Graphene Oxide-Supported Oxime Palladacycles as Efficient Catalysts for the Suzuki–Miyaura Cross-Coupling Reaction of Aryl Bromides at Room Temperature under Aqueous Conditions

Palladacycles are highly efficient precatalysts in cross-coupling reactions whose immobilization on carbonaceous materials has been hardly studied. Herein, we report a detailed study on the synthesis and characterization of new oxime palladacycle-graphene oxide non-covalent materials along with their catalytic activity in the Suzuki–Miyaura reaction. Catalyst 1-GO, which has been fully characterized by ICP, XPS, TGA, and UV-Vis analyses has been demonstrated to be an efficient catalyst for the Suzuki–Miyaura coupling between aryl bromides and arylboronic acids using very low catalyst loadings (0.002 mol % of Pd) at room temperature under aqueous conditions.Financial support from the University of Alicante (UAUSTI16-03, UAUSTI16-10, VIGROB-173), the Spanish Ministerio de Economía, Industria y Competitividad (CTQ2015-66624-P) is acknowledged

2-Aminobenzimidazole Organocatalyzed Asymmetric Amination of Cyclic 1,3-Dicarbonyl Compounds

The use of a trans-cyclohexanediamine benzimidazole derivative as a hydrogen-bond catalyst for the electrophilic amination of cyclic 1,3-dicarbonyl compounds is herein presented. High yields and enantioselectivities varying from moderate to excellent are generally obtained using mild reaction conditions and as low as 1 mol% of catalyst loading.Financial support from the University of Alicante (VIGROB-173, GRE12-03, UAUSTI13-01, UAUSTI13-02) is gratefully acknowledged

Palladium nanoparticles supported on graphene and reduced graphene oxide as efficient recyclable catalyst for the Suzuki–Miyaura reaction of potassium aryltrifluoroborates

Palladium nanoparticles supported on graphene platelets have been efficiently used as catalyst in the Suzuki–Miyaura coupling between aryl bromides and potassium aryltrifluoroborates using 0.1 mol% of Pd and potassium carbonate as base in MeOH/H2O as solvent at 80 °C. The reaction can be performed using conventional and microwave heating showing the catalyst high reusability, particularly with microwaves, where lower aggregation of Pd nanoparticles has been observed. A dissolution/re-deposition catalytic mechanism is proposed, based on the fact that palladium leaching to the solution is detected under microwave irradiation.Financial support from the University of Alicante (VIGROB-173, VIGROB-285, and UAUSTI13-01), and Spanish Ministerio de Economía y Competitividad (CTQ2011-24151 and CTQ2011-24165) is acknowledged

Readily Available Chiral Benzimidazoles-Derived Guanidines as Organocatalysts in the Asymmetric α-Amination of 1,3-Dicarbonyl Compounds

The synthesis and the evaluation as organocatalysts of new chiral guanidines derived from benzimidazoles in the enantioselective α-amination of 1,3-dicarbonyl compounds using di-t-butylazodicarboxylate as aminating agent is herein disclosed. The catalysts are readily synthesized through the reaction of 2-chlorobezimidazole and a chiral amine in moderate-to-good yields. Among all of them, those derived from (R)-1-phenylethan-1-amine (1) and (S)-1-(2-naphthyl)ethan-1-amine (3) turned out to be the most efficient for such asymmetric transformation, rendering good-to-high yields and moderate-to-good enantioselectivities for the amination products.Financial support from the University of Alicante (VIGROB-173, VIGROB-285, GRE12-03, UAUSTI13-01, UAUSTI13-02), and Spanish Ministerio de Economía y Competitividad (CTQ2011-24151) is acknowledged

Pursuing Chemical Efficiency by Using Supported Organocatalysts for Asymmetric Reactions under Aqueous Conditions

Over the past decade, a great effort has been made by the chemical community to improve the efficiency of organic transformations and allow sustainable processes. Merging the use of supported and recyclable organocatalysts and aqueous conditions for the asymmetric synthesis of valuable molecules, has led to outstanding contributions in the area of green chemistry. Recent progresses in the field include the implementation of these methodologies in the large scale production of chiral molecules using automated flow chemistry.This work was financially supported by the University of Alicante (VIGROB-173, GRE12-03, UAUSTI13-01, UAUSTI13-02)

Organocatalyzed Assembly of Chlorinated Quaternary Stereogenic Centers

The catalytic asymmetric construction of chiral quaternary stereocenters is a continual area of research for organic chemists. In this sense, when a chlorine atom is introduced to a quaternary stereocenter, the synthetic difficulty of the resulting molecule increases along with its significance. This is true not only because of the intrinsic interest in such chlorinated molecules but also because they are highly valuable chiral building blocks in organic synthesis, as they can be converted into more complex molecules by a SN2 displacement reaction. Among the different strategies to create chlorinated quaternary stereogenic centers, organocatalysis has played a pivotal role over the past decade. In this review, a comprehensive analysis of such organocatalyzed transformations with a focus on the α-chlorination of carbonyl compounds is presented.Financial support from the University of Alicante (VIGROB-173) and the Spanish Ministerio de Economía y Competitividad (CTQ2015-66624-P) is acknowledged

Design and Validation of a Process Based on Cationic Niosomes for Gene Delivery into Novel Urine-Derived Mesenchymal Stem Cells

