Heterogeneous glyoxal oxidation: a potential source of secondary organic aerosol

Laboratory studies are described that suggest reactive uptake of glyoxal on particulate containing HNO(3) could contribute to the formation of secondary organic aerosol (SOA) in the upper troposphere (UT). Using a Knudsen cell flow reactor, glyoxal is observed to react on supercooled H(2)O/HNO(3) surfaces to form condensed-phase glyoxylic acid. This product was verified by derivatization and GC-MS analysis. The reactive uptake coefficient, γ, of glyoxal varies only slightly with the pressure of nitric acid, from γ = 0.5 to 3.0 × 10(-3) for nitric acid pressures between 10(-8) and 10(-6) Torr. The data do not show any dependence on temperature (181-201 K) or pressure of glyoxal (10(-7) to 10(-5) Torr). Using the determined reactive uptake kinetics in a simple model shows that glyoxal uptake to supercooled H(2)O/HNO(3) may account for 4-53% of the total organic mass fraction of aerosol in the UT.     

Exceedance probability of the integral of a stochastic process

Let X={X(s)}_s∈S be an almost sure continuous stochastic process (S compact subset of R^d) in the domain of attraction of some max-stable process, with index function constant over S. We study the tail distribution of ∫_SX(s)ds, which turns out to be of Generalized Pareto type with an extra ‘spatial’ parameter (the areal coefficient from Coles and Tawn (1996) [3]). Moreover, we discuss how to estimate the tail probability P(∫_SX(s)ds>x) for some high value x, based on independent and identically distributed copies of X. In the course we also give an estimator for the areal coefficient. We prove consistency of the proposed estimators. Our methods are applied to the total rainfall in the North Holland area; i.e. X represents in this case the rainfall over the region for which we have observations, and its integral amounts to total rainfall.The paper has two main purposes: first to formalize and justify the results of Coles and Tawn (1996) [3]; further we treat the problem in a non-parametric way as opposed to their fully parametric methods.     

Capillary size exclusion chromatography with picogram sensitivity for analysis of monoclonal antibodies purified from harvested cell culture fluid

Size exclusion chromatography (SEC) is widely used in the characterization and quality control of therapeutic proteins to detect aggregates. Aggregation is a carefully monitored quality attribute from the earliest stages of clinical development owing to the possibility of eliciting an immunogenic response in the patient. During early stage molecule assessment for cell culture production, small-scale screening experiments are performed to permit rapid turn-around of results so as to not delay timelines. We report the development of a capillary SEC methodology for preliminary molecule assessment to support the evaluation of therapeutic candidates at an early stage of development. By making several key modifications to a commercially available liquid chromatography system, we demonstrate a platform process to perform capillary SEC with excellent precision, picogram sensitivity and good ruggedness. The limit of quantitation was determined to be approximately 15 pg; picogram sensitivity for SEC analysis of monoclonal antibodies had not been achieved prior to this work. In addition, we have developed a method to capture low levels of antibody (1 μg/mL) from harvested cell culture fluid (HCCF) for capillary SEC analysis. Up to 40% recovery efficiency was achieved using this micro-recovery method on 3 mL HCCF samples. Using early stage cell culture transient transfection samples, which typically have much lower titers than stable cell line samples, we demonstrate a consistent method for analyzing aggregates in low protein concentration HCCF samples for molecule assessment and early stage candidate screening.     

Using an incremental mean first passage approach to explore the viscosity dependent dynamics of the unbiased translocation of a polymer through a nanopore

Noting the limitations of the standard characterization of translocation dynamics, an incremental mean first passage process methodology is used to more completely map the unbiased translocation of a polymer through a nanopore. In this approach, the average time t(0) required to reach successively increasing displacements for the first time is recorded - a measure shown to be more commensurate with the mean first passage nature of translocation. Applying this methodology to the results of Langevin dynamics simulations performed in three dimensions across a range of viscosities, a rich set of dynamics spanning regular diffusion at low viscosities to sub-diffusion at higher viscosities is revealed. Further, while the scaling of the net translocation time τ with polymer length N is shown to be viscosity-dependent, common regimes are found across all viscosities: super-diffusive behaviour at short times, an N-independent backbone consistent with τ ～ N(2.0) at low viscosities and τ ～ N(2.2) at higher viscosities for intermediate times, and N-dependent deviations from the backbone near the completion of translocation.     

Core temperature and density profile measurements in inertial confinement fusion implosions

We have measured time-integrated and time-gated electron temperature (T_e) and density (N_e) spatial profiles from indirect-drive implosions. In our experiments, we used a multiple-pinhole two-dimensional imaging spectrometer to obtain multispectral X-ray images of the imploded core. Quantitative comparisons between quasi-monochromatic images in different energy bands allowed T_e and N_e spatial profiles to be determined using two independent and validated techniques: a multi-objective search and reconstruction analysis, and an analytical analysis. We then compared the results to a simple one-dimensional (1D) mix-free hydrodynamics simulation in order to evaluate the ability of such a model to predict our experiments. Our data show spatial T_e profiles that are qualitatively consistent with the predictions of our 1D simulations, but we observe central cores that are 10–25% cooler and emit X-rays as late as 200 ps after peak compression. We infer time-gated spatial N_e profiles that are consistent with our 1D simulations near the times of peak compression, but we find significant disagreement between time-integrated data and 1D simulation predictions at large radii. Careful analysis of the time-gated and time-integrated T_e and N_e spatial profiles, together with streaked X-ray emission spectra from core and shell dopants, suggests mixing of shell material into the core is an important process that our 1D hydrodynamics simulations fail to capture, and comparison between image data and a simple analytical model suggests that 2–5 μm of the initial inner shell thickness mixes into the core during the time period of significant X-ray emission. This mix width is consistent with the predictions of a growth-factor analysis that treats instability growth seeded by capsule surface roughness, and points to the need to consider time-dependent mixing effects when interpreting T_e and N_e spatial profiles derived from multispectral X-ray image data, particularly at large radii where mixing effects will be most significant.     

Rate of Convergence of Intermediate Order Statistics

Exact rates are derived for the uniform convergence of the density of intermediate order statistics towards the normal or lognormal density under certain smoothness conditions. Our methods also give the exact rate of convergence in the uniform metric and in the total variation metric.     

Stationary min-stable stochastic processes

Summary We consider the class of stationary stochastic processes whose margins are jointly min-stable. We show how the scalar elements can be generated by a single realization of a standard homogeneous Poisson process on the upper half-strip [0,1]×R ₊ and a group of L ₁-isometries. We include a Dobrushin-like result for the realizations in continuous time.     

Domains of attraction and regular variation in IRd

A general form for regular variation in IR² is introduced and applied to domains of attraction of stable distribution in IR² where the components have different indices. The situation in IR^d with d > 2 is more complicated but not essentially different. For simplicity this paper is limited to IR².     

Simulations of the magnetization reversal of clustered Co-Cr particles

Micromagnetic simulations of the magnetization reversal of clusters of 9 and 25 magnetostatically coupled Co-Cr particles are presented. The magnetostatic interaction between neighbouring particles facilitates reversal. The non-uniform magnetization configuration plays an important role in this effect.