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Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1′,2′-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel–Crafts acylation of ferrocene using succinic anhydride gave mono- or bis(3-carboxypropinoyl)-ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1′,2′-bis(α-ketotetramethylene)-ferrocene. The diastereomeric mixture of the latter diketones was separated using column chromatography, characterized via single-crystal X-ray analysis, and assigned its stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene)-ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges.

Climate change is expected to alter European floods and associated economic losses in various ways. Here we investigate the impact of precipitation change on European average winter and summer financial losses due to flooding under a 1.5 °C warming scenario (reflecting a projected climate in the year 2115 according to RCP2.6)and for a counterfactual current-climate scenario where the climate has evolved without anthropogenic influence (reflecting a climate corresponding to pre-industrial conditions). Climate scenarios were generated with the Community Atmospheric Model (CAM)version 5. For each scenario, we derive a set of weights that when applied to the current climate's precipitation results in a climatology that approximates that of the scenario. We apply the weights to annual losses from a well-calibrated (to the current climate)flood loss model that spans 50,000 years and re-compute the average annual loss to assess the impact of precipitation changes induced by anthropogenic climate change. The method relies on a large stochastic set of physically based flood model simulations and allows quick assessment of potential loss changes due to change in precipitation based on two statistics, namely total precipitation, and total precipitation of very wet days (defined here as the total precipitation of days above the 95th percentile of daily precipitation). We compute the statistics with the raw CAM precipitation and bias-corrected precipitation. Our results show that for both raw and bias-corrected statistics i)average flood loss in Europe generally tend to increase in winter and decrease in summer for the future scenario, and consistent with that change we also show that ii)average flood losses have increased (decreased)for winter (summer)from pre-industrial conditions to the current day. The magnitude of the change varies among scenarios and statistics chosen.

Climate models serve as indispensable tools to investigate the effect of anthropogenic emissions on current and future climate, including extremes. However, as low-dimensional approximations of the climate system, they will always exhibit biases. Several attempts have been made to correct for biases as they affect extremes prediction, predominantly focused on correcting model-simulated distribution shapes. In this study, the effectiveness of a recently published quantile-based bias correction scheme, as well as a new subset selection method introduced here, are tested out-of-sample using model-as-truth experiments. Results show that biases in the shape of distributions tend to persist through time, and therefore, correcting for shape bias is useful for past and future statements characterizing the probability of extremes. However, for statements characterized by a ratio of the probabilities of extremes between two periods, we find that correcting for shape bias often provides no skill improvement due to the dominating effect of bias in the long-term trend. Using a toy model experiment, we examine the relative importance of the shape of the distribution versus its position in response to long-term changes in radiative forcing. It confirms that the relative position of the two distributions, based on the trend, is at least as important as the shape. We encourage the community to consider all model biases relevant to their metric of interest when using a bias correction procedure and to construct out-of-sample tests that mirror the intended application.

We examine the effect of the 20th and recent 21st century anthropogenic climate change on high temperature extremes as simulated by four global atmospheric general circulation models submitted to the Climate of the 20th Century Plus Detection and Attribution project. This coordinated experiment is based upon two large ensembles simulations for each participating model. The “world that was” simulations are externally forced as realistically as possible. The “world that might have been” is identical except that the influence of human forcing is removed but natural forcing agents and variations in ocean and sea ice are retained. We apply a stationary generalized extreme value analysis to the annual maxima of the three day average of the daily maximum surface air temperature, finding that long period return values have been increased by human activities between 1 and 3 °C over most land areas. Corresponding changes in the probability of achieving long period non-industrial return values in the industrialized world are also presented. We find that most regions experience increases in the frequency and intensity of extremely hot three day periods, but anthropogenic sulfate aerosol forcing changes locally can decrease these measures of heat waves in some models.

