Novel nickel nanoparticles stabilized by imidazolium-amidinate ligands for selective hydrogenation of alkynes

[EN] The main challenge in the hydrogenation of alkynes into (E)- or (Z)-alkenes is to control the selective formation of the alkene, avoiding the over-reduction to the corresponding alkane. In addition, the preparation of recoverable and reusable catalysts is of high interest. In this work, we report novel nickel nanoparticles (Ni NPs) stabilized by three different imidazolium-amidinate ligands (ICy center dot(NCN)-N-(Ar); L1: Ar = p-tol, L2: Ar = p-anisyl and L3: Ar = p-ClC6H4). The as-prepared Ni NPs were fully characterized by (HR)-TEM, XRD, WASX, XPS and VSM. The nanocatalysts are active in the hydrogenation of various substrates. They present a remarkable selectivity in the hydrogenation of alkynes towards (Z)-alkenes, particularly in the hydrogenation of 3-hexyne into (Z)-3-hexene under mild reaction conditions (room temperature, 3% mol Ni and 1 bar H-2). The catalytic behaviour of Ni NPs was influenced by the electron donor/acceptor groups (-Me, -OMe, -Cl) in the N-aryl substituents of the amidinate moiety of the ligands. Due to the magnetic character of the Ni NPs, recycling experiments were successfully performed after decantation in the presence of an external magnet, which allowed us to recover and reuse these catalysts at least 3 times preserving both activity and chemoselectivity.The authors thank CNRS, UPS-Toulouse, INSA, "IDEX/Chaires d'attractivite l'Universite Federale Toulouse Midi-Pyrenees", "Instituto de Tecnologia Quimica" (ITQ; UPV-CSIC), "Juan de la Cierva" programme (IJCI-2016-27966), "Primero Proyectos de Investigacion" (PAID-06-18), "Instituto de Investigaciones Quimicas" (IIQ; CSIC-US), "Ministerio de Ciencia, Innovacion y Universidades" (MCIU/AEI), FEDER funds of the European Union (PGC2018-095768-B-I00) and ERC Advanced Grant (MONACAT 2015-694159) for financial support. We also thank L. Datas for the TEM facilities (UMS Castaing) and S. Cayez for the HRTEM measurements.López-Vinasco, AM.; Martínez-Prieto, LM.; Asensio, JM.; Lecante, P.; Chaudret, B.; Cámpora, J.; Van Leeuwen, PWNM. (2020). Novel nickel nanoparticles stabilized by imidazolium-amidinate ligands for selective hydrogenation of alkynes. Catalysis Science & Technology. 10(2):342-350. https://doi.org/10.1039/c9cy02172hS342350102Swamy, K. C. K., Reddy, A. S., Sandeep, K., & Kalyani, A. (2018). Advances in chemoselective and/or stereoselective semihydrogenation of alkynes. Tetrahedron Letters, 59(5), 419-429. doi:10.1016/j.tetlet.2017.12.057Lei, J., Su, L., Zeng, K., Chen, T., Qiu, R., Zhou, Y., … Yin, S.-F. (2017). Recent advances of catalytic processes on the transformation of alkynes into functional compounds. Chemical Engineering Science, 171, 404-425. doi:10.1016/j.ces.2017.05.021J. G. de Vries and C. 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Deterministic and time resolved thermo-magnetic switching in a nickel nanowire

[EN]Heating a ferromagnetic material is often perceived as detrimental for most applications. This is indeed the case for modern nano-scaled spintronic devices which are operated solely (at least ideally) by an electric current. Heat is a by-product of the current-driven operation and it deteriorates many functionalities of the device. A large scientific and technological effort is devoted these days to avoid heat in modern magnetic nano devices. Here we show that heat can be used to provide an additional and useful degree of freedom in the control of the local magnetization at the nanoscale. In a ferromagnetic nanowire, temperature is used to induce a magnetic switching through a perfectly deterministic mechanism. The nucleation of the magnetic domain walls that triggers the switching can be achieved at a field considerably smaller than the nucleation field and, importantly, the exact moment of the magnetic switching can be pre-determined with nanosecond precision by controlling the power delivered locally to the switching area. With the help of micromagnetic simulations and a theoretical model, we provide an accurate explanation of how this deterministic thermo-magnetic switching operates. The concepts described in this work may lead to an increased functionality in magnetic nano-devices based on magnetic domain walls.MAT2017-87072-C4-1-P,MAT2017-87072-C4-4-P and MAT2017-87072-C4-3-P from the Spanish government SA299P18 from the Junta de Castilla y Leon POCI-01-0145-FEDER-028676 from Portuguese FCT COMPETE 2020 (FEDER)

