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This dissertation represents the first formal analysis of the merger clause into the Spanish legal system genuinely conducted from the Spanish legal perspective. By analyzing the application of the merger clause and its legal effects in a system in which it currently lacks regulation and legal practice, a current gap in research will be closed. The analysis of current Spanish law, case law and doctrine clearly demonstrates that the “merger clause” is not only an instrument admissible within the Spanish legal system but is also proven to be an enforceable instrument of interpretation due to its indirect application enshrined in Art. 1282 CC. Accordingly, the legal certainty that the merger clause aims to provide to B2B contracts by integrating the parties’ understandings into the written version and discharging prior statements can still be achieved if Spanish law is chosen to govern the contract, despite the absence of formal regulation of merger clauses in current legislation, particularly the Civil Code.

The recent pandemic has forced most educational institutions to shift to distance learning. Teachers can perceive various non-verbal cues in face-to-face classrooms and thus notice when students are distracted, confused, or tired. However, the students’ non-verbal cues are not observable in online classrooms. The lack of these cues poses a challenge for the teachers and hinders them in giving adequate, timely feedback in online educational settings. This can lead to learners not receiving proper guidance and may cause them to be demotivated. This paper proposes a pragmatic approach to detecting student affect in online synchronized learning classrooms. Our approach consists of a method and a privacy-preserving prototype that only collects data that is absolutely necessary to compute action units and is highly scalable by design to run on multiple devices without specialized hardware. We evaluated our prototype using a benchmark for the system performance. Our results confirm the feasibility and the applicability of the proposed approach.

We investigate the numerical approximation of an elliptic optimal control problem which involves a nonconvex local regularization of the $L^q$-quasinorm penalization (with $q\in(0,1)$) in the cost function. Our approach is based on the \emph{difference-of-convex} function formulation, which leads to first-order necessary optimality conditions, which can be regarded as the optimality system of an auxiliar convex $L^1$-penalized optimal control problem. We consider piecewise-constant finite element approximation for the controls, whereas the state equation is approximated using piecewise-linear basis functions. Then, convergence results are obtained for the proposed approximation. Under certain conditions on the support's boundary of the optimal control, we deduce an order of $h^\frac12$ approximation rate of convergence where $h$ is the associated discretization parameter. We illustrate our theoretical findings with numerical experiments that show the convergence behavior of the numerical approximation

Additional file 1. Supplementary table 1: Risk of Heart Failure admission for the pre- and post-intervention period. Supplementary table 2: Comparison of the number the patients admitted, number of hospital admissions and length of stay between the pre- and post-intervention period. Supplementary table 3: Differences in total costs during the 12 months of follow-up for the pre-intervention and post-intervention groups by subgroups categories.

Methoxycarbonyl-1-phenyl-2-cyclopropylmethyl based derivatives cis-(+)-1a [cis-(+)-MR200], cis-(-)-1a [cis-(-)-MR201], and trans-(±)-1a [trans-(±)-MR204], have been identified as new potent sigma (σ) receptor ligands. In the present paper, novel enantiomerically pure analogues were synthesized and optimized for their σ receptor affinity and selectivity. Docking studies rationalized the results obtained in the radioligand binding assay. Absolute stereochemistry was unequivocally established by X-ray analysis of precursor trans-(+)-5a as camphorsulfonyl derivative 9. The most promising compound, trans-(+)-1d, showed remarkable selectivity over a panel of more than 15 receptors as well as good chemical and enzymatic stability in human plasma. An in vivo evaluation evidenced that trans-(+)-1d, in contrast to trans-(-)-1d, cis-(+)-1d, or cis-(-)-1d, which behave as σ1 antagonists, exhibited a σ1 agonist profile. These data clearly demonstrated that compound trans-(+)-1d, due to its σ1 agonist activity and favorable receptor selectivity and stability, provided an useful tool for the study of σ1 receptors., This work was supported by Research Funding for University (FIR) 2014 project code 108D20.This study was partially supported by the Spanish Ministry of Economy and Competitiveness (grant SAF2016-80540-R), the Junta de Andalucia (grant CTS109) and FEDER funds.

We consider the exact penalization of the incompressibility condition $div(u)=0$ for the velocity field of a Bingham fluid in terms of the $L^1$-norm. This penalization procedure results in a nonsmooth optimization problem for which we propose an algorithm using generalized second-order information. Our method solves the resulting nonsmooth problem by considering the steepest descent direction and extra generalized second-order information associated to the nonsmooth term. This method has the advantage that the divergence-free property is enforced by the descent direction proposed by the method without the need of build-in divergence-free approximation schemes. The inexact penalization approach, given by the $L^2$-norm, is also considered in our discussion and comparison.

As in other research fields, the development of learning analytics is influenced by the networks of researchers that contribute to it. This paper describes one of such networks: the Spanish Network of Learning Analytics (SNOLA). The paper presents the research lines of the members of SNOLA, as well as the main challenges that learning analytics has to address in the next few years as perceived by these researchers. This analysis is based on SNOLA's archival data and on a survey carried out to the current members of the network. Although this approach does not cover all the activity related to learning analytics in Spain, the results provide a representative overview of the current state of research related to learning analytics in this context. The paper describes these trends and the main challenges, among which we can point out the need to adopt an ethical commitment with data, to develop systems that respond to the requirements of the end users, and to reach a wider institutional impact. This research has been co-funded by the National Research Agency of the Spanish Ministry of Science, Innovation and Universities and the Structural Funds (FSE and FEDER) under project grants RED2018-102725-T, TIN2017-85179-C3-1-R, TIN2017-85179-C3-2-R, TIN2017-85179-C3-3-R and TIN2016-80172-R; by FEDER/Castille and Leon Regional Government grant VA257P18; by the Basque Government under grant number IT980-16 and by the Catalan Government under grant number 2017SGR1619. This work has been co-funded by the Madrid Regional Government, through the project e-Madrid-CM (S2018/TCS-4307), the e-Madrid-CM project is also co-financed by the Structural Funds (FSE and FEDER). D. Hernandez-Leo acknowledges the support by ICREA under the ICREA Academia programme.

A total regioselective synthesis of 1,4,5-trisubstituted-1,2,3-triazoles from aryl azides and enaminones is reported. The use of an ionic liquid in the presence of water and trimethylamine is crucial for the progress of the reaction. The process, consisting of a cascade starting with a water-promoted 1,3-dipolar cycloaddition (in agreement with DFT calculations) followed by a base-promoted retro-aza-Michael reaction, shows a completely different reactivity to previously reported base-promoted reactions between enaminones and sulfonyl azides only leading to disubstituted triazoles. Such reactivity, reported herein, allows preparation of trisubstituted triazoles in a complete regioselective way., We thank the Italian Ministry of University and Scientific Research (MIUR) for a doctoral grant and the University of Calabria for financial support. We also acknowledge the MINECO and FEDER Program (Madrid, Spain, project CTQ2016‐76155‐R) and the Government of Aragón (Zaragoza, Spain. Biological & Computational Chemistry Group. E34_17R) cofunded with Feder 2014‐2020 “Constructing Europe from Aragón”.

