Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production

[EN] The catalytic activity of "pyrrolidine type" fragments included or anchored in the mesoporous silica supports or polymeric frameworks have been fully reported for enantioselective transformation. Nevertheless, low attention was focused on their catalytic abilities to perform base-catalyzed reaction. Accordingly, hybrid materials including pyrrolidine fragments in the mesoporous silica supports were prepared following different synthesis methods, such as micellar and fluoride sol-gel routes in absence of structural directing agents. Their great catalytic performance was explored for various base-catalyzed reactions to the formation of C-C bond through Knoevenagel, Claisen-Schmidt and Henry condensations under microwave irradiation. The benefits of microwave irradiation combined with suitable catalytic properties of pyrrolidine hybrid materials with strong base sites and high accessibility to active centers, allowed carrying out successfully base-catalyzed condensation reactions for the production of fine chemicals. Moreover, the hybrid catalyst exhibited high selectivity and good stability over different catalytic cycles contributing to environmental sustainability.The authors are grateful for financial support from the Spanish Government, MAT2017-82288-C2-1-P and PID2020112590GB C21/AEI/10.13039/501100011033, and MULTY2HYCAT European project (EUHorizon 2020 funded project under grant agreement no. 720783).Llopis-Perez, S.; Velty, A.; Díaz Morales, UM. (2021). Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production. ChemCatChem. 13(23):5012-5024. https://doi.org/10.1002/cctc.202101031S50125024132

Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas

[EN] Three families of organosiliceous materials with different structuration level, order, and textural properties (non-ordered, M41S, and SBA-15 type materials) were prepared incorporating in their structural framework chiral pyrrolidine units with variable content. Likewise, non-ordered mesoporous hybrid solids were obtained through a sol-gel process in a fluoride medium, while M41S and SBA-15 type materials were obtained through micellar routes in the presence of long-chain neutral surfactants or block copolymers. Thanks to appropriate characterization studies and catalytic tests for the Michael addition between butyraldehyde and beta-nitrostyrene, we showed how the void shapes and sizes present in the structure of hybrid materials control the diffusion of reactants and products, as well as confine transition states and reactive intermediates. The best catalytic results, considering activity and enantioselectivity, were achieved in the presence of a non-ordered material, NOH-Pyr-5%, which exhibited the highest Brunauer-Emmett-Teller (BET) area, with a 96% yield and a 82% ee for the Michael adduct.This research was funded by the Spanish Government(MAT2017-82288-C2-1-P), Severo Ochoa Excellence Program (SEV-2016-0683), and MULTY2HYCAT (EU-Horizon 2020 funded project under grant agreement no. 720783). S. Ll. is thankful for the predoctoral fellowship from MINECO for financial support (BES-2015-072627).Llopis-Perez, S.; Velty, A.; Díaz Morales, UM. (2019). Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas. Catalysts. 9(8):1-21. https://doi.org/10.3390/catal9080654S12198Kuschel, A., Drescher, M., Kuschel, T., & Polarz, S. (2010). Bifunctional Mesoporous Organosilica Materials and Their Application in Catalysis: Cooperative Effects or Not? Chemistry of Materials, 22(4), 1472-1482. doi:10.1021/cm903412eDíaz, U., Brunel, D., & Corma, A. (2013). Catalysis using multifunctional organosiliceous hybrid materials. Chemical Society Reviews, 42(9), 4083. doi:10.1039/c2cs35385gKadib, A. E., Molvinger, K., Guimon, C., Quignard, F., & Brunel, D. (2008). Design of Stable Nanoporous Hybrid Chitosan/Titania as Cooperative Bifunctional Catalysts. Chemistry of Materials, 20(6), 2198-2204. doi:10.1021/cm800080sHorcajada, P., Serre, C., Vallet-Regí, M., Sebban, M., Taulelle, F., & Férey, G. (2006). Metal–Organic Frameworks as Efficient Materials for Drug Delivery. Angewandte Chemie International Edition, 45(36), 5974-5978. doi:10.1002/anie.200601878Zhang, J., Han, X., Wu, X., Liu, Y., & Cui, Y. (2019). Chiral DHIP- and Pyrrolidine-Based Covalent Organic Frameworks for Asymmetric Catalysis. ACS Sustainable Chemistry & Engineering, 7(5), 5065-5071. doi:10.1021/acssuschemeng.8b05887Loy, D. A., & Shea, K. J. (1995). Bridged Polysilsesquioxanes. Highly Porous Hybrid Organic-Inorganic Materials. Chemical Reviews, 95(5), 1431-1442. doi:10.1021/cr00037a013Inagaki, S., Guan, S., Fukushima, Y., Ohsuna, T., & Terasaki, O. (1999). Novel Mesoporous Materials with a Uniform Distribution of Organic Groups and Inorganic Oxide in Their Frameworks. Journal of the American Chemical Society, 121(41), 9611-9614. doi:10.1021/ja9916658Villaverde, G., Arnanz, A., Iglesias, M., Monge, A., Sánchez, F., & Snejko, N. (2011). Development of homogeneous and heterogenized rhodium(i) and palladium(ii) complexes with ligands based on a chiral proton sponge building block and their application as catalysts. Dalton Transactions, 40(37), 9589. doi:10.1039/c1dt10597cMelde, B. J., Holland, B. T., Blanford, C. F., & Stein, A. (1999). Mesoporous Sieves with Unified Hybrid Inorganic/Organic Frameworks. Chemistry of Materials, 11(11), 3302-3308. doi:10.1021/cm9903935García-García, P., Moreno, J. M., Díaz, U., Bruix, M., & Corma, A. (2016). Organic–inorganic supramolecular solid catalyst boosts organic reactions in water. Nature Communications, 7(1). doi:10.1038/ncomms10835Moreno, J. M., Velty, A., Díaz, U., & Corma, A. (2019). Synthesis of 2D and 3D MOFs with tuneable Lewis acidity from preformed 1D hybrid sub-domains. Chemical Science, 10(7), 2053-2066. doi:10.1039/c8sc04372hSzőllősi, G., Gombkötő, D., Mogyorós, A. Z., & Fülöp, F. (2018). Surface-Improved Asymmetric Michael Addition Catalyzed by Amino Acids Adsorbed on Laponite. Advanced Synthesis & Catalysis, 360(10), 1992-2004. doi:10.1002/adsc.201701627Feng, J., Li, X., & Cheng, J.-P. (2017). Enantioselective Organocatalyzed Vinylogous Michael Reactions of 3-Alkylidene Oxindoles with Enals. The Journal of Organic Chemistry, 82(3), 1412-1419. doi:10.1021/acs.joc.6b02582Bernardi, L., Fochi, M., Carbone, R., Martinelli, A., Fox, M. E., Cobley, C. J., … Carlone, A. (2015). Organocatalytic Asymmetric Conjugate Additions to Cyclopent-1-enecarbaldehyde: A Critical Assessment of Organocatalytic Approaches towards the Telaprevir Bicyclic Core. Chemistry - A European Journal, 21(52), 19208-19222. doi:10.1002/chem.201503352Afewerki, S., Ma, G., Ibrahem, I., Liu, L., Sun, J., & Córdova, A. (2015). Highly Enantioselective Control of Dynamic Cascade Transformations by Dual Catalysis: Asymmetric Synthesis of Polysubstituted Spirocyclic Oxindoles. ACS Catalysis, 5(2), 1266-1272. doi:10.1021/cs501975uMonge-Marcet, A., Pleixats, R., Cattoën, X., Man, M. W. C., Alonso, D. A., & Nájera, C. (2011). Prolinamide bridged silsesquioxane as an efficient, eco-compatible and recyclable chiral organocatalyst. New Journal of Chemistry, 35(12), 2766. doi:10.1039/c1nj20516aSagamanova, I., Rodríguez-Escrich, C., Molnár, I. G., Sayalero, S., Gilmour, R., & Pericàs, M. A. (2015). Translating the Enantioselective Michael Reaction to a Continuous Flow Paradigm with an Immobilized, Fluorinated Organocatalyst. ACS Catalysis, 5(11), 6241-6248. doi:10.1021/acscatal.5b01746Betancort, J. M., & Barbas, C. F. (2001). Catalytic Direct Asymmetric Michael Reactions:  Taming Naked Aldehyde Donors. Organic Letters, 3(23), 3737-3740. doi:10.1021/ol016700

