Diastereoselective multicomponent Amine-Aldehyde-Dienophile (AAD) process for the synthesis of polysubstituted cyclohex-2-enylamines

The multicomponent Amine-Aldehyde-Dienophile reaction is optimized employing benzyl or 4-methoxybenzylamine. The interest of the transformation consist in the synthesis of polysubstituted cyclohex-2-enylamines. The study of the scope of this AAD process is carried out, as well as the diastereoselective version, employing commercially available chiral benzylic amines and a maleimide with the chiral information at the N-substituent. VCD spectroscopy is a very useful tool for the determination of the absolute configuration of the isolated enantiomerically enriched compounds.We gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO), Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (Project Nos. CTQ2013-43446-P, CTQ2014-51912-REDC, CTQ2016-76782-P, CTQ2016-81797-REDC, CTQ2016-81893REDT, and CTQ2016-76155-R), the Generalitat Valenciana (PROMETEOII/2014/017) and the University of Alicante

Cholinesterase and phenyl valerate-esterase activities sensitive to organophosphorus compounds in membranes of chicken brain

Some effects of organophosphorus compounds (OPs) esters cannot be explained by action on currently recognized targets acetylcholinesterase or neuropathy target esterase (NTE). In previous studies, in membrane chicken brain fractions, four components (EPα, EPβ, EPγ and EPδ) of phenyl valerate esterase activity (PVase) had been kinetically discriminated combining data of several inhibitors (paraoxon, mipafox, PMSF). EPγ is belonging to NTE. The relationship of PVase components and acetylcholine-hydrolyzing activity (cholinesterase activity) is studied herein. Only EPα PVase activity showed inhibition in the presence of acetylthiocholine, similarly to a non-competitive model. EPα is highly sensitive to mipafox and paraoxon, but is resistant to PMSF, and is spontaneously reactivated when inhibited with paraoxon. In this papers we shows that cholinesterase activities showed inhibition kinetic by PV, which does not fit with a competitive inhibition model when tested for the same experimental conditions used to discriminate the PVase components. Four enzymatic components (CP1, CP2, CP3 and CP4) were discriminated in cholinesterase activity in the membrane fraction according to their sensitivity to irreversible inhibitors mipafox, paraoxon, PMSF and iso-OMPA. Components CP1 and CP2 could be related to EPα as they showed interactions between substrates and similar inhibitory kinetic properties to the tested inhibitors

Bioinsumos en la producción de algodón agroecológico

El módulo de algodón agroecológico instalado dentro de la EEA Sáenz Peña aborda la necesidad de llevar a la práctica en el campo los principios agroecológicos, generando un agroecosistema que: - fortalece la resistencia del cultivo ante plagas y enfermedades, - aporta diversidad, - disminuye el consumo de energía y materiales - promueve la generación y acumulación de biomasa vegetal y el sostenimiento de la fertilidad del suelo, - aumenta la resiliencia de los cultivos al cambio climático: ciclos más extremos y prolongados de sequía e inundación, y temperaturas máximas y mínimas extremas.Fil: Rojas, Julieta Mariana. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Sáenz Peña; ArgentinaFil: Spoljaric, Mónica. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Sáenz Peña; ArgentinaFil: Selva, María Verónica. La Tierra Sin Mal; ArgentinaFil: Frias, Jorge. La Tierra Sin Mal; Argentin

Synthesis of pharmacophores containing a prolinate core using a multicomponent 1,3-dipolar cycloaddition of azomethine ylides

A multicomponent 1,3-dipolar cycloaddition between heterocyclic aldehydes, amino esters and dipolarophiles is efficiently promoted by silver acetate as catalyst, and depending on the nature of the heterocycle and its reactivity the reaction requires 70 °C or rt to complete. Selected pharmacophores anchored to a formyl group are chromone, 5-methoxyindole, pyridoxal surrogates and a very attractive uracyl derivative. The preference of each tested amino esters towards different dipolarophiles is discussed. At the end, a selective reduction of the ester group allows to obtain a very interesting dideoxiazanucleoside derivative.We gratefully acknowledge financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387 and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO2009/039 and PROMETEOII/2014/017), the University of Alicante and Medalchemy S. L. E. Selva thanks Univerisdad de Alicante and Medalchemy S. L. for a predoctoral fellowship

