A new technique to examine individual pollutant particle and fibre deposition and transit behaviour in live mouse trachea

During respiration, particles suspended in the air are inhaled and unless cleared by airway defences they can remain and affect lung health. Their size precludes the use of standard imaging modalities so we have developed synchrotron phase-contrast X-ray imaging (PCXI) methods to non-invasively monitor the behaviour of individual particles in live mouse airways. In this study we used these techniques to examine post-deposition particle behaviour in the trachea. PCXI was used to monitor the deposition and subsequent behaviour of particles of quarry dust and lead ore; fibres of asbestos and fibreglass; and hollow glass micro-spheres. Visibility was examined in vitro and ex vivo to avoid the complicating effects of surrounding tissue and respiratory or cardiac motion. Particle behaviour was then examined after deposition onto the tracheal airway surfaces of live mice. Each particle and fibre looked and behaved differently on the airway surface. Particles lodged on the airway shortly after deposition, and the rate at which this occurred was dependent on the particle type and size. After the live-imaging experiments, excised airway samples were examined using light and electron microscopy. Evidence of particle capture into the airway surface fluids and the epithelial cell layer was found. PCXI is a valuable tool for examining post-deposition particulate behaviour in the tracheal airway. These first indications that the interaction between airways and individual particles may depend on the particle type and size should provide a novel approach to studying the early effects of respired particles on airway health.     

Distribution of hydraulic conductivity in single scale anisotropy

The cluster statistics of percolation theory are used to find the distributions of hydraulic conductivity, K, of anisotropic (truncated) random fractal media. Rescaling of variables to transform anisotropic to isotropic media also produces deformations of, for example experimental volumes, and the resulting non-equidimensional shapes may generate interesting size effects on K. Previously, the most likely value of K was obtained by comparing the correlation length from percolation theory with system dimensions, a procedure analogous to those developed for hopping conduction in disordered systems to calculate the longitudinal conductivity of thin films. The result probably explains the frequent tendencies of measurements of K in anisotropic fracture networks and agricultural soils to increase with the scale of measurement, similarly to how the longitudinal conductivity of a thick film would be larger than the corresponding conductivity of a thin film (three- rather than two-dimensional conduction). However, the same procedure applied to the conductivity in the perpendicular direction (analogous to the transverse electrical conductivity of a thin film) shows a diminishing function of spatial scale. Collectively, these ‘scale effects’ disappear if the shape of the experimental volume is selected to maintain the relationships of conduction in the various directions as the scale of the experiment is increased analogously to equidimensional volumes in isotropic media. The increase in K is, thus, merely due to an increase in the dimensionality of conduction from one to three with increasing system size. The paper, thus, provides a solid argument against a common assumption in the porous media communities that the connectivity of highly conducting regions of a medium should increase with increasing scale of measurement.     

Longitudinal dispersion of solutes in porous media solely by advection

The purpose of this work is to predict the transport of non-sorbing solutes through water flow in the subsurface. We derive what we consider to be the first reliable calculations of the entire distribution of arrival times, W(t), for non-sorbing solutes in advective flow in strongly disordered porous media. Solutes treated can be contaminant plumes from any source or radioactive tracers, both experimentally and naturally generated. Our approach is microscopic and based on effects of disorder. It generates longitudinal dispersion (in the direction of flow) in the absence of diffusion. Effects on dispersion from a single capillary tube velocity distribution, known to produce long-tailed arrival time distributions, are also neglected. On the other hand, our calculations are based on effects generated from real porous media, such as wide pore-size distributions and complex connectivity. In particular, the calculation of the distribution of arrival times is based on a distribution of conserved fluxes and the known tortuosity of the associated geometrical paths. The results are found to be predictive when compared with simulations of two-dimensional flow on percolation structures, and appear to have relevance for experiments as well.     

