Light-driven enantioselective synthesis of pyrroline derivatives by a radical/polar cascade reaction

This is the peer reviewed version of the following article: Angewandte Chemie - International Edition 60.9 (2021): 4555-4560, which has been published in final form at https://doi.org/10.1002/anie.202013020. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibitedHerein, a light-driven, atom-economical process that provides access to enantiomerically enriched substituted chiral 1-pyrroline derivatives is introduced. The strategy involves the distal functionalization of acyl heterocycles through a hydrogen-atom transfer (HAT) process and the use of tailor-made ketimines as reliable electrophilic partners. This transformation is translated into an enantiomerically controlled radical/polar cascade reaction in which water is produced as the sole by-product and stereoselectivity is dictated by coordination to a chiral-at-rhodium catalystFinancial support was provided by the European Research Council (ERC-CoG, contract number: 647550, 861930), Spanish Government (RTI2018-095038-B-I00), “Comunidadde Madrid” and European Structural Funds (S2018/NMT-4367

Magnesium Deintercalation From the Spinel-Type MgMn2-yFeyO4 (0.4≤y≤2.0) by Acid-Treatment and Electrochemistry

Rechargeable magnesium batteries attract lots of attention because of their high safety and low cost compared to lithium batteries, and it is needed to develop more efficient electrode materials. Although MgMn2O4 is a promising material for the positive electrode in Mg rechargeable batteries, it usually exhibits poor cyclability. To improve the electrochemical behavior, we have prepared nanoparticles of MgMn2-yFeyO4. The XRD results have confirmed that when Mn3+ (Jahn-Teller ion) ions are replaced by Fe3+ (non-Jahn-Teller ion), the resulting MgMn2-yFeyO4 is a cubic phase. The structure and theoretical voltage are theoretically calculated by using the DFT method. The obtained samples have been chemically treated in acid solution for partial demagnesiation, and it is observed that the presence of iron inhibits the deinsertion of Mg through disproportionation and favors the exchange reaction. The electrochemical behavior in non-aqueous magnesium cells has been explored

Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and ortho-Sulfinyl Carbanions

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.joc.7b02887The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp-Csp 3 bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) of the ortho-sulfinylbenzyl carbanions, followed by elimination of the arylsulfonyl moiety. The scope of this alkynylation reaction is also discussed. Moreover, the development of a new approach for the synthesis of optically active tertiary benzylpropargyl alcohols is described, discussing the possible stereocourse of the reaction so as the influence of the ether 18-crown-6 and steric importance of acetylenic substituentWe thank DGAPA-UNAM (project number PAPIITIN205316) for financial support. Financial support from the Spanish Government (CTQ2015-64561-R) is also gratefully acknowledge

Morphological studies of Hapalospongidion macrocarpum and Nemoderma tingitanum (phaeophyceae) from the Salvage Islands (Madeira archipelago).

Two species of encrusting brown algae (Phaeophyceae) are newly recorded for the Salvage Islands (Madeira Archipelago) viz. Nemoderma tingitanum and Hapalospongidion macrocarpum. The species are described, and information is presented concerning their ecology, morphology and geographical distribution in the Atlantic

Xyloglucan, Hibiscus and Propolis for the prevention of Urinary Tract Infections: results of in vitro studies

Aim: To assess the properties of a medical device containing xyloglucan, propolis and hibiscus to create a bioprotective barrier to avoid the contact of uropathogenic Escherichia coli strains on cell walls in models of intestinal (CacoGoblet) and uroepithelial (RWPE-1) cells (derived from normal human prostate epithelium). Materials & methods: Two uropathogenic E. coli strains (expressing type 1 fimbriae and P fimbriae) were used to assess, by electronic microscopy and ELISA, the barrier properties of the medical device. The antimicrobial activity was assessed in broth dilution assays. Results: The three components (xyloglucan, propolis and hibiscus) did not alter E. coli cell integrity in intestinal and uroepithelial cell models and were devoid of antibacterial activity. The three components avoided bacterial contact in both cell monolayers. Conclusion: The nonpharmacological barrier properties of xyloglucan, propolis and hibiscus confirm the role of the medical device for the management of urinary tract infections

