Eight-membered Palladacycles Derived from the Insertion of Olefines into the Pd–C Bond of Ortho-palladated Pharmaceuticals Phenethylamine and Phentermine. Synthesis of Stable Heck-type Intermediates Containing Accessible β-Hydrogens and its Use in the Synthesis of 2-Styryl-phenethylamines, Tetrahydroisoquinolines and Eight-membered Cyclic Amidines

This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/om100738zThe ortho-metalated complexes derived from phenethylamine and phentermine [Pd(C,N-C6H4CH2CR2NH2-2)(μ-X)]2 (R = H, X = Br (A); R = Me, X = Cl (B)) react with olefins giving (1) the product of its insertion into the Pd–C bond, [Pd{C,NCH( R’)CH2C6H4CH2CR2NH2-2}(μ-X)]2 (olefin = CH2=CHR’; R = H, X = Cl, R’ = C(O)Me (1a), CO2Et (1c); R = Me, X = Cl, R’ = C(O)Me (1b), CO2Et (1d)), [Pd{C,NCH( C5H8)CHC6H4(CH2CMe2NH2)-2}(μ-Cl)]2 (olefin = norbornene, C5H8; 1e) or (2) the decomposition products of 1, i.e., Pd(0) and the complexes containing the arylated olefin, trans-[PdX2(NH2CR2CH2C6H4CH=CHPh-2)2] (olefin = styrene; R = H, X = Cl (3f); R = Me, X = Br (3g)). While complexes 1c and 1d can be isolated but decompose in solution to afford Pd(0) and the corresponding complexes 3 (R = H, X = Cl (3c); R = Me, X = Br (3d)), the others are surprisingly stable. Neutral ligands L cleave the bridge of complexes 1 to afford [Pd(C^N)X(L)] (2) (L = 4-methyl-pyridine (pic), NH3, NHEt2, PPh3, tBuNC, XyNC). Complexes 3 react with 1,10-phenanthroline (phen) to give [PdX2(phen)] and the orthovinylated arylalkylamine RCH=CHC6H4CH2CR2NH2-2 (R = H (4f), Me (4g)), which in the case of 3c or 3d can not be isolated as it undergoes an intramolecular hydroamination process to afford the tetrahydroisoquinoline 5c or 5d, respectively. To prepare the tetrahydroisoquinoline 5b, it is necessary to heat a mixture of complex 1b with one equiv of TlOTf. The eight-membered cyclic amidine 7d is obtained from thermal decomposition of complex cis-[Pd{C,N-CH(CO2Et)CH2C6H4CH2CR2NH2-2}(CNXy)2]OTf (8d), prepared by reaction of 2d-5 with TlOTf and XyNC. The amidinium salt 7e-HOTf is formed by refluxing in toluene a mixture of 2e-4 and TlOTf. The crystal structures of compounds 2a·CHCl3, 2b-1, 3 2d-3·1/3CH2Cl2, 2e-4·1/2CHCl3, 3d, 3g, 6 and 7e-HOTf have been determined by X-ray diffraction studies

Non-Query-Based Pattern Mining and Sentiment Analysis for Massive Microblogging Online Texts

Pattern mining has been widely studied in the last decade given its great interest for research and its numerous applications in the real world. In this paper the definition of query and non-query based systems is proposed, highlighting the needs of non-query based systems in the era of Big Data. For this, we propose a new approach of a non-query based system that combines association rules, generalized rules and sentiment analysis in order to catalogue and discover opinion patterns in the social network Twitter. Association rules have been previously applied for sentiment analysis, but in most cases, they are used once the process of sentiment analysis is finished to see which tokens appear commonly related to a certain sentiment. On the other hand, they have also been used to discover patterns between sentiments. Our work differs from these in that it proposes a non-query based system which combines both techniques, in a mixed proposal of sentiment analysis and association rules to discover patterns and sentiment patterns in microblogging texts. The obtained rules generalize and summarize the sentiments obtained from a group of tweets about any character, brand or product mentioned in them. To study the performance of the proposed system, an initial set of 1.7 million tweets have been employed to analyse the most salient sentiments during the American pre-election campaign. The analysis of the obtained results supports the capability of the system of obtaining association rules and patterns with great descriptive value in this use case. Parallelisms can be established in these patterns that match perfectly with real life events.COPKIT Project, through the European Union's Horizon 2020 Research and Innovation Programme 786687Spanish Ministry for Economy and Competitiveness TIN2015-64776-C3-1-RAndalusian Government, through Data Analysis in Medicine: from Medical Records to Big Data Project P18-RT-2947Spanish Ministry of Education, Culture, and Sport FPU18/00150University of Granad

