The stereochemical role of the phosphoramidite ligand in the asymmetric conjugate addition of alkylzirconium species to cyclic enones has been established through experimental and computational studies. Systematic, synthetic variation of the modular ligand established that the configuration of the binaphthol backbone is responsible for absolute stereocontrol, whereas modulation of the amido substituents leads to dramatic variations in the level of asymmetric induction. Chiral amido substituents are not required for enantioselectivity, leading to the discovery of a new family of easily synthesized phosphoramidites based on achiral amines that deliver equal levels of selectivity to Feringa's ligand. A linear correlation between the length of the aromatic amido groups and experimentally determined enantioselectivity was uncovered for this class of ligand, which, following an optimisation, leading to the highly selective ligands (up to 94% ee) with naphthyl rather than phenyl groups. An electronic effect of sterically similar aromatic substituents was investigated through NMR and DFT studies, showing that electron rich aryl groups allow better Cu-coordination. An interaction between the metal center and an aromatic group is responsible for this enhanced affinity and leads to a more tightly-coordinated transition structure leading to the major enantiomer. These studies illustrate the use of parametric quantitative structure-selectivity relationships to generate mechanistic models for asymmetric induction and catalyst structures that may be further probed by experiment and computation. This integrated approach leads to the rational modification of chiral ligands to achieve enhanced levels of selectivity.
Abstract. Increasing amounts of data, together with more computing power and better machine learning algorithms to analyse the data, are causing changes in almost every aspect of our lives. This trend is expected to continue as more data keep becoming available, computing power keeps improving and machine learning algorithms keep improving as well. Flood risk and impact assessments are also being influenced by this trend, particularly in areas such as the development of mitigation measures, emergency response preparation and flood recovery planning. Machine learning methods have the potential to improve accuracy as well as reduce calculating time and model development cost. It is expected that in the future more applications will become feasible and many process models and traditional observation methods will be replaced by machine learning. Examples of this include the use of machine learning on remote sensing data to estimate exposure and on social media data to improve flood response. Some improvements may require new data collection efforts, such as for the modelling of flood damages or defence failures. In other components, machine learning may not always be suitable or should be applied complementary to process models, for example in hydrodynamic applications. Overall, machine learning is likely to drastically improve future flood risk and impact assessments, but issues such as applicability, bias and ethics must be considered carefully to avoid misuse. This paper presents some of the current developments on the application of machine learning in this field and highlights some key needs and challenges.
Hazard analysis is a crucial step in flood risk management, and for large rivers, the effects of breaches need to be taken into account. Hazard analyses that incorporate this overall "system behaviour" have become increasingly popular in flood risk assessment. Methods to perform such analyses often focus on high water levels as a trigger for dike breaching. However, the duration of high water levels is known to be another important failure criterion. This study aims to investigate the effect of including this duration dependency in system behaviour analyses, using a computational framework in which two dike breach triggering methods are compared. The first triggers dike breaches based on water levels, and the second one based on both water-level and duration. The comparison is made for the Dutch Rhine system, where the dike failure probabilities are assumed to conform to the new Dutch standards of protection. The results show that including the duration as a breach triggering variable has an effect on the hydraulic loads and overall behaviour in the system, therefore influencing the risk. Although further work is required to fully understand the potential impact, the study suggests that including this duration dependency is important for future hazard risk analyses.
To make informed flood risk management (FRM) decisions in large protected river systems, flood risk and hazard analyses should include the potential for dike breaching. ‘Load interdependency’ analyses attempt to include the system-wide effects of dike breaching while accounting for the uncertainty of both river loads and dike fragility. The intensive stochastic computation required for these analyses often precludes the use of complex hydraulic models, but simpler models may miss spatial inundation interactions such as flows that ‘cascade’ between compartmentalised regions and overland flows that ‘shortcut’ between river branches. The potential for these interactions in the Netherlands has previously been identified, and so a schematisation of the Dutch floodplain and protection system is here developed for use in a load interdependency analysis. The approach allows for the spatial distribution of hazard to be quantified under various scenarios and return periods. The results demonstrate the importance of including spatial inundation interactions on hazard estimation at three specific locations, and for the system in general. The modelling approach can be used at a local scale to focus flood-risk analysis and management on the relevant causes of inundation, and at a system-wide scale to estimate the overall impact of large-scale measures.
Reliable hazard analysis is crucial in the flood risk management of river basins. For the floodplains of large, developed rivers, flood hazard analysis often needs to account for the complex hydrology of multiple tributaries and the potential failure of dikes. Estimating this hazard using deterministic methods ignores two major aspects of large-scale risk analysis: the spatial–temporal variability of extreme events caused by tributaries, and the uncertainty of dike breach development. Innovative stochastic methods are here developed to account for these uncertainties and are applied to the Po River in Italy. The effects of using these stochastic methods are compared against deterministic equivalents, and the methods are combined to demonstrate applications for an overall stochastic hazard analysis. The results show these uncertainties can impact extreme event water levels by more than 2 m at certain channel locations, and also affect inundation and breaching patterns. The combined hazard analysis allows for probability distributions of flood hazard and dike failure to be developed, which can be used to assess future flood risk management measures.
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<p>Urbanization and climate change are making societies around the world more vulnerable to flooding. Effective and sustainable adaptation measures are needed to counteract the impacts of these changes and Nature-Based solutions have gained considerable attention for both mitigation and adaptation methods of flood risk reduction. However, methodologies to evaluate their performance and upscale their implementation are lacking. Performance evaluation in particular is an important process for decision-makers to be able to decide on the most desirable measures to be implemented. The present research aims to develop a methodology for evaluating the effectiveness of NBS in reducing flood risk. The hydrological model (HEC-HMS) and 1D-2D hydrodynamic model (HEC-RAS) were coupled to create probabilistic inundation depth maps. A detailed flood damage model is then built and applied to estimate damage with and without the measures. The flood damage model was developed within the model builder in ArcGIS so that it can be easily replicated with many scenarios. Four measures were selected for the analyses, namely; reforestation, retention ponds, riparian buffer stripes, and bridge removal. This methodology has been applied to the case study of the Tamnava River Basin in Serbia within the EU-funded RECONECT project.</p>
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