Nucleophilicity of 4-(Alkylthio)-3-imidazoline Derived Enamines

Imidazolidine-4-thiones (ITOs) are cyclic, secondary amines that were considered as potential prebiotic organocatalysts for lightdriven α-alkylations of aldehydes by bromoacetonitrile (BAN). Recent studies showed that the initially supplied ITOs represent the pre-catalyst because they undergo S-alkylation with BAN to give 4-(alkylthio)-3-imidazolines (TIMs). Given that the same reagent mix that undergoes light-driven α-alkylations is also effective in the dark, we synthesized ten ITO- or TIM-derived enamines of aldehydes and characterized their nucleophilic reactivities by kinetic studies in acetonitrile. The experimental second-order rate constants k2 for reactions of enamines with benzhydrylium ions (reference electrophiles) were evaluated by the Mayr-Patz equation, lg k2(20 °C)=sN(N+E). The determined nucleophilicities N (and sN) reveal the reactivity profiles of these enamines under prebiotically relevant conditions as well as their potential for use in organocatalytic synthesis

Future agroclimatic conditions and implications for European grasslands.

Grasslands play a significant role in livestock fodder production and thus, contribute to food security worldwide while providing numerous additional ecosystem services. However, how agroclimatic conditions and adverse weather events relevant for grasslands will change across the European grassland areas has not been examined to date. Using a single reference setup for soil and management over 476 European sites defined by climate stations, we show the probability of eight selected adverse weather events with the potential to significantly affect grassland productivity under climate change and how these events vary regionally across Europe. Changes in these eight key agroclimatic indicators create markedly specific spatial patterns. We found that by 2050, the exposure of the south and west European grasslands to heat and drought may double in comparison with today and that the area with frequent occurrences of heat and drought will expand northwards. However, across Ukraine, Belarus, and the Baltic countries to southern Finland and Sweden, the likelihood of these events is likely to decrease. While changing cultivars and management strategies are unavoidable, shifting grassland production to other regions to reduce the risk may not be possible as the risk of adverse events beyond the key grassland-growing areas increases even further. Moreover, we found marked changes in the overall thermal and water regimes across European regions. The effect of adverse weather events in the future could be different in other regions of the world compared to regions in Europe, emphasizing the importance of conducting similar analyses for other major grassland producing regions. To mitigate the impact of climate change, new ways of maintaining grassland productivity need to be developed. These methods include more efficient selection of species mixtures for specific regions, including increased use of legumes and forbs; incorporation of new genetic resources, including the development of hybrid cultivars, such as Festulolium hybrids; and incorporation of state-of-the-art technologies in breeding programs and new grazing management

High resistance towards herbivore-induced habitat change in a high Arctic arthropod community

Mammal herbivores may exert strong impacts on plant communities, and are often key drivers of vegetation composition and diversity. We tested whether such mammal-induced changes to a high Arctic plant community are reflected in the structure of other trophic levels. Specifically, we tested whether substantial vegetation changes following the experimental exclusion of muskoxen (Ovibos moschatus) altered the composition of the arthropod community and the predator-prey interactions therein. Overall, we found no impact of muskox exclusion on the arthropod community: the diversity and abundance of both arthropod predators (spiders) and of their prey were unaffected by muskox presence, and so was the qualitative and quantitative structure of predator-prey interactions. Hence, high Arctic arthropod communities seem highly resistant towards even large biotic changes in their habitat, which we attribute to the high connectance in the food web

Machine learning predicts new anti-CRISPR proteins

Abstract The increasing use of CRISPR–Cas9 in medicine, agriculture, and synthetic biology has accelerated the drive to discover new CRISPR–Cas inhibitors as potential mechanisms of control for gene editing applications. Many anti-CRISPRs have been found that inhibit the CRISPR–Cas adaptive immune system. However, comparing all currently known anti-CRISPRs does not reveal a shared set of properties for facile bioinformatic identification of new anti-CRISPR families. Here, we describe AcRanker, a machine learning based method to aid direct identification of new potential anti-CRISPRs using only protein sequence information. Using a training set of known anti-CRISPRs, we built a model based on XGBoost ranking. We then applied AcRanker to predict candidate anti-CRISPRs from predicted prophage regions within self-targeting bacterial genomes and discovered two previously unknown anti-CRISPRs: AcrllA20 (ML1) and AcrIIA21 (ML8). We show that AcrIIA20 strongly inhibits Streptococcus iniae Cas9 (SinCas9) and weakly inhibits Streptococcus pyogenes Cas9 (SpyCas9). We also show that AcrIIA21 inhibits SpyCas9, Streptococcus aureus Cas9 (SauCas9) and SinCas9 with low potency. The addition of AcRanker to the anti-CRISPR discovery toolkit allows researchers to directly rank potential anti-CRISPR candidate genes for increased speed in testing and validation of new anti-CRISPRs. A web server implementation for AcRanker is available online at http://acranker.pythonanywhere.com/

Priority questions in multidisciplinary drought research

Addressing timely and relevant questions across a multitude of spatio-temporal scales, state-of-the-art interdisciplinary drought research will likely increase in importance under projected climate change. Given the complexity of the various direct and indirect causes and consequences of a drier world, scientific tasks need to be coordinated efficiently. Drought-related research endeavors ranging from individual projects to global initiatives therefore require prioritization. Here, we present 60 priority questions for optimizing future drought research. This topical catalogue reflects the experience of 65 scholars from 21 countries and almost 20 fields of research in both natural sciences and the humanities. The set of drought-related questions primarily covers drought monitoring, impacts, forecasting, climatology, adaptation, as well as planning and policy. The questions highlight the increasingly important role of remote sensing techniques in drought monitoring, importance of drought forecasting and understanding the relationships between drought parameters and drought impacts, but also challenges of drought adaptation and preparedness policies

Past and future impacts of land-use changes on ecosystem services in Austria

Environmental and socio-economic developments induce land-use changes with potentially negative impacts on human well-being. To counteract undesired developments, a profound understanding of the complex relationships between drivers, land use, and ecosystem services is needed. Yet, national studies examining extended time periods are still rare. Based on the Special Report on land use, land management and climate change by the Austrian Panel on Climate Change (APCC), we use the Driver-Pressure-State-Impact-Response (DPSIR) framework to (1) identify the main drivers of land-use change, (2) describe past and future land-use changes in Austria between 1950 and 2100, (3) report related impacts on ecosystem services, and (4) discuss management responses. Our findings indicate that socio-economic drivers (e.g., economic growth, political systems, and technological developments) have influenced past land-use changes the most. The intensification of agricultural land use and urban sprawl have primarily led to declining ecosystem services in the lowlands. In mountain regions, the abandonment of mountain grassland has prompted a shift from provisioning to regulating services. However, simulations indicate that accelerating climate change will surpass socio-economic drivers in significance towards the end of this century, particularly in intensively used agricultural areas. Although climate change-induced impacts on ecosystem services remain uncertain, it can be expected that the range of land-use management options will be restricted in the future. Consequently, policymaking should prioritize the development of integrated land-use planning to safeguard ecosystem services, accounting for future environmental and socio-economic uncertainties