Estudio de la proteína transportadora de la hormona de crecimiento en los transtornos del crecimiento y en las alteraciones de la nutrición

Consultable des del TDXTítol obtingut de la portada digitalitzad

Pattern Dystrophy of the Macula in a Case of Steinert Disease

IntroductionMyotonic dystrophies are typically associated with ocular complications like ptosis, weakness of the ocular muscle and cataracts, but also with less recognized retinal changes.Case ReportA 41-year-old female with type 1 myotonic dystrophy complained of progressive vision loss. Slit lamp examination revealed the presence of typical bilateral polychromatic cataract with posterior subcapsular component. Dilated fundus examination was remarkable for bilateral macular depigmented changes. Multimodal imaging analysis of the macula suggested the presence of a butterfly-shaped pattern dystrophy.DiscussionIn cases of myotonic dystrophies it is of great relevance to analyze the presence of retinal changes that might limit the visual improvement following cataract extraction

Rituximab in refractory Vogt–Koyanagi–Harada disease

IntroductionVogt–Koyanagi–Harada (VKH) prognosis depends on early recognition and treatment; chronic disease may be developed when either delayed or inadequate treatment is performed, whereas other cases despite correct treatment are refractory to different drugs and also become chronic. We report a case of refractory VKH controlled with rituximab treatment.Case reportA 41-year-old female with painful visual loss and headache was examined. (VA 0.4 in RE and hand movements (HM) in LE). Retinal examination demonstrated multiple serous retinal detachments in both eyes. High-dose oral steroids were started, followed by progressive tapering of prednisone. New acute anterior and posterior relapses were achieved, and other immunommodulators were progressively added—new high-dose steroid treatment, adalimumab, cyclosporine, and methotrexate—but patient had new anterior and posterior recurrences associated with tinnitus and headache. Thus, an infusion of 1 g of rituximab was administered after 15 months follow-up; the VA was 0.2 in RE and counting fingers in LE. Three additional doses of 1 g each were administered 1, 6, and 16 months later. We have achieved a final VA after 34 months follow-up of 0.2 in RE and HM in LE, with definitive control of inflammation, without acute relapses since rituximab was administered.ConclusionAfter searching PubMed/Medline, this is the first report of VKH disease treated with rituximab. Additional studies are warranted to confirm the efficacy of this new approach for inflammatory control in refractory cases of VKH disease

