MRI technique which allows spins from right-sided arteries to be labeled separately from spins from left-sided arteries. This method uses two spatially-selective adiabatic inversion pulses to alternate the labeling of the right carotid and vertebral artery separate from the left carotid and vertebral artery. Normal volunteers were scanned on a clinical 1.5 T system and the resultant brain images correlated with the T2 anatomic images. Arterial anatomy was depicted using the new sequence and corresponded to the labeling scheme employed by the sequence. It was demonstrated that spatially selective inversion pulses permit the encoding of the spins within specific vascular origins and the observation of their run-off territory.     

Light-emitting iridium(III) and ruthenium(II) polypyridyl complexes containing quadruple hydrogen-bonding moieties

A novel compound containing both a 2,2'-bipyridine as well as a 2-ureido-4[1H]-ureidopyrimidinone supramolecular moiety (3) has been synthesised and fully characterized by 1H-NMR, MALDI-TOFMS, UV-vis and IR spectroscopy. Subsequent coordination to iridium and ruthenium polypyridyl precursors allowed the formation of iridium(III) and ruthenium(II) polypyridyl dimers (5 and 7) assembled via quadruple hydrogen-bonding as well as metal coordination interactions. The syntheses and complete characterization of these materials by means of two-dimensional NMR techniques (1H-1H COSY and 1H-1H DOSY) as well as IR and MALDI-TOFMS are described in detail. Comparative studies of the optical properties of the luminescent model complexes (5' and '7) and the dimer species (5 and 7) are also illustrated. In addition, good processability of the materials has been demonstrated by inkjet printing leading to thin films revealing their potential for light-emitting devices.     

Reduction of vanadium(V) by L-ascorbic acid at low and neutral pH: kinetic, mechanistic, and spectroscopic characterization

L-Ascorbic acid interacts with vanadium(V) over the pH range of 0.4-7.0 to form three different coordination complexes. Both inner- and outer-sphere electron-transfer pathways are proposed to form vanadium(IV) complexes with L-ascorbate or dehydroascorbate, respectively. Effects of the pH on the coordination of L-ascorbic acid to the vanadium(V) center were observed and are presumably related to the speciation of the vanadium(V) ion. Three vanadium(IV) complexes were observed using ambient-temperature electron paramagnetic resonance spectroscopy. Two of these complexes are proposed to be vanadium(IV) L-ascorbate complexes, and one is consistent with a vanadium(IV) dehydroascorbic acid complex proposed earlier. These reduction reactions will occur under physiological conditions and could be important to the reduction of vanadium(V)-containing coordination complexes used as insulin-enhancing agents for treatment of diabetes.