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The existence of a die-out threshold (different from the classic disease-invasion one) defining a region of slow extinction of an epidemic has been proved elsewhere for susceptible-aware-infectious-susceptible models without awareness decay, through bifurcation analysis. By means of an equivalent mean-field model defined on regular random networks, we interpret the dynamics of the system in this region and prove that the existence of bifurcation for this second epidemic threshold crucially depends on the absence of awareness decay. We show that the continuum of equilibria that characterizes the slow die-out dynamics collapses into a unique equilibrium when a constant rate of awareness decay is assumed, no matter how small, and that the resulting bifurcation from the disease-free equilibrium is equivalent to that of standard epidemic models. We illustrate these findings with continuous-time stochastic simulations on regular random networks with different degrees. Finally, the behaviour of solutions with and without decay in awareness is compared around the second epidemic threshold for a small rate of awareness decay This work has been partially supported by the Research Grant MTM2011-27739-C04-03 of the Spanish Government (D.J. and J.S.), the Project 2009-SGR-345 (J.S.) of the Generalitat de Catalunya, and IMA Collaborative Grant (SGS01/13), UK (I.K. and J.S.)

Background Mass drug administration (MDA) can rapidly reduce the burden of Plasmodium falciparum (Pf). However, concerns remain about its contribution to select for antimalarial drug resistance. Methods We used Sanger sequencing and real-time PCR to determine the proportion of molecular markers associated with antimalarial resistance (k13, pfpm2, pfmdr1 and pfcrt) in Pf isolates collected before (n = 99) and after (n = 112) the implementation of two monthly MDA rounds with dihydroartemisinin–piperaquine (DHAp) for two consecutive years in Magude district of Southern Mozambique. Results None of the k13 polymorphisms associated with artemisinin resistance were observed in the Pf isolates analyzed. The proportion of Pf isolates with multiple copies of pfpm2, an amplification associated with piperaquine resistance, was similar in pre- (4.9%) and post-MDA groups (3.4%; p = 1.000). No statistically significant differences were observed between pre- and post-MDA groups in the proportion of Pf isolates neither with mutations in pfcrt and pfmdr1 genes, nor with the carriage of pfmdr1 multiple copies (p>0.05). Conclusions This study does not show any evidence of increased frequency of molecular makers of antimalarial resistance after MDA with DHAp in southern Mozambique where markers of antimalarial resistance were absent or low at the beginning of the intervention.

Amultitude of pharmaceuticals enter surface waters via discharges of wastewater treatment plants (WWTPs), and many raise environmental and health concerns. Chemical fate models predict their concentrations using estimates of mass loading, dilution and in-stream attenuation. However, current comprehension of the attenuation rates remains a limiting factor for predictive models.We assessed in-stream attenuation of 75 pharmaceuticals in 4 river segments, aiming to characterize in-stream attenuation variability among different pharmaceutical compounds, as well as among river segments differing in environmental conditions. Our study revealed that in-streamattenuation was highly variable among pharmaceuticals and river segments and that none of the considered pharmaceutical physicochemical and molecular properties proved to be relevant in determining the mean attenuation rates. Instead, the octanol–water partition coefficient (Kow) influenced the variability of rates among river segments, likely due to its effect on sorption to sediments and suspended particles, and therefore influencing the balance between the different attenuation mechanisms (biotransformation, photolysis, sorption, and volatilization). The magnitude of themeasured attenuation rates urges scientists to consider themas important as dilutionwhen aiming to predict concentrations in freshwater ecosystems This research was supported by aMarie Curie European Reintegration Grant (PERG07-GA-2010-259219) and by a Marie Curie Career Integration Grant (PCIG9-GA-2011-293535) within the 7th European Community Framework Programme, aswell as by the SpanishMinistry of Economy and Competitiveness through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and ENDERUS (CTM-2009-13018), and the postdoctoral grants “Juan de la Cierva” (jci-2009-05604 and jci-2010- 06397), and by the European Union through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965)

Fullerene based molecular heterojunctions such as the [6,6]-pyrrolidine-C60 donor-acceptor conjugate containing triphenylamine (TPA) are potential materials for high-efficient dye-sensitized solar cells. In this work, we estimate the rate constants for the photoinduced charge separation and charge recombination processes in TPA-C60 using the unrestricted and time-dependent DFT methods. Different schemes are applied to evaluate excited state properties and electron transfer parameters (reorganization energies, electronic couplings, and Gibbs energies). The use of open-shell singlet or triplet states, several density functionals and continuum solvation models is discussed. Strengths and limitations of the computational approaches are highlighted. The present benchmark study provides an overview of the expected performance of DFT-based methodologies in the description of photoinduced charge transfer reactions in fullerene heterojunctions We are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (Project CTQ2014-54306-P), the Catalan DIUE (Project 2014SGR931, ICREA Academia 2014 Award to MS, and Xarxa de Referència en Química Teòrica i Computacional), and the FEDER fund (UNGI10-4E-801). JPM acknowledges the Mexican National Council of Science and Technology (CONACYT) for his PhD fellowship (register/application number 217067/312543).

When gases evolve during a chemical reaction, a fraction of the reaction heat is lost with them. We have analyzed, both theoretically and experimentally, the deviations that this effect can produce on the determination of the reaction heat by differential scanning calorimetry (DSC). It is shown that, even in the absence of gas overheating, deviations related to variations in the sample heat capacity can be substantial in experiments involving very intense DSC peaks. However, experiments performed on thermal decomposition of metal organic salts and on evaporation of liquids have shown that deviations usually arise from gas overheating This work was partially funded by the Spanish Programa Nacional de Materiales through projects MAT2011-28874-C02-02 and by the Generalitat de Catalunya contract No. 2009SGR185

Struvite crystallization has been widely investigated, but little attention has been focused on particle size, an important characteristic in fertilizers that affects the agronomic response. Although there is no standard, it is an interesting parameter to be controlled as each crop and soil require a specific fertilizer size. Few attempts have been made to increase particle size. In air-lift reactors, the up-flow velocity could be used as a controlling parameter for particle size. It is hypothesized that the up-flow velocity determines the minimum theoretical equivalent diameter that can be recovered. Its effectiveness as a controlling parameter for particle size was evaluated in a combined air-lift reactor at different up-flow velocities (from 13.3 to 26.3mh-1). Particle size was found to be directly correlated with the up-flow velocity, and according to the theoretical approach about the minimum equivalent diameter. Moreover, particle growth was promoted by operating the crystallizer in continuous mode at the best up-flow velocity (22.6mh-1), having an increase of the mean particle size in time (138.6h) from 201μm to 314μm, and recovering particles up to 800-1000μm. The up-flow velocity control did not affect the phosphate recovery rates (>90%) and XRD confirmed that only pure struvite crystals were recovered. Therefore, this study shows that struvite can be recovered from a waste stream and control its particle size using the up-flow velocity to adjust to the customers' requirements This research has received funding from the European Community’s Framework Programme (FP7/2007-2013) under Grant Agreement n 603744, within the ManureEcoMine project. E.T. was financially supported by the Catalan Government (2014FI_B 00264). LEQUIA has been recognized as a consolidated research group by the Catalan Government with code 2014-SGR-1168. LEQUIA would like to thank the University of Girona (MPCUdG2016/137) for its financial support

Measurements to determine coal quality as fuel include proximate analysis, ultimate analysis and calorific value. The latter is an attribute taking non-negative real values, so a simple transformation is sufficient for its spatial modeling applying geostatistics. The analyses, however, involve proportions that follow the properties of compositional data, thus requiring special preprocessing for an adequate modeling already described in a previous publication for the case of proximate analysis data.11Olea, R.A., Luppens, J.A., 2015. Mapping of coal quality using stochastic simulation and isometric logratio transformation with an application to a Texas lignite. International Journal of Coal Geology, 152, 80-93. Here we model the results of calorific value and ultimate analysis. We propose to use two different binary partitions, one per analysis, map the corresponding isometric logratio transformations, and backtransform the results. The methodology is illustrated using the same coal bed in the previous paper modeling proximate analysis data. Results are summarized using probability maps that, in the case of this deposit, show a prominent channel crossing the deposit and separating the best quality coal from that of lower quality J.J. Egozcue and V. Pawlowsky-Glahn have been supported by the Ministerio de Economía y Competividad (Spain) under the project “CODA-RETOS” (Ref. MTM2015-65016-C2-1-R) and the project “METRICS” (Ref.MTM2012-33236); and by the AGAUR of the Generalitat de Catalunya under the project “COSDA” (Ref: 2014SGR551)

