Significance of bound water to local chain conformations in protein crystals.

We examine how the polypeptide chain in protein crystal structures exploits the multivalent hydrogen-bonding potential of bound water molecules. This shows that multiple interactions with a single water molecule tend to occur locally along the chain. A distinctive internal-coordinate representation of the local water-binding segments reveals several consensus conformations. The fractional water occupancy of each was found by comparison of the total number of conformations in the database regardless of the presence or absence of bound water. The water molecule appears particularly frequently in type II beta-turn geometries and an N-terminal helix feature. This work constitutes a first step into assessing not only the generality but also the significance of specific water binding in globular proteins.

Selective hydrosilylation of 1,3-diynes catalyzed by titania-supported platinum

Titania-supported platinum (mainly as Pt(II)) has been found to effectively catalyze the hydrosilylation of 1,3-diynes at 70 °C with low catalyst loading (0.25 mol %) under solvent-free conditions. Monohydrosilylation was achieved for diaryl-substituted diynes, whereas dialkyl-substituted diynes were transformed into the corresponding dihydrosilylated products in good yields. In every case, the process was proven to be highly stereoselective, with syn addition of the silicon–hydrogen bond, and regioselective, with the silicon moiety exclusively bonded to the most internal carbon atom of the 1,3-diyne (β-E product), as confirmed by X-ray crystallography.

Prediction of hidden multiferroic order in graphene zigzag ribbons

An electronic phase with coexisting magnetic and ferroelectric order is predicted for graphene ribbons with zigzag edges. The electronic structure of the system is described with a mean-field Hubbard model that yields results very similar to those of density functional calculations. Without further approximations, the mean-field theory is recasted in terms of a BCS wave function for electron-hole pairs in the edge bands. The BCS coherence present in each spin channel is related to spin-resolved electric polarization. Although the total electric polarization vanishes, due to an internal phase locking of the BCS state, strong magnetoelectric effects are expected in this system. The formulation naturally accounts for the two gaps in the quasiparticle spectrun, Δ0 and Δ1, and relates them to the intraband and interband self-energies.

Geodynamic implications derived from Numidian-like distal turbidites deposited along the Internal–External Domain Boundary of the Betic Cordillera (S Spain)

New data reveal Early Burdigalian ‘Numidian-like lithofacies’ in successions of the internal (southernmost) part of the South Iberian Margin (SIM) and the south-western margin of the Mesomediterranean Microplate (MM). The well-known Numidian Formation was deposited in the external (Massylian) sub-domain of the Maghrebian Flysch Basin (a south-western branch of the Tethys Ocean). The anomalous occurrence of ‘Numidian-like lithofacies’ is induced by the particular Early Miocene palaeogeographical and geodynamic complexity of the sector. This consisted of a ‘triple point’ with a dextral transform fault between the SIM and the MM-Maghrebian Flysch Basin system. In this framework, the ageing of Iberian reliefs and the MM collapse, coupled with an African Margin upbulging, and a shortening of the Maghrebian Flysch Basin (both related to the subduction), could have resulted in the arrival of the Numidian depositional system from so far away.

La Galite Archipelago (Tunisia, North Africa): stratigraphic and petrographic revision and insights for geodynamic evolution of the Maghrebian Chain

The location of the La Galite Archipelago on the Internal/External Zones of the Maghrebian Chain holds strong interest for the reconstruction of the geodynamic evolution of the Mesomediterranean Microplate-Africa Plate Boundary Zone. New stratigraphic and petrographic data on sedimentary successions intruded upon by plutonic rocks enabled a better definition of the palaeogeographic and palaeotectonic evolutionary model of the area during the early-middle Miocene. The lower Miocene sedimentary units (La Galite Flysch and Numidian-like Flysch) belong to the Mauritanian (internal) and Massylian (external) sub-Domains of the Maghrebian Chain, respectively. These deposits are related to a typical syn-orogenic deposition in the Maghrebian Flysch Basin Domain, successively backthrusted above the internal units. The backthrusting age is post-Burdigalian (probably Langhian-Serravallian) and the compressional phase represents the last stage in the building of the accretionary wedge of the Maghrebian orogen. These flysch units may be co-relatable to the similar well-known formations along the Maghrebian and Betic Chains. The emplacement of potassic peraluminous magmatism, caused local metamorphism in the Late Serravallian-Early Tortonian (14–10 Ma), after the last compressional phase (backthrusting), during an extensional tectonic event. This extensional phase is probably due to the opening of a slab break-off in the deep subduction system. La Galite Archipelago represents a portion of the Maghrebian Flysch Basin tectonically emplaced above the southern margin of the “Mesomediterranean Microplate” which separated the Piemontese-Ligurian Ocean from a southern oceanic branch of the Tethys (i.e. the Maghrebian Flysch Basin). The possible presence of an imbricate thrust system between La Galite Archipelago and northern Tunisia may be useful to exclude the petroleum exploration from the deformed sectors of the offshore area considered.