In the context of ongoing climate change, extreme weather events are drawing increasing attention from the public and news media. A question often asked is how the likelihood of extremes might have changed by anthropogenic greenhouse-gas emissions. Answers to the question are strongly influenced by the model used, duration, spatial extent, and geographic location of the event—some of these factors often overlooked. Using output from four global climate models, we provide attribution statements characterised by a change in probability of occurrence due to anthropogenic greenhouse-gas emissions, for rainfall and temperature extremes occurring at seven discretised spatial scales and three temporal scales. An understanding of the sensitivity of attribution statements to a range of spatial and temporal scales of extremes allows for the scaling of attribution statements, rendering them relevant to other extremes having similar but non-identical characteristics. This is a procedure simple enough to approximate timely estimates of the anthropogenic contribution to the event probability. Furthermore, since real extremes do not have well-defined physical borders, scaling can help quantify uncertainty around attribution results due to uncertainty around the event definition. Results suggest that the sensitivity of attribution statements to spatial scale is similar across models and that the sensitivity of attribution statements to the model used is often greater than the sensitivity to a doubling or halving of the spatial scale of the event. The use of a range of spatial scales allows us to identify a nonlinear relationship between the spatial scale of the event studied and the attribution statement.

The half a degree additional warming, prognosis and projected impacts (HAPPI) experimental protocol provides a multi-model database to compare the effects of stabilizing anthropogenic global warming of 1.5 °C over preindustrial levels to 2.0 °C over these levels. The HAPPI experiment is based upon large ensembles of global atmospheric models forced by sea surface temperature and sea ice concentrations plausible for these stabilization levels. This paper examines changes in extremes of high temperatures averaged over three consecutive days. Changes in this measure of extreme temperature are also compared to changes in hot season temperatures. We find that over land this measure of extreme high temperature increases from about 0.5 to 1.5 °C over present-day values in the 1.5 °C stabilization scenario, depending on location and model. We further find an additional 0.25 to 1.0 °C increase in extreme high temperatures over land in the 2.0 °C stabilization scenario. Results from the HAPPI models are consistent with similar results from the one available fully coupled climate model. However, a complicating factor in interpreting extreme temperature changes across the HAPPI models is their diversity of aerosol forcing changes.

The United Nations Framework Convention on Climate Change (UNFCCC) invited the scientific community to explore the impacts of a world in which anthropogenic global warming is stabilized at only 1.5°C above preindustrial average temperatures. We present a projection of future tropical cyclone statistics for both 1.5 and 2.0°C stabilized warming scenarios with direct numerical simulation using a high-resolution global climate model. As in similar projections at higher warming levels, we find that even at these low warming levels the most intense tropical cyclones become more frequent and more intense, while simultaneously the frequency of weaker tropical storms is decreased. We also conclude that in the 1.5°C stabilization, the effect of aerosol forcing changes complicates the interpretation of greenhouse gas forcing changes.

When working with large, multidimensional and multivariate data, science users are frequently interested in understanding variation in data, as opposed to the actual data values. Our work focuses on exploring how a simple statistical metric, the Coefficient of Variation (or Cv), can be used in several different ways to facilitate understanding variation in large data. As a statistical measure, it offers a key advantage over more widely accepted measures like standard deviation, namely to its ability to capture local variation properties. As a multidimensional projection operator, Cv is an effective way of reducing data size while preserving the key variational signal. Visualizations produced from Cv that target conveying variation in data are highly informative, especially compared to those produced with more widely known methods. We demonstrate these ideas within the context of a two-part application case study focusing on understanding long-Term trends in the the changes in precipitation and winds in large-scale climate model ensemble output.

The effect of forcing wind resolution on the extremes of global wind-wave climate are investigated in numerical simulations. Forcing winds from the Community Atmosphere Model at horizontal resolutions of ∼1.0° and ∼0.25° are used to drive Wavewatch III. Differences in extreme wave height are found to manifest most strongly in tropical cyclone (TC) regions, emphasizing the need for high-resolution forcing in those areas. Comparison with observations typically show improvement in performance with increased forcing resolution, with a strong influence in the tail of the distribution, although simulated extremes can exceed observations. A simulation for the end of the 21st century under a RCP 8.5 type emission scenario suggests further increases in extreme wave height in TC regions.