The photophysics and photochemistry of DNA is of great importance due to the potential damage of the genetic code by UV light. Quantum mechanical studies have played a key role in interpretating the results of modern time-resolved pump-probe spectroscopy, and in elucidating the main photoactivated reactive paths. This review provides a concise, complete picture of the computational studies carried out, approximately, in the past decade. We start with an overview of the photophysics of the nucleobases in the gas phase and in solution. We discuss the proposed mechanisms for ultrafast decay to the ground state, that involve conical intersections, consider the role of triplet states, and analyze how the solvent modulates the photophysics. Then we move to larger systems, from dinucleotides to single- and double-stranded oligonucleotides. We focus on the possible role of charge transfer and delocalized or excitonic states in the photophysics of these systems and discuss the main photochemical paths. We finish with an outlook on the current challenges in the field and future directions of research R.I. and F.S. acknowledge support from Italian MIUR (PRIN 2010-2011 Prot. 2010ERFXKL), RI from LeggeRegionale5 2007 Campania and Progetto Bilaterale PICS CNR/CNRS, and L.B. acknowledges support by Grant 2014SGR1202 from the Agència de Gestiód’Ajuts Universitaris i de Recerca (AGAUR) from Catalonia (Spain) and Grant CTQ2015-69363-P from the Ministerio de Economıá y Competividad (Spain)

Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 7, p. 2420-2423. DOI http://dx.doi.org/10.1002/ange.201509057 In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h-C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h-C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes We are grateful to the Spanish MINECO (CTQ2014-54306-P, CTQ2014-52525-P, CTQ2014-59212-P, and JdlC contract to S.O.), the Catalan DIUE (2014SGR931, ICREA Academia 2014 Award to M.S. and XRQTC), and the FEDER fund (UNGI10-4E-801) for financial support. M.G.-B. thanks the Spanish MECD for a PhD grant (AP2010-2517) and S.O. the European Commission for CIG project (FP7-PEOPLE-2013- CIG-630978). CESCA and BSC-CNS are acknowledged. M.R.C, M.I. and L.E. thanks the NSF for generous support of this work under grant (CHE-1408865) and to the NSFPREM program (DMR-1205302). The Robert A. Welch Foundation is also gratefully acknowledged for an endowed chair to L.E. (grant AH-0033)

Addition of benzyne to carbon nanostructures can proceed via (4+2) (1,4-addition) or (2+2) (1,2-addition) cycloadditions depending on the species under consideration. In this work, we analyze by means of density functional theory calculations the reaction mechanisms for the (4+2) and (2+2) cycloadditions of benzyne to nanostructures of different curvature, namely, C60 and a series of zig-zag single-walled carbon nanotubes. Our DFT calculations reveal that, except for the concerted (4+2) cycloaddition of benzyne to zig-zag single-walled carbon nanotubes, all cycloadditions studied are stepwise processes with the initial formation of a biradical singly-bonded intermediate. From this intermediate, the rotation of the benzyne moiety determines the course of the reaction. The Gibbs energy profiles lead to the following conclusions: (i) except for the 1,4-addition of benzyne to a six-membered ring of C60, all 1,2- and 1,4-additions studied are exothermic processes; (ii) for C60, the (2+2) benzyne cycloaddition is the most favoured reaction pathway; (iii) for zig-zag single-walled carbon nanotubes, the (4+2) benzyne cycloaddition is preferred over the (2+2) reaction pathway; and (iv) there is a gradual decrease in the exothermicity of the reaction and an increase of energy barriers as the diameter of the nanostructure of carbon is increased. By making use of the activation strain model, it is found that the deformation of the initial reactants in the rate-determining transition state is the key factor determining the chemoselectivity of the cycloadditions with benzyne The following organizations are thanked for financial support: the Spanish government (MINECO, projects number CTQ2014-54306-P, CTQ2014-59212-P, and CTQ2013-48252-P), the Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia 2014 prize to M. S.), and the FEDER fund (European Fund for Regional Development) for the grant UNGI10-4E-801

Biogas upgrading is an expanding field dealing with the increase in methane content of the biogas to produce biomethane. Biomethane has a high calorific content and can be used as a vehicle fuel or directly injected into the gas grid. Bioelectrochemical systems (BES) could become an alternative for biogas upgrading, by which the yield of the process in terms of carbon utilisation could be increased. The simulated effluent from a water scrubbing-like unit was used to feed a BES. The BES was operated with the biocathode poised at −800 mV vs. SHE to drive the reduction of the CO2 fraction of the biogas into methane. The BES was operated in batch mode to characterise methane production and under continuous flow to demonstrate its long-term viability. The maximum methane production rate obtained during batch tests was 5.12 ± 0.16 mmol m−2 per day with a coulombic efficiency (CE) of 75.3 ± 5.2%. The production rate increased to 15.35 mmol m−2 per day (CE of 68.9 ± 0.8%) during the continuous operation. Microbial community analyses and cyclic voltammograms showed that the main mechanism for methane production in the biocathode was hydrogenotrophic methanogenesis by Methanobacterium sp., and that electromethanogenesis occurred to a minor extent. The presence of other microorganisms in the biocathode, such as Methylocystis sp. revealed the presence of side reactions, such as oxygen diffusion from the anode compartment, which decreased the efficiency of the BES. The results of the present work offer the first experimental report on the application of BES in the field of biogas upgrading processes This research was nancially supported by the Spanish Government (CTQ 2014-53718-R). P. B-V. and A. V-P. were supported by a project grant from the Catalan Government (2014 FIB1 00119 and 2014 FI-B 00093). LEQUIA has been recognised as consolidated research group by the Catalan Government with code 2014-SGR-1168. Authors acknowledge the collaboration of Lluis Baneras from the Group of Molecular Microbial Ecology (University of Girona), who helped with the microbial analyses

Several regions around the world present high levels of nitrate in groundwater. Due to its toxicity, nitrate must be removed before the groundwater is used as drinking-water. This study assessed how a denitrifying bioelectrochemical system could be operated to treat nitrate-polluted groundwater. It evaluated the cathode potential (from +597 to -703mV vs SHE) and the anode electron donor (acetate and water). Similar trends were found regardless of the anode electron donor. The nitrate removal rate increased from 1.05 to 5.44mgN-NO3 -LNCC -1h-1 when the cathode potential was lowered from +597 to -403mV vs SHE, where it stabilized. The nitrate reduction end-products (nitrite, nitrous oxide and dinitrogen gas) also changed with the different potentials of the cathode electrode. The World Health Organization nitrates and nitrites standards for drinking-water were reached at cathode potentials between -103 and -203mV vs SHE. The highest rate of nitrate conversion to N2 (2.59mgN-NO3 -LNCC -1h-1, 93.9%) occurred at -123mV using water as anode electron donor, with an estimated operational cost similar to conventional technologies (0.68·10-2kWhgN-NO3-removed-1). The long-term stability of proposed operation was demonstrated during 96days, and the rate of nitrate conversion to N2 even increased to 4.09mgN-NO3 -LNCC -1h-1. A carbon-free operation for a bioelectrochemical system has been developed to treat nitrate-polluted groundwater at a competitive cost This research was financially supported by the Spanish Government (CTQ2011-23632, CONSOLIDERCSD2007-00055) and the Catalan Government (2014-SGR-1168). Narcis Pous was supported by a project grant from the Catalan Government (2012 FI-B 00941)

Despite B and Al belong to the same group 13 elements, the B6²- cluster prefers the planar D2h geometry, whereas Al6²- favours the Oh structure. In this work, we analyse the origin of the relative stability of the D2h and Oh forms in these clusters by means of an energy decomposition analysis based on the turn-upside-down approach. Our results show that what causes the different trend observed is the orbital interaction term, which combined with the electrostatic component do (Al6²- and Ga6²-) or do not (B6²-) compensate the higher Pauli repulsion of the Oh form. Analysing the orbital interaction term in more detail, we find that the preference of B6²- for the planar D2h form has to be attributed to two particular molecular orbital interactions. Our results are in line with a dominant delocalisation force in Al clusters and the preference for more localised bonding in B metal clusters. For mixed clusters, we have found that those with more than two B atoms prefer the planar structure for the same reasons as for B6²- This work has been supported by the Ministerio de Economía y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P) and the Generalitat de Catalunya (project 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, ICREA Academia 2014 prize for M.S., and grant No. 2014FI_B 00429 to O.E.B.). The EU under the FEDER grant UNGI10-4E-801 (European Fund for Regional Development)has also funded this research. J. P. thanks the National Research School Combination - Catalysis (NRSCC), and The Netherlands Organization for Scientific Research (NWO/CW and NWO/NCF)