Background: Mesenchymal stem cells (MSCs) are stem cells present in adult tissues. They can be cultured, have great growth capacity, and can differentiate into several cell types. The isolation of urine-derived mesenchymal stem cells (hUSCs) was recently described. hUSCs present additional benefits in the fact that they can be easily obtained noninvasively. Regarding gene delivery, nonviral vectors based on cationic niosomes have been used and are more stable and have lower immunogenicity than viral vectors. However, their transfection efficiency is low and in need of improvement. Methods: We isolated hUSCs from urine, and the cell culture was tested and characterized. Different cationic niosomes were elaborated using reverse-phase evaporation, and they were physicochemically characterized. Then, they were screened into hUSCs for transfection efficiency, and their internalization was evaluated. Results: GPxT-CQ at a lipid/DNA ratio of 5:1 (w/w) had the best transfection efficiency. Intracellular localization studies confirmed that nioplexes entered mainly via caveolae-mediated endocytosis. Conclusions: In conclusion, we established a protocol for hUSC isolation and their transfection with cationic niosomes, which could have relevant clinical applications such as in gene therapy. This methodology could also be used for creating cellular models for studying and validating pathogenic genetic variants, and even for performing functional studies. Our study increases knowledge about the internalization of tested cationic niosomes in these previously unexplored cellsThis research was funded by a grant from the EITB Maratoia to G.P.d.N., C.M., and J.L.P. (BIO16/ER/005), from the University of the Basque Country UPV/EHU to Y.V. (PIF17/29), and from the Basque Government to S.J.-B. (PRE_2017-1-0365)

Actividades de evaluación continua y valoración del estudiante: Estudio sobre su correlación

La evaluación continua (EC) tiene una importante influencia en la calificación final de los estudiantes. En general, las calificaciones obtenidas durante el semestre en las diferentes actividades propuestas para la EC mejoran las notas finales de los estudiantes. De especial importancia son los créditos asociados a prácticas de laboratorio y la resolución de problemas. En el presente estudio se ha considerado la valoración de los estudiantes sobre estos créditos prácticos, así como la correlación entre la calificación de las actividades y la valoración de los estudiantes. La reflexión sobre este estudio nos proporciona una perspectiva de posibles acciones de mejora para la evaluación continua. El estudio se ha considerado para las asignaturas: Química (código 26510 de los Grados en Biología y en Ciencias del Mar) y Determinación Estructural de Compuestos Orgánicos (código 26030 del Grado en Química). Estas asignaturas ya han sido objeto de estudio previamente, lo que nos da una mejor visión de las cuestiones a valorar. Además, en estas asignaturas hay grupos que se imparten en otras lenguas (valenciano e inglés), por lo que se comentarán ciertos aspectos relacionados con esta característica

Recovery of green turtle populations and their interactions with coastal dune as a baseline for an integral ecological restoration

Antecedentes y Objetivos: La restauración ecológica se ha centrado en los componentes físicos y vegetales de los ecosistemas, y ha dejado de lado a la fauna silvestre y sus interacciones. Chelonia mydas es un macroherbívoro en peligro de extinción que anida en playas de México y Cuba, e influye en la vegetación costera con aportaciones de materia orgánica. Los objetivos de este estudio fueron analizar su recuperación poblacional, un índice del verdor de la vegetación de duna, así como la cantidad de materia orgánica estimada de sus nidadas antes y después de la implementación de una Norma Oficial Mexicana. Métodos: Se analizaron datos de entre dos y tres décadas de monitoreo biológico en 16 playas de anidación de Chelonia mydas; a partir de ellos se realizaron tres niveles de análisis de indicadores demográficos, la aportación de materia orgánica de las tortugas en la playa y el vigor vegetal a partir de sensores remotos, además de aplicar los estadísticos pertinentes. Resultados clave: Hubo un crecimiento exponencial del número de anidaciones de tortuga verde (entre 12 y 14% anual), asociado con pulsos de reclutamiento poblacional en los años 2000 y 2008. El aporte de materia orgánica a la playa fue significativamente mayor después de un cambio en la estrategia para manejo de las nidadas en México, y se detectó un incremento en el verdor de la vegetación de duna en zonas de anidación alta de Chelonia mydas. Conclusiones: El incremento de las poblaciones de tortuga verde lleva a reflexionar acerca de las implicaciones que tiene la recuperación de especies de fauna sobre otras comunidades en los ecosistemas que habitan, lo que demanda el análisis de los paradigmas actuales y la adaptación de estrategias que atiendan sus necesidades de manejo, procurando las condiciones de integridad ecológica de sus hábitats.Background and Aims: Ecological restoration has focused on the physical and vegetation components of ecosystems, leaving aside studies on wild fauna and their interactions. Chelonia mydas is an endangered macroherbivore that nests on sandy beaches of Mexico and Cuba, and influences the coastal vegetation with organic matter contributions. The objectives of this study were to analyze its population recovery, a greenness index for dune vegetation, and the amount of organic matter estimated from its clutches before and after the implementation of an official Mexican norm. Methods: Biological data obtained from two and three decades of monitoring 16 Chelonia mydas nesting beaches were analyzed; based on these, three levels of demographic indexes were carried out, the contribution of organic matter by marine turtles to the beach and the vegetal vigor using remote sensing, besides implementing the pertinent statistical analysis. Key results: There was an exponential increase of the green turtle nests (between 12 and 14% per year), associated with population recruitment pulses in 2000 and 2008. The contribution of organic matter to the beach was significantly higher after a change in clutches management in Mexico, and an increase in the dune vegetation greenness was detected in high Chelonia mydas nesting zones. Conclusions: The increase of the green turtle populations invites to reflex about the implications of the recovery of species of fauna have on other communities in the ecosystems they inhabit, demanding the analysis of the actual paradigms and the adaptation strategies that attend their management needs, procuring the ecological integrity conditions of their habitats