Ultrastable Magnetic Nanoparticles Encapsulated in Carbon for Magnetically Induced Catalysis

[EN] Magnetically induced catalysis using magnetic nanoparticles (MagNPs) as heating agents is a new efficient method to perform reactions at high temperatures. However, the main limitation is the lack of stability of the catalysts operating in such harsh conditions. Normally, above 500 degrees C, significant sintering of MagNPs takes place. Here we present encapsulated magnetic FeCo and Co NPs in carbon (Co@C and FeCo@C) as an ultrastable heating material suitable for high-temperature magnetic catalysis. Indeed, FeCo@C or a mixture of FeCo@C:Co@C (2:1) decorated with Ni or Pt-Sn showed good stability in terms of temperature and catalytic performances. In addition, consistent conversions and selectivities regarding conventional heating were observed for CO2 methanation (Sabatier reaction), propane dehydrogenation (PDH), and propane dry reforming (PDR). Thus, the encapsulation of MagNPs in carbon constitutes a major advance in the development of stable catalysts for high-temperature magnetically induced catalysis.The authors thank the Instituto de Tecnologia Quimica (ITQ), Consejo Superior de Investigaciones Cientificas (CSIC), Universitat Politecnica de València (UPV) for the facilities and Severo Ochoa programe (SEV-2016-0683), "Juan de la Cierva" by MINECO (IJCI-2016-27966), and Primero Proyectos de Investigación PAID-06-18 (SP20180088) for financial support. The authors acknowledge ERC Advanced Grants (MONACAT-2015-694159 and SynCatMatch-2014671093). We also thank the Electron Microscopy Service of the UPV for TEM facilities.Martínez-Prieto, LM.; Marbaix, J.; Asensio, JM.; Cerezo-Navarrete, C.; Fazzini, P.; Soulantica, K.; Chaudret, B.... (2020). Ultrastable Magnetic Nanoparticles Encapsulated in Carbon for Magnetically Induced Catalysis. 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Evaluación de las necesidades hídricas de tres variedades de fresas y de su respuesta frente a un recorte hídrico moderado

Instituto Nacional de Investigaciones RTA2012-00001-00-00FEDER CC10-009-C02-0

Emission polarization control in semiconductor quantum dots coupled to a photonic crystal microcavity

8 páginas, 5 figuras.-- OCIS codes: (160.4760) Optical properties; (230.5298) Photonic crystals; (230.5590) Quantumwell, -wire and –dot devices.We study the optical emission of single semiconductor quantum dots weakly coupled to a photonic-crystal micro-cavity. The linearly polarized emission of a selected quantum dot changes continuously its polarization angle, from nearly perpendicular to the cavity mode polarization at large detuning, to parallel at zero detuning, and reversing sign for negative detuning. The linear polarization rotation is qualitatively interpreted in terms of the detuning dependent mixing of the quantum dot and cavity states. The present result is relevant to achieve continuous control of the linear polarization in single photon emitters.This work has been supported by research contracts of the Spanish Ministry of Education Grants MAT2008-01555/NAN, Consolider CSD 2006-19 and Naninpho-QD TEC2008-06756-C03- 01, and the Community of Madrid Grant Grant CAM (S2009/ESP-1503).Peer reviewe

Sequential Loading of Cohesin Subunits during the First Meiotic Prophase of Grasshoppers

A previous version of this article appeared as an Early Online Release on January 2, 2007 (doi:10.1371/journal.pgen.0030028.eor).The cohesin complexes play a key role in chromosome segregation during both mitosis and meiosis. They establish sister chromatid cohesion between duplicating DNA molecules during S-phase, but they also have an important role during postreplicative double-strand break repair in mitosis, as well as during recombination between homologous chromosomes in meiosis. An additional function in meiosis is related to the sister kinetochore cohesion, so they can be pulled by microtubules to the same pole at anaphase I. Data about the dynamics of cohesin subunits during meiosis are scarce; therefore, it is of great interest to characterize how the formation of the cohesin complexes is achieved in order to understand the roles of the different subunits within them. We have investigated the spatio-temporal distribution of three different cohesin subunits in prophase I grasshopper spermatocytes. We found that structural maintenance of chromosome protein 3 (SMC3) appears as early as preleptotene, and its localization resembles the location of the unsynapsed axial elements, whereas radiation-sensitive mutant 21 (RAD21) (sister chromatid cohesion protein 1, SCC1) and stromal antigen protein 1 (SA1) (sister chromatid cohesion protein 3, SCC3) are not visualized until zygotene, since they are located in the synapsed regions of the bivalents. During pachytene, the distribution of the three cohesin subunits is very similar and all appear along the trajectories of the lateral elements of the autosomal synaptonemal complexes. However, whereas SMC3 also appears over the single and unsynapsed X chromosome, RAD21 and SA1 do not. We conclude that the loading of SMC3 and the non-SMC subunits, RAD21 and SA1, occurs in different steps throughout prophase I grasshopper meiosis. These results strongly suggest the participation of SMC3 in the initial cohesin axis formation as early as preleptotene, thus contributing to sister chromatid cohesion, with a later association of both RAD21 and SA1 subunits at zygotene to reinforce and stabilize the bivalent structure. Therefore, we speculate that more than one cohesin complex participates in the sister chromatid cohesion at prophase I.This work was supported by grants BFU2005–05668-C03–01, BFU2006–06655, BFU2005–01266, BFU2005–02431, and BFU2006–04406 from Ministerio de Educación y Ciencia, España, and grants 1001160016 and 11/BCB/013 from Universidad Autónoma de Madrid and Comunidad de Madrid. The Department of Immunology and Oncology was founded and is supported by the Spanish Council for Scientific Research (CSIC).Peer reviewe

