8 research outputs found

    Experimental And Theoretical Analysis Of The Electronic Behavior In Five-Coordinate Iron(iii) And Six-Coordinate Cobalt(iii) Complexes With Electroactive Phenol-Rich Ligands

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    Three 5 coordinate high-spin Iron(III) complexes containing pentadentate N2O5 ligands were synthesized and characterized, namely, (1) [FeIII(L1)] and (2) [FeIII(L2)]. Structural differences in ligand design,N,N,N\u27-tris(3,5-di-tert-butyl-2-hydroxybenzyl)benzene-1,2-diamine for (1) and N,N,N\u27-tris-(3,5-di-tert-butyl-2-hydroxybenzyl)-N\u27-methyl-benzene-1,2-diamine for (2), result in complexes that due to their forced geometry, asymmetry, and slightly different electronic structures are able to foster phenoxyl radicals although show a sensitive dependence to both the solvent and the electrolyte system in the cyclic voltammetry. In the presence of TBAClO4 (1) exhibits a two-electron oxidation, whereas in the presence of TBAPF6 (2), , shows three distinct phenolato/phenoxyl radical couples. Both (1) and (2) were redox-cycled 30 times without major decomposition at the surface of the electrode, indicating that the oxidized species are substitutionally inert. Three six coordinates low spin Co(III) complexes were synthesized and their electrochemical reactions were investigated in details

    Microbial narrow-escape is facilitated by wall interactions

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    Cells have evolved efficient strategies to probe their surroundings and navigate through complex environments. From metastatic spread in the body to swimming cells in porous materials, escape through narrow constrictions - a key component of any structured environment connecting isolated microdomains - is one ubiquitous and crucial aspect of cell exploration. Here, using the model microalgae Chlamydomonas reinhardtii, we combine experiments and simulations to achieve a tractable realization of the classical Brownian narrow-escape problem in the context of active confined matter. Our results differ from those expected for Brownian particles or leaking chaotic billiards and demonstrate that cell-wall interactions substantially modify escape rates and, under generic conditions, expedite spread dynamics.</p

    Microbial narrow-escape is facilitated by wall interactions

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    Cells have evolved efficient strategies to probe their surroundings and navigate through complex environments. From metastatic spread in the body to swimming cells in porous materials, escape through narrow constrictions—a key component of any structured environment connecting isolated microdomains—is one ubiquitous and crucial aspect of cell exploration. Here, using the model microalgae Chlamydomonas reinhardtii, we combine experiments and simulations to achieve a tractable realization of the classical Brownian narrow-escape problem in the context of active confined matter. Our results differ from those expected for Brownian particles or leaking chaotic billiards and demonstrate that cell-wall interactions substantially modify escape rates and, under generic conditions, expedite spread dynamics

    Microbial narrow-escape is facilitated by wall interactions: Simulation Supplementary material

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    Simulation codes and simulation results for the paper "Microbial narrow-escape is facilitated by wall interactions".We acknowledge financial support from grants CTM2017-83774-P and IED2019-000958-I (IT), PID2019-104232GB-I00 (IT and MP) from the Spanish Ministerio de Ciencia e Innovaci ́on (MICINN), the Ram ́on y Ca jal Program (RYC-2018-02534; MP), ECOST-STSM-Request-CA17120-47203 for the COST Action (European Cooperation in Science and Technol- ogy); RPG-2018-345 (AA and MP) from The Leverhulme Trust; H2020 MSCA ITN PHYMOT (Grant agreement No 955910; IT and MP). MS also acknowledges A. Marin for his support.Peer reviewe

    Microbial narrow-escape is facilitated by wall interactions

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    Cells have evolved efficient strategies to probe their surroundings and navigate through complex environments. From metastatic spread in the body to swimming cells in porous materials, escape through narrow constrictions - a key component of any structured environment connecting isolated micro-domains - is one ubiquitous and crucial aspect of cell exploration. Here, using the model microalgae Chlamydomonas reinhardtii, we combine experiments and simulations to achieve a tractable realization of the classical Brownian narrow escape problem in the context of active confined matter. Our results differ from those expected for Brownian particles or leaking chaotic billiards and demonstrate that cell-wall interactions substantially modify escape rates and, under generic conditions, expedite spread dynamics.We acknowledge financial support from grants CTM2017-83774-P and IED2019-000958-I (IT), PID2019-104232GB-I00 (IT and MP) from the Spanish Ministerio de Ciencia e Innovaci ́on (MICINN), the Ramón y Cajal Program (RYC-2018-02534; MP), ECOST-STSM-Request-CA17120-47203 for the COST Action (European Cooperation in Science and Technology); RPG-2018-345 (AA and MP) from The Leverhulme Trust; H2020 MSCA ITN PHYMOT (Grant agreement No 955910; IT and MP). MS also acknowledges A. Marin for his support.N

    Ultrahigh Energy Neutrinos at the Pierre Auger Observatory

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    Rare predicted loss-of-function variants of type I IFN immunity genes are associated with life-threatening COVID-19

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    BackgroundWe previously reported that impaired type I IFN activity, due to inborn errors of TLR3- and TLR7-dependent type I interferon (IFN) immunity or to autoantibodies against type I IFN, account for 15-20% of cases of life-threatening COVID-19 in unvaccinated patients. Therefore, the determinants of life-threatening COVID-19 remain to be identified in similar to 80% of cases.MethodsWe report here a genome-wide rare variant burden association analysis in 3269 unvaccinated patients with life-threatening COVID-19, and 1373 unvaccinated SARS-CoV-2-infected individuals without pneumonia. Among the 928 patients tested for autoantibodies against type I IFN, a quarter (234) were positive and were excluded.ResultsNo gene reached genome-wide significance. Under a recessive model, the most significant gene with at-risk variants was TLR7, with an OR of 27.68 (95%CI 1.5-528.7, P=1.1x10(-4)) for biochemically loss-of-function (bLOF) variants. We replicated the enrichment in rare predicted LOF (pLOF) variants at 13 influenza susceptibility loci involved in TLR3-dependent type I IFN immunity (OR=3.70[95%CI 1.3-8.2], P=2.1x10(-4)). This enrichment was further strengthened by (1) adding the recently reported TYK2 and TLR7 COVID-19 loci, particularly under a recessive model (OR=19.65[95%CI 2.1-2635.4], P=3.4x10(-3)), and (2) considering as pLOF branchpoint variants with potentially strong impacts on splicing among the 15 loci (OR=4.40[9%CI 2.3-8.4], P=7.7x10(-8)). Finally, the patients with pLOF/bLOF variants at these 15 loci were significantly younger (mean age [SD]=43.3 [20.3] years) than the other patients (56.0 [17.3] years; P=1.68x10(-5)).ConclusionsRare variants of TLR3- and TLR7-dependent type I IFN immunity genes can underlie life-threatening COVID-19, particularly with recessive inheritance, in patients under 60 years old

    Correction: Rare predicted loss-of-function variants of type I IFN immunity genes are associated with life-threatening COVID-19

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