The diastereoselective 1,3-dipolar cycloaddition between nitrones and enantiomerically pure 2,3-dihydrothiazoles derived from L-cysteine, with different oxidation states at the sulfur atom has been studied experimentally and computationally. The reaction takes place with complete regioselectivity and diastereofacial selectivity. On the other hand, the exo/endo selectivity showed a clear dependence of the oxidation state at the sulfur atom. The computational calculations agree with the experimental findings., This work was supported by the Spanish Ministerio de Economía y Competitividad (MINECO) (project number CTQ2016–76155‐R), by the Fondos Europeos para el Desarrollo Regional (FEDER) and the Gobierno de Aragón (Group E34_R17; Zaragoza, Spain, Biological and Computational Chemistry Group, BCC). J. G.‐V. thanks the Gobierno de Aragón–FSE for a pre‐doctoral Grant.

The seventh edition of the Learning Analytics Summer Institute Spain, LASI Spain 19 was held in Vigo on June 27th and 28th, 2019. Under the main theme of “Learning Analytics in Higher Education”, the conference was organized by Universidade de Vigo, in collaboration with the SNOLA (Spanish Network of Learning Analytics) research network and TELGalicia. LASI Spain 19 is conceived as a platform to catalyze educators, technologists, researchers, enterprise and policymakers around shaping the next generation of learning infrastructures to truly serve the needs now facing the education sector. LASI Spain 19 is part of the Learning Analytics Summer Institute locals; LASI worldwide events,sponsored by SoLAR (Society for Learning Analytics Research), are strategic events that bring the right mix of people together for an intensive ‘summer camp’ that serves as an intellectual and social springboard to accelerate the maturation of learning analytics.

Several types of C-functionalized 4-alkyl-2-aryl-1,2,3,4-tetrahydroquinolines underwent rearrangement of their functional groups to C, with concomitant aromatization, by simple reflux in 1,2-dichlorobenzene. The functional groups that were shown to undergo the C to C migration were –CH=CH-Z (where Z = COEt, CN, NO, COCH, CHOH) and –CH=C(Y)–Z (where Y = CN and Z = COEt or Y = Z = CN). On the other hand, the dimethylhydrazono group failed to migrate under thermal conditions but was shown to undergo a smooth dehydrogenation/C to C rearrangement/ dehydrogenation sequence at room temperature in the presence of DDQ, with a broad scope that includes 4-alkyl-2-aryl- and 2-acyl-1,2,3,4-tetrahydroquinolines. We also report a computational and experimental study of the mechanism of both reactions, which supports an unusual intramolecular aza-ene pathway. The ready availability by this method of 2,3-difunctionalized quinolines allowed the simple preparation of fused heterocyclic systems derived from the pyrrolo[3,4-b]quinoline framework, using both reductive and non-reductive domino processes., We gratefully acknowledge financial support from MINECO (grants CTQ2015‐68630‐R and CTQ‐RTI2018‐097662‐B‐I00, to JCM, and CTQ2016‐76155‐R, to PM) and Universidad Complutense (Ph. D. contract to JC).

En este artículo se pasa revista a las líneas de investigación en torno a la tecnología educativa que se realiza en el grupo de investigación GAST-UC3M del Departamento de Ingeniería Telemática de la Universidad Carlos III de Madrid, en concreto en el laboratorio GRADIENT, que es uno de los tres laboratorios de este grupo de investigación. La descripción se organiza en tres temas: (1) MOOCs, SPOCs y blended learning, (2) analítica del aprendizaje y (3) realidades mixtas (realidad aumentada y realidad virtual).

IBERTRIVA 2019 X Iberian Conference on Tribology – IBERTRIB, XI Iberian Vacuum Conference - RIVA, Seville, Spain,June 26-28, In this contribution, we report the direct growth of graphene structures by plasma-assisted CVD, namely atomically thin films, nanodots and nanorods that present a clean and optimal chemical junction with TiO2 (110) face [1].

Resumen del trabajo presentado al 12th Spanish-Italian Symposium on Organic Chemistry (SISOC), celebrado en Ferrara (Italia) del 2 la 4 de julio de 2018., Human O-GlcNAc transferase (hOGT) is a metal independent Leloir GT that transfers GlcNAc to Ser or Thr residues of intracellular proteins and peptides. hOGT is an essential enzyme for the proliferation of mammalian cells, and is an active actor in several serious illnesses, including Parkinson, Alzheimer and different types of cancer. Two series of glycomimetics of UDP-GlcNAc have been prepared. In the first one (A) the ß-phosphate has been replaced by an alkyl chain, through a S-mediated click-chemistry procedure. In the second family (B) the -phospahte has been replaced by a phosphonate, so the pyrophosphate moiety is conserved. In both cases, the sugar moiety has been replaced by a pyrrolidine ring have been synthesized by using different procedures. Their affinity for hOGT has been evaluated and computationally studied. The binding epitopes of the best ligands have been determined in solution using saturation transfer difference (STD) NMR spectroscopy. Experimental, spectroscopic and computational results are in agreement, pointing out the essential role for binding of the ß-phosphate, and, on the other hand, a great enhancement of the affinity by the hydrophobic groups attached to the pyrrolidine.

Resumen del trabajo presentado al XV Simposio de Jóvenes Investigadores de la Real Sociedad Española de Química – Sigma Aldrich, celebrado en Toledo del 5 al 8 de noviembre de 2018., UDP-GlcNAc and UDP-GalNAc are the most important Leloir substrates employed by glycosyltransferases (GTs). We are interested in two particular GTs: OGT and GalNAc-T2. The human O-GlcNAc transferase (hOGT) is a metal independent Leloir GT that transfers GlcNAc to Ser or Thr residues of intracellular proteins and peptides. hOGT is an essential enzyme for the proliferation of mammalian cells, and is an active actor in several serious illnesses, including Parkinson, Alzheimer and different types of cancer. GalNAc-T2 is an enzyme belonging to the glycosyl transferase family that catalyzes the transfer of N-acetylgalactosamine from the donor substrate UDP-GalNAc to an acceptor hydroxyl group of mucine-type proteins. In the human body it is present in twenty different isoforms and they are correlated to several metabolic disorders. In this communication we will present new synthetic approaches to different Leloir substrates analogues. We have developed new hOGT and GalNAc-T2 inhibitors by replacing the carbohydrate moiety, the pyrophosphate linker or both of them. Biological in vitro activity will be presented through different techniques, such as Kd measurements and NMR. Furthermore, we have justified by computational calculations and simulations the biological activity, obtaining a valuable feedback.

Resumen del póster presentado a la Conferencia bienal Fuerzas y Túnel, celebrada en Jaca (España) del 27 al 29 de junio de 2018., Polyaniline (PANI) has been studied since 1835 because of its interest as inherently conducting polymer due to its wide range of potential applications that range from batteries to biosensors. The interest of PANI lies on its capability to express different properties depending on its nitrogen oxidation state: leucoemeraldine (the fully reduced form), emeraldine (the half-oxidized form), and pernigraniline (the fully oxidized form). There are two conventional synthesis methods, electrochemical processing and chemical oxidative polymerization of aniline in a wet environment. Although doped emeraldine structure present good conductivity, it has been shown that the size, the preparation method and the existence of a metal-polymer interface, influence the physical properties of the final PANI. Here, we present a new route to synthesize 1D oligomers of PANI based on a specific on-surface synthesis process. The synthesis was carried out using p-aminophenol (p-Ap) molecules as building blocks on a Pt(111) single-crystal in a UHV environment. At 200°C p-Ap molecules are activated inducing a shift base reaction resulting in oligomer chains with pernigraniline structure. The mechanism of the chemical reaction was followed by XPS, LT-STM/STS and nc-AFM and confronted with theoretical calculations. XPS show that oxygen is removed from the p-AP molecule resulting in a coupling of the precursors via the nitrogen. STM and nc-AFM reveals that oligomers are formed by ca. 10 molecular precursors. STS shows the presence of two broad unoccupied electronic states around 200 mV and 650 mV above the Fermi level that we are able to resolve spatially. Finally, DFT calculations show that the atomic structure is influenced by the substrate crystallography.

