Electron spin resonance study of puff-resolved free radical formation in mainstream cigarette smoke

Puff-by-puff resolved gas phase free radicals were measured in mainstream smoke from Kentucky 2R4F reference cigarettes using ESR spectroscopy. Three spin-trapping reagents were evaluated: PBN, DMPO and DEPMPO. Two procedures were used to collect gas phase smoke on a puff-resolved basis: i) the accumulative mode, in which all the gas phase smoke up to a particular puff was bubbled into the trap (i.e., the 5th puff corresponded to the total smoke from the 1st to 5th puffs). In this case, after a specified puff, an aliquot of the spin trap was taken and analysed; or, ii) the individual mode, in which the spin trap was analysed and then replaced after each puff. Spin concentrations were determined by double-integration of the first derivative of the ESR signal. This was compared with the integrals of known standards using the TEMPO free radical. The radicals trapped with PBN were mainly carbon-centred, whilst the oxygen-centred radicals were identified with DMPO and DEPMPO. With each spin trap, the puff-resolved radical concentrations showed a characteristic pattern as a function of the puff number. Based on the spin concentrations, the DMPO and DEPMPO spin traps showed better trapping efficiencies than PBN. The implication for gas phase free radical analysis is that a range of different spin traps should be used to probe complex free radical reactions in cigarette smoke.

Electron paramagnetic resonance investigation of the free radicals in the gas and particulate phases of cigarette smoke using spin-trapping techniques

Free radicals in cigarette smoke have been studied using spin trapping EPR techniques. 2R4F reference cigarettes were smoked using 35 ml puff volumes of 2 seconds duration, once every 60 seconds. The particulate phase of the smoke was separated from the gas phase by passing the smoke through a Cambridge filter pad. For both phases, free radicals were measured and identified. A range of spin-traps was employed: PBN, DMPO, DEPMPO, and DPPH-PBN. In the gas-phase, short-lived carbon- and oxygen- centered radicals were identified; the ratios between them changed during the smoking runs. For the first puffs, C-centered radicals predominated while for the later puffs, O-centered radicals were mainly observed. The particulate phase and the ‘tar’ were studied as well.

Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes

UV–Vis absorption spectra of one-electron reduction products and 3MLCT excited states of [ReICl(CO)3- (N,N)] (N,N = 2,20-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV–Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [ReICl(CO)3(N,Nÿ)]ÿ and ⁄[ReIICl(CO)3(N,Nÿ)], respectively. UV–Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal a-diimines, for which similar spectroscopic behavior can be expected.

The molecular structure of propylene sulphide (methylthiirane) by gas-phase electron diffraction and theoretical calculations: a molecule used in MOCVD

Gas-phase electron-diffraction (GED) data together with results from ab initio molecular orbital calculations have been used to determine the structure of propylene sulphide. Values found for the main structural parameters for the molecule are consistent with those obtained from microwave studies and are compared here with those found for similar sulphur containing rings of general formula S(CH2)n (n = 2–5). A high ring strain enthalpy was calculated for propylene sulphide which is consistent with the small C–S–C angle (48.2(6)degrees) and the relatively long C–S bond lengths (ra = 1.831(2) Å). This is thought to account for the ease of ring opening in propylene sulphide observed in MOCVD reactions and the ready polymerisation of the molecule.

A closed paramagnetic electron-precise cluster

A pentametallic cluster is formed by addition of two [SnR2][R = CH(SiMe3)2] groups to [Os3(CO)8(µ-H)(C6H4PhPCH2PPh2)], in a reaction reversing the ortho-hydrogen abstraction and giving the first closed electron-precise paramagnetic cluster.

A transmission electron microscopy study of polymer-stabilised liquid crystal structure

A method has been established for observing the internal structure of the network component of polymer-stabilised liquid crystals. In situ photopolymerisation of a mesogenic diacrylate monomer using ultraviolet light leads to a sparse network (∼1 wt%) within a nematic host. Following polymerisation, the host was removed through dissolution in heptane, revealing the network. In order to observe a cross-section through the network, it was embedded in a resin and then sectioned using an ultramicrotome. However, imaging of the network was not possible due to poor contrast. To improve this, several reagents were used for network staining, but only one was successful: bromine. The use of a Melinex-resin composite for sectioning was also found to be advantageous. Imaging of the network using transmission electron microscopy revealed solid “droplets” of width 0.07–0.20 μm, possessing an open, yet homogeneous structure, with no evidence for any large-scale internal structures.