The Iberian Peninsula has a rich fauna of freshwater fish, with many endemics that are threatened. One of the threat causes is the introduction of exotic species or translocation of natives to new basins. In this paper, we review the ecological impacts of these introductions, from the genetic and individual to the community and global levels, primarily using studies from the Peninsula. Although the accumulated evidence is considerable, the ecological impact of most species and introductions has barely been studied and is probably much greater than is known La península ibérica goza de una rica fauna de peces continentales, muchos de ellos endémicos y amenazados. Una de las causas de su declive es la introducción de especies exóticas o la translocación de algunas nativas a nuevas cuencas. En este trabajo, revisamos los impactos ecológicos de estas introducciones, desde los niveles genético e individual a los de comunidad y global, basándonos principalmente en trabajos de la península. Aunque la evidencia acumulada es considerable, el impacto ecológico de la mayoría de especies e introducciones apenas ha sido estudiado y seguramente es mucho mayor del que se conoce Esta revisión es fruto en parte de numerosos proyectos de investigación, financiados básicamente por el Ministerio de Economía y Competitividad (proyectos REN2002-10059-E, REN2003-00477, CGL2006-11652-C02-01/BOS, CGL2009-12877-C02-01, CSD2009-00065 y CGL2013-43822-R), el Ministerio de Medio Ambiente, la Agencia Catalana del Agua, la Universidad de Girona (proyecto SING12/09), la Generalitat de Cataluña (2014 SGR 484) y la Comisión Europea (Acción COST TD1209). DA disfruta de un contrato postdoctoral financiado por la Generalitat de Cataluña (2013 BP_B 00172). MJB y KM se han beneficiado de contratos postdoctorales financiados por la Comisión Europea (Erasmus Mundus Partnership “NESSIE”, 372353-1-2012-1-FR-ERA MUNDUS-EMA22 y Marie Curie International Reintegration Grant). RM disfruta de una beca predoctoral del Ministerio de Educación y Deporte (AP2010-4025)

The expansion of low-cost airlines (LCAs) has led to a reduction of flight costs and has enabled tourists to redistribute their trip budget and spend a higher proportion at the destination. Analyses of absolute trip spending by parts (such as transportation) and of trip budget share (for example, the proportion of transportation within the total trip budget) serve different objectives. The first type of analysis refers to how much tourists spend and the second to how they spend. The aims of this article are, first, to provide a new methodological tool to combine the analysis of budget share and absolute expenditure and, second, to analyse the determinants of absolute expenditure on transportation and the relative importance of transportation expenditure compared to other trip budget components. The main findings are that traveller characteristics affecting high absolute transportation expenditure are different from those affecting a high share of transportation in the trip budget. This has implications for LCA pricing strategies The authors are pleased to acknowledge the support of the Spanish Institute of Tourism (Instituto de Turismo de España) in providing them with the raw data. The authors are entirely responsible for any lack of accuracy or reliability in the data analysis. All authors wish to thank Neelu Seetaram and Juan José Egozcue for their comments on previous versions of the article and to acknowledge the support of the Catalan Autonomous Government Consolidated Research Group Grant 2014SGR551 for funding their research group ‘Compositional and Spatial Data Analysis (COSDA)’; the Spanish Health Ministry grant CB06/02/1002 for funding the research group “CIBER of Epidemiology and Public Health (CIBERESP)”; the Spanish Economy and Competitiveness Ministry grants MTM2015-65016-C2-1-R and EDU2015-68610-R, respectively, for funding the projects “COmpositional Data Analysis and RElated meThOdS (CODA-RETOS)” and “Assessing Individual and Team Entrepreneurial Potential”; and the University of Girona grants MPCUdG2016/069 and MPCUdG2016/098

The electric grid is evolving. Smart grids and demand response systems will increase the performance of the grid in terms of cost efficiency, resilience and safety. Accurate load forecasting is an important issue in the daily operation and control of a power system. A suitable short term load forecasting will enable a utility provider to plan the resources and also to take control measures to balance the supply and demand of electricity. The aim of this paper is to create a method to forecast the electric load in a non-residential building. Another goal is to analyse what kind of data, as weather, indoor ambient, calendar and building occupancy, is the most relevant in building load forecasting. A simple method, tested with three different models, such as MLR, MLP and SVR, is proposed. The results, from a real case study in the University of Girona, show that the proposed forecast method has high accuracy and low computational cost This research has been partially supported by the Spanish Government project MESC (Ref. DPI2013-47450-C2-1-R). Also we would like to thank the Department of Physics and acknowledge the technical assistance and maintenance service of the UdG (SOTIM) which provided the weather and consumption data respectively. The authors belong to the ‘Smart IT Engineering and Solutions’ accredited research group (Generalitat de Catalunya, 2014 SGR 1052)

The low-lying triplet state of a recently published compound (TMTQ, Angew. Chem. Int. Ed. 2015, 20, 5888), was analyzed quantum chemically in light of suggestions that it is influenced by Baird-aromaticity. Two mesomeric structures describe this state; a zwitterionic Baird-aromatic structure with a triplet biradical 8pi-electron methano[10]annulene (M10A) dicationic ring, and a Hückel-aromatic with a neutral closed-shell 10pi-electron ring. According to charge and spin density distributions, the Hückel-aromatic structure dominates the triplet state (the Baird-aromatic contributes at most 12%), and separation of the FLU aromaticity index into alpha and beta electron contributions emphasizes this finding. The small singlet-triplet energy gap is due to Hückel-aromaticity of the M10A ring, clarified by comparison to the smaller analogues of TMTQ. Yet, TMTQ and its analogues are Hückel-Baird hybrids allowing for tuning between closed-shell 4n+2 Hückel-aromaticity and open-shell 4n Baird-aromaticity This work has been supported by the Swedish Research Council (project grant 621-2011-4177), Ministerio de Economía y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P) and the Generalitat de Catalunya (project 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia 2014 prize for M.S.). F.F. acknowledges financial support of the Beatriu de Pinós programme from AGAUR for the postdoctoral grants BP_A_00339 and BP_A2_00022. M.S. and F.F. are grateful to the European Union (EU) for FEDER fund number UNGI10-4E-801

The effective atomic orbitals have been realized in the framework of Bader's atoms in molecules theory for a general wavefunction. This formalism can be used to retrieve from any type of calculation a proper set of orthonormalized numerical atomic orbitals, with occupation numbers that sum up to the respective Quantum Theory of Atoms in Molecules (QTAIM) atomic populations. Experience shows that only a limited number of effective atomic orbitals exhibit significant occupation numbers. These correspond to atomic hybrids that closely resemble the core and valence shells of the atom. The occupation numbers of the remaining effective orbitals are almost negligible, except for atoms with hypervalent character. In addition, the molecular orbitals of a calculation can be exactly expressed as a linear combination of this orthonormalized set of numerical atomic orbitals, and the Mulliken population analysis carried out on this basis set exactly reproduces the original QTAIM atomic populations of the atoms. Approximate expansion of the molecular orbitals over a much reduced set of orthogonal atomic basis functions can also be accomplished to a very good accuracy with a singular value decomposition procedure Financial help has been furnished by the Spanish MICINN Project No. CTQ2011-23441/BQU and Accion Complementaria del MCI (PCI2006-A7-0631). Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNGI08-4E-003. Financial support from the Generalitat de Catalunya (SGR528 and Xarxa de Referncia en Qumica Terica i Computacional) is also acknowledged. E.R-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231)

Understanding photoinduced charge separation in fullerene-based dye-sensitized solar cells is crucial for the development of photovoltaic devices. We investigate here how the driving force of the charge separation process in conjugates of M@C80 (M=Sc3N, Sc3CH, Sc3NC, Sc4O2, and Sc4O3) with triphenylamine (TPA) depends on the nature of the metal cluster. Both singlet and triplet excited-state electron-transfer reactions are considered. These results based on TD-DFT calculations demonstrate that the driving force of charge separation in TPA-M@C80 can be tuned well by varying the structure of the metal cluster encapsulated inside the fullerene cage We are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (Projects CTQ2014-54306-P and CTQ2015-69363-P), the Catalan DIUE (Project 2014SGR931, ICREA Academia 2014 Award to MS, and Xarxa de Referència en Química Teòrica i Computacional), and the FEDER fund (UNGI10-4E-801). J.P.M. acknowledges the Mexican National Council of Science and Technology (CONACYT) for his PhD fellowship (register/application number 217067/312543)

The rich chemical and structural versatility of transition metal complexes provide numerous novel paths to be pursued in the design of molecules that exert particular chemical of physicochemical effects that could operate over specific biological targets. However, the poor cell permeability of metallodrugs represents an important barrier for their therapeutic use. The conjugation between metal complexes and a functional peptide vector can be regarded as a versatile and potential strategy to improve their bioavailability and accumulation inside cells, and the site selectivity of their effect. This perspective lies on reviewing the recent advances on the design of metallopeptide conjugates for biomedical applications. Additionally, we highlight the studies where this approach has been directed towards the incorporation of redox active metal centers in living organisms for modulating the cellular redox balance, as a tool with application in anticancer therapy We acknowledge financial support by Consolider Ingenio CSD/CSD2010-00065 from MICINN of Spain. We also thank the Catalan DIUE of the Generalitat de Catalunya (2014 SGR 862). X.R. thanks financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1