Additional file 1. Mean survival time (days) in the SOFA

The numerical approximation of an optimal control problem with $L^1$-control of a Timoshenko beam is considered and analyzed by using the finite element method. From the practical point of view, inclusion of the $L^1$--norm in the cost functional is interesting in the case of beam vibration model, since the sparsity enforced by the $L^1$--norm is very useful for localizing actuators or control devices. The discretization of the control variables is performed by using piecewise constant functions. The states and the adjoint states are approximated by a \emph{locking free scheme} of linear finite elements. Analogously to the purely $L^2$--norm penalized optimal control, it is proved that this approximation have optimal convergence order, which do not depend on the thickness of the beam.

Resumen del póster presentado al XIII Simposio de Investigadores Jóvenes de la Real Sociedad Española de Química Sigma-Aldrich, celebrado en Logroño del 8 al 11 de noviembre de 2016., During the last years bisubstrate inhibitors are playing a growing role in drug design, finding an intense application in enzymes such as glycosyltransferases. Recently this approach was used to build selective ligands targeting the OGlcNAc transferase (OGT) in which the donor (uridine based), and the acceptor (peptide based) moieties, are covalently linked in a single substrate. However; the synthesis of these ligands usually involves low yield and difficult synthetic pathways. Herein we present an efficient protocol for the synthesis of useful N-Fmoc-protected, uridine-based amino acids; that can be directly employed as building blocks in solid-phase peptide synthesis. Furthermore, these amino acids were functionalized with different linker between the uridine and the amino acidic fragment giving the possibility to play with neutral or coordinating uridine-peptide bridges, making of them a versatile synthetic instrument to build new inhibitors targeting OGT and more uridinebased glycosyltransferases.

Resumen del trabajo presentado a la VII International Conference on Molecular Recognition, celebrada en Zaragoza (España) del 1 al 3 de febrero de 2016., Fungi cell wall remodeling is controlled by the equilibrium between glycoside hydrolases, glycosyltransferases, and transglycosylases. Family 72 glycoside hydrolases (GH72) are ubiquitous in fungal organisms and are known to possess significant transglycosylase activity, producing elongated beta(1-3) glucan chains. Among them are the Gas (in S. cerevisiae), Gel (in A. fumigates) or Phr and Pga (in C. albicans), and all of them with a well conserved catalytic site. The only protein whose structure has been resolved within this family is ScGas2, which will be our model for ligands and inhibitors design. In this communication, they will be presented the design, synthesis and the study of the molecular recognition of novel beta(1-3)glucan-based ligands with ScGas2. To characterize the protein-ligand interactions several techniques were employed, such as saturation transfer difference NMR experiments (STD-NMR), molecular docking, molecular dynamics, non-covalent-interaction calculation (NCI) and X-ray diffraction of protein complexes.

The modes of catalytic action of three squaramide-derived bifunctional organocatalysts have been investigated using DFT methods. The [5+2] cycloaddition between oxidopyrilium ylides and enals has been used as model reaction. Two primary modes are possible for the different catalysts studied. The preference for one mode over the other is due to the possibility of additional favourable π,π-interactions between the H-bond activated pyrilium ylide and an electron-deficient aromatic ring bonded to a squaramide NH-group. The model can be extended to other reactions catalyzed by the same catalysts such as formal [2+2] cycloadditions between nitroalkenes and α,β-unsaturated aldehydes. The computational results are in excellent concurrence with the available experimental reports on the observed total enantioselectivity and differences in diastereoselectivity depending on the substrate and the reaction This work was supported by Spanish MINECO Contracts CTQ2013-44367-C2-1-P (to P.M.) and CTQ2014-52107 (to J.L.V.). We also acknowledge the Government of Aragón (Spain) (Group E-10), the Basque Government (Spain) (IT328-10) and Aarhus University (Denmark) for financial support. We acknowledge the Institute of Biocomputation and Physics of Complex Systems (BIFI) at the University of Zaragoza (Spain) for computer time at clusters Terminus and Memento. D.R.-L. Thanks the Spanish Ministry of Education (MEC) for a predoctoral grant (FPU program).

Cloud technology has provided a set of tools to learners and tutors to create a virtual personal learning environment. As these tools only support basic tasks, users of learning environments are looking for specialized tools to exploit the uncountable learning elements available on the internet. Thus, one of the most common functionalities in cloud-based learning environments is the recommendation of learning elements and several approaches have been proposed to deploy recommender systems into an educational environment. Currently, there is an increasing interest in including affective information into the process to generate the recommendations for the learner; and services offering this functionality on cloud environments are scarce. Hence in this paper, we propose a generic cloud-based architecture for a system that recommends learning elements according to the affective state of the learner. Furthermore, we provide the description of some use cases along with the details of the implementation of one of them. We also provide a discussion on the advantages and disadvantages of the proposal. Work partially funded by the EEE project, “Plan Nacional de I+D+I TIN2011-28308-C03-01”, the “Emadrid: Investigación y desarrollo de tecnologías para el e-learning en la Comunidad de Madrid” project 2009/TIC-1650), and “Consejo Social - Universidad Carlos III de Madrid”. Publicado

This chapter analyzes the different implications of the new MOOC paradigm in assessment activities, emphasizing the differences with respect to other non MOOC educational technology environments and giving an insight about the redesign of assessment activities for MOOCs. The chapter also compares the different assessment activities that are available in some of the most used MOOC platforms at present. In addition, the process of design of MOOC assessment activities is analyzed. Specific examples are given about how to design and create different types of assessment activities. The Genghis authoring tool as a solution for the creation of some types of exercises in the Khan Academy platform is presented. Finally, there is an analysis of the learning analytics features related to assessment activities that are present in MOOCs. Moreover, some guidelines are provided about how to interpret and take advantage of this information. TRUE pub

Resumen del póster presentado al XII Simposio de Investigadores Jóvenes de la Real Sociedad Española de Química Sigma-Aldrich, celebrado en Barcelona del 3 al 6 de noviembre de 2015., Los catalizadores bifuncionales han jugado un papel fundamental en el desarrollo de la organocatálisis enantioselectiva: Como los enzimas, estos catalizadores son capaces de activar (al menos) dos reactivos simultáneamente, mediante interacciones covalentes y no covalentes, consiguiendo en el proceso altas estereoselectividades. El patrón más utilizado en el diseño de nuevos catalizadores es, sin duda, la combinación de un grupo amino (capaz de reaccionar con carbonilos) junto uno o varios grupos capaces de formar puentes de H, típicamente una tiourea. No obstante, recientemente las escuaramidas han emergido como una alternativa a las tioureas como organocatalizadores bifuncionales. En 2012, Jørgensen et al. publicaron los primeros catalizadores derivados de escuaramida y pirrolidina: 1 y 2. En particular, el catalizador 2 demostró una gran eficiencia en la cicloadición enantioselectiva (5+2) ente los enales 3 y 4 y el oxidopirilio‐4-olato 5 mediante activación vía dienamina. Los estudios computacionales llevados a cabo para esclarecer el mecanismo de la reacción, así como el modo de actuación de los catalizadores 1 y 2 serán analizados con el fin de racionalizar la enantio y diastereoselectividad observada.