Evaluation of DNA Single and Double Strand Breaks in Women with Cervical Neoplasia Based on Alkaline and Neutral Comet Assay Techniques

A hospital-based unmatched case-control study was performed in order to determine the relation of DNA single (ssb) and double (dsb) strand breaks in women with and without cervical neoplasia. Cervical epithelial cells of 30 women: 10 with low grade squamous intraepithelial lesions (LG-SIL), 10 with high-grade SIL (HG-SIL), and 10 without cervical lesions were evaluated using alkaline and neutral comet assays. A significant increase in global DNA damage (ssb + dsb) and dsb was observed in patients with HG-SIL (48.90 ± 12.87 and 23.50 ± 13.91), patients with LG-SIL (33.60 ± 14.96 and 11.20 ± 5.71), and controls (21.70 ± 11.87 and 5.30 ± 5.38; resp.). Pearson correlation coefficient reveled a strong relation between the levels ssb and dsb (2=0.99, =0.03, and 2=0.94, =0.16, resp.) and progression of neoplasia. The increase of dsb damage in patients with HG-SIL was confirmed by DNA breakage detection-FISH (DBD-FISH) on neutral comets. Our results argue in favor of a real genomic instability in women with cervical neoplasia, which was strengthened by our finding of a higher proportion of DNA dsb

Examination of the Feynman-Hibbs Approach in the Study of NeN_N-Coronene Clusters at Low Temperatures

Feynman-Hibbs (FH) effective potentials constitute an appealing approach for investigations of many-body systems at thermal equilibrium since they allow us to easily include quantum corrections within standard classical simulations. In this work we apply the FH formulation to the study of Ne$_N$-coronene clusters ($N=$ 1-4, 14) in the 2-14 K temperature range. Quadratic (FH2) and quartic (FH4) contributions to the effective potentials are built upon Ne-Ne and Ne-coronene analytical potentials. In particular, a new corrected expression for the FH4 effective potential is reported. FH2 and FH4 cluster energies and structures -obtained from energy optimization through a basin-hoping algorithm as well as classical Monte Carlo simulations- are reported and compared with reference path integral Monte Carlo calculations. For temperatures $T> 4$ K, both FH2 and FH4 potentials are able to correct the purely classical calculations in a consistent way. However, the FH approach fails at lower temperatures, especially the quartic correction. It is thus crucial to assess the range of applicability of this formulation and, in particular, to apply the FH4 potentials with great caution. A simple model of $N$ isotropic harmonic oscillators allows us to propose a means of estimating the cut-off temperature for the validity of the method, which is found to increase with the number of atoms adsorbed on the coronene molecule

Ordenha mecânica nas explorações de caprinos de Trás-os-Montes (Portugal): problemas e dificuldades para a sua divulgação