Validation of a simple method for the interpretation of uterine cytology in cows

One of the main drawbacks of using endometrial cytology in cows is the time required for sample collection and interpretation. It is recommended to count a large number of polymorphonuclear neutrophils (PMN) and to calculate their overall percentage. However, since counting a large number of cells is a laborious method, it would be preferable to simplify the analysis by counting the number of PMN in few microscopic fields. Therefore, the aim of this study was to assess whether a simple test, based on calculating the average number of PMN in 10 fields at 1000×, could be a reliable technique for the diagnosis of endometritis. Two hundred and sixty endometrial samples were taken from Holstein cows at different postpartum stages using an adapted cytobrush. Smears obtained were air-dried for fixing and stained with a Romanowsky-type procedure. To evaluate the counting method, the percentage of PMN in 150 cells was calculated as well as the average number of PMN in 10 fields at 1000×. Receiver operating characteristic (ROC) curves was constructed to evaluate both methods, the percentage of PMN (used as reference) and the average number of PMN. It was observed that the area under the curve is (regardless of cut-off used) higher than 0.99 and the correspondence between both methods were 1.58 PMN/field for the cut-off value of 15% and 2.40 PMN/field for the cut-off value of 20%. These results show that this simple method could be used to determine the percentage of PMN in endometrial cytological samples and to diagnose endometritis in cowsSupported by the Xunta de Galicia (Galician Plan for Research and Technological Development; Grant No. PGIDIT07MRU002E) and the Friesian Federation of Galician, A Coruna, SpainS

Reuse Detector: improving the management of STT-RAM SLLCs

Various constraints of Static Random Access Memory (SRAM) are leading to consider new memory technologies as candidates for building on-chip shared last-level caches (SLLCs). Spin-Transfer Torque RAM (STT-RAM) is currently postulated as the prime contender due to its better energy efficiency, smaller die footprint and higher scalability. However, STT-RAM also exhibits some drawbacks, like slow and energy-hungry write operations that need to be mitigated before it can be used in SLLCs for the next generation of computers. In this work, we address these shortcomings by leveraging a new management mechanism for STT-RAM SLLCs. This approach is based on the previous observation that although the stream of references arriving at the SLLC of a Chip MultiProcessor (CMP) exhibits limited temporal locality, it does exhibit reuse locality, i.e. those blocks referenced several times manifest high probability of forthcoming reuse. As such, conventional STT-RAM SLLC management mechanisms, mainly focused on exploiting temporal locality, result in low efficient behavior. In this paper, we employ a cache management mechanism that selects the contents of the SLLC aimed to exploit reuse locality instead of temporal locality. Specifically, our proposal consists in the inclusion of a Reuse Detector (RD) between private cache levels and the STT-RAM SLLC. Its mission is to detect blocks that do not exhibit reuse, in order to avoid their insertion in the SLLC, hence reducing the number of write operations and the energy consumption in the STT-RAM. Our evaluation, using multiprogrammed workloads in quad-core, eight-core and 16-core systems, reveals that our scheme reports on average, energy reductions in the SLLC in the range of 37–30%, additional energy savings in the main memory in the range of 6–8% and performance improvements of 3% (quad-core), 7% (eight-core) and 14% (16-core) compared with an STT-RAM SLLC baseline where no RD is employed. More importantly, our approach outperforms DASCA, the state-of-the-art STT-RAM SLLC management, reporting—depending on the specific scenario and the kind of applications used—SLLC energy savings in the range of 4–11% higher than those of DASCA, delivering higher performance in the range of 1.5–14% and additional improvements in DRAM energy consumption in the range of 2–9% higher than DASCA.Peer ReviewedPostprint (author's final draft