Resumen del trabajo presentado al XII Simposio de Investigadores Jóvenes de la Real Sociedad Española de Química Sigma-Aldrich, celebrado en Barcelona del 3 al 6 de noviembre de 2015., Se estima que alrededor de 1.200 millones de personas en todo el mundo han sufrido alguna infección fúngica. La mayor parte son poco invasivas, pero algunas especies de Candida o Aspergillus son más peligrosas y llegan a matar entre 1,5 y 2 millones de personas al año (más que la malaria o la tuberculosis). Proponemos un diseño racional de glicomiméticos que tendrían como diana transglicosilasas de la pared celular del hongo. Hasta ahora hemos desarrollado compuestos que funcionan como inhibidores de Saccharomyces cerevisiae Gas2 (ScGas2). Recientemente, se han preparado azidas de β(1-­3) oligosacáridos y varios alquinos con residuos aromáticos. Mediante reacciones click catalizadas por cobre se ha sintetizado una biblioteca de oligosacáridos modificados que han sido estudiados mediante diversas técnicas (STD‐RMN, inhibición enzimática, fluorescencia, cristalografía) tanto en ScGas2 como en enzimas de Aspergillus fumigatus.

Resumen del trabajo presentado al XII Simposio de Investigadores Jóvenes de la Real Sociedad Española de Química Sigma-Aldrich, celebrado en Barcelona del 3 al 6 de noviembre de 2015., GalNAc‐T2 is an enzyme that catalyze the transfer of N-­Acetylgalactosamine from the donor substrate UDP‐GalNAc to the acceptor hydroxyl groups in mucine-‐type proteins. It belongs to a wide family of glycosyltransferase of which twenty isoforms are present in the human body. At the present time, despite the importance of this enzyme, involved in several metabolic disorders; very few binding substrates exists for this family of enzymes and no inhibitors have been reported. Here, we propose a new method to generate a new family of α-C‐glycoside ligands, based on the reactivity of the phosphonate group, miming the natural substrate but suppressing one phosphate function; leading to a new class of non‐too polar and non-­hydrolyzable compounds. We standardize the synthesis on a wide pool of different carbohydrates. Afterwards a docking study confirmed the binding capability of these new molecules with the GalNAc-­T2 enzyme and a biological assay and a crystal structure validated the in-­silico predicted binding capability. This method can be efficiently used to synthetize a wide variety of new compounds, and is easily extendable to different class of molecules and nucleosides to find new glycosyltransferase ligands.

Resumen del póster presentado al XII Simposio de Investigadores Jóvenes de la Real Sociedad Española de Química Sigma-Aldrich, celebrado en Barcelona del 3 al 6 de noviembre de 2015., La reacción de iluros de nitrona con olefinas deficientes en densidad electrónica ha sido estudiada en nuestro grupo de investigación. Esta reacción transcurre a través de un mecanismo por pasos: reacción de adición Michael y posterior ciclación intramolecular de tipo Mannich para proporcionar N-­hidroxipirrolidinas. Con el fin de ampliar este estudio, se ha llevado a cabo la reacción con diversos aldehídos. En este caso, la regioselectividad de la reacción varía en función del sustituyente unido al grupo nitrona (R1). Así, con R1=Arilo el ataque sobre el aldehído se produce a través del carbono del iluro unido al grupo éster, mientras que con R1 =Alquilo, el ataque lo lleva a cabo el átomo de carbono del grupo nitrona. En la comunicación se describen las experiencias realizadas y una propuesta para justificar la regioselectividad observada.

Massive Open Online Courses (MOOCs) have grown up to the point of becoming a new learning scenario for the support of large amounts of students. Among current research efforts related to MOOCs, some are studying the application of well-known characteristics and technologies. An example of these characteristics is adaptation, in order to personalize the MOOC experience to the learner’s skills, objectives and profile. Several educational adaptive systems have emphasized the advantages of including affective information in the learner profile. Our hypothesis, based on theoretical models for the appraisal of emotions, is that we can infer the learner’s emotions by analysing their actions with tools in the MOOC platform. We propose four models, each to detect an emotion known to correlate with learning gains and they have been implemented in the Khan Academy Platform. This article presents the four models proposed, the pedagogical theories supporting them, their implementation and the result of a first user study. pub

We discuss the possibility of a two-dimensional ordered structure formed upon deposition of Si on metal surfaces. We investigate the atomic and electronic structure of the Si-(19×19)R23.4°/Pt(111) surface reconstruction by means of a set of experimental surface-science techniques supported by theoretical calculations. The theory achieves very good agreement with the experimental results and is corroborating beyond any doubt that this phase is a surface alloy consisting of Si3Pt tetramers that resembles a twisted kagome lattice. These findings render unlikely any formation of silicene or germanene on Pt(111) and other transition-metal surfaces., We acknowledge the support by GACR, Grant No. 14-02079S; MSMT Project No. LM2011029; and the Spanish Ministry of Science and Technology Project No. MAT2011-26534. P.M. acknowledges the R. C. Rodes grant.

The Universidad Carlos III de Madrid has been offering several face-to-face remedial courses for freshmen to review or learn concepts and practical skills that they should know before starting their degree programme. During the last two years, our University has adopted MOOC-like technologies to support some of these courses so that a "fipping the classroom" methodology can be applied to a particular small educational context. This paper gathers a list of issues and challenges encountered when using Khan Academy technologies for small private online courses (SPOCs). These issues and challenges include the absence of a single platform that supports all the requirements, the need for integration of different learning platforms, the complexity of the authoring process, the need for an adaptation of gamifcation during the learning process and the adjustment of the learning analytics functionality. In addition, some lessons learned are presented, as well as specifc actions taken in response, where MOOCs do not replace teachers and classrooms for these remedial courses, but improve their effectiveness. This work was partially funded by the EEE project, “Plan Nacional de I+D+i TIN2011-28308-C03-01” and the “eMadrid: Investigación y desarrollo de tecnologías para el e-learning en la Comunidad de Madrid” project (S2009/TIC-1650)”. The last author wishes to acknowledge support from Fundación CajaMadrid to visit Harvard University and MIT in the academic year 2012-13.

