Do one‐step mechanisms always involve simultaneous evolution of electron density? QTAIM/IQA analysis of the Curtius rearrangement

The Curtius rearrangement reaction is studied by using quantum theory of atoms in molecules (QTAIM) analysis of the electron density and the interacting quantum atoms (IQA) formalism. Although the rearrangements take place in one stage, two phases are distinguished when the rearranged atom is H: the first one corresponds to the separation of N2, and the second one to the N‐H/C‐H bond rearrangement. The transition state (TS) for the reaction does not represent an intermediate between reagent and product for the migration but for the isolation of the N2 molecule. When the migration is undergone by a fluorine atom, no electronic phases can be distinguished and the process is really concerted. As the migration happens closer to the TS, the TS is more similar to the product. The IQA analysis reveals different electron density evolutions for H and F migrations, and the scarce relevance (in terms of energy) of the point where BCPs appear or disappear.Xunta de Galicia | Ref. ED431C 2019/2

Risk prediction and assessment of intervention, re-education and reintegration of juvenile offenders: development and psychometric properties of the PREVI-A

This paper proposes and analyzes the psychometric properties of the PREVI-A scale (Predicción del Riesgo y Valoración de la Intervención en la ARRMI—-Risk Prediction and Intervention Assessment in the ARRMI). It describes the process of item development, the factorial structure of the scale, reliability, evidence of validity and diagnostic performance with regard to recidivism risk in juvenile offenders. The sample was made up of 212 juvenile offenders held at detention centers run by the Madrid Agency for Reeducation and Reintegration of Juvenile Offenders, a regional government body. Statistical analyses were used to corroborate the theoretical factorial structure of the PREVI-A, which consists of six risk/protection dimensions (64 items) based on the Risk- Needs-Responsivity Model, and to obtain empirical support for the reliability and validity of PREVI-A as a tool to assess the risk of recidivism by juvenile offenders in Spai

Hybrid Modeling of Deformable Linear Objects for Their Cooperative Transportation by Teams of Quadrotors

his paper deals with the control of a team of unmanned air vehicles (UAVs), specifically quadrotors, for which their mission is the transportation of a deformable linear object (DLO), i.e., a cable, hose or similar object in quasi-stationary state, while cruising towards destination. Such missions have strong industrial applications in the transportation of hoses or power cables to specific locations, such as the emergency power or water supply in hazard situations such as fires or earthquake damaged structures. This control must be robust to withstand strong and sudden wind disturbances and remain stable after aggressive maneuvers, i.e., sharp changes of direction or acceleration. To cope with these, we have previously developed the online adaptation of the proportional derivative (PD) controllers of the quadrotors thrusters, implemented by a fuzzy logic rule system that experienced adaptation by a stochastic gradient rule. However, sagging conditions appearing when the transporting drones are too close or too far away induce singularities in the DLO catenary models, breaking apart the control system. The paper’s main contribution is the formulation of the hybrid selective model of the DLO sections as either catenaries or parabolas, which allows us to overcome these sagging conditions. We provide the specific decision rule to shift between DLO models. Simulation results demonstrate the performance of the proposed approach under stringent conditions.This work has been partially supported by spanish MICIN project PID2020-116346GB-I00, and project KK-2021/00070 of the Elkartek 2021 funding program of the Basque Government. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 777720

A Hybrid Control Approach for the Swing Free Transportation of a Double Pendulum with a Quadrotor

In this article, a control strategy approach is proposed for a system consisting of a quadrotor transporting a double pendulum. In our case, we attempt to achieve a swing free transportation of the pendulum, while the quadrotor closely follows a specific trajectory. This dynamic system is highly nonlinear, therefore, the fulfillment of this complex task represents a demanding challenge. Moreover, achieving dampening of the double pendulum oscillations while following a precise trajectory are conflicting goals. We apply a proportional derivative (PD) and a model predictive control (MPC) controllers for this task. Transportation of a multiple pendulum with an aerial robot is a step forward in the state of art towards the study of the transportation of loads with complex dynamics. We provide the modeling of the quadrotor and the double pendulum. For MPC we define the cost function that has to be minimized to achieve optimal control. We report encouraging positive results on a simulated environmentcomparing the performance of our MPC-PD control circuit against a PD-PD configuration, achieving a three fold reduction of the double pendulum maximum swinging angle.This work has been partially supported by FEDER funds through MINECO project TIN2017-85827-P, and project KK-202000044 of the Elkartek 2020 funding program of the Basque Government. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 777720

Above-ground biomass estimation from LiDAR data using random forest algorithms

Random forest (RF) models were developed to estimate the biomass for the Pinus radiata species in a region of the Basque Autonomous Community where this species has high cover, using the National Forest Inventory, allometric equations and low-density discrete LiDAR data. This article explores the tuning for RF hyperparameters, obtaining two models with an R2 higher than 0.7 using 2-fold cross-validation. The models selected were applied in Orozko, a municipality with more than 5000 ha of this species, where the model predicts a biomass of 1.06–1.08 Mton, which is between 16–18 % higher than the biomass predicted by the Basque Government.The work reported in this paper was partially supported by FEDER funds for the MINECO project TIN2017-85827-P and project KK-202000044 of the Elkartek 2020 funding program of the Basque Government. Additional support comes from grant IT1284-19 of the Basque Autonomous Community

Biogenic synthesis of metal nanoparticles using a biosurfactant extracted from corn and their antimicrobial properties