A new iron complex mediates stereospecific hydroxylation of alkyl C-H bonds with hydrogen peroxide, exhibiting excellent efficiency. Isotope labelling studies provide evidence that the relative reactivity of tautomerically related oxo-iron species responsible for the C-H hydroxylation reaction is dominated by steric factors This work has been supported by the European Union (the Erasmus Mundus program), the International Research Training Group Metal Sites in Biomolecules: Structures, Regulation and Mechanisms (www.biometals.eu), and COST Action CM1003. M.C. acknowledges ERC-29910, MINECO of Spain for CTQ2012- 37420-C02-01/BQU and CSD2010-00065, catalan DIUE (2009SGR637) and an ICREA academia award. J.Ll. thanks MICINN for a RyC contract

A key parameter of many transformations when heated at a constant rate is the peak temperature, i.e., the temperature at which the transformation rate is at its maximum. The most universal approach to determine the peak temperature for thermally activated transformations is the Kissinger equation. In this paper, we solve Kissinger equation to deduce the exact dependence of the peak temperature on the heating rate. This analytical solution is based on the Lambert W-function. In addition, an approximate solution is derived that is used to infer general properties of thermally activated processes and to obtain a test to check the validity of Kissinger method This work was partially funded by the Spanish Programa Nacional de Materiales through project MAT2011-28874-C02-02 and by the Generalitat de Catalunya contract No. 2009SGR-185

The reaction mechanisms for alkane hydroxylation catalyzed by non-heme FeVO complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary CH bonds) through a FeVO species, [FeV(O)(OH)(PyTACN)]2+ (PyTACN = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the CH bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [FeIV(OH)2(PyTACN)]2+, or through hydride transfer to form a cationic substrate interacting with the [FeIII(OH)2(PyTACN)]+ species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R+ and [FeIII(OH)2(PyTACN)]+ is more stable than that involving the alkyl radical and the [FeIV(OH)2(PyTACN)]2+ complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane CH bonds by non-heme FeV(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by FeVO species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature This work has been supported by Ministerio de Economiá y Competitividad of Spain (Projects CTQ2014-54306-P, CTQ2014-52525-P, and CTQ2012-37420-C02-01, Ramón y Cajal contract to A.C., and grant No. BES-2012-052801 to V.P.), Generalitat de Catalunya (project numbers 2014SGR931, 2014SGR862, Xarxa de Refereǹ cia en Quiḿ ica Teor̀ ica i Computacional, and ICREA Academia prizes for M.S. and M.C.), the European Commission (ERC-2009-StG-239910 to M.C. and FP7-PEOPLE-2011-CIG-303522 to A.C.), and European Fund for Regional Development (FEDER grant UNGI10-4E-801)

One of the fundamental steps toward malaria control is the use of antimalarial drugs. The success of antimalarial treatment can be affected by the presence of drug-resistant populations of Plasmodium falciparum. To assess resistance, we used molecular methods to examine 351 P. falciparum isolates collected from 4 sentinel sites in Mozambique for K13, pfmdr1, pfcrt, and pfdhps polymorphisms and for plasmepsin2 (pfpm2) and pfmdr1 copy numbers. We found multiple copies of pfpm2 in 1.1% of isolates. All isolates carried K13 wild-type alleles (3D7-like), except 4 novel polymorphisms (Leu619Leu, Phe656Ile, Val666Val, Gly690Gly). Prevalence of isolates with pfcrt mutant (K76T) allele was low (2.3%). Prevalence of isolates with pfdhps mutant alleles (A437G and K540E) was >80%, indicating persistence of sulfadoxine/pyrimethamine resistance; however, markers of artemisinin were absent, and markers of piperaquine resistance were low. Piperaquine resistance isolates may spread in Mozambique as dihydroartemisinin/piperaquine drug pressure increases.

The Diels-Alder reactivity of different bowl-shaped polycyclic aromatic hydrocarbons (namely, corannulene, cyclopentacorannulene, diindenochrysene, hemifullerene, and circumtrindene) has been explored computationally within the DFT framework. To this end, both the increase in reactivity with the size of the buckybowl and complete [6,6]-regioselectivity in the process have been analyzed in detail by using the activation strain model of reactivity in combination with the energy decomposition analysis method. These results have been compared with the parent C60 fullerene, which also produces the corresponding [6,6]-cycloadduct exclusively. The behavior of the buckybowls considered herein resembles, in general, that of C60. Whereas the interaction energy between the deformed reactants along the reaction coordinate mainly controls the regioselectivity of the process, it is the interplay between the activation strain energy and the transition-state interaction that governs the reactivity of the system. Bigger bowls, better reactivity: Starting from corannulene, there is a smooth convergence to the C60 energy barrier and reaction energy for the Diels-Alder reaction with cyclopentadiene when the size of the buckybowl is increased (see figure). Through density functional calculations, the origins of both this trend of reactivity and the observed exclusive [6,6]-regioselectivity are analyzed in detail We are grateful for financial support from the Spanish MINECO-FEDER (grants CTQ2013-44303-P and CTQ2014-51912-REDC to I.F. and CTQ2014-54306-P to M.S.), Fundaciûn BBVA (Convocatoria 2015 de Ayudas Fundaciûn BBVA a Investigadores y Creadores Culturales), Catalan DIUE (projects 2014SGR931 and XRQTC to M.S.), the National Research School Combination—Catalysis (NRSC-C), and The Netherlands Organization for Scientific Research (NWO/ALW, NWO/CW, NWO/EW). Support for the research of M.S. was received through the ICREA Academia 2014 prize of the Catalan DIUE. The FEDER grant UNGI10-4E-801 (European Fund for Regional Development) also funded this research. Y.G.-R. acknowledges the MINECO for a FPI grant

The spectroscopic, electrochemical, and crystallographic characterization of [(Me,HPyTACN)NiII(CH3CN)2](OTf)2 (1) (Me,HPyTACN = 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, OTf = CF3SO3) is described together with its reactivity with NaOCl. 1 catalyzes the chlorination of alkanes with NaOCl, producing only a trace amount of oxygenated byproducts. The reaction was monitored spectroscopically and by high resolution electrospray-mass spectrometry (ESI-MS) with the aim to elucidate mechanistic aspects. NaOCl reacts with 1 in acetonitrile to form the transient species [(L)NiII-OCl(S)]+ (A) (L = Me,HPyTACN, S = solvent), which was identified by ESI-MS. UV/vis absorption, electron paramagnetic resonance, and resonance Raman spectroscopy indicate that intermediate A decays to the complex [(L)NiIII-OH(S)]2+ (B) presumably through homolytic cleavage of the O-Cl bond, which liberates a Cl• atom. Hydrolysis of acetonitrile to acetic acid under the applied conditions results in the formation of [(L)NiIII-OOCCH3(S)]2+ (C), which undergoes subsequent reduction to [(L)NiII-OOCCH3(S)]2+ (D), presumably via reaction with OCl- or ClO2 -. Subsequent addition of NaOCl to [(L)NiII-OOCCH3(S)]+ (D) regenerates [(L)NiIII-OH(S)]2+ (B) to a much greater extent and at a faster rate. Addition of acids such as acetic and triflic acid enhances the rate and extent of formation of [(L)NiIII-OH(S)]2+ (B) from 1, suggesting that O-Cl homolytic cleavage is accelerated by protonation. Overall, these reactions generate Cl• atoms and ClO2 in a catalytic cycle where the nickel center alternates between Ni(II) and Ni(III). Chlorine atoms in turn react with the C-H bonds of alkanes, forming alkyl radicals that are trapped by Cl• to form alkyl chlorides Financial support comes from the European Research Council (ERC-2011-StG-279549, W.R.B. and ERC-2009-StG-239910, M.C.), The Netherlands Fund for Technology and Science STW (11059, W.R.B.) the Ministry of Education, Culture and Science (Gravity program 024.001.035, A.D., W.R.B.) and the Ubbo Emmius Fund of the University of Groningen (AD). M.C. thanks MINECO of Spain (CTQ2012 37420-C02-01/BQU, CSD2010-00065) and Generalitat de Catalunya (2009SGR637, and ICREA Acadèmia Award)

Understanding the variation of fish assemblages in reservoirs is crucial for precise interpretations of ecological processes. However, representative samples in such environments are subjected both to spatial zonation (longitudinal and transversal gradients) and limitations of fishing gears. We used a large zoned reservoir (Itaipu, Brazil) to perform a quasi-experiment that assessed the relative role of spatial gradients and fishing methods on fish diversity and composition. Active (cast nets, electrofishing and seines) and passive (gillnets and longlines) fishing gears were employed in lotic, transitional and lentic habitats of the reservoir and three large tributaries. In total 6281 individuals of 101 species were captured. Sampling methods and spatial gradients had an influence on species composition, with significant interactions between these factors. In addition, results produced by a variation partitioning analysis suggested that 21 % of the species richness was explained by the sampling methods and 7 % by the longitudinal gradient; whereas for species composition, 12 and 3 % corresponded to sampling methods and transversal gradients, respectively. Overall, our results suggest that variations among fishing gears is greater than across strong spatial gradients, emphasizing the importance of using multiple and complementary fishing methods in reservoirs for characterization of fish assemblages. The interactions between spatial gradients and sampling methods were higher with transversal than with longitudinal gradients, suggesting that substantial differences in species richness and composition among sampling gears depend to some extent on habitat. The approach used here would be applicable to any large zoned inland waterscape Financial support was provided by the Spanish Ministry of Economy and Competitiveness (project CGL2013-43822-R), the Government of Catalonia (ref. 2014 SGR 484), and CAPES (Programa Pesquisador Visitante Especial, ref. 88881.068352/2014-01).

