Oxoiron(V) Complexes of Relevance in Oxidation Catalysis of Organic Substrates

The selective oxidation of alkane and olefin moieties are reactions of fundamental importance in both chemical synthesis and biology. Nature efficiently catalyzes the oxidation of hydrocarbons using iron-dependent enzymes, which operate through the mediation of oxoiron(IV) or oxoiron(V) species. In the quest for chemo, regio and stereoselective transformations akin to those taking place in nature, bioinspired iron catalysts have been developed and understanding their mechanism of action has become a particularly relevant area of research. While a prominent advance in the preparation and characterization of oxoiron(IV) species has been accomplished, oxoiron(V) species remain exceedingly rare, presumably because the high reactivity that makes them particularly interesting also makes them difficult to observe. This review summarizes the advances in the field, focusing in synthetic systems for which the oxoiron(V) species relevant in these transformations have been directly detected and spetroscopically characterized.     

Assessment of construction defects in residential buildings in Spain

The building industry is noted for its repeated building defects causing cost increases and time delays during construction. In Spain, despite the Ley de Ordenación de la Edificación (Building Regulation Act), which establishes a general framework to promote overall building quality, construction defects in residential buildings remain a pervasive problem. An analysis of 3647 construction defects is presented which identified the location within the building, subcontractors and building element in 68 residential building developments undertaken by two large Spanish contractors. The research reveals that the most common defects that arise during construction are related to the stability of the structure and inappropriate installation of roofs and facades. These technical faults are caused by poor workmanship rather than by the quality of the materials or products used. By comparing these results with a previous study on defects after handover, it can be concluded that while the nature of defects during construction is basically technical, at handover it is aesthetic or technical.     

Resilience to increasing temperatures: residential building stock adaptation through codes and standards

The resilience of the current Spanish residential building stock to increased temperatures is modelled. Homogenized daily temperature data recorded at 50 Spanish meteorological stations for the periods 1950–1979 and 1981–2010 were used to investigate anticipated climate warming on the Spanish residential building stock by means of the degree-day method. Impacts on residential buildings were investigated for three different future time periods (2011–2040, 2041–2070 and 2071–2100) for three representative Spanish provincial capitals. Future climate change scenarios comprising two statistical downscaling methods, three general circulation models and two carbon emission scenarios were used to project local climate. Results show that 72% of current residential building stock in Spain is thermally unprotected. In addition, the energy demand for heating the building sector in Spain is expected to decrease by between 30% (Barcelona, B2 scenario) and 36% (Valencia, A2 scenario) by 2100, while the respective energy demand for cooling could increase by between 107% (Valencia, B2 scenario) and 296% (Madrid, A2 scenario) by 2100. To increase resilience to higher winter and summer temperatures, strategies for modifying the built environment are needed, particularly for the role of building codes and standards.

La résilience du parc bâti résidentiel espagnol actuel face à l'augmentation des températures est modélisée. Les données homogénéisées des température journalières enregistrées dans 50 stations météorologiques espagnoles pour les périodes 1950–1979 et 1981–2010 ont été utilisées pour étudier le réchauffement climatique prévu sur le parc bâti résidentiel espagnol en utilisant la méthode des degrés-jours. Les répercussions sur les immeubles résidentiels ont été étudiées pour trois périodes futures différentes (2011–2040, 2041–2070 et 2071–2100) et pour trois capitales provinciales espagnoles représentatives. Il a été utilisé des scénarios de changement climatique futur comprenant deux méthodes de réduction d'échelle statistique, trois modèles de circulation générale et deux scénarios d'émission de carbone pour prévoir le climat local. Les résultats montrent que 72 % du parc bâti résidentiel actuel de l'Espagne est dépourvu de protection thermique. Il est en outre prévu que la demande énergétique liée au chauffage dans le secteur du logement en Espagne diminue de 30 % (Barcelone, scénario B2) à 36 % (Valence, scénario A2) d'ici à 2100, tandis que la demande énergétique respective liée à la climatisation pourrait augmenter de 107 % (Valence, scénario B2) à 296 % (Madrid, scénario A2) d'ici à 2100. Afin d'augmenter la résilience face à des températures hivernales et estivales plus élevées, il est nécessaire de disposer de stratégies de modification du cadre bâti, concernant en particulier le rôle des codes et des normes du bâtiment.

Mots clés: stratégies d'adaptation, performances des bâtiments, réglementation du bâtiment, parc bâti, changement climatique, degrés-jours, surchauffe, confort thermique, vulnérabilité, Espagne     

Multi‐phosphorylation of the Intrinsically Disordered Unique Domain of c‐Src Studied by In‐Cell and Real‐Time NMR Spectroscopy

Intrinsically disordered regions (IDRs) are preferred sites for post‐translational modifications essential for regulating protein function. The enhanced local mobility of IDRs facilitates their observation by NMR spectroscopy in vivo. Phosphorylation events can occur at multiple sites and respond dynamically to changes in kinase–phosphatase networks. Here we used real‐time NMR spectroscopy to study the effect of kinases and phosphatases present in Xenopus oocytes and egg extracts on the phosphorylation state of the “unique domain” of c‐Src. We followed the phosphorylation of S17 in oocytes, and of S17, S69, and S75 in egg extracts by NMR spectroscopy, MS, and western blotting. Addition of specific kinase inhibitors showed that S75 and S69 are phosphorylated by CDKs (cyclin‐dependent kinases) differently from Cdk1. Moreover, although PKA (cAMP‐dependent protein kinase) can phosphorylate S17 in vitro, this was not the major S17 kinase in egg extracts. Changes in PKA activity affected the phosphorylation levels of CDK‐dependent sites, thus suggesting indirect effects of kinase–phosphatase networks. This study provides a proof‐of‐concept of the use of real‐time in vivo NMR spectroscopy to characterize kinase/phosphatase effects on intrinsically disordered regulatory domains.