Water simulation model with explicit three-molecule interactions

Much effort has been directed at developing models for the computer simulation of liquid water. The simplest models involve effective two-molecule interactions, parametrized from experiment, for use in classical molecular dynamics simulations. These models have been very successful in describing the structure and dynamics of liquid water at room temperature and one atmosphere pressure. A completely successful model, however, should be robust enough to describe the properties of liquid water at other thermodynamic points, water's complicated phase diagram, heterogeneous situations like the liquid/vapor interface, ionic, and other aqueous solutions, and confined and biological water. In this paper, we develop a new classical simulation model with explicit three-molecule interactions. These interactions presumably make the model more robust in the senses described above, and since they are short-ranged, the model is efficient to simulate. The model is formulated as a perturbation from a classical two-molecule interaction model, where the forms of the correction to the two-molecule term and the three-molecule terms result from electronic structure calculations on dimers and trimers. The magnitudes of these perturbations, however, are determined empirically. The resulting model improves upon the well-known two-molecule interaction models for both static and dynamic properties.     

Genetic microheterogeneity of human transthyretin detected by IEF

Mutations of the human transthyretin (TTR) gene have attracted medical interest as a cause of amyloidosis. Recently, we have described in detail an electrophoretic procedure with PAGE followed by IEF in urea gradients for the study of the microheterogeneity of TTR monomers (Altland, K., Winter, P., Sauerborn, M. K., Electrophoresis 1999, 20, 1349-1364). In this paper, we present a study on 49 different mutations of TTR including 33 that result in electrically neutral amino acid substitutions. The aims of the investigation were to test the sensitivity of the procedure to detect TTR variants in patients with TTR amyloidosis and their relatives and to identify some common characteristics that could explain the amyloidogenicity of these variants. We found that all tested amyloidogenic mutations could be detected by our method with the exception of those for which the corresponding variant was absent in plasma samples. Most of the electrically neutral amyloidogenic TTR variants had in common a reduced conformational stability of monomers by the activity of protons and urea. For three variants, e.g. TTR-F64L, TTR-I107V and TTR-V122I, the monomers had a conformational stability close to that of normal monomers but we found experimental and structural arguments for a weakening of the monomer-monomer contact. All types of amyloidogenic mutations affected the stability of TTR tetramers.     

Dynamical effects in line shapes for coupled chromophores: time-averaging approximation

For an isolated resonance of an isolated chromophore in a condensed phase, the absorption line shape is often more sharply peaked than the distribution of transition frequencies as a result of motional narrowing. The latter arises from the time-dependent fluctuations of the transition frequencies. It is well known that one can incorporate these dynamical effects into line shape calculations within a semiclassical approach. For a system of coupled chromophores, both the transition frequencies and the interchromophore couplings fluctuate in time. In principle one can again solve this more complicated problem with a related semiclassical approach, but in practice, for large numbers of chromophores, the computational demands are prohibitive. This has led to the development of a number of approximate theoretical approaches to this problem. In this paper we develop another such approach, using a time-averaging approximation. The idea is that, for a single chromophore, a motionally narrowed line shape can be thought of as a distribution of time-averaged frequencies. This idea is developed and tested on both stochastic and more realistic models of isolated chromophores, and also on realistic models of coupled chromophores, and it is found that in all cases this approximation is quite satisfactory, without undue computational demands. This approach should find application for the vibrational spectroscopy of neat liquids, and also for proteins and other complicated multichromophore systems.     

Sampling systems for isotope-ratio mass spectrometry of atmospheric ammonia

Passive and active ammonia (NH(3)) sampling devices have been tested for their nitrogen (N) capture potential and delta(15)N fractionation effects. Several sampling techniques produced significantly different delta(15)NH(3) signals when sampling the same NH(3) source released from field site fumigation campaigns. Conventional passive NH(3)-monitoring systems have shown to provide insufficient N for isotope-ratio mass spectrometry and various modified devices have been developed, based on existing diffusion tube designs, to overcome this problem. The final sampler design was then tested in a wind tunnel to verify that sampling NH(3) in different environmental conditions did not significantly fractionate the delta(15)N signal.     

