Enantioselective Acylation of Silyl Ketene Acetals through Fluoride Anion-Binding Catalysis

A highly-enantioselective acylation of silyl ketene acetals with acyl fluorides has been developed to generate useful $\alpha$, $\alpha$-disubstituted butyrolactone products. This reaction is promoted by a new thiourea catalyst and 4-pyrrolidinopyridine and represents the first example of enantioselective thiourea anion-binding catalysis with fluoride.Chemistry and Chemical Biolog

Localized Strain and Associated Failure of Structural Materials

Aircraft are made primarily out of strong and lightweight aluminum alloys, which are relatively low cost, easy to produce, and have allowed for several innovations in the airplane industry. Even though these alloys are highly corrosion resistant, they are susceptible to failure since airplanes experience some of the harshest fatigue and corrosion conditions. Predicting the location of crack initiation on these corroded materials could lead to preventative safety of aluminum components on an aircraft. To study the mechanisms leading to cracking, precorroded AA7050 samples were fatigue loaded to failure, virtually reconstructed form post-mortem characterizations, and modeled accordingly to obtain the micromechanical state of the material. Fatigue indicator parameters were calculated from the resulting stresses and strains. The initial corrosion front was then analyzed at the reconstructed crack plane, using a metric that identifies the most active slip planes per grain. The reconstructed data is masked over onto planes that have the same orientation as the [111] slip planes. Then, the data is analyzed quantitatively for each slip plane, looking for the highest median fatigue indicator parameter value. The slip plane on the grain closest to the crack initiation site was found to have a slip plane roughly parallel to the crack plane. On this plane, many significantly larger fatigue indicator parameter values were found, with the highest value pinpointing the region where crack initiation was experimentally observed

Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer biisonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveals ultra-fast intramolecular vibronic coupling, particularly during excitation into the LUMO-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the timescale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond timescale in this system

Probing the face-on disc-corona system of the bare AGN Mrk 110 from UV to hard X-rays: a moderate changing-state AGN?

[Abridged] The X-ray broadband spectra of the bare AGN Mrk 110, obtained by simultaneous XMM-Newton and NuSTAR observations (Nov 2019 and April 2020), are characterised by the presence of a prominent and absorption-free smooth soft X-ray excess, moderately broad OVII and Fe Kalpha emission lines, and a lack of a strong Compton hump. While relativistic reflection as the sole emission is ruled out, a simplified combination of soft and hard Comptonisation from a warm and a hot coronae, plus mild relativistic disc reflection reproduces the data very well. We aim to confirm the physical origin of the soft X-ray excess of Mrk 110 and to determine its disc-corona system properties from its energetics using two new sophisticated models: reXcor and relagn, respectively. At both epochs, the inferred high-values of the warm-corona heating from the X-ray broadband spectral analysis using reXcor confirm that the soft X-ray excess originates mainly from a warm corona rather than relativistic reflection. The intrinsic best-fit SED determined at both epochs using relagn show a high X-ray contribution relative to the UV and are very well reproduced by a warm and hot coronae plus mild relativistic reflection. The outer radii of the hot and warm coronae are located at a few 10s and ~100 Rg, respectively. Moreover, combining the inferred low Eddington ratio (~ a few %) from this work, and previous multi-wavelength spectral and timing studies suggests that Mrk 110 could be classified as a moderate changing-state AGN. Our analysis confirms the existence of a warm corona as a significant contribution to the soft X-ray excess and UV emission in Mrk 110, adding to growing evidence that AGN accretion deviates from standard disc theory. This strengthens the importance of long-term multi-wavelength monitoring on both single targets and large AGN surveys to reveal the real nature of disc-corona system in AGN.Comment: 12 pages, 7 figures, accepted for publication in A&