Multicomponent Diastereoselective Synthesis of Indolizidines via 1,3-Dipolar Cycloadditions of Azomethine Ylides

The synthesis of polyfunctionalized indolizidines from pipecolinic acid alkyl ester derivatives, aldehydes and a wide range of dipolarophiles by multicomponent 1,3-dipolar cycloadditions is developed in a diastereoselective manner. The cycloadditions take place in toluene with short reaction times at 70 °C, giving good yields. The synthesis of these fused heterocycles is also studied starting from pipecolinic acid, generating the dipole through a decarboxylative route at 120 °C. The relative configuration of the resulting products as well as the mechanistic pathways are also explained.The Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economia y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), and the University of Alicante. L. C. M. thanks Spanish Government for a fellowship

Role of MUC1 rs4072037 polymorphism and serum KL-6 levels in patients with antisynthetase syndrome

Biomarkers; Idiopathic inflammatory myopathiesBiomarcadores; Miopatías inflamatorias idiopáticasBiomarcadors; Miopaties inflamatòries idiopàtiquesMucin 1/Krebs von den Lungen-6 (KL-6) is proposed as a serum biomarker of several interstitial lung diseases (ILDs), including connective tissue disorders associated with ILD. However, it has not been studied in a large cohort of Caucasian antisynthetase syndrome (ASSD) patients. Consequently, we assessed the role of MUC1 rs4072037 and serum KL-6 levels as a potential biomarker of ASSD susceptibility and for the differential diagnosis between patients with ILD associated with ASSD (ASSD-ILD +) and idiopathic pulmonary fibrosis (IPF). 168 ASSD patients (149 ASSD-ILD +), 174 IPF patients and 523 healthy controls were genotyped for MUC1 rs4072037 T > C. Serum KL-6 levels were determined in a subgroup of individuals. A significant increase of MUC1 rs4072037 CC genotype and C allele frequencies was observed in ASSD patients compared to healthy controls. Likewise, MUC1 rs4072037 TC and CC genotypes and C allele frequencies were significantly different between ASSD-ILD+ and IPF patients. Additionally, serum KL-6 levels were significantly higher in ASSD patients compared to healthy controls. Nevertheless, no differences in serum KL-6 levels were found between ASSD-ILD+ and IPF patients. Our results suggest that the presence of MUC1 rs4072037 C allele increases the risk of ASSD and it could be a useful genetic biomarker for the differential diagnosis between ASSD-ILD+ and IPF patients.Study partially supported by a grant from Spanish Society of Pulmonology and Thoracic Surgery (SEPAR 474-2017) and from Euronanomed III / Instituto de Salud Carlos III (ISCIII) (AC17/00027) awarded to SC. SR-M is supported by funds of the RETICS Program (RD16/0012/0009) from the ISCIII, co-funded by the European Regional Development Fund. BA-M is recipient of a ‘López Albo’ Post-Residency Programme funded by Servicio Cántabro de Salud. VP-C is supported by a pre-doctoral grant from IDIVAL (PREVAL 18/01). LL-G is supported by funds from IDIVAL (INNVAL 20/06). RP-F is supported by funds of START project (FOREUM18/34). DP-P is a recipient of a Río Hortega programme fellowship from the ISCIII, co-funded by the European Social Fund (ESF, ‘Investing in your future’) (CM20/00006). OG is staff personnel of Xunta de Galicia (Servizo Galego de Saude (SERGAS)) through a research-staff stabilization contract (ISCIII/SERGAS) and his work is funded by ISCIII and the European Union FEDER fund (RD16/0012/0014 (RIER) and PI17/00409). He is beneficiary of project funds from the Research Executive Agency (REA) of the European Union in the framework of MSCA-RISE Action of the H2020 Programme, Project 734899—Olive-Net. RL-M is a recipient of a Miguel Servet type I programme fellowship from the ISCIII, co-funded by the ESF (CP16/00033)

