79 research outputs found
α‐Functionalization of imines via visible light photoredox catalysis
The innate electrophilicity of imine building blocks has been exploited in organic synthetic chemistry for decades. Inspired by the resurgence in photocatalysis, imine reactivity has now been redesigned through the generation of unconventional and versatile radical intermediates under mild reaction conditions. While novel photocatalytic approaches have broadened the range and applicability of conventional radical additions to imine acceptors, the possibility to use these imines as latent nucleophiles via single‐electron reduction has also been uncovered. Thus, multiple research programs have converged on this issue, delivering creative and practical strategies to achieve racemic and asymmetric α‐functionalizations of imines under visible light photoredox catalysisThis research was funded by the European Research Council, grant number 647550; the Spanish Government, grant number RTI2018-095038-B-I00; the “Comunidad de Madrid” and European Structural Funds, grant number S2018/NMT-436
Rheology of Water-in-water emulsions: Caseinate-pectin and caseinatealginate systems
Conventional models developed for oil-water emulsions do not fit viscosity of caseinate-pectin and caseinatealginate water-in water emulsions, which is always lower than predicted, except for high viscosities of disperse phase. These models do not consider strong deformations, prevented by the high interfacial tension of oil-water interphases. The ultra-low interfacial tension of water-in-water emulsions facilitates the creation of interphase and very elongated droplets. Capron model considers interfacial tension, fitting results when the dispersed phase is the most viscous, but, for other cases, lower experimental values are obtained related to the shear-induced stratification. Even values below the stratification model are observed for some samples, related to the influence of the interphase in the viscosity of the emulsion. A model that takes into account the presence of a relatively thick interphase poor in both polymers is proposed. Intermediate structures between highly elongated and stratified fluids, with influence of interphase viscosity could explain results
Stereochemical aspects and the synthetic scope of the SHi at the sulfur atom. Preparation of enantiopure 3-substituted 2,3-dihydro-1,2- benzoisothiazole 1-oxides and 1,1-dioxides
Intramolecular homolytic substitution (SHi) on the sulfur atom at acyclic N-(o-bromobenzyl)sulfinamides takes place with a complete inversion of the configuration and
provides an excellent tool to connect N-tert-butanesulfinylimines with enantiopure 3-substituted benzo-fused sulfinamides (1,2-benzoisothiazoline 1-oxides) and the related pharmacologically relevant sulfonamidesThe Spanish Government (grant CTQ2012-35957) and Comunidad de Madrid (CCG08-UAM/PPQ-4151; S2009/PPQ1634
Gellan hydrogels: preparation, rheological characterization and application in encapsulation of curcumin
Hydrogels can be used to protect some labile active principles, as polyphenol-rich substances, that can be added to foods to prepare functional ones. Rheological properties of gels formed through the addition of calcium chloride to gellan solutions were studied. It can be concluded that preparation variables and not only formulation ones are determinant in rheological properties of the resulting gels, as they are not in an equilibrium state but they are continuously evolving during hours to stronger gels corresponding to a denser network. It could be related to the fact that local non-gelled domains are formed surrounded by a shell of gel where Ca2+ ions take some time to arrive. A minimum Ca2+/gellan ratio (CG) is required to reach the gel point (GP), determined as the CG where the ratio loss modulus/elastic modulus (G^/G') collapse for all frequencies. Calcium-induced external gelation of oil-in-water (O/W) emulsions where a curcumin-in-oil solution is the disperse phase and a watery solution of gellan is the continuous phase was used to prepare beads were curcumin is entrapped in order to prevent its degradation. Smaller droplet-sized emulsions were obtained with higher gellan concentrations, since a higher viscosity of the continuous phase allowed to reach the critical Capillary number CaC at lower radius of droplets. An encapsulation yield around 90% was reached for gellan concentrations of 1% w/v, and the resulting encapsulated curcumin presented around 6 times slower light degradation than free curcumin-in-oil solutions
Metal-free visible light-promoted synthesis of isothiazoles: a catalytic approach for N-S bond formation from iminyl radicals under batch and flow conditions
A sustainable synthesis of isothiazoles has been developed using an α-amino-oxy acid auxiliary and applying photoredox catalysis. This simple strategy features mild conditions, broad scope and wide functional group tolerance representing a new enviromentally friendly option to prepare these highly valuable heterocycles. Furthermore, the synthetic value of the method is highlighted by the preparation of a natural product derivative and the implementation of the reaction in a continuous flow setupWe acknowledge the financial support by the Spanish Government (RTI2018-095038-B-I00) and ERC (ERC-CG, 647550
Formation of stellar inner discs and rings in spiral galaxies through minor mergers
Recent observations show that inner disks and rings (IDs and IRs) are not preferentially found in barred galaxies, pointing to the relevance of formation mechanisms different to the traditional bar-origin scenario. Nevertheless, the role of minor mergers in the formation of these inner components (ICs), while often invoked, is still poorly understood. We have investigated the capability of minor mergers to trigger the formation of IDs and IRs in spiral galaxies through collisionless N-body simulations. Our models prove that minor mergers are an efficient mechanism to form rotationally-supported stellar ICs in spirals, neither requiring strong dissipation nor noticeable bars, and suggest that their role in the formation of ICs must have been much more complex than just bar triggering
Intramolecular hydrogen-bond activation for the addition of nucleophilic imines: 2-hydroxybenzophenone as a chemical auxiliary
The addition of nucleophilic imines, using 2-hydroxybenzophenone as a chemical auxiliary, is presented. An intramolecular six-membered ring via hydrogen bonding that enhances the reactivity and selectivity is the key of this strategy, which is supported by DFT calculations and experimental trialsSpanish Government (CTQ2015-64561-R, CTQ2016-76061-P, and MDM-2014-0377), Prodep (UJAT-PTC-247) and CCC-UAM are acknowledged. A. G. thanks MINECO for a PhD fellowship (FPI) and A. M. S. thanks CAM for a postdoctoral contract (2016-T2/IND-1660
Red de seguimiento y coordinación del Máster en Ciencia de Materiales
El Máster en Ciencia de Materiales se imparte en la Facultad de Ciencias de la Universidad de Alicante, consta de 60 créditos ECTS que se cursan durante 1 año académico. El máster está implantado desde el curso 2010-2011 por lo que durante el actual curso 2014-2015 tendremos la quinta promoción de egresados. La red docente está formada por la comisión académica del Máster en Ciencia de Materiales. Esta comisión (profesorado, alumno y personal de administración y servicios) lleva realizando un seguimiento de la titulación durante los 4 cursos anteriores. Por tanto la red tiene como objetivo principal el seguimiento, coordinación, evaluación y mejora de la planificación realizada con las experiencias recogidas a lo largo de estos años. Además, se realizará un estudio de los diferentes indicadores de calidad que utilizan las agencias de acreditación puesto que este año el Máster se someterá a la renovación de la acreditación
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