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The easily accessible (R)-3-phenylbutanol (1) can be transformed into the novel enantiopure ligand diphenyl((R)-3-phenylbutyl)phosphane (3). 3 splits the complex dimer [{RuCl 2 (η 6 -C 6 H 5 CO 2 Me)} 2 ] (6) by adding as a σ-ligand to form mononuclear [RuCl 2 (η 6 -C 6 H 5 COOMe)-((R)-η 1 -PPh 2 (CH 2 ) 2 CH(CH 3 )Ph)] ( 7). An intramolecular arene ligand displacement reaction leads to [RuCl 2 ((R)-η 1 -PPh 2 (CH 2 ) 2 CH(CH 3 )-η 6 -C 6 H 5 )] ( 8) with a tethered side chain of the arene ligand. Nucleophilic substitution of a chloride ligand by primary or secondary amines with the assistance of NaBF 4 gives access to the diastereomeric complex salts [RuCl(amine)-((R)-η 1 -PPh 2 (CH 2 ) 2 CH(CH 3 )-η 6 -C 6 H 5 )]BF 4 . Good diastereoselectivities were obtained for aniline, piperidine, benzylamine, and butylamine complex salts 9-12 (de ) 82-90%). The absolute structures of 8-10 have been determined by X-ray structure analysis. S Ru ,R C configurations were found for the major diastereomers of aniline and piperidine complex salts 9 and 10. Not only the side chain stereogenic center but also the metal configuration of the cation of salt 9 is stable for longer periods at low and at elevated temperatures in different solutions.

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Molybdenum(II) complexes [MoX(CO)2(η3‐allyl)(CH3CN)2] (X = Cl or Br) were encapsulated in an aluminium‐pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid‐state techniques. Powder XRD, and 27Al and 29Si MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. 13C CP MAS NMR, FTIR, elemental analyses and low‐temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand‐substitution reaction. The new complex [MoBr(CO)2(η3‐allyl)(2‐aminodipyridyl)] was characterised by single‐crystal X‐ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis‐cyclooctene using tert‐butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Spinal cord injury (SCI) is a complex condition, with limited therapeutic options, that results in sensory and motor disabilities. To boost discovery of novel therapeutics, we designed a simple and efficient drug screening platform. This innovative approach allows to determine locomotor rescue properties of small molecules in a zebrafish ( Danio rerio ) larval spinal cord transection model. We validated our screening platform by showing that Riluzole and Minocycline, two molecules that are in clinical trials for SCI, promote rescue of the locomotor function of the transected larvae. Further validation of the platform was obtained through the blind identification of D-Cycloserine, a molecule scheduled to enter phase IV clinical trials for SCI. Importantly, we identified Tranexamic acid and further showed that this molecule maintains its locomotor recovery properties in a rodent female contusion model. Our screening platform, combined with drug repurposing, promises to propel the rapid translation of novel therapeutics to improve SCI recovery in humans.

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New challenges in flood risk management are raised by climate change and land-use development. These challenges are particularly complex in estuarine and coastal systems, where different hazard sources interact in a dynamic socio-economic context. This paper presents an innovative approach to support flood risk management in estuaries. The approach, developed at a local-scale basis, is applied in the case study of the Tagus estuary (Portugal). The methodology is supported by the regional framing of the study area and integrates hazard, exposed elements, territorial vulnerability and risk assessments

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