Evaluation of a multiple spin- and gradient-echo (SAGE) EPI acquisition with SENSE acceleration: Applications for perfusion imaging in and outside the brain

Perfusion-based changes in MR signal intensity can occur in response to the introduction of exogenous contrast agents and endogenous tissue properties (e.g. blood oxygenation). MR measurements aimed at capturing these changes often implement single-shot echo planar imaging (ssEPI). In recent years ssEPI readouts have been combined with parallel imaging (PI) to allow fast dynamic multi-slice imaging as well as the incorporation of multiple echoes. A multiple spin- and gradient-echo (SAGE) EPI acquisition has recently been developed to allow measurement of transverse relaxation rate (R₂ and R₂^?) changes in dynamic susceptibility contrast (DSC)-MRI experiments in the brain. With SAGE EPI, the use of PI can influence image quality, temporal resolution, and achievable echo times. The effect of PI on dynamic SAGE measurements, however, has not been evaluated. In this work, a SAGE EPI acquisition utilizing SENSE PI and partial Fourier (PF) acceleration was developed and evaluated. Voxel-wise measures of R₂ and R₂^? in healthy brain were compared using SAGE EPI and conventional non-EPI multiple echo acquisitions with varying SENSE and PF acceleration. A conservative SENSE factor of 2 with PF factor of 0.73 was found to provide accurate measures of R₂ and R₂^? in white (WM) (r_R2 = [0.55–0.79], r_R2? = [0.47–0.71]) and gray (GM) matter (r_R2 = [0.26–0.59], r_R2? = [0.39–0.74]) across subjects. The combined use of SENSE and PF allowed the first dynamic SAGE EPI measurements in muscle, with a SENSE factor of 3 and PF factor of 0.6 providing reliable relaxation rate estimates when compared to multi-echo methods. Application of the optimized SAGE protocol in DSC-MRI of high-grade glioma patients provided T₁ leakage-corrected estimates of CBV and CBF as well as mean vessel diameter (mVD) and simultaneous measures of DCE-MRI parameters K^trans and v_e. Likewise, application of SAGE in a muscle reperfusion model allowed dynamic measures of R₂′, a parameter that has been shown to correlate with muscle oxy-hemoglobin saturation.     

Determination of contact angles, silane coverage, and hydrophobicity heterogeneity of methylated quartz surfaces using ToF-SIMS

Methylated quartz surfaces are extensively used in colloid science for wettability studies and the control and impact of hydrophobicity in key physicochemical processes. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to correlate the surface chemistry of trimethylchlorosilane-methylated quartz surfaces with the contact angle. Models have been developed for the calculation of both advancing and receding contact angles based on measurements of the ToF-SIMS signals for SiC(3)H(9)(+) (TMCS) and Si(+) (quartz). These models enable the contact angle across surfaces and, more importantly, that of individual particles to be determined on a micrometer scale. Distributions of contact angles in large ensembles of particles, therefore, can now be determined. In addition, from the ToF-SIMS analysis, the surface coverage of the methylated species can be quantitatively determined, in line with the Cassie equation. Moreover, advancing and receding contact angle maps can be calculated from ToF-SIMS images, and hence the variation in microscopic hydrophobicity (e.g., at the particle level) can be extracted directly from the images.     

Structural transformation and oxidation of Sr2MnO3.5+x determined by in-situ neutron powder diffraction

The oxidation of the n = 1 Ruddlesden-Popper phase, Sr₂MnO_3.5+x, where 0 ≤ x ≤ 0.5 has been investigated using a combination of in-situ diffraction techniques. In agreement with previous reports the room temperature structure of Sr₂MnO_3.5+x was determined to be monoclinic crystallising in space group P2₁/c. On heating in air the material undergoes rapid oxidation at a relatively modest temperature, ∼275 °C. The oxidation process is coincident with a significant change in the structure, with the material now adopting a tetragonal I4/mmm structure. In the oxygen deficient phase where x > 0 the Mn coordination is square pyramidal, with a sixth partially occupied oxygen position giving rise to octahedral coordination. Oxidation of Sr₂MnO_3.5+x results in the filling of the partially occupied O4 positions and a resulting increase in symmetry, with the Mn coordination now adopting solely a distorted octahedral environment.