A new and promising biosurfactant extracted from corn steep liquor has been used for the green synthesis of gold and silver nanoparticles (NPs) in a one-step procedure induced by temperature. Most of the biosurfactants proposed in the literature are produced by pathogenic microorganisms; whereas the biosurfactant used in the current work was extracted from a liquid stream, fermented spontaneously by lactic acid bacteria, which are generally recognized as safe (GRAS) microorganisms. The reduction of a gold precursor in the presence of a biosurfactant gives rise to a mixture of nanospheres and nanoplates with distinct optical features. Moreover, the growth of nanoplates can be promoted by increasing the reaction temperature to 60 °C. In the case of silver, the biosurfactant just induces the formation of pseudo-spherical NPs. The biosurfactant plays a key role in the reduction of the metal precursor, as well as in the stabilization of the resulting NPs. Furthermore, the antimicrobial activity of the resulting silver colloids has been analyzed against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. The biosurfactant stabilized NPs slightly increased the inhibition of E. coli in comparison with citrate stabilized Ag NPs. The use of this biosurfactant extracted from corn steep liquor for the synthesis of metal NPs contributes to enhancing the application of green technologies and increasing the utilization of clean, non-toxic and environmentally safe production processes. Therefore, it can help to reduce environmental impact, minimize waste and increase energy efficiency in the field of nanomaterials.This work was supported by the Spanish MINECO (MAT2013-45168-R and MAT2016-77809-R) and Fundación Ramón Areces. Also, Xanel Vecino gratefully acknowledges her post-doctoral grant (SFRH/BPD/101476/2014) supported by the Portuguese Foundation for Science and Technology (FCT, Portugal).info:eu-repo/semantics/publishedVersio

Biogenic synthesis of metal nanoparticles using a biosurfactant extracted from corn and their antimicrobial properties

A new and promising biosurfactant extracted from corn steep liquor has been used for the green synthesis of gold and silver nanoparticles (NPs) in a one-step procedure induced by temperature. Most of the biosurfactants proposed in the literature are produced by pathogenic microorganisms; whereas the biosurfactant used in the current work was extracted from a liquid stream, fermented spontaneously by lactic acid bacteria, which are “generally recognized as safe” (GRAS) microorganisms. The reduction of a gold precursor in the presence of a biosurfactant gives rise to a mixture of nanospheres and nanoplates with distinct optical features. Moreover, the growth of nanoplates can be promoted by increasing the reaction temperature to 60 °C. In the case of silver, the biosurfactant just induces the formation of pseudo-spherical NPs. The biosurfactant plays a key role in the reduction of the metal precursor, as well as in the stabilization of the resulting NPs. Furthermore, the antimicrobial activity of the resulting silver colloids has been analyzed against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. The biosurfactant stabilized NPs slightly increased the inhibition of E. coli in comparison with citrate stabilized Ag NPs. The use of this biosurfactant extracted from corn steep liquor for the synthesis of metal NPs contributes to enhancing the application of green technologies and increasing the utilization of clean, non-toxic and environmentally safe production processes. Therefore, it can help to reduce environmental impact, minimize waste and increase energy efficiency in the field of nanomaterials. View Full-Text Keywords: biosurfactant; corn stream; silver NPs; gold NPs; green synthesis.Ministerio de Economía y Competitividad | Ref. MAT2013-45168-RMinisterio de Economía y Competitividad | Ref. MAT2016-77809-RFundação para a Ciência e a Tecnologi

Polyethylene microplastics do not increase bioaccumuation or toxicity of nonylphenol and 4-MBC to marine zooplankton

Global production of synthetic polymers, led by polyethylene (PE), rose steadily in the last decades, and marine ecosystems are considered as a global sink. Although PE is not biodegradable, in coastal areas it fragments into microplastics (MP) readily taken up by biota, and have been postulated as vectors of hydrophobic chemicals to marine organisms. We have tested this hypothesis using two organisms representative of the marine plankton, the holoplanktonic copepod Acartia clausi, and the meroplanktonic larva of the Paracentrotus lividus sea-urchin, and two model chemicals with similar hydrophobic properties, the 4-n-Nonylphenol and the 4-Methylbenzylidene-camphor used as plastic additive and UV filter in cosmetics. Both test species actively ingested the MP particles. However, the presence of MP never increased the bioaccumulation of neither model chemicals, nor their toxicity to the exposed organisms. Bioaccumulation was a linear function of waterborne chemical disregarding the level of MP. Toxicity, assessed by the threshold (EC10) and median (EC50) effect levels, was either independent of the level of MP or even in some instances significantly decreased in the presence of MPs. These consistent results challenge the assumption that MP act as vectors of hydrophobic chemicals to planktonic marine organismsThis study has received funding by the Spanish Government (MINECO/AEI) through Projects PCIN-2015-187-C03-03 (JPI Oceans EPHEMARE), PCIN-2015-170-C02-01 (JPI Oceans BASEMAN), CTM2016-77945-C3, and CTM2017-84763-C3-2-R, by Xunta de Galicia through “Program of Consolidation and structuring of competitive research groups in the University system of Galicia” (Refs GRC2013-004, ED431C 2017/28 and ED431C 2017/36), and by the European Union through the European Regional Development Fund (ERDF). N. S.-G. was granted with a postdoctoral fellowship Mod. A (2016) by Axencia Galega de Innovación (GAIN), Xunta de GaliciaS