The Intergovernmental Panel on Climate Change (IPCC) has accepted the invitation from the UNFCCC to provide a special report on the impacts of global warming of 1.5 °C above pre-industrial levels and on related global greenhouse-gas emission pathways. Many current experiments in, for example, the Coupled Model Inter-comparison Project (CMIP), are not specifically designed for informing this report. Here, we document the design of the half a degree additional warming, projections, prognosis and impacts (HAPPI) experiment. HAPPI provides a framework for the generation of climate data describing how the climate, and in particular extreme weather, might differ from the present day in worlds that are 1.5 and 2.0 °C warmer than pre-industrial conditions. Output from participating climate models includes variables frequently used by a range of impact models. The key challenge is to separate the impact of an additional approximately half degree of warming from uncertainty in climate model responses and internal climate variability that dominate CMIP-style experiments under low-emission scenarios. Large ensembles of simulations (> 50 members) of atmosphere-only models for three time slices are proposed, each a decade in length: the first being the most recent observed 10-year period (2006-2015), the second two being estimates of a similar decade but under 1.5 and 2 °C conditions a century in the future. We use the representative concentration pathway 2.6 (RCP2.6) to provide the model boundary conditions for the 1.5 °C scenario, and a weighted combination of RCP2.6 and RCP4.5 for the 2 °C scenario.

The annual "State of the Climate" report, published in the Bulletin of the American Meteorological Society (BAMS), has included a supplement since 2011 composed of brief analyses of the human influence on recent major extreme weather events. There are now several dozen extreme weather events examined in these supplements, but these studies have all differed in their data sources as well as their approaches to defining the events, analyzing the events, and the consideration of the role of anthropogenic emissions. This study reexamines most of these events using a single analytical approach and a single set of climate model and observational data sources. In response to recent studies recommending the importance of using multiple methods for extreme weather event attribution, results are compared from these analyses to those reported in the BAMS supplements collectively, with the aim of characterizing the degree to which the lack of a common methodological framework may or may not influence overall conclusions. Results are broadly similar to those reported earlier for extreme temperature events but disagree for a number of extreme precipitation events. Based on this, it is advised that the lack of comprehensive uncertainty analysis in recent extreme weather attribution studies is important and should be considered when interpreting results, but as yet it has not introduced a systematic bias across these studies.

We find that the deadly heat waves in India and Pakistan in 2015 were exacerbated by anthropogenic climate change. Although the impacts of both events were severe, the events themselves were not connected to each other.

Detection and attribution (D and A) simulations were important components of CMIP5 and underpinned the climate change detection and attribution assessments of the Fifth Assessment Report of the Intergovernmental Panel on Climate Change. The primary goals of the Detection and Attribution Model Intercomparison Project (DAMIP) are to facilitate improved estimation of the contributions of anthropogenic and natural forcing changes to observed global warming as well as to observed global and regional changes in other climate variables; to contribute to the estimation of how historical emissions have altered and are altering contemporary climate risk; and to facilitate improved observationally constrained projections of future climate change. D and A studies typically require unforced control simulations and historical simulations including all major anthropogenic and natural forcings. Such simulations will be carried out as part of the DECK and the CMIP6 historical simulation. In addition D and A studies require simulations covering the historical period driven by individual forcings or subsets of forcings only: such simulations are proposed here. Key novel features of the experimental design presented here include firstly new historical simulations with aerosols-only, stratospheric-ozone-only, CO2-only, solar-only, and volcanic-only forcing, facilitating an improved estimation of the climate response to individual forcing, secondly future single forcing experiments, allowing observationally constrained projections of future climate change, and thirdly an experimental design which allows models with and without coupled atmospheric chemistry to be compared on an equal footing.

