Estudi de la diversitat de picoflagel·lats heterotròfics a la zona de Blanes mitjançant tècniques moleculars i de cultiu

S'ha estudiat la diversitat de picoflagel·lats heterotròfics, d'aigües del nord-oest del mar Mediterrani, mitjançant DGGE , biblioteques de clons i enriquiments. S'ha trobat que la diversitat és alta (índex Shannon 2,227), com en d'altres estudis, però que disminueix en afegir matèria orgànica (extracte de llevat o d'arròs), amb índex de Shannon de fins a 0,731. Per una entrada d'aigua continental rica en nutrients, s'han desenvolupat millor les crisofícies en detriment d'altres organismes habituals al medi marí, com els MAST.Se ha estudiado la diversidad de picoflagelados heterotróficos de aguas del norte-oeste del mar Mediterráneo, mediante DGGE, bibliotecas de clones i cultivos. Se ha visto que la diversidad es alta (índice de Shannon de 2,227), como en otros estudios, pero que disminuye al añadir materia orgánica (extracto de levadura o de arroz), con índices de Shannon de hasta 0,731. A causa de una entrada de agua continental rica en nutrientes, se han desarrollado mejor las crisofíceas en detrimento de otros organismos habituales al medio marino, como los MAST.We have studied the diversity of heterotrophic picoflagellates, on the northwest of the Mediterranean Sea, with DGGE, clone libraries and enrichments. We have found a high diversity (Shannon index of 2,227), like in other studies, but it decreased with the addition of organic materia (with both yeast and rice extract) until a Shannon index of 0,731. Other organisms not as habitual in this area as MAST have been better developed: the crysophycea. The possible cause is a contamination of the study area by urban residual waters

Predesigned covalent organic frameworks as effective platforms for Pd(II) coordination enabling cross-coupling reactions under sustainable conditions

The phenanthroline unit in an imine-based covalent organic framework (Phen-COF) offers a robust coordination site for Pd(OAc)2 centers. Coordination of palladium centers is demonstrated by a variety of techniques, including X-ray photoelectron spectroscopy and total X-ray fluorescence. The stable phenanthroline-Pd(II) coordination avoids leaching of metal centers to the reaction medium, where deactivation processes through nanoparticle formation limits the catalytic activities observed for homogeneous systems. Thus, because of isolation and immobilization of catalytic sites in the Pd@Phen-COF the performance of material, the catalytic outputs are dramatically increased with respect to the performance observed for analogous molecular catalysts. This concept is applied in this work to C-C cross-coupling reactions under mild and environmentally benign conditions. The activities found for Suzuki-Miyaura and Mizoroki-Heck reactions allow thousands of turnover numbers in the transformation of a wide scope of precursors with a high degree of recyclability. The results reported in this work contribute to the design of greener protocols for transformations that have a crucial role in the industrial synthesis of high-added value fine chemical

Visible light mediated photocatalytic [2 + 2] cycloaddition/ring-opening rearomatization cascade of electron-deficient azaarenes and vinylarenes

The broad presence of azaarene moieties in natural products has promoted the development of new functionalization reactions, giving access to larger libraries of bioactive compounds. The light promoted [2+ 2] photocycloaddition reaction to generate cyclobutanes has been extensively studied in photochemistry. In particular, De Mayo reported the [2 + 2] cycloaddition followed by retroaldol condensation between enols of 1,3-dicarbonyls and double bonds to synthesize 1,5-dicarbonyls. Herein, we describe the [2 + 2] photocycloaddition followed by a ring-opening rearomatization reaction between electron-deficient 2-methylene-azaarenes and double bonds, taking advantage of the ability of these heterocyclic derivatives to form the corresponding pseudo-enamine intermediate. The procedure shows a high functional group tolerance either on the double bond or the heteroarene side and allows the presence of different electron-withdrawing groups. In addition, the wide applicability of this reaction has been demonstrated through the late-stage derivatization of several natural products. Photochemical studies, together with theoretical calculations, support a mechanism involving the photosensitization of the pseudo-enamine intermediateWe acknowledge the financial support from the Spanish Government (RTI2018–095038-B-I00), CAM_UAM (SI1/PJI/2019-00237), CCC-UAM (computing time), and ERC (ERC-CG, 647550). The authors also wish to thank the ‘Comunidad de Madrid’ and European Structural Funds for their financial support to FotoArt-CM project (S2018/NMT-4367

Nanotribology and electrical properties of carbon nanotubes hybridized with covalent organic frameworks

