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Gold-Catalyzed Reactions of 2-Alkynyl-1-indolyl-1,2-diols with Thiols: Stereoselective Synthesis of (Z)-α-Indol-3-yl α-(2-Thioalkenyl) Ketones
Get PDFPropargylic glycols, 2-alkynyl-1-(indol-3-yl)-1,2-diols, react with thiols undergoing a complex but
selective gold-catalyzed transformation that gives rise to α-indol-3-yl α-((Z)-2-thioalkenyl) ketones. The
sequence is triggered by the regioselective thiolation of indolyl diols followed by an attack of the sulfur instead
of the indole over the activated alkyne. The final compounds are obtained in remarkably high yields and arise
from simple starting materials such as indolyl acyloins, ethynyl magnesium bromide and thiols.Ministerio de Ciencia e Innovación
and FEDER (CTQ2016-75023-C2-1-P and PID2020-
115789GB-C21), and Junta de Castilla y León and FEDER
(BU291P18 and BU049P20) for financial support. The project
leading to these results has received funding from “la Caixa”
Foundation, under the Agreement LCF/PR/PR18/51130007>
(CAIXA-UBU001). F. M.-L., N. V. and S. S.-P. thank Junta de
Castilla y León (Consejería de Educación) and Fondo Social
Europeo for predoctoral (F. M.-L. and N. V) and postdoctoral
(S. S.-P.) contracts, respectively
Synthesis and oxidative stability of monoacylglycerols containing polyunsaturated fatty acids by enzymatic glycerolysis in a solvent-free system
Get PDFMonoacylglycerols (MAG) containing polyunsaturated fatty acids (PUFA) have been synthesized by glycerolysis of anchovy oil using Lipozyme RM-IM in a solvent-free system. The experimental conditions, reaction temperature, substrate molar ratio (glycerol/triacylglycerol, Gly/TAG) and enzyme concentration were studied. A response surface methodology was employed to analyze the effect of the individual variables on MAG production and oxidative stability with respect to induction time. The operating conditions that simultaneously optimized MAG yields and oxidative stability were a reaction temperature of 40 °C, a Gly/TAG molar ratio of 2:1 and 6% enzyme load. The yield obtained was 20.34% of MAG (with 12.12% of 2-MAG) and an induction time of 1.88 h
Lab Virtual: atención temprana. Intervención temprana en niños y niñas con retraso madurativo
No full textEntrenamiento en relajación muscular progresiva. 3ª fase (Evocación)
No full textPRÁCTICA 3. Técnicas de Control de la Activación para su Aplicación en Enfermería de Salud Mental. Dentro de esta práctica 3º, para ayudar a los alumnos a realizarla, se han elaborado cuatro laboratorios virtuales que se corresponden con distintas fases del entrenamiento en Relajación Muscular Progresiva, propuesto por Bernstein y Borkovec (1983) y recogido en Serrano y Escolar (2015)
Practicum management and enhancement through an online tool in foreign language teacher education
Get PDFPracticum is an essential and meaningful part of teacher education but due to the great diversity of educational programmes worldwide, their nature and quality depend too much on each particular situation. There is an urgent need to unify and upgrade practicum formats. This paper reports a proposal for technology enhancement and structure reconfiguration of the practicum within the wider curricula. Added to that, we present an Interactive Digital Notepad (IDN) prototype, based on Kanban and powered up by Trello, as an optimal solution to the challenges posed in practicum management in foreign language teacher education programmes. Circumscribed to the Spanish educational context, this IDN is an online tool designed to improve the monitoring of the learning process in order to foster interactive and effective communication among the participants, and to promote critical thinking and autonomy. Results are promising and further steps for further improvement and implementation are outlined.Erasmus + VIRTEACH project (Project Reference: 2018-1-ES01-KA203-050045)
Rational design of mitochondria targeted thiabendazole-based Ir(III) biscyclometalated complexes for a multimodal photodynamic therapy of cancer
Get PDFDespite their outstanding properties as potential photosensitizers for photodynamic therapy (PDT), Ir(III) biscyclometalated complexes need both further developments to overcome remaining limitations and in-depth
investigations into their mechanisms of action to reach clinic application in the treatment of cancer. This
work describes the synthesis of a family of Ir(III) complexes of general formula [Ir(C^N)2(N^N′
)]Cl (N^N′ =
thiabendazole-based ligands; C^N = ppy (2-phenylpyridinate) (Series A), or dfppy (2-(2,4-difluorophenyl)pyridinate) (Series B)) and their evaluation as potential PDT agents. These complexes are partially soluble in water
and exhibit cytotoxic activity in the absence of light irradiation versus several cancer cell lines. Furthermore, the
cytotoxic activity of derivatives of Series A is enhanced upon irradiation, particularly for complexes [1a]Cl and
[3a]Cl, which show phototoxicity indexes (PI) above 20. Endocytosis was established as the uptake mechanism
for [1a]Cl and [3a]Cl in prostate cancer cells by flow cytometry. These derivatives mainly accumulate in the
mitochondria as shown by colocalization confocal microscopy experiments. Presumably, [1a]Cl and [3a]Cl
induce death on cancer cells under irradiation through apoptosis triggered by a multimodal mechanism of action,
which likely involves damage over mitochondrial DNA and mitochondrial membrane depolarization. Both
processes seem to be the result of photocatalytic oxidation processes.We acknowledge the financial support provided by the Spanish Ministerio de Ciencia, Innovacion ´ y Universidades (RTI2018-100709-BC21, RTI2018-100709-B-C22) and CTQ (QMC)-RED2018-102471-T), Junta de Castilla y Leon ´ (BU087G19), Junta de Comunidades de CastillaLa Mancha-FEDER (JCCM) (grant SBPLY/19/180501/000260) and UCLM-FEDER (grants 2019-GRIN-27183 and 2019-GRIN-27209). I. Echevarría wants to acknowledge his fellowship to both the European Social Fund and Consejería de Educacion ´ de la Junta de Castilla y Leon ´ (EDU/1100/2017). E. Zafon wants to acknowledge her predoctoral fellowship to the Generalitat de Catalunya (AGAUR; 2021 FI_B 01036). We are also indebted to Jacinto Delgado, Pilar Castroviejo and Marta Mansilla (PCT of the Universidad de Burgos) for technical support and Jos´e Vicente Cuevas Vicario for advice and support with theoretical calculations and Gabriel García-Herbosa for providing us access to CV equipment