NOFACE: A new framework for irrelevant content filtering in social media according to credibility and expertise

Social networks have taken an irreplaceable role in our lives. They are used daily by millions of people to communicate and inform themselves. This success has also led to a lot of irrelevant content and even misinformation on social media. In this paper, we propose a user-centred framework to reduce the amount of irrelevant content in social networks to support further stages of data mining processes. The system also helps in the reduction of misinformation in social networks, since it selects credible and reputable users. The system is based on the belief that if a user is credible then their content will be credible. Our proposal uses word embeddings in a first stage, to create a set of interesting users according to their expertise. After that, in a later stage, it employs social network metrics to further narrow down the relevant users according to their credibility in the network. To validate the framework, it has been tested with two real Big Data problems on Twitter. One related to COVID-19 tweets and the other to last United States elections on 3rd November. Both are problems in which finding relevant content may be difficult due to the large amount of data published during the last years. The proposed framework, called NOFACE, reduces the number of irrelevant users posting about the topic, taking only those that have a higher credibility, and thus giving interesting information about the selected topic. This entails a reduction of irrelevant information, mitigating therefore the presence of misinformation on a posterior data mining method application, improving the obtained results, as it is illustrated in the mentioned two topics using clustering, association rules and LDA techniques.European Commission 786687Andalusian government FEDER operative program P18-RT-2947 B-TIC-145-UGR18University of Granada's internal plan PPJIB2021-04Spanish Government FPU18/0015

El desarrollo profesional del profesorado ante el actual desarrollo tecnológico

En este artículo presentamos las principales aportaciones de un estudio realizado sobre la utilización de diferentes medios tecnológicos realizada por una muestra de profesores y profesoras universitarias. Entre las categorías que ayudan a entender los usos de dichas herramientas en las prácticas docentes está la finalidad instructiva o formativa de los mismos, las estrategias organizativas utilizadas en los centros para ubicar los medios y, finalmente, la formación y apoyo técnico disponible en las mencionadas instituciones de enseñanza superior.In this article we present the main contributions of a study carried out on the use of different technological means carried out by a sample of university teachers. The instructive or formative purpose of the same ones is among the categories that they help to understand the uses of this tools in the educational practices, the organizational strategies used in the centers to locate the means and, finally, the formation and available technical support in the mentioned higher education institutions

Otras vías de aprendizaje: el reconocimiento de la experiencia profesional en la universidad. El caso de la UNED

It is out of the question that a great source of learning takes place in the field of daily work, in which all professionals solve the functions and tasks that have to confront on a daily basis and based on their training and experience. Recognizing this experience in the Bachelor’s degrees remains as an unresolved issue. But this recognition requires a process of evaluation, supported by reliable, valid and credible methodologies and tools, from which it can be recognized and certified that a professional has acquired a certain level of achievement in the competencies in the context of a particular professional qualification. The results were obtained in 2 editions of the Social Education Degree imparted by UNED in which the recognition of professional experience was addressed.  This article conducts an analysis of descriptive and comparative perspectives between the two editions (2011-12 and 2012-13) to assess the relevance of this process, the quality of the results and the response to this demand. Of the 199 applications in the first round and 222 in the second, it was confirmed that this was a study in which a significant number of students came from the same professional field, with proven experience of more than 9000 hours in an area of social intervention. This reality showed which areas are more demanded, the strengths and weaknesses of these professionals, as well as less consolidated competencies according to the degree, which was taught, etc. This information could enhance the professional development of our students, as it provides key information to sharpen specific competencies in these degrees, to work in a coordinated and collaborative relationship between academic and professional world, as well as to respond to a lawful right of our students.Nadie cuestiona que una fuente de aprendizaje es el propio ámbito de trabajo, en el que todo profesional resuelve las funciones y tareas a las que se enfrenta diariamente a partir de su formación y de su experiencia. Reconocer esta experiencia en las titulaciones de Grado es un tema aún no resuelto. Pero este reconocimiento exige un proceso de evaluación, apoyado en metodologías y herramientas fiables y válidas, a partir del cual se valide que una persona ha adquirido un determinado nivel de logro en unas competencias en el marco de una cualificación profesional determinada. A raíz de los resultados obtenidos en 2 convocatorias dirigidas al reconocimiento de la experiencia profesional en el Grado en Educación Social impartido por la UNED, este articulo lleva a cabo un análisis de carácter descriptivo y en perspectiva comparada, entre ambas ediciones (2011-12 y 2012-13), con el fin de valorar la pertinencia de este proceso y la calidad de los resultados obtenidos. Con una muestra de 421 estudiantes hemos inferido la validez del procedimiento propuesto. Además, esta realidad nos muestra cuáles son las áreas de intervención más demandadas, los puntos fuertes y débiles de estos profesionales, las competencias más y menos consolidadas de acuerdo a la titulación que se imparte, etc. Disponer de estos datos, además de favorecer el desarrollo profesional de nuestros estudiantes, aporta una información clave para perfilar mejor las competencias específicas del título, trabajar de forma coordinada y colaborativa entre el mundo académico y el profesional, a la vez que responder a un derecho de nuestros estudiantes.