This paper presents a study describing the development of an Evaluation Framework (EF) for data competitions in TEL. The study applies the Group Concept Method (GCM) to empirically depict criteria and their indicators for evaluating software applications in TEL. A statistical analysis including multidimensional scaling and hierarchical clustering on the GCM data identified the following six evaluation criteria: 1.Educational Innovation, 2.Usability, 3.Data, 4.Performance, 5.Privacy, and 6.Audience. Each of them was operationalized through a set of indicators. The resulting Evaluation Framework (EF) incorporating these criteria was applied to the first data competition of the LinkedUp project. The EF was consequently improved using the results from reviewers' interviews, which were analysed qualitatively and quantitatively. The outcome of these efforts is a comprehensive EF that can be used for TEL data competitions and for the evaluation of TEL tools in general. The final publication is available at Springer via http://dx.doi.org/10.1007/978-3-319-11200-8_6. EC/FP7/LinkedUp EC/FP7/DURAARK

Trabajo presentado al XXXII Convegno Interregionale delle Sezioni Toscana Umbria Marche Abruzzo della Società Chimica Italiana celebrado en Florencia (Italia) del 1 al 2 de julio de 2013., The ongoning progress in protein crystallography and NMR techniques (e.g. STD) provides increasing importance to the structure-based drug design in the search of new therapeutic agents of interest. Starting from the 3D structure of a transglycosylase new molecules have been designed to be complementary to the binding site as well as in the geometry. In addition to an efficient chemical synthesis, based on stereoselective reactions including dipolar cycloadditions and nucloephilic additions to nitrones as well as as simple glycosylation reactions, a variety of structural studies of the potential inhibitors including docking studies and STD-NMR experiments will be presented.

A full experimental study of the activation energy required for the hitherto unknown neutral 2-aza-Cope rearrangement is presented. A kinetic study of the process showed activation energies in the range of 22.91-24.06 kcal/mol, in agreement with a process operating at moderate temperature (70°C). Calculations at B3LYP/6-311+G(d,p) and M06-2X/6-311+G(d,p) levels of theory considering solvent (dimethyl sulfoxide (DMSO) and toluene) effects (PCM model) predict reaction energy barriers that are in agreement with the values obtained from 1H NMR-based kinetic experiments. Results obtained by using enantiomerically pure substrates demonstrate that the rearrangement takes place with complete transfer of chirality, in contrast to previously described cationic processes. The effects of solvent and acid catalysis, which converts the process into the more common cationic rearrangement, have also been studied. DFT calculations also predict correctly the acceleration of the process under acid catalysis, estimating energy barriers in the range of 16.80-18.57 kcal/mol., The authors thank for support by the Spanish Ministry of Science and Innovation (MICINN) (project number CTQ2010-19606), by the European Union (EU) (FEDER Program) and by the Government of Aragon (Research group E-10, Zaragoza, Spain). A. M. thanks the European Commission and European Social Fund (POR Calabria 2007/2013) for a grant.

Trabajo presentado al 15th JCF Frühjahrssymposium (Congreso de Jóvenes Investigadores de la Sociedad Alemana de Química) celebrado en Berlín (Alemania) del 6 al 9 de marzo de 2013., The [3+2] cycloaddition reaction of olefinic dipolarophiles with 1,3-dipoles, such as nitrile oxides or nitrones, is one of the best known and most widely used method for constructing five-membered heterocycles. Nitrile oxides easily dimerize to furoxans, and the mechanism of the process has been already elucidated. However, the analogous process with nitrones is a rarely reported event witnessed previously in few cases for cyclic nitrones. Recently, the cyclodimerization of several six-membered nitrones was investigated,[3] but only configurational and conformational features of the dimers were studied, without shedding light on the mechanism, which remains in controversy. Especially, because the apparent dimerization process consists in an unfavored thermal [4π+4π] cycloadition reaction, and no information exists to date about the electronic and steric effects on dimerization of nitrones and the nature of the transition states for such a process. In this work, we report DFT studies (both open- and closed-shell) on the dimerization of nitrones, first on a simple model and after on the 2,3,4,5-tetrahydropyridine-1-oxide, using up to the PCM(dichloromethane)/M06–2X/cc–pVTZ level of calculation., D. R.-L. thanks the Spanish Ministry of Education (MED) for a FPU-Predoctoral grant.

Trabajo presentado al 15th JCF Frühjahrssymposium (Congreso de Jóvenes Investigadores de la Sociedad Alemana de Química) celebrado en Berlín (Alemania) del 6 al 9 de marzo de 2013., Transglycosydases are a group of key enzymes in preserving the structure of the cell-wall in most fungi. Therefore, the study of their active site and preparation of inhibitors could lead to the obtention of powerful fungicides which could be active against infectious organisms such as Aspergillus fumigatus or Candida albicans. We were able to study the x-ray crystalline structure of Gas2, a membrane bound enzyme from Saccharomices cerevisae, a fungus that is usually studied in Biochemistry because of its genetical and structural analogies to pathogens like A. fumigatus and C. albicans. Knowing the active site and the optimal substrate for the enzyme, molecular docking studies were carried out to design the target molecules to be synthesized. We have optimized a purification method of β(1,3)-oligosaccharides from commercially available glucans and we have studied the synthesis of cyclic six membered nitrones that can be functionalized with hydrophobic substituents (R) which will be able to fit in a lipophilic cavity close to Gas2 active site. Nowadays, new docking, molecular dynamics and inhibition studies are being carried out to determine the activity as fungicides of the prepared compounds., F. G.-B. thanks the Spanish Council for Scientific Research (CSIC) for a JAE-Predoctoral grant. R. H.-G. thanks the ARAID Foundation for a permanent position.

Trabajo presentado al 15th JCF Frühjahrssymposium (Congreso de Jóvenes Investigadores de la Sociedad Alemana de Química) celebrado en Berlín (Alemania) del 6 al 9 de marzo de 2013., Even though they are not the most understood molecules in biology, it is well known that glycans are a primary class of biomolecules, as important as DNA, RNA, proteins or lipids. For instance, carbohydrates decorate the surface of most cells directing the interactions between them. Therefore, studying the enzymes that synthesize and modify membrane-attached glycans may lead to the understanding of very important biological pathways. Also, by preparing and studying modified sugars to inhibit this enzymes we can achieve potencial antibiotics, fungicides or antitumoral agents. In our laboratory, thanks to the vast experience we have in the chemistry of nitrones, we are developing several methods for the preparation of five and six membered nitrones that can be functionalized and then reduced to give pirrolidines and piperidines, classic inhibitors of glycosidases and transglycosidades. The products obtained are currently being tested in molecular docking, molecular dynamics and inhibition assays., M. G. thanks the Spanish Ministry of Education, Culture and Sports for a FPU Predoctoral grant. F. G.-B. and D. S. are grateful to the Spanish Council for Scientific Research (CSIC) for their JAE Predoctoral grants.

Trabajo presentado al 15th JCF Frühjahrssymposium (Congreso de Jóvenes Investigadores de la Sociedad Alemana de Química) celebrado en Berlín (Alemania) del 6 al 9 de marzo de 2013., Five-membered cyclic nitrones have been demonstrated to be interesting heterocycles and attractive building blocks for the synthesis of a variety of nitrogenated compounds containing a pyrrolidine ring in their structure, many of them of biological interest. Most of the reported syntheses of enantiomerically pure five-membered cyclic nitrones employ natural sugars as starting materials. A different approach was carried out in order to prepare other cyclic nitrones with different substituents, using common reactants such as nitrostyrene. In this work, a new three-step one-pot methodology was developed. The first step is a Michael addition reaction of an aldehyde to a nitroalkene. This is an organocatalytic reaction mediated by a prolinol chiral derivative. This reaction generates two chiral carbons in a γ-nitroaldehyde compound. In the following step, the reduction of the nitro group to hydroxylamine group was done and, in situ, the condensation of the latter one with the aldehyde to yield the nitrone took place. The treatment of the reaction mixture provided alkenyl nitrones (3d) gave spontaneously an intramolecular 1,3-dipolar cycloaddition leading to tricyclic derivatives., D. S. thanks the Spanish Council for Scientific Research (CSIC) for his JAE-predoctoral grant.