Retrieval of mesospheric electron densities using an optimal estimation inverse method

We present a new method to determine mesospheric electron densities from partially reflected medium frequency radar pulses. The technique uses an optimal estimation inverse method and retrieves both an electron density profile and a gradient electron density profile. As well as accounting for the absorption of the two magnetoionic modes formed by ionospheric birefringence of each radar pulse, the forward model of the retrieval parameterises possible Fresnel scatter of each mode by fine electronic structure, phase changes of each mode due to Faraday rotation and the dependence of the amplitudes of the backscattered modes upon pulse width. Validation results indicate that known profiles can be retrieved and that χ2 tests upon retrieval parameters satisfy validity criteria. Application to measurements shows that retrieved electron density profiles are consistent with accepted ideas about seasonal variability of electron densities and their dependence upon nitric oxide production and transport.

Hydrogen bonding in the gas-phase: the molecular structures of 2‑hydroxybenzamide (C7H7NO2) and 2‑methoxybenzamide (C8H9NO2), obtained by gas-phase electron diffraction and theoretical calculations

The structures of 2-hydroxybenzamide(C7H7NO2) and 2-methoxybenzamide (C8H9NO2) have been determined in the gas-phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict four stable conformers for both 2-hydroxybenzamide and 2-methoxybenzamide. For both compounds, evidence for intramolecular hydrogen bonding is presented. In 2-hydroxybenzamide, the observed hydrogen bonded fragment is between the hydroxyl and carbonyl groups, while in 2-methoxybenzamide, the hydrogen bonded fragment is between one of the hydrogen atoms of the amide group and the methoxy oxygen atom.

Do magnetospheric shear Alfvén waves generate sufficient electron energy flux to power the aurora?

Using a self-consistent drift-kinetic simulation code, we investigate whether electron acceleration owing to shear Alfvén waves in the plasma sheet boundary layer is sufficient to cause auroral brightening in the ionosphere. The free parameters used in the simulation code are guided by in situ observations of wave and plasma parameters in the magnetosphere at distances >4 RE from the Earth. For the perpendicular wavelength used in the study, which maps to ∼4 km at 110 km altitude, there is a clear amplitude threshold which determines whether magnetospheric shear Alfvén waves above the classical auroral acceleration region can excite sufficient electrons to create the aurora. Previous studies reported wave amplitudes that easily exceed this threshold; hence, the results reported in this paper demonstrate that auroral acceleration owing to shear Alfvén waves can occur in the magnetosphere at distances >4 RE from the Earth.

Electron trapping in shear Alfvén waves that power the aurora

Results from 1D Vlasov drift-kinetic plasma simulations reveal how and where auroral electrons are accelerated along Earth’s geomagnetic field. In the warm plasma sheet, electrons become trapped in shear Alfven waves, preventing immediate wave damping. As waves move to regions with larger vTe=vA, their parallel electric field decreases, and the trapped electrons escape their influence. The resulting electron distribution functions compare favorably with in situ observations, demonstrating for the first time a self-consistent link between Alfven waves and electrons that form aurora.

An assessment of a three-beam Doppler lidar wind profiling method for use in urban areas

Currently there are few observations of the urban wind field at heights other than rooftop level. Remote sensing instruments such as Doppler lidars provide wind speed data at many heights, which would be useful in determining wind loadings of tall buildings, and predicting local air quality. Studies comparing remote sensing with traditional anemometers carried out in flat, homogeneous terrain often use scan patterns which take several minutes. In an urban context the flow changes quickly in space and time, so faster scans are required to ensure little change in the flow over the scan period. We compare 3993 h of wind speed data collected using a three-beam Doppler lidar wind profiling method with data from a sonic anemometer (190 m). Both instruments are located in central London, UK; a highly built-up area. Based on wind profile measurements every 2 min, the uncertainty in the hourly mean wind speed due to the sampling frequency is 0.05–0.11 m s−1. The lidar tended to overestimate the wind speed by ≈0.5 m s−1 for wind speeds below 20 m s−1. Accuracy may be improved by increasing the scanning frequency of the lidar. This method is considered suitable for use in urban areas.

Electron acceleration and parallel electric fields due to kinetic Alfvén waves in plasma with similar thermal and Alfvén speeds

We investigate electron acceleration due to shear Alfven waves in a collissionless plasma for plasma parameters typical of 4–5RE radial distance from the Earth along auroral field lines. Recent observational work has motivated this study, which explores the plasma regime where the thermal velocity of the electrons is similar to the Alfven speed of the plasma, encouraging Landau resonance for electrons in the wave fields. We use a self-consistent kinetic simulation model to follow the evolution of the electrons as they interact with a short-duration wave pulse, which allows us to determine the parallel electric field of the shear Alfven wave due to both electron inertia and electron pressure effects. The simulation demonstrates that electrons can be accelerated to keV energies in a modest amplitude sub-second period wave. We compare the parallel electric field obtained from the simulation with those provided by fluid approximations.