Material Extrusion Additive Manufacturing of Poly(Lactic Acid): Influence of infill orientation angle
Get PDFThe effect that the infill orientation angle has on the strain-rate dependence of the yield stress for material
extrusion additive manufactured (ME-AM) PolyLactic Acid (PLA) material was investigated. Symmetric angleply stacking sequences were used to produce ME-AM tensile test samples. Measured yield stresses were
compensated for the voided structure, typical of ME-AM components. Furthermore, molecular orientation and
stretch was macroscopically assessed by a thermal shrinkage procedure. Additionally, hot-press compression
molded (CM) samples were manufactured and mechanically characterized in uniaxial tensile and compression
in order to determine the material’s isotropic bulk properties. Initial model parameters for the Ree–Eyring
modification of the Eyring flow rule were determined using CM data. According to SEM fractography, all
samples showed microscopically brittle fracture behavior. Notwithstanding, contrary to CM samples, ME-AM
specimens showed macroscopically ductile stress–strain behavior and a transition from a regime with only
a primary ��-deformation process, at low strain rates, to a regime with 2 deformation processes (�� + ��), at
high strain rates. These effects are an influence of the processing step and are attributed to the molecular
orientation and stretch of the polymer chains, provoking anisotropic mechanical properties. As a consequence,
a deformation-induced change of the Eyring rate constants is needed to adequately describe the strain-rate
dependence of the ME-AM yield stress behavior, leaving the initial activation volumes unchanged. Taking this
deformation-dependence of the rate constants into account, yield stresses as a function of infill orientation
angle can be appropriately predicted.The authors gratefully thank Carlos D. Jaramillo Vicente for the hot-press compression molded sample experiments and Miguel Casado Ortega for the material extrusion additive manufacturing experiments. Thanks is also acknowledged to Pedro Luis Sánchez Ortega and José María Cámara Nebreda of the DINper research group at the Universidad de Burgos for their initial help with ME-AM processing. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors
Improvements for Therapeutic Intervention from the Use of Web Applications and Machine Learning Techniques in Different Affectations in Children Aged 0–6 Years
Get PDFTechnological advances together with machine learning techniques give health science
disciplines tools that can improve the accuracy of evaluation and diagnosis. The objectives of this
study were: (1) to design a web application based on cloud technology (eEarlyCare-T) for creating
personalized therapeutic intervention programs for children aged 0–6 years old; (2) to carry out a
pilot study to test the usability of the eEarlyCare-T application in therapeutic intervention programs.
We performed a pilot study with 23 children aged between 3 and 6 years old who presented a
variety of developmental problems. In the data analysis, we used machine learning techniques of
supervised learning (prediction) and unsupervised learning (clustering). Three clusters were found in
terms of functional development in the 11 areas of development. Based on these groupings, various
personalized therapeutic intervention plans were designed. The variable with most predictive value
for functional development was the users’ developmental age (predicted 75% of the development
in the various areas). The use of web applications together with machine learning techniques
facilitates the analysis of functional development in young children and the proposal of personalized
intervention programs.The development of the “eEarly Care” and “Therapeutic intervention programs” web applications has been financed by FEDER FOUNDS: VI Edition of the Call for Proofs of Concept: Impulse for the valorization and marketing of research results (2018–2019), VII Edition of the Call for Proofs of Concept: Impulse for the valorization and marketing of research results (2019–2020) and VII Edition of the Call for Proofs of Concept: Impulse for the valorization and marketing of research results (2020–2021), all managed by the JUNTA DE CASTILLA Y LÉON (SPAIN). Currently, training in the use of these web applications has been co-funded by the EUROPEAN UNION in the e-EarlyCare-T research project No. 2021-1-ES01-KA220-SCH-9A787316
The “best ending for a perfect work”: the Cathedral tower in Murcia
Get PDFEn el siglo XVIII, al retomar tras más de doscientos años la construcción y finalización de la torre
de la Catedral de Murcia, los esfuerzos continuaron para que destacara por su magnificencia y
extraordinaria altura. El diseño se alteró conforme al gusto imperante, fines requeridos y temor al
desplomo. Se analizan las intenciones del cabildo y el impacto de este hito urbano y símbolo del
poder eclesiástico. La arquitectura se convirtió en miradero, para otear el paisaje y no solo para
ser (ad)mirada. También en conjuratorio para apartar el maligno. La torre es sitial de protectoras
imágenes marianas y santos vinculados al territorio, que son atributo de exaltación diocesana.In the 18th century, after a two-hundred-years gap, when the Cathedral Tower in Murcia was
re-started and completed, efforts were made to retain the intended magnificence and extraordinary height. Its design was altered to fit new tastes and purposes and because of fear of collapse.
We analyze the intentions of the church council and the impact of this new urban landmark and
symbol of the church´s power. The tower became a look-out point to survey the landscape as
much as an icon to look at. It was also an object to conjure evil, as well as been the support of
numerous images of the Virgin and Saints assocciated to the land and expression of local pride