Resumen del póster presentado al IX Simposio de Investigadores Jóvenes Real Sociedad Española de Química - Sigma Aldrich celebrado en Zaragoza del 7 al 10 de noviembre de 2012., La adición de indoles a alquenos pobres en electrones, la cual puede ser considerada en muchos aspectos una alquilación tipo Friedel-Crafts, es una reacción clave para la formación de derivados indólicos de interés. A pesar de que la primera versión catalítica enantioselectiva de esta reacción, llevada a cabo con tioureas, se conoce desde hace unos años, el mecanismo de la reacción no ha sido perfectamente establecido aún, debido principalmente a las diversas posibilidades de formación de puentes de hidrógeno que se podrían establecer entre el catalizador tiourea bifuncional y los sustratos de la reacción en el estado de transición. En este trabajo presentamos las conclusiones obtenidas a nivel M06-2X / 6-311G(d,p) del estudio computacional del paso clave de la reacción de adición de indoles a nitroalquenos. se ha estudiado la reacción original en profundidad con el objeto de conocer mejor el papel que juega el catalizador tiourea bifuncional, y se han aplicado los reesultados a la predicción de reactividad-selectividad con derivados tiourea similares., Agradecemos al MICINN la concesión de una beca FPU (D R.-L.) y la financiación de nuestra investigación (CTQ2010-1966-C02-01).

En este artículo se presenta un resumen de las líneas de investigación que se realizan en el Laboratorio Gradient perteneciente al Grupo GAST (Grupo de Aplicaciones y Servicios Telemáticos) del Departamento de Ingeniería Telemática de la Universidad Carlos III de Madrid. La temática principal de investigación es la aplicación de tecnologías para la mejora de la enseñanza y el aprendizaje. El resumen se centra en tres líneas: Personalización del aprendizaje, uso de dispositivos móviles con fines educativos y aplicaciones de Realidad Virtual y Realidad Aumentada en educación.En este artículo se presenta un resumen de las líneas de investigación que se realizan en el Laboratorio Gradient perteneciente al Grupo GAST (Grupo de Aplicaciones y Servicios Telemáticos) del Departamento de Ingeniería Telemática de la Universidad Carlos III de Madrid. La temática principal de investigación es la aplicación de tecnologías para la mejora de la enseñanza y el aprendizaje. El resumen se centra en tres líneas: Personalización del aprendizaje, uso de dispositivos móviles con fines educativos y aplicaciones de Realidad Virtual y Realidad Aumentada en educación. Publicado

Resumen del póster presentado al IX Simposio de Investigadores Jóvenes Real Sociedad Española de Química - Sigma Aldrich celebrado en Zaragoza del 7 al 10 de noviembre de 2012., La reacción de adición aza-Michael es uno de los métodos más importantes para la formación de nuevos enlaces C-N. Este campo ha experimentado un gran auge en los últimos diez años, lográndose notables avances en el área de la organocatálisis asimétrica. La hidrazida es un motivo estructural interesante ya que se encuentra presente en numerosos compuestos heterocíclicos biológicamente activos. Por otra parte, su uso como material de partida resulta particularmente atractivo debido a la dificultad que presenta modular la competitiva reactividad entre los dos grupos aminos que posee en su estructura. En este sentido, queremos dar a conocer los resultados preliminares obtenidos empleando hidrazidas como nucleófilos en la reacción de adición de aza-Michael con nitroalquenos. Se trata de una estrategia pionera para la síntesis de β-nitrohidrazidas quirales basada en el uso de tioureas quirales como organozatalizadores., Agradecemos al Gobierno español la financiación de nuestra investigación (CTQ2010-19606-C02-01 y CTQ2010-20500-C02-01).

Trabajo presentado en la European Geosciences Union, celebrada en Viena del 3 al 8 de abril de 2011.

Resumen del póster presentado al VII Simposio Investigadores Jóvenes de la Real Sociedad Española de Química-Sigma Aldrich celebrado en Valencia del 10 al 12 de noviembre de 2010., Las reacciones tipo Mannich entre derivados de carbonilo enolizables y una variedad de sistemas C=N, han sido ampliamente estudiadas como paso efectivo en la síntesis de compuestos nitrogenados de reconocido interés biológico. Por ello, en los últimos años se han publicado un gran número de reacciones de Mannich directas con iminas como sustratos. Sin embargo, no siempre es posible controlar la regio- y estereoselectividad de la reacción. A pesar de esta limitación, la excepcional versatilidad de esta reacción incita al desafío de superar tales desventajas. En esta comunicación se discutirá el efecto de la adición nucleófila de enolatos de silicio (silil acetales de cetena) y de litio derivados de acetato de metilo, a nitronas quirales no racémicas derivadas de amino ácidos. La aparente reactividad dual del grupo funcional nitrona, isoelectrónico con un anión alilo y un enolato, pero de reactividad bien diferente, parece tener su origen en sus particulares características electrónicas que permiten alterar su reactividad mediante el empleo de reactivos organometálicos y/o ácidos de Lewis (A.L.). El resto sobre el átomo de nitrógeno, introducido a partir del 1,2-aminoalcohol correspondiente, permite la adición estereoselectiva del enolato, actuando como inductor de quiralidad y puede ser eliminado posteriormente, permitiendo la preparación de los compuestos objetivo. Asimismo, se discutirá sobre el posible mecanismo de la reacción y sus implicaciones en la selectividad de la reacción. Cálculos computacionales a nivel CPCM-B3LYP/6-31+G*//B3LYP/6-31G* para la adición de silil acetales de cetena y B3LYP/6-31G* para la adición de enolatos de litio (modelizando el disolvente con moléculas discretas), permiten racionalizar los resultados experimentales observados en base al tipo de reacción y los sustratos quirales empleados.

Resumen del trabajo presentado al VII Simposio Investigadores Jóvenes de la Real Sociedad Española de Química-Sigma Aldrich celebrado en Valencia del 10 al 12 de noviembre de 2010., El diseño de moléculas estructuralmente cada vez más complejas y con actividades biológicas interesantes ha hecho esencial la búsqueda de nuevos procesos eficientes en síntesis orgánica. Dado el interés creciente por llevar a cabo química más sostenible, la Química Orgánica cada vez más está cambiando hacia un área más ecológica y en este sentido, el desarrollo de nuevos métodos de síntesis enantioselectiva y de alto rendimiento mediante procesos de naturaleza catalítica, constituye todo un reto para este campo. En este contexto, la organocatálisis enantioselectiva, se ha convertido en los últimos 10 años en una alternativa complementaria a los procedimientos más clásicos de catálisis mediada por especies metálicas y enzimáticas. Uno de los grandes campos dentro de esta interesante e importante área, es el de la química desarrollada empleando catalizadores de tipo tiourea quirales con los que poseemos una gran experiencia. En esta comunicación queremos presentar algunos de nuestros trabajos, pioneros en el momento de su publicación, y que se desarrollaron empleando por primera vez este tipo de organocatalizadores, el último de los cuales se muestra en el siguiente esquema.