Evaluation of an integrated system for classification, assessment and comparison of services for long-term care in Europe: the eDESDE-LTC study

Background: The harmonization of European health systems brings with it a need for tools to allow the standardized collection of information about medical care. A common coding system and standards for the description of services are needed to allow local data to be incorporated into evidence-informed policy, and to permit equity and mobility to be assessed. The aim of this project has been to design such a classification and a related tool for the coding of services for Long Term Care (DESDE-LTC), based on the European Service Mapping Schedule (ESMS). Methods: The development of DESDE-LTC followed an iterative process using nominal groups in 6 European countries. 54 researchers and stakeholders in health and social services contributed to this process. In order to classify services, we use the minimal organization unit or “Basic Stable Input of Care” (BSIC), coded by its principal function or “Main Type of Care” (MTC). The evaluation of the tool included an analysis of feasibility, consistency, ontology, inter-rater reliability, Boolean Factor Analysis, and a preliminary impact analysis (screening, scoping and appraisal). Results: DESDE-LTC includes an alpha-numerical coding system, a glossary and an assessment instrument for mapping and counting LTC. It shows high feasibility, consistency, inter-rater reliability and face, content and construct validity. DESDE-LTC is ontologically consistent. It is regarded by experts as useful and relevant for evidence-informed decision making. Conclusion: DESDE-LTC contributes to establishing a common terminology, taxonomy and coding of LTC services in a European context, and a standard procedure for data collection and international comparison.

Redescription of Anomala eucoma Bates, 1888 and a description of three new species from Costa Rica (Coleoptera: Scarabaeidae: Rutelinae)

Anomala eucoma Bates, 1888 is redescribed and a lectotype from Guatemala is designated. Three new species from Costa Rica, A. flavacoma new species, A. megaparamera new species, and A. pseudoeucoma new species, are described, and a distribution map is given. The internal sac (endophallus) of the species covered is illustrated, and its use in separating closely related species in this region is discussed. An identification key for morphologically similar species from the Neotropical region is provided.

Improvements in DFT Calculations of Spin–Spin Coupling Constants

Different types of spin–spin coupling constants (SSCCs) for several representative small molecules are evaluated and analyzed using a combination of 10 exchange functionals with 12 correlation functionals. For comparison, calculations performed using MCSCF, SOPPA, other common DFT methods, and also experimental data are considered. A detailed study of the percentage of Hartree–Fock exchange energy in SSCCs and in its four contributions is carried out. From the above analysis, a combined functional formed with local Slater (34%), Hartree–Fock exchange (66%), and P86 correlation functional (S66P86) is proposed in this paper. The accuracy of the values obtained with this hybrid functional (mean absolute deviation of 4.5 Hz) is similar to that of the SOPPA method (mean absolute deviation of 4.6 Hz).

Twenty-year advanced DInSAR analysis of severe land subsidence: The Alto Guadalentín Basin (Spain) case study