Fast Modal Sounds with Scalable Frequency-Domain Synthesis

International audienceAudio rendering of impact sounds, such as those caused by falling objects or explosion debris, adds realism to interactive 3D audiovisual applications, and can be convincingly achieved using modal sound synthesis. Unfortunately, mode-based computations can become prohibitively expensive when many objects, each with many modes, are impacted simultaneously. We introduce a fast sound synthesis approach, based on short-time Fourier Tranforms, that exploits the inherent sparsity of modal sounds in the frequency domain. For our test scenes, this "fast mode summation" can give speedups of 5-8 times compared to a time-domain solution, with slight degradation in quality. We discuss different reconstruction windows, affecting the quality of impact sound "attacks". Our Fourier-domain processing method allows us to introduce a scalable, real-time, audio processing pipeline for both recorded and modal sounds, with auditory masking and sound source clustering. To avoid abrupt computation peaks, such as during the simultaneous impacts of an explosion, we use crossmodal perception results on audiovisual synchrony to effect temporal scheduling. We also conducted a pilot perceptual user evaluation of our method. Our implementation results show that we can treat complex audiovisual scenes in real time with high quality

Limited antigenic diversity of Plasmodium falciparum apical membrane antigen 1 supports the development of effective multi-allele vaccines

BackgroundPolymorphism in antigens is a common mechanism for immune evasion used by many important pathogens, and presents major challenges in vaccine development. In malaria, many key immune targets and vaccine candidates show substantial polymorphism. However, knowledge on antigenic diversity of key antigens, the impact of polymorphism on potential vaccine escape, and how sequence polymorphism relates to antigenic differences is very limited, yet crucial for vaccine development. Plasmodium falciparum apical membrane antigen 1 (AMA1) is an important target of naturally-acquired antibodies in malaria immunity and a leading vaccine candidate. However, AMA1 has extensive allelic diversity with more than 60 polymorphic amino acid residues and more than 200 haplotypes in a single population. Therefore, AMA1 serves as an excellent model to assess antigenic diversity in malaria vaccine antigens and the feasibility of multi-allele vaccine approaches. While most previous research has focused on sequence diversity and antibody responses in laboratory animals, little has been done on the cross-reactivity of human antibodies.MethodsWe aimed to determine the extent of antigenic diversity of AMA1, defined by reactivity with human antibodies, and to aid the identification of specific alleles for potential inclusion in a multi-allele vaccine. We developed an approach using a multiple-antigen-competition enzyme-linked immunosorbent assay (ELISA) to examine cross-reactivity of naturally-acquired antibodies in Papua New Guinea and Kenya, and related this to differences in AMA1 sequence.ResultsWe found that adults had greater cross-reactivity of antibodies than children, although the patterns of cross-reactivity to alleles were the same. Patterns of antibody cross-reactivity were very similar between populations (Papua New Guinea and Kenya), and over time. Further, our results show that antigenic diversity of AMA1 alleles is surprisingly restricted, despite extensive sequence polymorphism. Our findings suggest that a combination of three different alleles, if selected appropriately, may be sufficient to cover the majority of antigenic diversity in polymorphic AMA1 antigens. Antigenic properties were not strongly related to existing haplotype groupings based on sequence analysis.ConclusionsAntigenic diversity of AMA1 is limited and a vaccine including a small number of alleles might be sufficient for coverage against naturally-circulating strains, supporting a multi-allele approach for developing polymorphic antigens as malaria vaccines

Tropical river suspended sediment and solute dynamics in storms during an extreme drought