El e-learning es un factor clave en la actual sociedad de la información. El poder habilitar las mejores prácticas de enseñanza a través de las tecnologías de la información para posibilitar un aprendizaje más efectivo para los alumnos, así como proporcionar un sencillo y flexible acceso a todas las potencialidades para los profesores, al mismo tiempo que se maximiza la eficiencia y adecuación de su implementación usando las tecnologías de la información, supone un reto en el que hay que tener en cuenta multitud de variables y factores. Ello engloba las teorías tradicionales de aprendizaje en aula, pero también muchos nuevos aspectos que surgen o se enfatizan por el uso de las tecnologías de la información. Numerosas investigaciones se han llevado a cabo para el avance en esta materia. Tales investigaciones se centran por lo general en aspectos específicos, pero no obstante creemos también necesaria una teoría de modelado del e-learning integradora de diferentes variables y aspectos involucrados para poder comprender mejor esta materia tan compleja, así como cubrir ciertas carencias específicas de modelado para la conformación de dicha teoría. En esta tesis se proporciona una teoría de modelado del e-learning, que incluye una visión global sobre qué modelar y cómo hacerlo, las interrelaciones entre diferentes conceptos y elementos, una visión ideal sobre el e-learning, una propuesta de proceso de desarrollo en ciclo de vida, y un plan general de evaluación de los diferentes aspectos involucrados (llevándolo a la práctica con la valoración de diferentes funcionalidades de sistemas de gestión del aprendizaje). Además, como parte de esta teoría, se han analizado las relaciones entre las funcionalidades de sistemas de gestión del aprendizaje y los est´andares de e-learning actuales, se ha definido un nuevo modelo que extiende UML y otro basado en la especificación IMS-CP (Content Packaging) para el modelado de cursos completos en sistemas de gestión del aprendizaje, se ha contribuido en varias herramientas de autor que pueden verse como modelados en lenguaje natural de diferentes aspectos del e-learning de forma que sean sencillos de utilizar por profesores sin grandes conocimientos tecnológicos, y se ha creado una nueva teoría de reglas de adaptación personalizadas que son atómicas, reusables, intercambiables, e interoperables. Finalmente, en la parte de arquitecturas, se ha definido una nueva arquitectura que permite combinar sistemas de tutoría inteligente existentes con técnicas de Web semántica, explicando sus elementos, relaciones, retos, y los diferentes criterios de diseño, ofreciendo algunas guías para la toma de decisiones cuando diferentes soluciones de implementación son posibles. Esta arquitectura definida, permite incorporar las ventajas de la Web semántica dentro de los sistemas de tutoría inteligente. Adicionalmente, esta teoría se ha aplicado en profundidad a un caso concreto, que es la provisión de pistas en el aprendizaje basado en problemas a través de ordenador. La idea general de la provisión de pistas consiste en ofrecer una ayuda al estudiante para la resolución de ciertas tareas. Este es un aspecto muy relevante que ha sido abordado en diversos estudios desde diferentes puntos de vista. No obstante, debido a su complejidad y número de variables involucradas, quedan diversos aspectos por estudiar. Esta tesis contribuye en algunos de esos aspectos sobre las pistas a través de ordenador. En primer lugar, se ha definido una nueva especificación de pistas para el aprendizaje basado en problemas, que recopila funcionalidades de otros sistemas del estado del arte, pero también incluye nuevas funcionalidades basadas en nuestras propias ideas, dando una justificación pedagógica de cada aspecto. En relación con esta especificación de pistas, se ha establecido un mapeo a XML, y otra representación a UML. Así mismo, se ha diseñado una herramienta de autor que permite a profesores sin grandes conocimientos tecnológicos crear los ejercicios con pistas de acuerdo con la especificación. Para poner en práctica este modelo de pistas, se ha implementado un módulo reproductor de pistas programado en python como una extesión al tutor inteligente XTutor. Este reproductor permite desplegar ejercicios con pistas que cubren los casos de la nueva especificación definida y que quedan disponibles vía Web para su uso por parte de los alumnos. También se ha diseñado una herramienta de competición innovadora para aprovechar la motivación junto con el aprendizaje basado en problemas. Para la evaluación del modelo de pistas definido, se han realizado diferentes experiencias en un total de tres asignaturas, en una de ellas durante cuatro ediciones. Se han tomado datos cuantitativos y cualitativos globales de la herramienta y las interacciones de los alumnos, se ha comparado el incremento de aprendizaje con respecto a un sistema de evaluación sin pistas, y con respecto a tutores humanos generando pistas. Los resultados sobre estos aspectos concluyen un efecto positivo del modelo de pistas y del sistema reproductor de pistas implementado. Además, hemos analizado qué estrategias de provisión pistas producen mayores incrementos de aprendizaje, cómo diferentes técnicas de provisión de pistas producen diferentes comportamientos de los alumnos, y la opini´on de los alumnos con respecto a diferentes estrategias de pistas del modelo. Estas contribuciones, las cuales son explicadas en la tesis, permiten concluir sobre qué técnicas de pistas pueden ser mejor y sobre las necesidades de adaptación de los sistemas. Finalmente, en relación con la evaluación, proponemos un modelo inicial para utilizar el sistema de pistas como una herramienta para ayudar en la evaluación de contenidos y alumnos. A pesar de que existen algunas soluciones que aplican técnicas de Web semántica para lograr la adaptación de algunos aspectos en e-learning debido a las ventajas que presenta, sin embargo el dominio de la provisión de pistas adaptativas usando técnicas de Web semántica no había sido explorado. En esta tesis se contribuye con una nueva solución para la generación de pistas adaptativas personalizadas usando técnicas deWeb semántica. Para ello, se ha implementado una instancia de la arquitectura general propuesta en la teoría de modelado del e-learning, que en este caso concreto combina el tutor inteligente XTutor con la extensión del módulo de pistas implementado, y el razonador deWeb semántica CWM. Las reglas adaptativas y personalizadas de pistas se han articulado en base a la teoría global de reglas adaptativas, y en base a las mejores prácticas. Además, como parte de las contribuciones, hemos definido nuevas ontologías en este marco sobre usuarios, problemas, pistas, conceptos, etc. de forma que definan un marco de datos sobre el que se pueda realizar inferencias mediante las reglas definidas ejecutándose en el razonador CWM. Con todo ello, se aporta una solución a la integración de la Web semántica en sistemas de pistas para aprendizaje basado en problemas, logrando todas las ventajas de la Web semántica. _____________________________________________, The e-learning is a key factor in the present information society. The fact of being able to enable the best teaching practices using the information technologies in order to make possible a more effective students0 learning, as well as to provide an easy and flexible access to all the potentialities for teachers, at the same time that the efficiency and adjustment of its implementation is maximazed using the information technologies, means a challenge in which a lot of variables and factors must be taken into account. It includes the traditional classroom learning theories, but also a lot of new issues that arise or emphasize because of the use of the information technologies. There have been many researches for the advance of this topic. Such researches usually focus on specific e-learning issues, but nevertheless we think there is a need of a theory of the e-learning modeling which integrates different aspects and variables involved in order to be able to understand better this complex topic, as well as to cover certain specific modeling lacks for formulating such theory. In this thesis, we provide a theory of the e-learning modeling, which includes a global view about what to model and how to do it, the relationships among different concepts and elements, an ideal e-learning view, a proposal of an e-learning process development, and a general plan for the evaluation of the different aspects involved (with a practical example, rating the importance of different learning management system functionalities). In addition to it, as part of this theory, we have analyzed the relationships between different learning management systems functionalities and present e-learning standards, we have defined a new model which extends UML and another one based on the IMS-CP (Content Packaging) specification for the modeling of complete courses within learning management systems, we have made contributions regarding several authoring tools which can be seen as natural language modelings about different e-learning aspects in a way that are easy to use by teachers without high technological expertise, and we have created a new theory of personalized adaptive rules which are atomic, reusable, interchangeable, and interoperable. Finally, regarding the architecture topic, we have defined a new architecture that permits combining existing intelligent tutoring systems with semantic Web techniques, explaining its elements, relationships, challenges, and the different design criterions, offering some guidelines to make decisions when different implementation solutions are possible. This defined architecture permits to introduce the semantic Web advantages within the intelligent tutoring systems. In addition to it, we have applied this theory deeply to a specific case, which is the computer based generation of hints in problem based learning. The general idea under the generation of hints consists of offering some help to the student for solving certain tasks. This is a relevant issue that has been studied by different researches from different points of view. Nevertheless, because of its complexity and high number of variables involved, there are several issues to study. This thesis contributes in some of these computer based hinting issues. First of all, we have defined a new specification of hints for problem based learning, which compiles functionalities from other hinting systems of the state of the art, but it also includes new functionalities based on our new ideas, giving a pedagogical justification for each aspect. Regarding this specification of hints, we have defined an XML binding, and another UML representation. Moreover, we have designed an authoring tool which permits teachers without high technological expertise to create exercises with hints according to the specification. In order to put into practice this hinting model, we have implemented a hinting player module programmed in python as an extension of the XTutor intelligent tutoring system. This hinting software player allows loading and executing exercises with hints covering the different cases of the new defined hinting specification, and these exercises with hints are made available via Web for the students. Furthermore, we have designed an innovative competition tool to take advantage of motivation together with problem based learning. In order to evaluate the defined hinting model, we have performed different experiences in a total of three courses, in one of them during four editions.We have taken quantitative and qualitative global data from the implemented hinting system and the students0 interactions, we have compared the learning gains of the hinting system with respect to an assessments0 system without hinting functionalities, and with respect to human tutors providing hints. The results about these aspects conclude a positive effect of the hinting model and the implemented hinting player system. In addition, we have analyzed which hinting strategies produce better learning gains, how different hinting techniques produce different students’behaviors, and the students0 opinions about different hinting strategies of the model. These contributions, which are explained in the thesis, permit to conclude about which hinting techniques might be better and about the adaptation needs of the systems. Finally, regarding the evaluation, we propose an initial model to use the hinting system as a tool to help in the evaluation of contents and students. Although there exist some solutions to apply semantic Web techniques to achieve adaptation of some e-learning aspects because of its advantages, however the domain of the provision of adaptive hints using semantic Web techniques had not been explored. This thesis contributes with a new solution for the generation of personalized adaptive hints using semantic Web techniques. To do so, we have implemented an instance of the general architecture we proposed in the theory of the e-learning modeling, combining in this specific case the XTutor intelligent tutoring system with its hinting module extension that we implemented, and the CWM semanticWeb reasoner. The adaptive and personalized hinting rules have been created based on the global theory of adaptive rules, and on best practices. In addition, as part of the contributions, we have defined new ontologies in this framework for users, problems, hints, concepts, etc. so that they define a data framework in order to make inferences based on defined rules executing within the CWM reasoner. With all of this, we provide a solution for integrating the semantic Web with hinting systems in problem based learning, achieving all the advantages of the semantic Web.