A family of imine-based nonheme iron(II) complexes (LX)2Fe(OTf)2 has been prepared, characterized, and employed as C-H oxidation catalysts. Ligands LX (X = 1, 2, 3, and 4) stand for tridentate imine ligands resulting from spontaneous condensation of 2-pycolyl-amine and 4-substituted-2-picolyl aldehydes. Fast and quantitative formation of the complex occurs just upon mixing aldehyde, amine, and Fe(OTf)2 in a 2:2:1 ratio in acetonitrile solution. The solid-state structures of (L1)2Fe(OTf)(ClO4) and (L3)2Fe(OTf)2 are reported, showing a low-spin octahedral iron center, with the ligands arranged in a meridional fashion. 1H NMR analyses indicate that the solid-state structure and spin state is retained in solution. These analyses also show the presence of an amine-imine tautomeric equilibrium. (LX)2Fe(OTf)2 efficiently catalyze the oxidation of alkyl C-H bonds employing H2O2 as a terminal oxidant. Manipulation of the electronic properties of the imine ligand has only a minor impact on efficiency and selectivity of the oxidative process. A mechanistic study is presented, providing evidence that C-H oxidations are metal-based. Reactions occur with stereoretention at the hydroxylated carbon and selectively at tertiary over secondary C-H bonds. Isotopic labeling analyses show that H2O2 is the dominant origin of the oxygen atoms inserted in the oxygenated product. Experimental evidence is provided that reactions involve initial oxidation of the complexes to the ferric state, and it is proposed that a ligand arm dissociates to enable hydrogen peroxide binding and activation. Selectivity patterns and isotopic labeling studies strongly suggest that activation of hydrogen peroxide occurs by heterolytic O-O cleavage, without the assistance of a cis-binding water or alkyl carboxylic acid. The sum of these observations provides sound evidence that controlled activation of H2O2 at (LX)2Fe(OTf)2 differs from that occurring in biomimetic iron catalysts described to dat This work was also partially supported by Università di Roma La Sapienza- Area Supporto alla Ricerca (Progetti di Ricerca 2014 and Avvio alla Ricerca 2014). M.C. acknowledges financial support from ERC-2009-StG-239910 (to M.C.), the Spanish Ministry of Science (Nos. CTQ2012-37420-C02-01/BQU and CSD2010-00065, to M.C.) and Generalitat de Catalunya (ICREA Academia Award and No. SGR-862

L'Arbreda Cave is one of the southernmost of the Reclau Caves (Serinya, Girona, northeastern Iberian Peninsula), located between the west margin of the Pla d'Usall and the Serinyadell river, at an altitude of about 211 m a.s.l. The Pla d'Usall forms part of the Banyoles-Besald Basin, which is bounded by Eocene and Neogene reliefs. It is filled with sediments of Plio-Pleistocene age. The cave is a shelter formed by travertine cascades with a degree of karstification, and contains sedimentary deposits ranging from the end of the Middle Pleistocene to the Early Holocene, thus constituting an important archaeo-palaeontological record for an understanding of the prehistoric occupation of northeastern Iberia. It is one of the most complete and best-dated terrestrial sequences in Iberia from the Mousterian to the Early Holocene period. In this paper we present a palaeoenvironmental and palaeoclimatic reconstruction of the sequence based on non-flying small mammals (insectivores and rodents) and pollen analyses. The environmental and climatic results, together with the absolute dating of the sequence and direct comparison with NorthGRIP delta O-18 and the sea-surface temperatures (SST) of the Alboran Sea, allow us to identify various climatic periods within our sequence: a cold period between interstadials 12 and 10 in Level I, probably interstadial 10 in Level H-2 the Last Glacial Maximum (LGM) in Levels C and B, the Bolling-Allered interstadial (B/A) in Level A, and the Preboreal/Boreal (Pr/B) in the Terra Rossa Level We want to thank the editor Dr. Paul Hesse and the three reviewers (Prof. Gloria Cuenca-Bescos and two anonymous) for their comments that improve the final version of the manuscript. This paper is part of the projects HAR2013-48784-C3-2-P, CGL2012-38358 and 2014-SGR900. Excavations ara funded by "Conselleria de Cultura Generalitat de Catalunya". J.M. Lopez-Garcia is a beneficiary of a Beatriu de Pinos postdoctoral fellowship (2011BP-A200001) from the Generalitat de Catalunya, a grant co-funded by the European Union through the Marie Curie Actions of the 7th Framework Program for R + D

This paper puts forward an analysis of Spanish denominal parasynthetic verbs based on the assumption that these formations express an event of change (either of state or of location), and that their meaning depends on three elements: the type of noun they incorporate, the directionality encoded by the prefix, and the kind of internal argument they select. In order to carry out such an analysis, two semantic theories of lexical decomposition have been used: Jackendoff’s (1983, 1990) model of Conceptual Semantics and Pustejovsky’s (1995) theory of the Generative Lexicon. The first model allows us to classify the verbs under study from the standpoint of their lexical-conceptual structure, which makes evident the structural parallelisms existing in their meaning. On the other hand, the model developed by Pustejovsky gives us the opportunity to explore some additional aspects related to the compositional meaning of these formations, enabling us to demonstrate the relevance of the internal argument in relation to the (regular and irregular) polysemy of these constructions This research has been supported by two projects funded by the Ministerio de Ciencia e Innovación—FFI2011-29440-CO3-02 (Periferias y cambio lingüístico: descripción, teoría y aplicaciones) and FFI2011-24183 (Portal de léxico hispánico: documentación y morfología derivativa)—, one project granted by the Ministerio de Economía y Competitividad—FFI2014-56968-C4-4-P (Variación en la interficie morfología-sintaxis)— and by the FPU grant AP2012-1445 from the Ministerio de Educación, Cultura y Deporte. Our work has also benefited from a grant from the Departament de Filologia i Comunicació at the Universitat de Girona (Ajut a la recerca 2014), as well as from the program Suport als Grups de Recerca (2014 SGR 1013) financed by the Generalitat de Catalunya.

Animal behaviour is of fundamental importance but is often overlooked in biological invasion research. A problem with such studies is that they may add pressure to already threatened species and subject vulnerable individuals to increased risk. One solution is to obtain the maximum possible information from the generated data using a variety of statistical techniques, instead of solely using simple versions of linear regression or generalized linear models as is customary. Here, we exemplify and compare the use of modern regression techniques which have very different conceptual backgrounds and aims (negative binomial models, zero-inflated regression, and expectile regression), and which have rarely been applied to behavioural data in biological invasion studies. We show that our data display overdispersion, which is frequent in ecological and behavioural data, and that conventional statistical methods such as Poisson generalized linear models are inadequate in this case. Expectile regression is similar to quantile regression and allows the estimation of functional relationships between variables for all portions of a probability distribution and is thus well suited for modelling boundaries in polygonal relationships or cases with heterogeneous variances which are frequent in behavioural data. We applied various statistical techniques to aggression in invasive mosquitofish, Gambusia holbrooki, and the concomitant vulnerability of native toothcarp, Aphanius iberus, in relation to individual size and sex. We found that medium sized male G. holbrooki carry out the majority of aggressive acts and that smaller and medium size A. iberus are most vulnerable. Of the regression techniques used, only negative binomial models and zero-inflated and expectile Poisson regressions revealed these relationships This research was supported by a Marie Curie International Reintegration Grant within the 7th European Community Framework Programme (KM). Additional support was provided by the Spanish Ministry of Economy and Competitiveness (project CGL2013-43822-R), the University of Girona (project SING12/09), the Government of Catalonia (ref. 2014 SGR 484), and the European Commission (COST Action TD1209)

