Real‐time non‐invasive detection of inhalable particulates delivered into live mouse airways

Fine non‐biological particles small enough to be suspended in the air are continually inhaled as we breathe. These particles deposit on airway surfaces where they are either cleared by airway defences or can remain and affect lung health. Pollutant particles from vehicles, building processes and mineral and industrial dusts have the potential to cause both immediate and delayed health problems. Because of their small size, it has not been possible to non‐invasively examine how individual particles deposit on live airways, or to consider how they behave on the airway surface after deposition. In this study, synchrotron phase‐contrast X‐ray imaging (PCXI) has been utilized to detect and monitor individual particle deposition. The in vitro detectability of a range of potentially respirable particulates was first determined. Of the particulates tested, only asbestos, quarry dust, fibreglass and galena (lead sulfate) were visible in vitro. These particulates were then examined after delivery into the nasal airway of live anaesthetized mice; all were detectable in vivo but each exhibited different surface appearances and behaviour along the airway surface. The two fibrous particulates appeared as agglomerations enveloped by fluid, while the non‐fibrous particulates were present as individual particles. Synchrotron PCXI provides the unique ability to non‐invasively detect and track deposition of individual particulates in live mouse airways. With further refinement of particulate sizing and delivery techniques, PCXI should provide a novel approach for live animal monitoring of airway particulates relevant to lung health.     

Incorporation of Effects of Diffusion into Advection-Mediated Dispersion in Porous Media

The distribution of solute arrival times, W(t;x), at position x in disordered porous media does not generally follow Gaussian statistics. A previous publication determined W(t;x) in the absence of diffusion from a synthesis of critical path, percolation scaling, and cluster statistics of percolation. In that publication, W(t;x) as obtained from theory, was compared with simulations in the particular case of advective solute transport through a two-dimensional model porous medium at the percolation threshold for various lengths x. The simulations also did not include the effects of diffusion. Our prediction was apparently verified. In the current work we present numerical results related to moments of W(x;t), the spatial solute distribution at arbitrary time, and extend the theory to consider effects of molecular diffusion in an asymptotic sense for large Peclet numbers, P_e. However, results for the scaling of the dispersion coefficient in the range 1<P_e<100 agree with those of other authors, while results for the dispersivity as a function of spatial scale also appear to explain experiment.     

Absorption of H and D Ly-α radiation by O2 molecules at high temperatures

Absorption cross sections of molecular oxygen were measured at the H and D Ly-α wavelengths (1215.67 and 1215.34 Å) between 800 and 1700°K, the cross sections being given by the equation σ (cm²) = 4.2E-18 exp(-3070/T) (4.2E-18 = 4.2 × 10^-18). The absorption cross section for v = 1 is (9±2)E-19 cm² and that for v = 2 is (7±3)E-18 cm², compared to 1.E-20 cm² for v = 0. Vibrational relaxation times were found to be in agreement with literature data over the range of common temperatures.     

Investigation of the origin of the glucose response in a glucose oxidase|polyaniline system

The origin of the signal seen in response to glucose in a polyaniline|glucose oxidase system is explored by immittance spectroscopy, by comparing data from an equivalent circuit model and the parameters obtained from a solution of the faradaic branch of the frequency dispersion for a coupled chemical—electrochemical reaction mechanism. It was shown that an RC subcircuit in the equivalent circuit model was sensitive to peroxide concentration, and the interaction of peroxide with polyaniline at potentials where it either oxidised or reduced the polyaniline was discussed. This information was used to compare the data obtained in a bulk and entrapped glucose oxidaselglucose system, and it was seen that the origin of the response could not be fully attributed to peroxide interaction in the latter case. Under anaerobic conditions with entrapped enzyme, it was proposed that a complex between the gluconolactone product of the enzyme reaction and the polymer leads to a more conducting polymer, with inherent charge compensation, and this results in the observed enhanced current signal.     

Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation

A selection of dimeric tetraethynylethenes (TEEs) and perethynylated expanded radialenes, containing different donor/acceptor substitution patterns, have been prepared and fully characterized. The first X-ray crystal structure of an expanded [6]radialene, with twelve peripheral 3,5-di(tert-butyl)phenyl substituents, is presented. This macrocycle, the all-carbon core of which is isomeric with fullerene C60, adopts a non-planar, "chair-like" conformation. Also a TEE dimer, carrying N,N-dimethylaniline donor substituents, has been subjected to an X-ray crystallographic analysis. The electronic properties were studied by UV/Vis spectroscopy and electrochemistry, providing fundamental insight into mechanisms of pi-electron delocalization in the acyclic and macrocyclic chromophores. Donor or donor-acceptor-substituted dimeric TEE derivatives show very strong absorptions extending over the entire UV/Vis region; their longest wavelength absorption bands have high charge-transfer character. Macrocyclic cross-conjugation in the expanded radialenes becomes increasingly efficient with increasing donor-acceptor polarization. A dual, strongly solvent-polarity-dependent fluorescence was observed for a tetrakis(N,N-dimethylaniline)-substituted dimeric TEE; this interesting emission behavior is explained by the twisted intramolecular charge-transfer (TICT) state model. Donor-substituted expanded radialenes display huge resonance-enhanced third-order nonlinear optical coefficients.     

On the mode-coupling theory of vibrational line broadening in near-critical fluids

Molecular-dynamics simulations of a neat atomic fluid, coupled with a simple model for vibrational frequency perturbations, are used to investigate vibrational line broadening near the liquid-gas critical point. All features of our simulations are in qualitative agreement with recent Raman experiments on nitrogen. We also use our simulation results to assess the validity of the mode-coupling theories that have been used to analyze experiment. We find that the theoretical results are not in good agreement with simulation, both for the temperature dependence of the linewidth, and for the frequency time-correlation functions. However, the mode-coupling prediction that critical line broadening is due to the diverging correlation time of the frequency fluctuations is shown to be correct.     

An improved synthesis of [2.2.3]cyclazines from 3H-pyrrolizines

[2.2.3]Cyclazines are obtained in moderate yields by reaction of 3$\text{H}$-pyrrolizines bearing conjugative substituents (Ph or CO₂Me) with vinamidinium salts in the presence of strong bases. Syntheses of the previously unknown 2-phenyl-3$\text{H}$-pyrrolizine and 1-methoxycarbonylcyclopenta [$\text{h}$] [2.2.4] cyclazine are also described.