Droughts, which can strongly affect both hydrologic and biogeochemical systems, are projected to become more prevalent in the tropics in the future. We assessed the effects of an extreme drought during 2015 on stream water composition in the Luquillo Mountains of Puerto Rico. We demonstrated that drought base flow in the months leading up to the study was sourced from trade-wind orographic rainfall, suggesting a resistance to the effects of an otherwise extreme drought. In two catchments (Mameyes and Icacos), we sampled a series of four rewetting events that partially alleviated the drought. We collected and analyzed dissolved constituents (major cations and anions, organic carbon, and nitrogen) and suspended sediment (inorganic and organic matter (particulate organic carbon and particulate nitrogen)). The rivers appeared to be resistant to extreme drought, recovering quickly upon rewetting, as (1) the concentration-discharge (C-Q) relationships deviated little from the long-term patterns; (2) “new water” dominated streamflow during the latter events; (3) suspended sediment sources had accumulated in the channel during the drought flushed out during the initial events; and (4) the severity of the drought, as measured by the US drought monitor, was reduced dramatically after the rewetting events. Through this interdisciplinary study, we were able to investigate the impact of extreme drought through rewetting events on the river biogeochemistry

Soil Aggregates as a Source of Dissolved Organic Carbon to Streams: An Experimental Study on the Effect of Solution Chemistry on Water Extractable Carbon

Over the past two decades, headwater streams of the northern hemisphere have shown increased amounts of dissolved organic carbon (DOC), coinciding with decreased acid deposition. The exact nature of the mechanistic link between precipitation composition and stream water DOC is still widely debated in the literature. We hypothesize that soil aggregates are the main source of stream water DOC and that DOC release is greater in organic rich, riparian soils vs. hillslope soils. To test these hypotheses, we collected soils from two main landscape positions (hillslope and riparian zones) from the acid-impacted Sleepers River Research Watershed in northeastern Vermont. We performed aqueous soil extracts with solutions of different ionic strength (IS) and composition to simulate changes in soil solution. We monitored dynamic changes in soil particle size, aggregate architecture and composition, leachate DOC concentrations, dissolved organic matter (DOM) characteristics by fluorescence spectroscopy and trends in bioavailability. In low IS solutions, extractable DOC concentrations were significantly higher, particle size (by laser diffraction) was significantly smaller and organic material was separated from mineral particles in scanning electron microscope observations. Furthermore, higher DOC concentrations were found in Na+ compared to Ca2+ solutions of the same IS. These effects are attributed to aggregate dispersion due to expanding diffuse double layers in decreased IS solutions and to decreased bridging by divalent cations. Landscape position impacted quality but not quantity of released DOC. Overall, these results indicate that soil aggregates might be one important link between Critical Zone inputs (i.e., precipitation) and exports in streams

Phylogenomic analysis of protein-coding genes resolves complex gall wasp relationships

International audienceAbstract Gall wasps (Hymenoptera: Cynipidae) comprise 13 distinct tribes whose interrelationships remain incompletely understood. Recent analyses of ultra‐conserved elements (UCEs) represent the first attempt at resolving these relationships using phylogenomics. Here, we present the first analysis based on protein‐coding sequences from genome and transcriptome assemblies. Unlike UCEs, these data allow more sophisticated substitution models, which can potentially resolve issues with long‐branch attraction. We include data for 37 cynipoid species, including two tribes missing in the UCE analysis: Aylacini (s. str.) and Qwaqwaiini. Our results confirm the UCE result that Cynipidae are not monophyletic. Specifically, the Paraulacini and Diplolepidini + Pediaspidini fall outside a core clade (Cynipidae s. str.), which is more closely related to the insect‐parasitic Figitidae, and this result is robust to the exclusion of long‐branch taxa that could mislead the analysis. Given this, we here divide the Cynipidae into three families: the Paraulacidae stat. prom., Diplolepididae stat. prom. and Cynipidae (s. str.). Our results suggest that the Eschatocerini are the sister group of the remaining Cynipidae (s. str.). Within the Cynipidae (s. str.), the Aylacini (s. str.) are more closely related to oak gall wasps (Cynipini) and some of their inquilines (Ceroptresini) than to other herb gallers (Aulacideini and Phanacidini), and the Qwaqwaiini likely form a clade together with Synergini (s. str.) and Rhoophilini. Several alternative scenarios for the evolution of cynipid life histories are compatible with the relationships suggested by our analysis, but all are complex and require multiple shifts among parasitoids, inquilines and gall inducers