Identification of solar nebula condensates in interplanetary dust particles and unequilibrated ordinary chondrites

Orthopyroxene and olivine grains, low in FeO, but containing MnO contents up to 5 wt percent were found in interplanetary dust particles (IDP) collected in the stratosphere. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt percent MnO. Orthopyroxenes and olivines high in Mn and low in FeO have only been reported from a single coarse grained chondrule rim in the Allende meteorite and from a Tieschitz matrix augite grain. The bulk MnO contents of the extraterrestrial dust particles with high MnO olivines and pyroxenes are close to CI chondrite abundances. High MnO, low FeO olivines and orthopyroxenes were also found in the matrix of Semarkona, an unequilibrated ordinary chondrite. This may indicate a related origin for minerals in extraterrestrial dust particles and in the matrix of unequilibrated ordinary chondrites

Computational study of the hydrodefluorination of fluoroarenes at [Ru(NHC)(PR₃)<sub style="vertical-align: sub;">2</sub>(CO)(H)<sub style="vertical-align: sub;">2</sub>]: predicted scope and regioselectivities

Density functional theory calculations have been employed to investigate the scope and selectivity of the hydrodefluorination (HDF) of fluoroarenes, C6F6-nHn (n = 0-5), at catalysts of the type [Ru(NHC)(PR3)(2)(CO)(H)(2)]. Based on our previous study (Angew. Chem., Int. Ed., 2011, 50, 2783) two mechanisms featuring the nucleophilic attack of a hydride ligand at a fluoroarene substrate were considered: (i) a concerted process with Ru-H/C-F exchange occurring in one step; and (ii) a stepwise pathway in which the rate-determining transition state involves formation of HF and a Ru-sigma-fluoroaryl complex. The nature of the metal coordination environment and, in particular, the NHC ligand was found to play an important role in both promoting the HDF reaction and determining the regioselectivity of this process. Thus for the reaction of C6F5H, the full experimental system (NHC = IMes, R = Ph) promotes HDF through (i) more facile initial PR3/fluoroarene substitution and (ii) the ability of the NHC N-aryl substituents to stabilise the key C-F bond breaking transition state through F center dot center dot center dot HC interactions. This latter effect is maximised along the lower energy stepwise pathway when an ortho-H substituent is present and this accounts for the ortho-selectivity seen in the reaction of C6F5H to give 1,2,3,4-C6F4H2. Computed C-F bond dissociation energies (BDEs) for C6F6-nHn substrates show a general increase with larger n and are most sensitive to the number of ortho-F substituents present. However, HDF is always computed to remain significantly exothermic when a silane such as Me3SiH is included as terminal reductant. Computed barriers to HDF also generally increase with greater n, and for the concerted pathway a good correlation between C-F BDE and barrier height is seen. The two mechanisms were found to have complementary regioselectivities. For the concerted pathway the reaction is directed to sites with two ortho-F substituents, as these have the weakest C-F bonds. In contrast, reaction along the stepwise pathway is directed to sites with only one ortho-F substituent, due to difficulties in accommodating ortho-F substituents in the C-F bond cleavage transition state. Calculations predict that 1,2,3,5-C6F4H2 and 1,2,3,4-C6F4H2 are viable candidates for HDF at [Ru(IMes)(PPh3)(2)(CO)(H)(2)] and that this would proceed selectively to give 1,2,4-C6F3H3 and 1,2,3-C6F3H3, respectively.</p

Lunar hydrogen: A resource for future use at lunar bases and space activities

Hydrogen abundances were determined for grain size separates of five lunar soils and one soil breccia. The hydrogen abundance studies have provided important baseline information for engineering models undergoing study at the present time. From the studies is appears that there is sufficient hydrogen present in selected lunar materials which could be recovered to support future space activities. It is well known that hydrogen can be extracted from lunar soils by heating between 400 and 800 C. Recovery of hydrogen for regolith materials would involve heating with solar mirrors and collecting the released hydrogen. Current baseline models for the lunar base are requiring the production of 1000 metric tons of oxygen per year. From this requirement it follows that around 117 metric tons per year of hydrogen would be required for the production of water. The ability to obtain hydrogen from the lunar regolith would assist in lowering the operating costs of any lunar base

Deconvolving mutational patterns of poliovirus outbreaks reveals its intrinsic fitness landscape.

Vaccination has essentially eradicated poliovirus. Yet, its mutation rate is higher than that of viruses like HIV, for which no effective vaccine exists. To investigate this, we infer a fitness model for the poliovirus viral protein 1 (vp1), which successfully predicts in vitro fitness measurements. This is achieved by first developing a probabilistic model for the prevalence of vp1 sequences that enables us to isolate and remove data that are subject to strong vaccine-derived biases. The intrinsic fitness constraints derived for vp1, a capsid protein subject to antibody responses, are compared with those of analogous HIV proteins. We find that vp1 evolution is subject to tighter constraints, limiting its ability to evade vaccine-induced immune responses. Our analysis also indicates that circulating poliovirus strains in unimmunized populations serve as a reservoir that can seed outbreaks in spatio-temporally localized sub-optimally immunized populations

Direct and indirect selection on flowering time, water-use efficiency (WUE, δ (13)C), and WUE plasticity to drought in Arabidopsis thaliana.

Flowering time and water-use efficiency (WUE) are two ecological traits that are important for plant drought response. To understand the evolutionary significance of natural genetic variation in flowering time, WUE, and WUE plasticity to drought in Arabidopsis thaliana, we addressed the following questions: (1) How are ecophysiological traits genetically correlated within and between different soil moisture environments? (2) Does terminal drought select for early flowering and drought escape? (3) Is WUE plasticity to drought adaptive and/or costly? We measured a suite of ecophysiological and reproductive traits on 234 spring flowering accessions of A. thaliana grown in well-watered and season-ending soil drying treatments, and quantified patterns of genetic variation, correlation, and selection within each treatment. WUE and flowering time were consistently positively genetically correlated. WUE was correlated with WUE plasticity, but the direction changed between treatments. Selection generally favored early flowering and low WUE, with drought favoring earlier flowering significantly more than well-watered conditions. Selection for lower WUE was marginally stronger under drought. There were no net fitness costs of WUE plasticity. WUE plasticity (per se) was globally neutral, but locally favored under drought. Strong genetic correlation between WUE and flowering time may facilitate the evolution of drought escape, or constrain independent evolution of these traits. Terminal drought favored drought escape in these spring flowering accessions of A. thaliana. WUE plasticity may be favored over completely fixed development in environments with periodic drought

Ways of escape

This is the author accepted manuscript. The final version is available from Elsevier: Lancet via the DOI in this record

Letting Go: Conceptualizing intervention de-implementation in public health and social service settings

The discontinuation of interventions that should be stopped, or de-implementation, has emerged as a novel line of inquiry within dissemination and implementation science. As this area grows in human services research, like public health and social work, theory is needed to help guide scientific endeavors. Given the infancy of de-implementation, this conceptual narrative provides a definition and criteria for determining if an intervention should be de-implemented. We identify three criteria for identifying interventions appropriate for de-implementation: (a) interventions that are not effective or harmful, (b) interventions that are not the most effective or efficient to provide, and (c) interventions that are no longer necessary. Detailed, well-documented examples illustrate each of the criteria. We describe de-implementation frameworks, but also demonstrate how other existing implementation frameworks might be applied to de-implementation research as a supplement. Finally, we conclude with a discussion of de-implementation in the context of other stages of implementation, like sustainability and adoption; next steps for de-implementation research, especially identifying interventions appropriate for de-implementation in a systematic manner; and highlight special ethical considerations to advance the field of de-implementation research