Social economy and participatory guarantee systems: systematisation of an agroecological experience

[EN] Sustainability considerations have not gone unnoticed in the agri-food sector, which has always been perceived as a traditional sector. More and more producers and consumers are demanding agroecological products that respect not only the environment but also guarantee the socioeconomic quality of society. Within the social and solidarity economy framework, the Participatory Guarantee Systems (PGS) are known as agroecological quality certification instruments used mainly by agricultural producers. Farms are worldwide managed by individual producers or families (more than 90%), which underlines the importance of family farming in the agri-food sector. Considering the importance of sustainability and agroecology in this sector, this paper aims to analyze how PGSs contribute to local sustainable development, as well as to determine their implications for the local economy. For this purpose, a case study has been conducted in the Villarino district, located in the province of Buenos Aires in Argentina. The results show that agroecological certification encourages the adoption of collaborative strategies that positively affect the organization of the territory, such as increasing the small producers¿ power, income, and knowledge of sustainable production. Therefore, PGSs could be used to reinforce the food system and the stakeholders involved in this sector, achieving a greater scope of the Sustainable Development Goals.[ES] Las consideraciones de sostenibilidad no han pasado desapercibidas en el sector agroalimentario el cual ha sido siempre percibido como un sector tradicional. Cada vez son más los productores y consumidores que demandan productos agroecológicos que no solo respeten el medio ambiente, sino que también tengan presentes elementos sociales. En el marco de la economía social y solidaria, se encuadran los Sistemas de Garantía Participativa (SPG) conocidos como instrumentos de certificación de calidad agroecológica utilizados por productores agrarios A nivel mundial, los productores individuales o las familias son las que gestionan más del 90% de explotaciones agrarias lo cual destaca la importancia de la agricultura familiar en el sector agroalimentario. Teniendo en cuenta la importancia de la sostenibilidad y agroecología en dicho sector, la presente investigación pretende analizar cómo los SPG contribuyen al desarrollo local sostenible, así como determinar sus implicaciones. Para ello, se ha realizado un estudio de caso del Partido de Villarino, en la provincia de Buenos Aires en Argentina. Los resultados muestran que la certificación agroecológica fomenta la adopción de estrategias de colaboración las cuales tienen efectos positivos en la organización del territorio como el aumento de poder de los pequeños productores, de los ingresos de los productores y del conocimiento en materia de producción sostenible. Por tanto, los SPG pueden utilizarse como estrategia para el fortalecimiento del sistema alimentario y los stakeholders que participan en este sector logrando una mayor contribución a los Objetivos de Desarrollo Sostenible.Piñeiro, V.; Comezaña, MM.; Cuppari, SY.; Palacios, P.; Saldungaray, MC.; Roig-Tierno, N. (2022). Economía social y sistemas participativos de garantía: sistematización de una experiencia agroecológica. Revista del Ministerio de Trabajo y Economía Social. 153:113-128. https://doi.org/10.55617/revmites.1711312815

Caracterización fisicoquímica y sensorial de bebidas fermentadas a base de miel elaboradas en Argentina