A twenty-year period of severe land subsidence evolution in the Alto Guadalentín Basin (southeast Spain) is monitored using multi-sensor SAR images, processed by advanced differential interferometric synthetic aperture radar (DInSAR) techniques. The SAR images used in this study consist of four datasets acquired by ERS-1/2, ENVISAT, ALOS and COSMO-SkyMed satellites between 1992 and 2012. The integration of ground surface displacement maps retrieved for different time periods allows us to quantify up to 2.50 m of cumulated displacements that occurred between 1992 and 2012 in the Alto Guadalentín Basin. DInSAR results were locally compared with global positioning system (GPS) data available for two continuous stations located in the study area, demonstrating the high consistency of local vertical motion measurements between the two different surveying techniques. An average absolute error of 4.6 ± 4 mm for the ALOS data and of 4.8 ± 3.5 mm for the COSMO-SkyMed data confirmed the reliability of the analysis. The spatial analysis of DInSAR ground surface displacement reveals a direct correlation with the thickness of the compressible alluvial deposits. Detected ground subsidence in the past 20 years is most likely a consequence of a 100–200 m groundwater level drop that has persisted since the 1970s due to the overexploitation of the Alto Guadalentín aquifer system. The negative gradient of the pore pressure is responsible for the extremely slow consolidation of a very thick (> 100 m) layer of fine-grained silt and clay layers with low vertical hydraulic permeability (approximately 50 mm/h) wherein the maximum settlement has still not been reached.

Regional subsidence modelling in Murcia city (SE Spain) using 1-D vertical finite element analysis and 2-D interpolation of ground surface displacements

Subsidence is a hazard that may have natural or anthropogenic origin causing important economic losses. The area of Murcia city (SE Spain) has been affected by subsidence due to groundwater overexploitation since the year 1992. The main observed historical piezometric level declines occurred in the periods 1982–1984, 1992–1995 and 2004–2008 and showed a close correlation with the temporal evolution of ground displacements. Since 2008, the pressure recovery in the aquifer has led to an uplift of the ground surface that has been detected by the extensometers. In the present work an elastic hydro-mechanical finite element code has been used to compute the subsidence time series for 24 geotechnical boreholes, prescribing the measured groundwater table evolution. The achieved results have been compared with the displacements estimated through an advanced DInSAR technique and measured by the extensometers. These spatio-temporal comparisons have showed that, in spite of the limited geomechanical data available, the model has turned out to satisfactorily reproduce the subsidence phenomenon affecting Murcia City. The model will allow the prediction of future induced deformations and the consequences of any piezometric level variation in the study area.

Application of multi-sensor advanced DInSAR analysis to severe land subsidence recognition: Alto Guadalentín Basin (Spain)

Multi-sensor advanced DInSAR analyses have been performed and compared with two GPS station measurements, in order to evaluate the land subsidence evolution in a 20-year period, in the Alto Guadalentín Basin where the highest rate of man-induced subsidence (> 10 cm yr−1) of Europe had been detected. The control mechanisms have been examined comparing the advanced DInSAR data with conditioning and triggering factors (i.e. isobaths of Plio-Quaternary deposits, soft soil thickness and piezometric level).

Evaluation of the potential of InSAR time series to study the spatio-temporal evolution of piezometric levels in the Madrid aquifer

The Tertiary detritic aquifer of Madrid (TDAM), with an average thickness of 1500 m and a heterogeneous, anisotropic structure, supplies water to Madrid, the most populated city of Spain (3.2 million inhabitants in the metropolitan area). Besides its complex structure, a previous work focused in the north-northwest of Madrid city showed that the aquifer behaves quasi elastically trough extraction/recovery cycles and ground uplifting during recovery periods compensates most of the ground subsidence measured during previous extraction periods (Ezquerro et al., 2014). Therefore, the relationship between ground deformation and groundwater level through time can be simulated using simple elastic models. In this work, we model the temporal evolution of the piezometric level in 19 wells of the TDAM in the period 1997–2010. Using InSAR and piezometric time series spanning the studied period, we first estimate the elastic storage coefficient (Ske) for every well. Both, the Ske of each well and the average Ske of all wells, are used to predict hydraulic heads at the different well locations during the study period and compared against the measured hydraulic heads, leading to very similar errors when using the Ske of each well and the average Ske of all wells: 14 and 16 % on average respectively. This result suggests that an average Ske can be used to estimate piezometric level variations in all the points where ground deformation has been measured by InSAR, thus allowing production of piezometric level maps for the different extraction/recovery cycles in the TDAM.