Nanostructured Ti thin films by magnetron sputtering at oblique angles

The growth of Ti thin films by the magnetron sputtering technique at oblique angles and at room temperature is analysed from both experimental and theoretical points of view. Unlike other materials deposited in similar conditions, the nanostructure development of the Ti layers exhibits an anomalous behaviour when varying both the angle of incidence of the deposition flux and the deposition pressure. At low pressures, a sharp transition from compact to isolated, vertically aligned, nanocolumns is obtained when the angle of incidence surpasses a critical threshold. Remarkably, this transition also occurs when solely increasing the deposition pressure under certain conditions. By the characterization of the Ti layers, the realization of fundamental experiments and the use of a simple growth model, we demonstrate that surface mobilization processes associated to a highly directed momentum distribution and the relatively high kinetic energy of sputtered atoms are responsible for this behaviourJunta de Andalucía P12-FQM- 2265Ministerio de Ciencia e Innovación CSD2008- 00023, MAT2013-42900-P, MAT2013-40852-R, MAT2014-59772-C2-1, MAT2011- 2908

Insertion of benzyne into the Pd–C bond. Synthesis of unnatural amino acid derivatives by sequential insertion of benzyne and CO: 2,2’-functionalized biaryls containing alkylamino and carboxymethyl substituents. Isolation of stable carbopalladated-benzyne intermediates

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemical Communications, copyright © Royal Society of Chemistry after peer review and technical editing by the publisher. This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/Reaction of ortho-palladated derivatives of phentermine and homoveratrylamine with benzyne allows the synthesis of enlarged eight-membered palladacycles resulting from the insertion of the aryne into the Pd–C bond, which subsequently react with CO, to render unnatural amino acid derivatives

Reactivity toward CO of Eight-Membered Palladacycles Derived from the Insertion of Alkenes into the Pd–C Bond of Cyclopalladated Primary Arylalkylamines of Pharmaceutical Interest. Synthesis of Tetrahydrobenzazocinones, Ortho-Functionalized Phenethylamines, Ureas, and an Isocyanate

This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society, after peer review and technical editing by the publisher.The ortho-metalated complex [Pd{C,N-C6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (1a) derived from homoveratrylamine reacts with ethyl acrylate, methyl vinyl ketone or 2-norbornene to give the dimeric complex arising from the insertion of the alkene into the Pd–C bond, [Pd{C,N-CH(R)CH2C6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (R = CO2Et (2a1), C(O)Me (2a2)) or [Pd{C,N-CH(C5H8)CHC6H2CH2CH2NH2-2,(OMe)2-4,5}(μ-Br)]2 (2a3). Complexes 2a and the phentermine homologues 2b react with CO to afford Pd(0) and (1) tetrahydrobenzazocinones, the heterocycles resulting from CO insertion into the Pd–C bond and C–N coupling, (2) unnatural aminoacid derivatives resulting from CO insertion and the reaction of the obtained acyl complex with the solvent (MeOH), or the product of protonolysis of the Pd–C bond, depending on the nature of the initial cyclopalladated compound or (3) ureas, alone or mixed with an isocyanate, in the presence of a base. Phentermine derivatives 2b react with HCl to give a dinuclear palladium complex [PdCl(μ- Cl)(L)], where L is the amine arising from the protonolysis of the Pd–C bond or the alkyl group resulting from Pd–N bond protonolysis, depending on the nature of the inserted alkene. The crystal structures of some palladium complexes and organic compounds have been determined by X-ray diffraction studies