PosterArgentina es el quinto productor y el segundo exportador mundial de miel a granel, mercado donde comercializa el 90-95% de la miel que cosecha. La elaboración de bebidas fermentadas a base de miel, cómo lo es la hidromiel o aguamiel, es una alternativa para el agregado de valor a la miel. En los últimos años se han desarrollado emprendimientos mayoritariamente de pequeña y mediana escala a lo largo del país para producir bebidas fermentadas a base de miel aprovechando insumos locales y buscando una identidad que les permita instalarse en el mercado y proyectarse a nivel nacional. El objetivo del presente trabajo fue caracterizar fisicoquímica y sensorialmente bebidas fermentadas a base de miel de Argentina. En el marco de un encuentro con elaboradores de todo el país, estos presentaron 24 bebidas que fueron agrupadas de acuerdo al proceso de elaboración declarado por el fabricante (hidromieles clásicas, especiadas, frutadas, lupuladas y cervezas con miel). A cada grupo de bebidas se le realizaron análisis fisicoquímicos, siendo los más relevantes la concentración de alcohol y el contenido de azúcares que permite clasificar las muestras en secas, semidulces y dulces según el Código Alimentario Argentino (CAA). Al momento de analizar sensorialmente las bebidas se establecieron cuatro descriptores (vista, gusto, olfato, equilibrio global), en base a los cuales un panel de 34 consumidores evaluó cada bebida y la clasificó con un puntaje del 1 al 6 para cada uno de los descriptores propuestos. Los datos obtenidos se analizaron estadísticamente. Si bien se elaboran diferentes tipos de bebidas fermentadas a base de miel en el país, la mitad de los productos presentados por los elaboradores fueron hidromieles clásicas. Todas las hidromieles analizadas (clásicas, frutadas, especiadas y lupuladas) tienen una concentración de alcohol de entre 4 y 14% v/v como exige el CAA. La mayoría de las bebidas tienen valores de alcohol menores a 10% v/v y presentan una concentración de azúcares ≤10 g/L por lo que se las clasifica como secas. Teniendo en cuenta el análisis sensorial de las bebidas fermentadas a base de miel, los descriptores utilizados permitieron diferenciar los distintos productos. Las bebidas mejor evaluadas fueron la número 22 (cerveza de miel negra), seguida por la número 20 (cerveza de miel dorada), siendo más valoradas por el gusto. Además, las hidromieles clásicas 6 (dulce) y 11 (seca) fueron asociadas a los descriptores olfato y equilibrio global. Existe una gran variedad de estilos de bebidas fermentadas a base de miel que se comercializan en el país. Esto agrega valor a la miel en las diferentes regiones y les proporciona a los elaboradores alternativas para diferenciarse dentro del mercado.EEA La ConsultaFil: Marini, Gina Veronica. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria La Consulta; ArgentinaFil: Peinado Manzur, Horacio Hernan. Ministerio de Agricultura, Ganaderia y Pesca de la NacionFil: Chimeno, Selva Valeria. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Mendoza; ArgentinaFil: Mercado, Laura Analia. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Mendoza; ArgentinaFil: Massera, Ariel Fernando. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Mendoza; Argentin

Diastereoselective [3 + 2] vs [4 + 2] Cycloadditions of Nitroprolinates with α,β-Unsaturated Aldehydes and Electrophilic Alkenes: An Example of Total Periselectivity

Diastereoselective multicomponent reactions of enantioenriched 4-nitroprolinates, obtained by enantiocatalyzed 1,3-dipolar cycloaddition (1,3-DC) of imino esters and nitroalkenes, with α,β-unsaturated aldehydes and electrophilic alkenes proceed with total periselectivity depending on the structure of the aldehyde employed. This process evolves through a [3 + 2] 1,3-DC when cinnamaldehyde is used in the presence of an azomethine ylide, giving the corresponding highly substituted pyrrolizidines with endo selectivity. However, in the case of the α,β-unsaturated aldehyde, which contains a hydrogen atom at the γ position, an amine–aldehyde–dienophile (AAD) [4 + 2] cycloaddition takes place by formation of an intermediate 1-amino-1,3-diene, affording highly functionalized cyclohexenes with high endo diastereoselectivity. This AAD process only occurred when a nitro group is bonded to the 4-position of the initial enantiomerically enriched pyrrolidine ring. DFT calculations have been carried out with the aim of explaining this different behavior between pyrrolidines with or without a nitro group, demonstrating the strong nitro-group-dependent periselectivity. The results of these computational studies also support the experimentally obtained absolute configuration of the final adducts.Financial support was provided by the Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P, CTQ2016-80375-P, and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), the University of Alicante, the Gobierno Vasco/Eusko Jaurlaritza (Grant IT673-13), and the University of the Basque Country UPV/EHU (UFI11/22 QOSYC). O.L. gratefully acknowledges the UPV/EHU for her postdoctoral grant