Poland and Greece - two contrasting EU enlargement experiences. ZEI Discussion Paper C213, 2012

The aim of this contribution is a comparative analysis of the challenges Poland and Greece (and more broadly – CEE-10 and GIPS countries) had to face in the past as latecomers to the European Union and are facing now, in the aftermath of the world financial and economic crisis of 2008-09. The main underlying message conveyed in this text is two-fold. Firstly, the author is going to argue that the breadth and complexity of the challenges Poland and other CEE-10 countries had to face while entering the road of systemic transformation was by far greater compared to past and in particular – current problems of Greece (and the remaining GIPS countries) in the aftermath of the global financial and economic crisis of 2008-09. Secondly, a resilience of Poland and other CEE-10 economies, relative to Greece and other GIPS, to the recent crisis was due to a comparatively higher level of institutional development of the former group at the time of their EU accession and at present. The ensuing discussion is organized as follows. Section 2 below provides comparative background information on the two reference groups. In Section 3 we discuss the most salient features of the design of the command economy and its legacy, as a key determinant of the initial conditions of systemic transformation. Next, in Section 4 we overview the basic indicators of growth performance and institutional reforms in CEE-10 countries between 1990 and 2011. Section 5 offers a picture of economic growth and real economic convergence in Greece and the remaining GIPS countries. In Section 6 we embark on comparative analysis of the institutional quality of Greece and Poland against a broader background of GIPS, CEE-10 and the remaining EU member countries. Section 7 concludes with a summary of major findings.

Money for structural reforms in the eurozone: making sense of contractual arrangements. Egmont Paper 57, May 2013

Executive Summary. Both the Commission’s proposal for a ‘Competitiveness and Convergence Instrument’ and the ‘contractual arrangement’ presented by President Van Rompuy share a common concept: associating EU money with national structural reforms under a binding arrangement. The targeted ‘structural reforms’ are the labour market reforms and product and services market reforms in eurozone ‘peripheral’ countries facing the most severe external imbalances. Their implementation would speed up and facilitate the ‘internal devaluation’ process of these countries. In the worst case scenario, failure to adopt the necessary reforms and to adjust wages and prices downwards may lead the most vulnerable countries to leave the eurozone under social and political pressure. Contracts seek to reduce this risk by increasing compliance with the country-specific recommendations for structural reforms issued by the EU institutions within the European Semester, and in particular with the Macroeconomic Imbalance Procedure (MIP). As for the financial support, it follows two different, albeit overlapping rationales. First, the perspective of obtaining EU funding would incentivize the governments of vulnerable countries to adopt reforms that would bear a high political and social cost in the short term. That is, without some form of incentive, it is unlikely that the necessary reforms would be undertaken and this could have significant negative consequences for the EMU as a whole. The second rationale amounts to outright solidarity: EU support is needed to cushion the inevitable socio-economic costs implied not only by the structural reform, but also by the internal devaluation taking place. To make sense of contractual arrangements, some points should be considered in future discussions: 1. Contracts on a voluntary basis only: Contracts cannot be mandatory unlike initially suggested in the Van Rompuy report. This stems not only from the inherent definition of a ‘contract’ – where mutual consent is key – but also from the non-binding nature of the preventive arm of the MIP. Making the country-specific recommendations issued by the EU institutions systematically binding would imply transfers of sovereignty from the national to the EU level that go well beyond the present discussion. Instead, contracts would introduce the possibility of making the preventive arm binding for some countries where corrections are most needed and urgent for the EMU as a whole.

The EU’s comprehensive approach towards security: the Lisbon Treaty and “smart power”. EU Centre Singpore Policy Brief No. 6, May 2013

The European Union (EU) has increasingly become a comprehensive security actor. With the development of the Common Foreign and Security Policy (CFSP), including the Common Security and Defence Policy (CSDP) as a reaction to the failure of the EU to act during the wars in Yugoslavia/Western Balkans in the 1990s, the EU has a wide range of instruments for crisis prevention, crisis management as well as post-crisis intervention at its disposal. Observers typically agree that “hard power” is no longer sufficient to address the complex security challenges of today’s world while the EU, often criticised for only utilising “soft power”, is now able to exercise “smart power”. Through a comprehensive approach, facilitated by the Lisbon Treaty, the EU can now use the various instruments at its disposal, such as diplomacy, development aid, humanitarian assistance, trade, sanctions, international cooperation and crisis management capabilities in a joined-up manner. This mix of tools and instruments is helping the EU to achieve the aim set out in its European Security Strategy: “a secure Europe in a better world”.