The Paris Climate Agreement is an important step for international climate policy, but the compensation for negative effects of climate change based on clear assignment of responsibilities remains highly debated. From both a policy and a science perspective, it is unclear how responsibilities should be defined and on what evidence base. We explore different normative principles of justice relevant to climate change impacts, and ask how different forms of causal evidence of impacts drawn from detection and attribution research could inform policy approaches in accordance with justice considerations. We reveal a procedural injustice based on the imbalance of observations and knowledge of impacts between developed and developing countries. This type of injustice needs to be considered in policy negotiations and decisions, and efforts strengthened to reduce it.

Impacts of recent regional changes in climate on natural and human systems are documented across the globe, yet studies explicitly linking these observations to anthropogenic forcing of the climate are scarce. Here we provide a systematic assessment of the role of anthropogenic climate change for the range of impacts of regional climate trends reported in the IPCC's Fifth Assessment Report. We find that almost two-thirds of the impacts related to atmospheric and ocean temperature can be confidently attributed to anthropogenic forcing. In contrast, evidence connecting changes in precipitation and their respective impacts to human influence is still weak. Moreover, anthropogenic climate change has been a major influence for approximately three-quarters of the impacts observed on continental scales. Hence the effects of anthropogenic emissions can now be discerned not only globally, but also at more regional and local scales for a variety of natural and human systems.

Assessing past impacts of observed climate change on natural, human and managed systems requires detailed knowledge about the effects of both climatic and other drivers of change, and their respective interaction. Resulting requirements with regard to system understanding and long-term observational data can be prohibitive for quantitative detection and attribution methods, especially in the case of human systems and in regions with poor monitoring records. To enable a structured examination of past impacts in such cases, we follow the logic of quantitative attribution assessments, however, allowing for qualitative methods and different types of evidence. We demonstrate how multiple lines of evidence can be integrated in support of attribution exercises for human and managed systems. Results show that careful analysis can allow for attribution statements without explicit end-to-end modeling of the whole climate-impact system. However, care must be taken not to overstate or generalize the results and to avoid bias when the analysis is motivated by and limited to observations considered consistent with climate change impacts.

Projections of global mean temperature changes (ΔT) in the future are associated with intrinsic uncertainties. Much climate policy discourse has been guided by "current knowledge" of the ΔTs uncertainty, ignoring the likely future reductions of the uncertainty, because a mechanism for predicting these reductions is lacking. By using simulations of Global Climate Models from the Coupled Model Intercomparison Project Phase 5 ensemble as pseudo past and future observations, we estimate how fast and in what way the uncertainties of ΔT can decline when the current observation network of surface air temperature is maintained. At least in the world of pseudo observations under the Representative Concentration Pathways (RCPs), we can drastically reduce more than 50% of the ΔTs uncertainty in the 2040 s by 2029, and more than 60% of the ΔTs uncertainty in the 2090 s by 2049. Under the highest forcing scenario of RCPs, we can predict the true timing of passing the 2 °C (3 °C) warming threshold 20 (30) years in advance with errors less than 10 years. These results demonstrate potential for sequential decision-making strategies to take advantage of future progress in understanding of anthropogenic climate change.

© 2016, the Meteorological Society of Japan. We describe two unprecedented large (100-member), longterm (61-year) ensembles based on MRI-AGCM3.2, which were driven by historical and non-warming climate forcing. These ensembles comprise the "Database for Policy Decision making for Future climate change (d4PDF)". We compare these ensembles to large ensembles based on another climate model, as well as to observed data, to investigate the influence of anthropogenic activities on historical changes in the numbers of record-breaking events, including: the annual coldest daily minimum temperature (TNn), the annual warmest daily maximum temperature (TXx) and the annual most intense daily precipitation event (Rx1day). These two climate model ensembles indicate that human activity has already had statistically significant impacts on the number of record-breaking extreme events worldwide mainly in the Northern Hemisphere land. Specifically, human activities have altered the likelihood that a wider area globally would suffer record-breaking TNn, TXx and Rx1day events than that observed over the 2001- 2010 period by a factor of at least 0.6, 5.4 and 1.3, respectively. However, we also find that the estimated spatial patterns and amplitudes of anthropogenic impacts on the probabilities of record-breaking events are sensitive to the climate model and/or natural-world boundary conditions used in the attribution studies.