Nanomanipulation of molecular materials such as carbon nanotubes (CNTs) or new covalent organic frameworks (COFs) is key not only for the study of their fundamental physicochemical properties, but also for building and probing nanodevices. Therefore, we have investigated the tribological properties of oxidized MWCNTs (ox-MWCNTs) and their hybridization with COF building blocks (ox-MWCNTs@COF) adsorbed on a mica surface. We used the AFM tip to apply torsional forces on individual nanotubes. Depending on the manipulation parameters, the lateral displacements of the AFM tip slide and/or bend nanotubes enabling the direct quantification of the nanotube-mica adhesion. We found striking changes in the behaviour of the lateral force needed to manipulate each carbon nanotube variant which indicates an increased adhesion of ox-MWCNTs@COF with respect to ox-MWCNTs (∼10x). In addition, the use of the AFM tip as a mobile electrode enabled the measurement of electrical transport through individual nanotubes that revealed a rectifying behaviour of the ox-MWCNTs@COF with high resistivity, which was in contrast with the near ohmic performance of ox-MWCNTsP. J.d.P. acknowledges support by grants from the Ministerio de Ciencia e Innovacion (FIS2017- 89549-R; “Maria de Maeztu” Program for Units of Excellence in R&D MDM2014-0377; and FIS2017-90701- REDT) and the Human Frontiers Science Program (HFSPO RGP0012/ 2018). R. M. ackowledges support by grant PID2019-110637RB-10

Photoredox heterobimetallic dual catalysis using engineered covalent organic frameworks

The functionalization of an imine-based layered covalent organic framework (COF), containing phenanthroline units as ligands, has allowed the obtention of a heterobimetallated material. Photoactive Ir and Ni fragments were immobilized within the porous structure of the COF, enabling heterogeneous light-mediated Csp 3 -Csp 2 cross-couplings. As radical precursors, potassium benzyl- and alkoxy-trifluoroborates, organic silicates, and proline derivatives were employed, which brings out the good versatility of Ir,Ni@Phen-COF. Moreover, in all the studied cases, an enhanced activity and stability have been observed in comparison with analogous homogenous systems

Imine-Based Covalent Organic Frameworks as Photocatalysts for Metal Free Oxidation Processes under Visible Light Conditions

Embargo de 12 meses tras la publicación exigido por la editorialPhotochemistry of extended polyimine COF structures with laminar, spherical and 3D architectures has been examined. We show that these materials, composed by undecorated phenyl rings and imine fragments, can act as photocatalyts in oxidative transformations, being the crystalline laminar material the most active photocatalyst. The sulfoxidation reaction proceeds with good yields for a large variety of different sulfides. This process was carried out under visible light conditions (20 W), ethanol/H2O as solvent, and the heterogeneous porous material can be recycled up to 9 times. The crystallinity favours the behavior as photocatalyst of laminar and spherical COFs whereas any particular effect on the 3D material activity was observed. Sulfoxidation reaction mainly proceeds through an energy transfer mechanism using crystalline laminar material. In addition, these materials as photocatalysts were used for the oxidation of phenyl boronic acid into phenolWe are grateful to the Spanish Government (CTQ2015- 64561-R and RTI2018-095038-B-I00), “Comunidad de Madrid” and European Structural Funds (S2018/NMT-4367). Leyre Marzo thanks to CAM for the Atracción de Talento fellowship (2/ 2017-T2/AMB-5037

Engineering photocatalytic porous organic materials for directing redox versus energy transfer processes

Two organic materials containing phenanthroline and triazine fragments, but connected in different ways, are presented. The imine-based material Phen–Tz–covalent organic framework (COF) preferentially shows photocatalytic activity through an energy transfer pathway as observed for olefin photoisomerization. However, an analogous covalent triazine framework (Phen–CTF) behaves as a powerful photoredox catalyst able to activate C-X (X=Br, Cl) bonds. The analysis of this phenomenon by means of theoretical calculations enables the rationalization of the different photocatalytic behavior observed. Phen–CTF behaves as a donor–acceptor material resulting in efficient charge separation upon excitation, while the imine groups present in Phen–Tz–COF hamper charge separation contributing to the rapid recombination between electrons and holes. This justifies a better activation via electron transfer in Phen–CTF and via energy transfer in Phen–Tz–COFPID2021-122299NB-I0, PID2019-110637RB-I00, ID2020-112715GB-I00, PID2022-141016OB-I00, TED2021-130470B-I0, TED2021-129999B-C32, S2018/NMT-4367, Y2020/NMT64

Optical Coherence Tomography for the Diagnosis of Exercise-Related Acute Cardiovascular Events and Inconclusive Coronary Angiography