Adult Coats’ Disease Successfully Managed with the Dexamethasone Intravitreal Implant (Ozurdex®) Combined with Retinal Photocoagulation

Purpose: To report a case of Coats’ disease managed with the dexamethasone intravitreal implant Ozurdex® (Allergan, Inc., Irvine, Calif., USA) combined with retinal photocoagulation. Methods: A 46-year-old female with 20/200 visual acuity was diagnosed with Coats’ disease with secondary retinal vasoproliferative tumor. An initial approach was performed with an intravitreal injection of the sustained-release dexamethasone implant Ozurdex. After reattachment of the retina, the telangiectatic vessels were treated with laser photocoagulation. Results: The patient’s visual acuity improved to 20/25 after the intravitreal Ozurdex. No further recurrences of exudation were evident through the 12-month follow-up. Conclusions: Ozurdex may be an effective initial therapeutic approach for Coats’ disease with immediate anatomical response and visual improvement

Acute endothelial failure after cosmetic iris implants (NewIris®)

We report a case of an acute endothelial failure after the implantation of a new cosmetic, colored, artificial iris diaphragm implant called NewIris®. A 21-year-old woman came to us complaining of progressive loss of vision and pain after NewIris lenses had been implanted. Decreased visual acuity, corneal edema, and increased intraocular pressure in both eyes appeared only 3 weeks after the surgery. The lenses were removed as soon as possible but had already severely affected the endothelial cell count. NewIris implants are an alternative to cosmetic contact lenses, but they are not as safe as other phakic anterior chamber intraocular lenses, nor are they a good option for the patient

Manipulación, persuasión y discurso

Verba Hispanica cumple treinta ediciones. Esta trigésima edición, cuya orientación temática propuesta y anunciada en febrero pasado gira en torno a la Manipulación, Persuasión y Discurso, trae a colación la manipulación lingüística desde muy variadas perspectivas: la sociológica, bien política o mediática, que es la que mayor eco ha tenido por parte de las contribuciones, la léxica, la del análisis del discurso, la pragmática, la multimodal, y también la metafórica, cubriendo todas ellas aspectos y consideraciones histórico-culturales. Junto al análisis del discurso de la prensa tienen fuerte presencia, como no podía ser de otra manera en nuestro actual universo digitalizado, las redes sociales. Igualmente, y sin que haya mediado acción alguna por parte de quienes firmamos esta introducción, dos temas sobresalen en el contenido de los artículos aquí incluidos: discurso político, especialmente el comúnmente denominado conservador, y reacciones (a menudo violentas) ante el feminismo. Los artículos aquí compilados contribuyen a darnos una visión crítica e informada de las narrativas sociales que imperan y proliferan tanto en la prensa que leemos, como en los medios de comunicación y agentes discursivos que elegimos (o no) seguir. Es la intención de este volumen ofrecer a los lectores perspectivas de pensamiento desde el análisis del discurso en temas como la política, el feminismo, los nacionalismos o la inclusividad. El presente número quiere ser también un homenaje a los primeros esfuerzos para apuntalar la Filología Hispánica en la Universidad de Ljubljana, de la mano del querido y ya legendario prof. Skubic en 1981

Javier Muñoz-Basols y Yolanda Pérez Sinusía (2022). Técnicas de escritura en español y géneros textuales / Developing Writing Skills in Spanish

La obra Técnicas de escritura en español y géneros textuales / Developing Writing Skills in Spanish es un volumen publicado por dos prestigiosos profesionales de la enseñanza del español: Javier Muñoz-Basols, profesor titular y coordinador de español en la Universidad de Oxford (Reino Unido), y Yolanda Pérez Sinusía, profesora titular de español en la Escuela Oficial de Idiomas n.⁰ 1 de Zaragoza (España). La segunda edición de Routledge incluye numerosas novedades respecto a la de 2011, que consisten en un esfuerzo de enriquecimiento al incluir la consulta de diferentes obras como el Diccionario panhispánico de dudas (2005), la Nueva gramática de la lengua española (2009), la Nueva gramática básica de la lengua española (2010), la 23.ᵃ edición del Diccionario de la lengua española (2014) y el Libro de estilo de la lengua española según la norma panhispánica (2018), así como los nuevos descriptores del Common European Framework of Reference for Languages: Learning, Teaching, Assessment (2018) o MCER, teniendo sobre todo en cuenta el modo en que se potencia la mediación lingüística en la enseñanza de las lenguas