134 research outputs found

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

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    [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.; DĂ­az 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

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    [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). 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    Pattern Dystrophy of the Macula in a Case of Steinert Disease

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    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

    Acute endothelial failure after cosmetic iris implants (NewIris®)

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    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

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

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    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

    Doppler ultrasound and giant cell arteritis

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    ObjectiveTo evaluate the utility of ultrasound in aiding the diagnosis of giant cell arteritis (GCA), in monitoring the response to corticotherapy, and in detecting early relapses.MethodsA pilot study, prospective, included 10 patients with suspected GCA. All patients underwent ultrasound examination of both temporal arteries before temporal artery biopsy (TAB), 3 weeks after starting treatment, and 3 months after diagnosis. For this study, the histological findings alone were used to define if patients were suffering from GCA. The findings on ultrasound were compared with the results of biopsy. The best place to perform TAB was observed by ultrasound.ResultsAll patients with positive biopsy were detected with ultrasound. No false positives were observed on ultrasound. The results presented give a sensibility, specificity, and positive predictive value of 100% for the use of ultrasound in the diagnosis of GCA. Two relapses were detected early by ultrasound during the follow-up.ConclusionsThis pilot study suggests that eco-doppler may be a useful tool in diagnosis and clinic follow-up in patients with suspected GCA

    Intravitreal docosahexaenoic acid in a rabbit model: preclinical safety assessment

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    Purpose The purpose of the present study was to evaluate the retinal toxicity of a single dose of intravitreal docosahexaenoic acid (DHA) in rabbit eyes over a short-term period. Methods Sixteen New Zealand albino rabbits were selected for this pre-clinical study. Six concentrations of DHA (Brudy Laboratories, Barcelona, Spain) were prepared: 10 mg/50 µl, 5 mg/50 µl, 2'5 mg/50 µl, 50 µg/50 µl, 25 µg/50 µl, and 5 µg/50 µl. Each concentration was injected intravitreally in the right eye of two rabbits. As a control, the vehicle solution was injected in one eye of four animals. Retinal safety was studied by slit-lamp examination, and electroretinography. All the rabbits were euthanized one week after the intravitreal injection of DHA and the eyeballs were processed to morphologic and morphometric histological examination by light microscopy. At the same time aqueous and vitreous humor samples were taken to quantify the concentration of omega-3 acids by gas chromatography. Statistical analysis was performed by SPSS 21.0. Results Slit-lamp examination revealed an important inflammatory reaction on the anterior chamber of the rabbits injected with the higher concentrations of DHA (10 mg/50 µl, 5 mg/50 µl, 2'5 mg/50 µ) Lower concentrations showed no inflammation. Electroretinography and histological studies showed no significant difference between control and DHA-injected groups except for the group injected with 50 µg/50 µl. Conclusions Our results indicate that administration of intravitreal DHA is safe in the albino rabbit model up to the maximum tolerated dose of 25 µg/50 µl. Further studies should be performed in order to evaluate the effect of intravitreal injection of DHA as a treatment, alone or in combination, of different retinal diseases
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