Summary: Bispecific antibodies (Bispecifics) demonstrate exceptional clinical potential to address some of the most complex diseases. However, Bispecific production in a single cell often requires the correct pairing of multiple polypeptide chains for desired assembly. This is a considerable hurdle that hinders the development of many immunoglobulin G (IgG)-like bispecific formats. Our approach focuses on the rational engineering of charged residues to facilitate the chain pairing of distinct heavy chains (HC). Here, we deploy structure-guided protein design to engineer charge pair mutations (CPMs) placed in the CH3-CH3′ interface of the fragment crystallizable (Fc) region of an antibody (Ab) to correctly steer heavy chain pairing. When used in combination with our stable effector functionless 2 (SEFL2.2) technology, we observed high pairing efficiency without significant losses in expression yields. Furthermore, we investigate the relationship between CPMs and the sequence diversity in the parental antibodies, proposing a rational strategy to deploy these engineering technologies.

We use the background-field method and the heat kernel to obtain all counterterms to two-loop order of conformally coupled multiflavor Pdbl3 theory in six spacetime dimensions, defined in curved spacetime and with spacetime-dependent couplings. We also include spacetime-dependent mass terms for completeness. We use these results to write a general expression for the trace anomaly. With the use of Weyl consistency conditions, we are able to show that the strong a-theorem for a certain natural candidate quantity a is violated in this theory and obtain a three-loop expression for the coefficient a of the Euler term in the anomaly.

Anthropogenic climate change has triggered impacts on natural and human systems world-wide, yet the formal scientific method of detection and attribution has been only insufficiently described. Detection and attribution of impacts of climate change is a fundamentally cross-disciplinary issue, involving concepts, terms, and standards spanning the varied requirements of the various disciplines. Key problems for current assessments include the limited availability of long-term observations, the limited knowledge on processes and mechanisms involved in changing environmental systems, and the widely different concepts applied in the scientific literature. In order to facilitate current and future assessments, this paper describes the current conceptual framework of the field and outlines a number of conceptual challenges. Based on this, it proposes workable cross-disciplinary definitions, concepts, and standards. The paper is specifically intended to serve as a baseline for continued development of a consistent cross-disciplinary framework that will facilitate integrated assessment of the detection and attribution of climate change impacts. © 2013 The Author(s).

The running of quantum field theories can be studied in detail with the use of a local renormalization group equation. The usual beta-function effects are easy to include, but by introducing spacetime-dependence of the various parameters of the theory one can efficiently incorporate renormalization effects of composite operators as well. An illustration of the power of these methods was presented by Osborn in the early 90s, who used consistency conditions following from the Abelian nature of the Weyl group to rederive Zamolodchikov's c-theorem in d = 2 spacetime dimensions, and also to obtain a perturbative a-theorem in d = 4. In this work we present an extension of Osborn's work to d = 6 and to general even d. We compute the full set of Weyl consistency conditions, and we discover among them a candidate for an a-theorem in d = 6, similar to the d = 2, 4 cases studied by Osborn. Additionally, we show that in any even spacetime dimension one finds a consistency condition that may serve as a generalization of the c-theorem, and that the associated candidate c-function involves the coefficient of the Euler term in the trace anomaly. Such a generalization hinges on proving the positivity of a certain "metric" in the space of couplings. © SISSA 2013.

In April-July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (∼100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm-3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.