Na região de Trás-os-Montes (nordeste de Portugal) a exploração de cabras de leite, principalmente da raça Serrana, autóctone, é uma actividade relativamente importante do ponto de vista socioeconómico, porque se trata de uma região pobre e onde são raras as actividades económicas alternativas para a população rural. Para o desenvolvimento da actividade e para a melhoria da qualidade e quantidade de leite produzido, é importante melhorar as condições de ordenha, especialmente quanto às instalações e equipamentos; e às condições de trabalho do ordenhador. A maioria das explorações de caprinos da região pratica a ordenha manual. Este tipo de ordenha tem vários problemas quanto às condições de trabalho e à qualidade do leite recolhido. Nos últimos anos desenvolveram-se várias acções no sentido de melhorar as condições de ordenha e de incentivar os criadores para a adopção de ordenha mecânica. No entanto, verificam-se alguns problemas e dificuldades dos criadores na adopção e utilização destes equipamentos. Com este trabalho, pretende-se identificar os problemas e dificuldades que resultaram da adopção/utilização de equipamentos de ordenha mecânica em explorações de cabras de leite da região de Trás-os-Montes. O estudo da ordenha mecânica abrangeu vários aspectos: os equipamentos utilizados; a organização do trabalho e das instalações; e os procedimentos do ordenhador no trabalho de ordenha. Foram estudadas as explorações de caprinos de raça Serrana da região de Trás-os-Montes que utilizam qualquer tipo de ordenha mecânica. A informação recolhida permite concluir que há dificuldades na adaptação ao uso de novas técnicas de ordenha e equipamentos. Os problemas estão, principalmente, relacionados com a organização do trabalho e do local da ordenha, e com a aprendizagem da correcta utilização dos equipamentos. De futuro, será importante considerar o desenvolvimento de acções de apoio técnico aos criadores, no sentido de melhorar as instalações/local de ordenha e a utilização dos equipamentosIn the national context, the region of Trás-os-Montes, in Northeastern Portugal, is one of the most depopulated and least favoured areas. In this region, goat breeding has great socioeconomic importance due to the number of families that are economically dependent on these activities. This importance is particularly due to the scarcity of alternative economic activities. To improve goat breeding, milk production and milk quality, it is important to enhance milking conditions, mainly in facilities, equipment and working conditions. Presently, there are very few farms with milking machines. Mostly, goats are hand-milked inside the shelters. As a result of actions carried out over the recent years involving strategies to improve milking conditions on goat farms in the region, some breeders adopted mechanical milking. For these breeders, mechanical milking is a new technology, they are inexperienced and they lack knowledge about the correct use of these machines and best milking practices. To study mechanical milking we established the following aspects to consider: working organization and facilities, milking operations, and procedures performed by milkers. Goat farms that used mechanical milking in the region of Trás-os-Montes were studied. From the information collected, it was found some difficulties in the adaptation to the use of new milking techniques. Main problems are related to working organization, facilities and equipment utilization

Improving an Ambient Intelligence Based Multi-Agent System for Alzheimer Health Care using Wireless Sensor Networks

This paper describes last improvements made on ALZ-MAS; an Ambient Intelligence based multi-agent system aimed at enhancing the assistance and health care for Alzheimer patients. The system makes use of several context-aware technologies that allow it to automatically obtain information from users and the environment in an evenly distributed way, focusing on the characteristics of ubiquity, awareness, intelligence, mobility, etc., all of which are concepts defined by Ambient Intelligence. Among these context-aware technologies we have Wireless Sensor Networks. In this sense, ALZ-MAS is currently being improved by the use of a new platform of ZigBee devices that provides the system with new telemonitoring and locating engine

Coronene molecules in helium clusters: Quantum and classical studies of energies and configurations

Under the terms of the Creative Commons Attribution (CC BY) license to their work.Coronene-doped helium clusters have been studied by means of classical and quantum mechanical (QM) methods using a recently developed He–C24H12 global potential based on the use of optimized atom-bond improved Lennard-Jones functions. Equilibrium energies and geometries at global and local minima for systems with up to 69 He atoms were calculated by means of an evolutive algorithm and a basin-hopping approach and compared with results from path integral Monte Carlo (PIMC) calculations at 2 K. A detailed analysis performed for the smallest sizes shows that the precise localization of the He atoms forming the first solvation layer over the molecular substrate is affected by differences between relative potential minima. The comparison of the PIMC results with the predictions from the classical approaches and with diffusion Monte Carlo results allows to examine the importance of both the QM and thermal effects.This work has been supported by MICINN Grant Nos. FIS2011-29596-C02-01, FIS2013-48275-C2-1-P, and FIS2014-51993-P. R.R.-C. acknowledges funding from the Grant No. JAE-Pre-2010-01277. J.H.-R. and J.B. acknowledge the financial support from Ministerio de Economía y Competitividad under Grant No. FIS2013-41532-P.Peer reviewe