Zooplankton is generally affected by both top-down and bottom-up regulations in aquatic ecosystems. However, the relative strength of top-down and bottom-up controls on zooplankton assemblages is not well understood. Here, we analyzed this question in five lakes of the Yangtze River basin, an area with high population density and thousands of lakes, many of them suffering multiple environmental pressures. We sampled the whole communities of five lakes in the middle reaches of Yangtze River basin from 2006 to 2011 and used structural equation modeling to evaluate the relative importance of joint top-down and bottom-up effects. With increasing total phosphorous (TP), a major shift occurred in trophic structure. Biomass of phytoplankton, rotifers, cyclopoids, and planktivorous fish significantly increased, while cladocerans and calanoids were negatively correlated with increasing TP. The bottom-up effects were strongest at the bottom of the food web (e.g., effects of TP on phytoplankton). Direct bottom-up effects of phytoplankton and other food resources (latent variable) on rotifers and cyclopoids were greater than top-down controls from planktivores. The predation pressure on crustacean zooplankton by planktivores was higher than that on rotifers. In planktivore-dominated systems, piscivores only played a marginal role, whereas they seem affected by water quality. These results suggest not only in the food web processes the important role of nutrient pollution in affecting the top of the food web in these lakes, but also that the impacts and relative strength of bottom-up and top-down controls may vary with zooplankton assemblages, indicating the complexity of food webs in degraded lakes in China We thank Sabine Giessler, the editor, and two anonymous reviewers for helpful comments and suggestions on the manuscript. This work was supported by a Special Fund for Agro-scientific Research in the Public Interest (Grant No. 20130356); the R and D Project of the Ministry of Science and Technology of China (Grant No. 2012BAD25B08); and Projects of the National Natural Science Foundation of China (Grant Nos. 30830025 and 31201994). Financial support to EGB was provided by the Spanish Ministry of Economy and Competitiveness (Project CGL2013-43822-R), the Government of Catalonia (Ref. 2014 SGR 484), and the European Commission (Erasmus Mundus Partnerships "TECHNO'' and "TECHNO II'')

Three algorithms for optimization of minimum energy conical intersections (MECI) are implemented inside an ONIOM(QM:MM) scheme combined with microiterations. The algorithms follow the composed gradient (CG), composed gradient-composed steps (CG-CS), and double Newton-Raphson-composed step (DNR-CS) schemes developed previously for purely QM optimizations. The CASSCF and UFF methods are employed for the QM and MM calculations, respectively. Conical intersections are essential to describe excited state processes in chemistry, including biological systems or functional molecules, and our approach is suitable for large molecules or systems where the excitation is well localized on a fragment that can be treated at the CASSCF level. The algorithms are tested on a set of 14 large hydrocarbons composed of a medium-sized chromophore (fulvene, benzene, butadiene, and hexatriene) derivatized with alkyl substituents. Thanks to the microiteration technique, the number of steps required to optimize the MECI of the large molecules is similar to the one needed to optimize the unsubstituted chromophores at the QM level. The three tested algorithms have a similar performance, although the CG-CS implementation is the most efficient one on average. The implementation can be straightforwardly applied to ONIOM(QM:QM) schemes, and its potential is further demonstrated locating the MECI of diphenyl dibenzofulvene (DPDBF) in its crystal, which is relevant for the aggregation induced emission (AIE) of this molecule. A cluster of 12 molecules (528 atoms) is relaxed during the MECI optimization, with one molecule treated at the QM level. Our results confirm the mechanistic picture that AIE in DPDBF is due to the packing of the molecules in the crystal. Even when the molecules surrounding the excited molecule are allowed to relax, the rotation of the bulky substituents is hindered, and the conical intersection responsible for radiationless decay in solution is not accessible energetically This work has been supported by grant CTQ2011-26573 from the Spanish Ministerio de Economia y Competividad (MINECO), 2014SGR1202 from the Catalan Agencia de Gestio d'Ajuts Universitaris i de Recerca (AGAUR), UNGI10-4E-801 from the Spanish Ministerio de Ciencia e Innovacion (MICINN) and the European Fund for Regional Development, and the Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya from AGAUR. S.R.-B. thanks the MINECO for grant BES-2009-029177 and a travel grant EEBB-I-12-04604

We present the formulation and implementation of a polarizable quantum mechanics/molecular mechanics (QM/MM) strategy to describe environment effects in multiconfiguration self-consistent field calculations. The strategy is applied to the calculation of the vertical absorption spectrum of cytosine in water. In our approach, mutual polarization of the solute and the solvent is solved self-consistently at the complete-active-space self-consistent-field (CASSCF) level, and the resulting set of charges and dipoles is used to calculate vertical excitation energies using the complete-active-space second-order perturbative (CASPT2) approach and its multistate (MS-CASPT2) variant. In order to treat multiple excited states, we converge the solvent polarization with respect to the state-averaged density of the solute. In order to obtain the final energies, however, we introduce a state-specific correction, where the solvent polarization is recomputed with the density of each state, and demonstrate that this correction brings the excitation energies closer to the values obtained with state-optimized orbitals. Comparison with PCM and nonpolarizable QM/MM calculations shows the importance of specific solute solvent interactions and environment polarization in describing experiments. Overall, the calculated excitations for the π → π* states in water show good agreement with the experimental spectrum, whereas the n → π* appear at energies above 6 eV, approximately 1 eV higher than in the gas phase. Beyond solvents, the new method will allow studying the impact of heterogeneous biological environments in multiple excited states, as well as the treatment of multichromophoric systems where charge transfer and exciton states play important roles.

Emission of odours during the thermal drying in sludge handling processes is one of the main sources of odour problems in wastewater treatment plants. The objective of this work was to assess the use of the response surface methodology as a technique to optimize the chemical conditioning process of undigested sewage sludges, in order to improve the dewaterability, and to reduce the odour emissions during the thermal drying of the sludge. Synergistic effects between inorganic conditioners (iron chloride and calcium oxide) were observed in terms of sulphur emissions and odour reduction. The developed quadratic models indicated that optimizing the conditioners dosage is possible to increase a 70% the dewaterability, reducing a 50% and 54% the emission of odour and volatile sulphur compounds respectively. The optimization of the conditioning process was validated experimentally R. Gonzalez-Olmos thanks MICINN (Ministerio de Ciencia e Innovacion) for the Juan de la Cierva fellowship (JCI-2010-07104). H. Monclus thanks to People Programme (Marie Curie Action) of the European Union's Seventh Framework Programme (FP7/2007-2013) and from ACCIO under REA grant agreement (no 600388) for TECNIOSPRING fellowship (TECSPR13-1-0050). The authors also greatly appreciate financial support from the Spanish MICINN (projects PET2008_0261, CTQ2011-24114). LEQUIA has been recognised as consolidated research group by the Catalan Government with code 2014-SGR-1168

The missing entry, namely, the "C-anagostic" or δ1-C interaction, closing the agostic-anagostic series of metal-CH(aryl) interactions is found in a bis(amidiniophosphine) P(CH)P pincer rhodium complex. The three entries, namely, agostic δ2-(C,H), anagostic (related to hydrogen bonding, thus recoined here as "H-anagostic"), and C-anagostic interactions, are unambiguously characterized by electron localization function (ELF) topological analysis. Other theoretical tools such as noncovalent interaction (NCI) analysis and multicenter electron delocalization indices (MCIs) support the ELF characterization. A δ2-(C,H) agostic interaction is evidenced by a disynaptic V(C,H) or trisynaptic V(M,C,H) ELF basin with a significant quantum topological atoms in molecules (QTAIM) atomic contribution of the metal M and a large covariance (in absolute value) with the metal core basin C(M). The C-anagostic δ1-C interaction is characterized by a disynaptic V(M,C) basin, a weak covariance (in absolute value) of V(C,H) and C(M) populations, and a negligible QTAIM atomic contribution of M to V(C,H). The relevance of these ELF signatures is evidenced in a selected series of related rhodium and osmium complexes The theoretical studies were performed using HPC resources from CALMIP (Grant 2011-2013[0851]) and from GENCI-[CINES/IDRIS] (Grant 2011-2013[085008]). J.P. and M.S. are grateful to the following organizations for financial support: the Ministerio de Ciencia e Innovacion (Projects CTQ2011-23156/BQU and CTQ2011-25086/BQU) and the Generalitat de Catalunya (Projects 2014SGR931, 2009SGR528, and 2009SGR637; AIRE-CTP2012 fellowship for J.P.; 2014 ICREA Academia prize for excellence in research funded by the DIUE for M.S.)