Objectives: The aim of this study is to assess the utility of optical coherence tomography (OCT) in patients with exercise-related acute coronary syndrome (ACS) presenting with inconclusive angiographic findings. Background: Regular physical activity reduces the incidence of cardiovascular events. Nevertheless, the risk of ACS or sudden cardiac death (SCD) increases during sport. In adults older than 35 years, exercise-related ACS or SCD is associated with plaque rupture, but not infrequently patients present ambiguous angiographic findings. Methods: Between September 2015 and January 2020, patients admitted for ACS or SCD triggered by physical exertion and with coronary stenosis ≤50% were included in this prospective observational study. OCT was performed on the artery deemed to be responsible of the event. Results: Ten patients were enrolled, predominantly men (80%) of middle age (51 years old, IQR 41-63) with low cardiovascular risk burden. Cycling was the most frequent (50%) exercise-related trigger, 8 patients were regular sport practitioners, and 7 had the clinical event during strenuous exertion. Five patients presented with non-ST-elevation ACS, two with ST-elevation ACS, and three with SCD. Angiographic analysis showed nonsignificant stenosis in all patients (42% stenosis, IQR 36-46). OCT identified the etiology of the event in 9 patients (4 plaque erosion, 3 plaque rupture, 1 eruptive calcific nodule, and 1 coronary dissection). Treatment was adjusted according to OCT findings. Conclusions: OCT is a valuable technique to identify the etiology of exercise-related ACS or SCD in patients with nonobstructive coronary arteries and, as a result, may lead to a more specific treatment

Characterisation of the ex vivo virulence of Leishmania infantum isolates from Phlebotomus perniciosus from an outbreak of human leishmaniosis in Madrid, Spain

BACKGROUND: Since mid 2009, an outbreak of human leishmaniosis in Madrid, Spain, has involved more than 560 clinical cases. Many of the cases occurred in people who live in areas around a newly constructed green park (BosqueSur). This periurban park provides a suitable habitat for sand flies (the vectors of Leishmania infantum). Indeed, studies of blood meals from sand flies captured in the area showed a strong association between the insect vector, hares or rabbits, and humans in the area. Interestingly, up to 70% of cases have been found in immunocompetent patients (aged between 46-60 years). This study was designed to evaluate the ex vivo virulence of the L. infantum isolates from Phlebotomus perniciosus captured in this area of Madrid. METHODS: Murine macrophages and dendritic cells were infected ex vivo with L. infantum strain BCN150, isolate BOS1FL1, or isolate POL2FL7. At different times after infection, the infection indices, cytokine production (IL-12p40 and IL-10), NO release and arginase activities were evaluated. RESULTS: Using an ex vivo model of infection in murine bone marrow-derived cells, we found that infection with isolates BOS1FL1 and POL2FL7 undermined host immune defence mechanisms in multiple ways. The main factors identified were changes in both the balance of iNOS versus arginase activities and the equilibrium between the production of IL-12 and IL-10. Infection with isolates BOS1FL1 and POL2FL7 also resulted in higher infection rates compared to the BCN150 strain. Infection index values at 24 h were as follows: BCN150-infected cells, 110 for infected MØ and 115 for infected DC; BOS1FL1-infected cells, 300 for infected MØ and 247 for infected DC; and POL2FL7-infected cells, 275 for infected MØ and 292 for infected DC. CONCLUSIONS: Our data indicate that L. infantum isolates captured from this endemic area exhibited high virulence in terms of infection index, cytokine production and enzymatic activities involved in the pathogenesis of visceral leishmaniosis. Altogether, these data provide a starting point for the study of the virulence behaviour of parasites (BOS1FL1 and POL2FL7) isolated from P. perniciosus during the outbreak of human leishmaniosis in Madrid, Spain, and their involvement in infecting immunocompetent hosts.This study was supported by Grants AGL2010-17394 and AGL2013-44100R from the Spanish Ministry of Economy and Competitiveness and was partially funded by EU grant FP7-2011-261504 EDENext and the paper is catalogued by the EDENext Steering Committee as EDENext 276 (http://www.edenext.eu).S

Fruit Morphology and Ripening-Related QTLs in a Newly Developed Introgression Line Collection of the Elite Varieties ‘Védrantais’ and ‘Piel de Sapo’

Melon is an economically important crop with widely diverse fruit morphology and ripening characteristics. Its diploid sequenced genome and multiple genomic tools make this species suitable to study the genetic architecture of fruit traits. With the development of this introgression line population of the elite varieties ‘Piel de Sapo’ and ‘Védrantais’, we present a powerful tool to study fruit morphology and ripening traits that can also facilitate characterization or pyramidation of QTLs in inodorous melon types. The population consists of 36 lines covering almost 98% of the melon genome, with an average of three introgressions per chromosome and segregating for multiple fruit traits: morphology, ripening and quality. High variability in fruit morphology was found within the population, with 24 QTLs affecting six different traits, confirming previously reported QTLs and two newly detected QTLs, FLQW5.1 and FWQW7.1. We detected 20 QTLs affecting fruit ripening traits, six of them reported for the first time, two affecting the timing of yellowing of the rind (EYELLQW1.1 and EYELLQW8.1) and four at the end of chromosome 8 affecting aroma, abscission and harvest date (EAROQW8.3, EALFQW8.3, ABSQW8.3 and HARQW8.3). We also confirmed the location of several QTLs, such as fruit-quality-related QTLs affecting rind and flesh appearance and flesh firmness.info:eu-repo/semantics/publishedVersio