Fecha de solicitud: 11-06-2009.- Titular: Consejo Superior de Investigaciones Científicas (CSIC), The invention relates to a method for the selective hydrogenation of substituted nitroaromatic compounds, comprising the hydrogenation of the corresponding nitro compound using a supported or encapsulated metallic catalyst, said metal being selected from Ni, Pt, Ru, Pd, Rh, Ir, Fe, Cu, Ag and combinations of same, in which the catalyst can also include a modifying metal., La invención se refiere a un método para la hidrogenación selectivo de compuestos nitroaromatic sustituidos, comprendiendo la hidrogenación del compuesto correspondiente del nitro usando un catalizador metálico soportado o encapsulado, dijo el ser del metal seleccionado del Ni, de la pinta, del Ru, del paladio, del derecho, de Ir, fe, Cu, AG y las combinaciones de mismo, en las cuales el bote del catalizador también incluye un metal que modifica.

[EN] The present invention relates to a procedure for the selective hydrogenation of nitrocycloalkanes, substituted or not, comprising carrying out a catalytic hydrogenation of said compounds utilising a catalyst comprising at least one metal, being Pt, supported on titanium oxide, iron oxide, cerium oxide, alumina, carbon, active carbon, magnesium oxide, zirconium oxide, silica, silicic acid, lanthanum oxide, zinc oxide, calcium carbonate, calcium phosphate, calcium sulphate, barium sulphate and combinations thereof. Furthermore said catalyst may comprise a modifier metal selected fkom one or more alkaline or alkaline earth metals., [ES] La presente invención se refiere a un procedimiento para Ia hidrogenación selectiva de nitrocicloalcanos, sustituidos o no, que comprende llevar a cabo una hidrogenación catalítica de dichos compuestos utilizando un catalizador que comprende, al menos un metal que es Pt, soportado sobre óxido de titanio, óxido de hierro, óxido de cerio, alúmina, carbón, carbón activo, óxido de magnesio, óxido de zirconio, sílice, ácido silícico, óxido de lantano, óxido de zinc, carbonato cálcico, fosfato cálcico, sulfato cálcico, sulfato de bario y combinaciones de los mismos. Además dicho catalizador puede comprender un metal modificador seleccionado entre uno o más metales alcalinos o alcalinotérreos., Universidad Politécnica de Valencia (UPV), Consejo Superior de Investigaciones Científicas (España), A1 Solicitud de patentes con informe sobre el estado de la técnica

The well-known problem of state space explosion in model checking is even more critical when applying this technique to programming languages, mainly due to the presence of complex data structures. One recent and promising approach to deal with this problem is the construction of an abstract and correct representation of the global program state allowing to match visited states during program model exploration. In particular, one powerful method to implement abstract matching is to fill the state vector with a minimal amount of relevant variables for each program point. In this paper, we combine the on-the-fly model-checking approach (incremental construction of the program state space) and the static analysis method called influence analysis (extraction of significant variables for each program point) in order to automatically construct an abstract matching function. Firstly, we describe the problem as an alternation-free value-based mu-calculus formula, whose validity can be checked on the program model expressed as a labeled transition system (LTS). Secondly, we translate the analysis into the local resolution of a parameterised boolean equation system (PBES), whose representation enables a more efficient construction of the resulting abstract matching function. Finally, we show how our proposal may be elegantly integrated into CADP, a generic framework for both the design and analysis of distributed systems and the development of verification tools., Comment: Submitted to an international 2006 conference

Tras definir los procedimientos de aprendizaje se analiza: el tratamiento de los procedimientos de aprendizaje en el marco curricular, el aprendizaje de los procedimientos, la enseñanza de los procedimientos, la evaluación de los procedimientos y se presentan propuestas de organización de los procedimientos y los principales procedimientos en Ciencias Sociales, Ciencias Naturales, Matemáticas y Lenguaje. Extremadura ESP