An unprecedented type of excited state intramolecular proton transfer in a series of benzo[h]quinoline (BHQ) derivatives substituted at position 10 with strong CH acid character is described using density functional theory/time-dependent density functional theory computational approaches with a hybrid functional and the 6-311++G(d,p) triple- quality basis set. Our results show that for 10-malononitrile-substituted BHQ (2CNBHQ) the excited state intramolecular proton transfer C-H···N reaction is a barrierless process. Calculations also reveal that the reaction profiles of the 4-amino-substituted 2CNBHQ show a large dependence on the polarity of the environment A.J.S., M.K.C., and D.T.G. gratefully acknowledge the Foundation for Polish Science for supporting this work under Project MPD/2010/4 ("Towards Advanced Functional Materials and Novel Devices-Joint UW and WUT International PhD Programme"). This work has been also supported by the Ministerio de Economia y Competitividad (MINECO) of Spain (Project CTQ2011-23156/BQU) and the Generalitat de Catalunya (Project 2014SGR931, Xarxa de Referencia en Quimica Teorica i Computacional, and ICREA Academia 2014 prize for M.S.). A.J.S. gratefully acknowledges the European Social Fund through the Warsaw University of Technology Development Programme, realized by the Center for Advanced Studies

Arsenic contamination of soil and groundwater is a serious problem worldwide. Here we show that anaerobic oxidation of As(III) to As(V), a form which is more extensively and stably adsorbed onto metal-oxides, can be achieved by using a polarized (+497 mV vs. SHE) graphite anode serving as terminal electron acceptor in the microbial metabolism. The characterization of the microbial populations at the electrode, by using in situ detection methods, revealed the predominance of gammaproteobacteria. In principle, the proposed bioelectrochemical oxidation process would make it possible to provide As(III)-oxidizing microorganisms with a virtually unlimited, low-cost and low-maintenance electron acceptor as well as with a physical support for microbial attachment This work was supported by MIUR PRIN 2010-2011 project (grant agreement No 2010JBNLJ7-002). The authors thank the Advanced Centre for Microscopy "P. Albertano" of University of Rome "Tor Vergata" for CLSM analyses. Narcis Pous and Sebastia Puig were supported by a project grant from the Catalan Government (2012 FI-B 00941) and the Spanish Government (CTQ2011-23632). Narcis Pous was also supported by a COST Action ES1202 in the context of Water 2020 (COST-STSM-ECOST-STSM-ES1202-011013-035423)

Several approximations to the third-order reduced density matrices (3-RDM) are applied to compute approximate three-center electron sharing indices (3c-ESI) and average number of three particles (3-AN) for correlated and uncorrelated wave functions with different atomic partition schemes. Exact and approximated 3c-ESI are calculated for a set of molecules with three-center two-electron (3c-2e) and three-center four-electron (3c-4e) bonding. Results show that 3c-2e bonding is associated with positive values of 3c-ESI irrespective of the method of calculation, atomic partition employed, and approximation to the third-order density matrix used. Single-determinant calculations yield negative 3c-ESI values for 3c-4e bonds, whereas the exact CASSCF 3c-ESIs are positive or close to zero. Some approximations to the 3-RDM preserve the negative sign of the 3-ESI for 3c-4e bonds, however they perform poorly on the calculation of 3-AN. The adequacy of the 3-RDM approximation to calculate 3-AN is also analyzed, revealing that Valdemoro's approximation to the 3-RDM is the best approximation while Mazziotti's and natural-orbital based approximations yield the lowest maximum errors The following organizations are thanked for financial support: the Spanish Ministry (MICINN, Project numbers CTQ2011-23156/BQU and CTQ2011-25086/BQU and MINECO, Europa Excelencia project CTQ2013-41236-ERC), the Generalitat de Catalunya (Projects number 2009SGR637, 2014SGR931, 2009SGR528, and Xarxa de Referencia en Quimica Tearica i Computacional), the Marie Curie Career Integration grant PCI09-GA-2011-294240 (E.M.), and the FEDER fund (European Fund for Regional Development) for the Grant UNGI08-4E-003. Support for the research of M. Sola was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. F.F. and M.R-M, acknowledges financial support from the Beatriu de Finds program (AGAUR) for the postdoctoral grant BP_A_00339 (F.F.) and doctoral fellowship FI-DGR2014-00003 (M.R.-M.) Excellent service by the Centre de Serveis Cientifics i Academics de Catalunya (CESCA) is gratefully acknowledged

We have developed a new method to measure the thermal conductivity of powders by differential scanning calorimetry (DSC) that works with masses in amounts as low as tens of mg. The method is based on that used by Camirand to determine the thermal conductivity of materials in the form of thin sheets but introducing a hemispherical pan to contain powders in such a way that the issue of heat transfer is reduced to a one-dimensional problem. The modification of the method was successfully validated on obtaining identical results in determining the thermal conductivity of a commercial silicone with both Camirand"s method and the modified method. We have also tested our method with materials that, in bulk, cover a wide range of thermal conductivities and have performed the experiments with several atmospheres and reference metals. The results are consistent with already published general trends in that they confirm that thermal conductivity of powders is mainly governed by thermal conduction through the surrounding gas This work was partially funded by the Spanish Programa Nacional de Materiales through projects MAT2011-28874-C02-02 and by the Generalitat de Catalunya contract No. 2009SGR-185

High-valent terminal metal-oxygen adducts are hypothesized to be the potent oxidizing reactants in late transition metal oxidation catalysis. In particular, examples of high-valent terminal nickel-oxygen adducts are scarce, meaning there is a dearth in the understanding of such oxidants. A monoanionic NiII-bicarbonate complex has been found to react in a 1:1 ratio with the one-electron oxidant tris(4-bromophenyl)ammoniumyl hexachloroantimonate, yielding a thermally unstable intermediate in high yield (ca. 95%). Electronic absorption, electronic paramagnetic resonance, and X-ray absorption spectroscopies and density functional theory calculations confirm its description as a low-spin (S = 1/2 ), square planar NiIII-oxygen adduct. This rare example of a high-valent terminal nickel-oxygen complex performs oxidations of organic substrates, including 2,6-di-tert-butylphenol and triphenylphosphine, which are indicative of hydrogen atom abstraction and oxygen atom transfer reactivity, respectively This publication has emanated from research supported in part by the European Union (FP7-333948, AMcD), a research grant from Science Foundation Ireland (SFI/12/RC/2278, AMcD), and COST Action CM1305 (ECOSTBio). M.S. acknowledges MINECO (CTQ2011-25086/BQU), DIUE of the Generalitat de Catalunya (2014SGR1202), MICINN (Ministry of Science and Innovation, Spain), the FEDER fund (UNGI08-4E-003) and CESCA. Operation of NSLS X3B is supported by NIH grant P30-EB-009998. The NSLS is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-98CH10886

Aquest mateix article està publicat a l'edició alemanya de la revista 'Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), vol. 127, núm. 9, p. 2767-2771. DOI http://dx.doi.org/10.1002/ange.201410557 Highly enantioselective epoxidation of -substituted styrenes with aqueous H2O2 is described by using a chiral iron complex as the catalyst and N-protected amino acids (AAs) as coligands. The amino acids synergistically cooperate with the iron center in promoting an efficient activation of H2O2 to catalyze epoxidation of this challenging class of substrates with good yields and stereoselectivities (up to 97%ee) in short reaction times We acknowledge group LIPPSO from UdG for providing amino acid samples and A. Riera (IRB) for access to a polarimeter. We acknowledge financial support from the European Research Council (ERC-2009-StG-239910), MINECO of Spain (CTQ2012-37420-C02-01/BQU, CSD2010-00065), and Generalitat de Catalunya (2009SGR637). J.L.-F. thanks MICINN for a RyC contract. X.R. and M.C. thank ICREA-Academia awards

Denitrifying bioelectrochemical systems (d-BES) are a promising technology for nitrate removal from wastewaters. Microbial community monitoring is required to pave the way to application. In this study, for the first time flow cytometry combined with molecular biology techniques is exploited to monitor and determine the structure-function relationship of the microbiome of a denitrifying biocathode. Stable cathode performance at poised potential (-0.32 V vs. Ag/AgCl) was monitored, and different stress-tests were applied (reactor leakage, nitrate concentration, buffer capacity). Stress-tests shifted the reactor microbiome and performance. The monitoring campaign covered a wide range of nitrate consumption rates (from 15 to 157 mg N L-NCC(-1) d(-1)), current densities (from 0 to 25 mA L-NCC(-1)) and denitrification intermediates (nitrite and nitrous oxide consumption rates varied from 0 to 56 mg N L-NCC(-1) d(-1)). The reactor microbiome (composed of 21 subcommunities) was characterized and its structure-function relationship was revealed. A key role for Thiobacillus sp. in the bioelectrochemical reduction of nitrate was suggested, while a wider number of subcommunities were involved in NO2- and N2O reduction. It was demonstrated that different bacteria catalyze each denitrification step in a biocathode. This study contributed significantly to understanding denitrifying biocathodes, paving the way for their knowledge-driven engineering This work was supported by the Spanish Government (CTQ2011-23632, CTQ2014-SGR-1168) and the Helmholtz-Association within the Research Programme Terrestrial Environment. F.H. acknowledges support by the BMBF (Research Award "Next generation biotechnological processes - Biotechnology 2020+") and the Helmholtz-Association (Young Investigators Group). N.P. was supported by the Catalan Government (2012FI-B00941) and the University of Girona (MOB2014-ref22)

Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules We thank the European Research Council (ERC-2011-StG- 277801 to X.R., ERC-2009-StG-239910 to M.C., and ERC- 2013-AdG-339782-NAT_CAT to J.N.H.R.), the Spanish MINECO (Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1, and CTQ2012-32436), and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and PhD grant to C.G.S.)

