Detection of Aliphatically Bridged Multi-Core Polycyclic Aromatic Hydrocarbons in Sooting Flames with Atmospheric-Sampling High-Resolution Tandem Mass Spectrometry.

This paper provides experimental evidence for the chemical structures of aliphatically substituted and bridged polycyclic aromatic hydrocarbon (PAH) species in gas-physe combustion environments. The identification of these single- and multicore aromatic species, which have been hypothesized to be important in PAH growth and soot nucleation, was made possible through a combination of sampling gaseous constituents from an atmospheric pressure inverse coflow diffusion flame of ethylene and high-resolution tandem mass spectrometry (MS-MS). In these experiments, the flame-sampled components were ionized using a continuous VUV lamp at 10.0 eV and the ions were subsequently fragmented through collisions with Ar atoms in a collision-induced dissociation (CID) process. The resulting fragment ions, which were separated using a reflectron time-of-flight mass spectrometer, were used to extract structural information about the sampled aromatic compounds. The high-resolution mass spectra revealed the presence of alkylated single-core aromatic compounds and the fragment ions that were observed correspond to the loss of saturated and unsaturated units containing up to a total of 6 carbon atoms. Furthermore, the aromatic structures that form the foundational building blocks of the larger PAHs were identified to be smaller single-ring and pericondensed aromatic species with repetitive structural features. For demonstrative purposes, details are provided for the CID of molecular ions at masses 202 and 434. Insights into the role of the aliphatically substituted and bridged aromatics in the reaction network of PAH growth chemistry were obtained from spatially resolved measurements of the flame. The experimental results are consistent with a growth mechanism in which alkylated aromatics are oxidized to form pericondensed ring structures or react and recombine with other aromatics to form larger, potentially three-dimensional, aliphatically bridged multicore aromatic hydrocarbons

Can the Heinrich ratio be used to predict harm from medication errors?

The purpose of this study was to establish whether, for medication errors, there exists a fixed Heinrich ratio between the number of incidents which did not result in harm, the number that caused minor harm, and the number that caused serious harm. If this were the case then it would be very useful in estimating any changes in harm following an intervention. Serious harm resulting from medication errors is relatively rare, so it can take a great deal of time and resource to detect a significant change. If the Heinrich ratio exists for medication errors, then it would be possible, and far easier, to measure the much more frequent number of incidents that did not result in harm and the extent to which they changed following an intervention; any reduction in harm could be extrapolated from this

Generalizations of Ripley's K-function with Application to Space Curves

The intensity function and Ripley's K-function have been used extensively in the literature to describe the first and second moment structure of spatial point sets. This has many applications including describing the statistical structure of synaptic vesicles. Some attempts have been made to extend Ripley's K-function to curve pieces. Such an extension can be used to describe the statistical structure of muscle fibers and brain fiber tracks. In this paper, we take a computational perspective and construct new and very general variants of Ripley's K-function for curves pieces, surface patches etc. We discuss the method from [Chiu, Stoyan, Kendall, & Mecke 2013] and compare it with our generalizations theoretically, and we give examples demonstrating the difference in their ability to separate sets of curve pieces.Comment: 9 pages & 8 figure

Solving high-dimensional parameter inference: marginal posterior densities & Moment Networks

High-dimensional probability density estimation for inference suffers from the "curse of dimensionality". For many physical inference problems, the full posterior distribution is unwieldy and seldom used in practice. Instead, we propose direct estimation of lower-dimensional marginal distributions, bypassing high-dimensional density estimation or high-dimensional Markov chain Monte Carlo (MCMC) sampling. By evaluating the two-dimensional marginal posteriors we can unveil the full-dimensional parameter covariance structure. We additionally propose constructing a simple hierarchy of fast neural regression models, called Moment Networks, that compute increasing moments of any desired lower-dimensional marginal posterior density; these reproduce exact results from analytic posteriors and those obtained from Masked Autoregressive Flows. We demonstrate marginal posterior density estimation using high-dimensional LIGO-like gravitational wave time series and describe applications for problems of fundamental cosmology

Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

Increasing interest in high-energy lithium-ion batteries has triggered the demand to clarify the reaction mechanism in battery cathodes during high-potential operation. However, the reaction mechanism often involves both transition-metal and oxygen activities that remain elusive. Here we report a comprehensive study of both cationic and anionic redox mechanisms of LiNiO2 nearly full delithiation. Selection of pure LiNiO2 removes the complication of multiple transition metals. Using combined X-ray absorption spectroscopy, resonant inelastic X-ray scattering, and operando differential electrochemical mass spectrometry, we are able to clarify the redox reactions of transition metals in the bulk and at the surface, reversible lattice oxygen redox, and irreversible oxygen release associated with surface reactions. Many findings presented here bring attention to different types of oxygen activities and metal-oxygen interactions in layered oxides, which are of crucial importance to the advancement of a Ni-rich layered oxide cathode for high capacity and long cycling performance

Predicting ecosystem shifts requires new approaches that integrate the effects of climate change across entire systems.

Most studies that forecast the ecological consequences of climate change target a single species and a single life stage. Depending on climatic impacts on other life stages and on interacting species, however, the results from simple experiments may not translate into accurate predictions of future ecological change. Research needs to move beyond simple experimental studies and environmental envelope projections for single species towards identifying where ecosystem change is likely to occur and the drivers for this change. For this to happen, we advocate research directions that (i) identify the critical species within the target ecosystem, and the life stage(s) most susceptible to changing conditions and (ii) the key interactions between these species and components of their broader ecosystem. A combined approach using macroecology, experimentally derived data and modelling that incorporates energy budgets in life cycle models may identify critical abiotic conditions that disproportionately alter important ecological processes under forecasted climates

Genotype dependent callus induction and shoot regeneration in sunflower (Helianthus annuus L.)

This study aims to observe the effect of genotype, hormone and culture conditions on sunflower (Helianthus annuus L.) callus induction and indirect plant regeneration. Calli were obtained from hypocotyl and cotyledon explants of five different sunflower genotypes; Trakya 80, Trakya 129, Trakya 259, Trakya 2098 and Viniimk 8931, which are commercially important for Turkey. Seeds germinated on Murashige and Skoog (MS) media contained no hormones. Hypocotyl and cotyledon explants were cultured on MS media supplemented with 1 mg/l 2,4-D (2,4-dichlorophenoxy acetic acid) and different percentage of callus inductions were obtained. Calli were cultured on MS + 1 mg/l BA (6-benzylaminopurine) and 0.5 mg/l NAA (-naphthalene acetic acid). Some genotypes showed high regeneration response while others showed lower on the same media with hypocotyl and cotyledon derived calli. This study showed that genotypic differences affect callus induction and plant regeneration in sunflower tissue culture studies

Facilitators and Barriers to Safe Medication Administration to Hospital Inpatients: A Mixed Methods Study of Nurses' Medication Administration Processes and Systems (the MAPS Study).

Research has documented the problem of medication administration errors and their causes. However, little is known about how nurses administer medications safely or how existing systems facilitate or hinder medication administration; this represents a missed opportunity for implementation of practical, effective, and low-cost strategies to increase safety