Aromaticity cannot be measured directly by any physical or chemical experiment because it is not a well-defined magnitude. Its quantification is done indirectly from the measure of different properties that are usually found in aromatic compounds such as bond length equalisation, energetic stabilisation, and particular magnetic behaviour associated with induced ring currents. These properties have been used to set up the myriad of structural-, energetic-, and magnetic-based indices of aromaticity known to date. The cyclic delocalisation of mobile electrons in two or three dimensions is probably one of the key aspects that characterise aromatic compounds. However, it has not been until the last decade that electron delocalisation measures have been widely employed to quantify aromaticity. Some of these new indicators of aromaticity such as the PDI, FLU, ING, and INB were defined in our group. In this paper, we review the different existing descriptors of aromaticity that are based on electron delocalisation properties, we compare their performance with indices based on other properties, and we summarise a number of applications of electronic-based indices for the analysis of aromaticity in interesting chemical problems.

Multi-attribute resource allocation problems involve the allocation of resources on the basis of several attributes, therefore, the definition of a fairness method for this kind of auctions should be formulated from a multi-dimensional perspective. Under such point of view, fairness should take into account all the attributes involved in the allocation problem, since focusing on just a single attribute may compromise the allocations regarding the remainder attributes (e.g. incurring in delayed or bad quality tasks). In this paper, we present a multi-dimensional fairness approach based on priorities. For that purpose, a recurrent auction scenario is assumed, in which the auctioneer keeps track of winner and losers. From that information, the priority methods are defined based on the lost auctions number, the number of consecutive loses, and the fitness of their loser bids. Moreover, some methods contain a probabilistic parameter that enables handling wealth ranking disorders due to fairness. We test our approach in real-data based simulator which emulates an industrial production environment where several resource providers compete to perform different tasks. The results pointed that multi-dimensional fairness incentives agents to remain in the market whilst it improves the equity of the wealth distribution without compromising the quality of the allocation attributes This research project has been partially funded through the BR10/18 Scholarship granted to the first author of the paper. Work developed with the support of the research group SITES awarded with distinction by the Generalitat de Catalunya (SGR 2014-2016) and the MESC project funded by the Spanish MINECO (Ref. DPI2013-47450-C2-1-R)

The undecapeptide KKLFKKILKKL-NH2 (BP16) is a non-toxic cell-penetrating peptide (CPP) that is mainly internalized into cancer cells through a clathrin dependent endocytic mechanism and localizes in late endosomes. Moreover, this CPP is able to enhance the cellular uptake of chlorambucil (CLB) improving its cytotoxicity. In this work, we further explored the cell-penetrating properties of BP16 and those of its arginine analogue BP308. We investigated the influence on the cytotoxicity and on the cellular uptake of conjugating CLB at the N- or the C-terminal end of these undecapeptides. The effect of incorporating the cathepsin B-cleavable sequence Gly-Phe-Leu-Gly in CLB-BP16 and CLB-BP308 conjugates was also evaluated. The activity of CLB was significantly improved when conjugated at the N- or the C-terminus of BP16, or at the N-terminus of BP308. While CLB alone was not active (IC50 of 73.7 to >100 μM), the resulting conjugates displayed cytotoxic activity against CAPAN-1, MCF-7, PC-3, 1BR3G and SKMEL-28 cell lines with IC50 values ranging from 8.7 to 25.5 μM. These results were consistent with the internalization properties observed for the corresponding 5(6)-carboxyfluorescein-labeled conjugates. The presence of the tetrapeptide Gly-Phe-Leu-Gly at either the N- or the C-terminus of CLB-BP16 conjugates further increased the efficacy of CLB (IC50 of 3.6 to 16.2 μM), which could be attributed to its selective release in the lysosomal compartment. Enzymatic assays with cathepsin B showed the release of CLB-Gly-OH from these sequences within a short time. Therefore, the combination of BP16 with an enzymatic cleavable sequence can be used as a drug delivery system for the effective uptake and release of drugs in cancer cells This work was supported by Consolider Ingenio CSD/CSD2010-00065 from MICINN of Spain. We also thank the Catalan DIUE of the Generalitat de Catalunya (2009SGR637). X. R. acknowledges financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1

Thermoelectric generators (TEGs) make use of the Seebeck effect in semiconductors for the direct conversion of heat into electrical energy, being of particular interest for high reliability systems or for waste heat recovery. Although several TEG models can be found in the literature, many of them not offer a theoretical solution because they are based on steady-state solutions or they are assuming fixed parameters as boundary conditions. Consequently, to assess and optimize thermoelectric generators in real applications a numerical transient simulation tool, which takes into account the whole energy system, is mandatory. For that purpose, a new TRNSYS type is developed. This TEG component, which can be used as a design tool, is presented in this paper and validated using experimental data.The results show that the proposed component is able to cope with both thermal and electrical dynamics. The comparison between theoretic and experimental results has approved the reasonability of the new component. The normalized root mean square errors are 3.53% and 2.33% for temperature difference between hot and cold sides and electrical output power, respectively This work has been partially funded by the Generalitat de Catalunya under Grant No. 2009.SGR-374 and the MICINN-FEDER under Grants Nos. FIS-2009-13050 and FIS-2012-31307

Intracranial self-stimulation (SS) in the lateral hypothalamus, a rewarding deep-brain stimulation, is able to improve acquisition and retention of implicit and explicit memory tasks in rats. SS treatment is also able to reverse cognitive deficits associated with aging or with experimental brain injuries and evaluated in a two-way active avoidance (2wAA) task. The main objective of the present study was to explore the potential of the SS treatment to reverse the complete learning and memory impairment caused by bilateral lesion in the lateral amygdala (LA). The effects of post-training SS, administered after each acquisition session, were evaluated on distributed 2wAA acquisition and 10-day retention in rats with electrolytic bilateral LA lesions. SS effect in acetylcholinestaresase (AchE) activity was evaluated by immunohistochemistry in LA-preserved and Central nuclei (Ce) of the amygdala of LA-damaged rats. Results showed that LA lesion over 40% completely impeded 2wAA acquisition and retention. Post-training SS in the LA-lesioned rats improved conditioning and retention compared with both the lesioned but non-SS treated and the non-lesioned control rats. SS treatment also seemed to induce a decrease in AchE activity in the LA-preserved area of the lesioned rats, but no effects were observed in the Ce. This empirical evidence supports the idea that self-administered rewarding stimulation is able to completely counteract the 2wAA acquisition and retention deficits induced by LA lesion. Cholinergic mechanisms in preserved LA and the contribution of other brain memory-related areas activated by SS could mediate the compensatory effect observed This research was supported by an I+D (Mineco) grant (PSI2009-07491) and a Generalitat of Catalunya grant (2009SGR)

This paper presents an analysis of the overestimation bias in common used filtering kernels in the context of photon mapping density estimation. We use the joint distribution of order statistics to calculate the expected value of the estimators of irradiance, and show that the estimator provided by the cone filter is not consistent unless the slope is one (yielding the triangular kernel), and that the Epanechnikov and Silverman kernels are consistent. The Gaussian filter has two different estimation biases: the original normalization constant α underestimates radiance by 46.9 percent, and the use of the th nearest photon reduces this underestimation slightly. We also show that a new normalization constant for the Gaussian filter together with discarding the contribution of the th nearest photon in the Gaussian and cone filter estimators produces new, consistent estimators. The specialized differential filter also benefits from the new estimate This work has been supported by the research projects coded TIN2010-21089-C03-01 and IPT-2011-0885-430000 (Spanish Commission for Science and Technology), by Grant 2009SGR643 (Catalan Government), and by FEDER funding from the European Union