Folding and Unfolding in the Blue Copper Protein Rusticyanin: Role of the Oxidation State

The unfolding process of the blue copper protein rusticyanin has been studied from the structural and the thermodynamic points of view at two pH values (pH 2.5 and 7.0). When Rc unfolds, copper ion remains bound to the polypeptide chain. Nuclear magnetic resonance data suggest that three of the copper ligands in the folded state are bound to the metal ion in the unfolded form, while the other native ligand is detached. These structural changes are reflected in the redox potentials of the protein in both folded and unfolded forms. The affinities of the copper ion in both redox states have been also determined at the two specified pH values. The results indicate that the presence of two histidine ligands in the folded protein can compensate the change in the net charge that the copper ion receives from their ligands, while, in the unfolded protein, charges of aminoacids are completely transferred to the copper ion, altering decisively the relative stability of its two-redox states

Enhancing methane production from the invasive macroalga Rugulopteryx okamurae through anaerobic co-digestion with olive mill solid waste: process performance and kinetic analysis

The biomass valorisation of the invasive brown alga Rugulopteryx okamurae (Dictyotales, Phaeophyceae) is key to curbing the expansion of this invasive macroalga which is generating tonnes of biomass on southern Spain beaches. As a feasible alternative for the biomass management, anaerobic co-digestion is proposed in this study. Although the anaerobic digestion of macroalgae barely produced 177 mL of CH4 g−1 VS, the co-digestion with a C-rich substrate, such as the olive mill solid waste (OMSW, the main waste derived from the two-phase olive oil manufacturing process), improved the anaerobic digestion process. The mixture improved not only the methane yield, but also its biodegradability. The highest biodegradability was found in the mixture 1 R. okamurae—1 OMSW, which improved the biodegradability of the macroalgae by 12.9% and 38.1% for the OMSW. The highest methane yield was observed for the mixture 1 R. okamurae—3 OMSW, improving the methane production of macroalgae alone by 157% and the OMSW methane production by 8.6%. Two mathematical models were used to fit the experimental data of methane production time with the aim of assessing the processes and obtaining the kinetic constants of the anaerobic co-digestion of different combination of R. okamurae and OMSW and both substrates independently. First-order kinetic and the transference function models allowed for appropriately fitting the experimental results of methane production with digestion time. The specific rate constant, k (first-order model) for the mixture 1 R. okamurae- 1.5 OMSW, was 5.1 and 1.3 times higher than that obtained for the mono-digestion of single OMSW and the macroalga, respectively. In the same way, the transference function model revealed that the maximum methane production rate (Rmax) was also found for the mixture 1 R. okamurae—1.5 OMSW (30.4 mL CH4 g−1 VS day−1), which was 1.6 and 2.2 times higher than the corresponding to the mono-digestions of the single OMSW and sole R. okamurae (18.9 and 13.6 mL CH4 g−1 VS day−1), respectively.Ministerio de Ciencia e Innovación PID2020-114975RB-10

Cobalt metal-organic framework based on layered double nanosheets for enhanced electrocatalytic water oxidation in neutral media

A new cobalt metal-organic framework (2D-Co-MOF) based on well-defined layered double cores that are strongly connected by intermolecular bonds has been developed. Its 3D structure is held together by π-π stacking interactions between the labile pyridine ligands of the nanosheets. In aqueous solution, the axial pyridine ligands are exchanged by water molecules, producing a delamination of the material, where the individual double nanosheets preserve their structure. The original 3D layered structure can be restored by a solvothermal process with pyridine, so that the material shows a "memory effect" during the delamination-pillarization process. Electrochemical activation of a 2D-Co-MOF@Nafion-modified graphite electrode in aqueous solution improves the ionic migration and electron transfer across the film and promotes the formation of the electrocatalytically active cobalt species for the oxygen evolution reaction (OER). The so-activated 2D-Co-MOF@Nafion composite exhibits an outstanding electrocatalytic performance for the OER at neutral pH, with a TOF value (0.034 s-1 at an overpotential of 400 mV) and robustness superior to those reported for similar electrocatalysts under similar conditions. The particular topology of the delaminated nanosheets, with quite distant cobalt centers, precludes the direct coupling between the electrocatalytically active centers of the same sheet. On the other hand, the increase in ionic migration across the film during the electrochemical activation stage rules out the intersheet coupling between active cobalt centers, as this scenario would impair electrolyte permeation. Altogether, the most plausible mechanism for the O-O bond formation is the water nucleophilic attack to single Co(IV)-oxo or Co(III)-oxyl centers. Its high electrochemical efficiency suggests that the presence of nitrogen-containing aromatic equatorial ligands facilitates the water nucleophilic attack, as in the case of the highly efficient cobalt porphyrins

Bimetallic Intersection in PdFe@FeOx-C Nanomaterial for Enhanced Water Splitting Electrocatalysis

Supported Fe-doped Pd-nanoparticles (NPs) are prepared via soft transfor-mation of a PdFe-metal oraganic framework (MOF). The thus synthesized bimetallic PdFe-NPs are supported on FeOx@C layers, which are essential for developing well-defined and distributed small NPs, 2.3 nm with 35% metal loading. They are used as bifunctional nanocatalysts for the electro-catalytic water splitting process. They display superior mass activity for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), both in alkaline and acid media, compared with those obtained for benchmarking platinum HER catalyst, and ruthenium, and iridium oxide OER catalysts. PdFe-NPs also exhibit outstanding stability against sintering that can be explained by the protecting role of graphitic carbon layers provided by the organic linker of the MOF. Additionally, the superior electrocatalytic performance of the bimetallic PdFe-NPs compared with those of monometallic Pd/C NPs and FeOx points to a synergetic effect induced by Fe-Pd interactions that facilitates the water splitting reaction. This is supported by additional characterization of the PdFe-NPs prior and post electrolysis by TEM, XRD, X-ray photoelectron spectroscopy, and Raman revealing that dispersed PdFe NPs on FeOx@C promote interactions between Pd and Fe, most likely to be Pd-O-Fe active centers

Cobalt Metal-Organic Framework based on two dinuclear secondary building units for electrocatalytic oxygen evolution

The synthesis of a new microporous metal-organic framework (MOF) based on two secondary building units, with dinuclear cobalt centers, has been developed. The employment of a well-defined cobalt cluster results in an unusual topology of the Co2-MOF, where one of the cobalt centers has three open coordination positions, which has no precedent in MOF materials based on cobalt. Adsorption isotherms have revealed that Co2-MOF is in the range of best CO2 adsorbents among the carbon materials, with very high CO2/CH4 selectivity. On the other hand, dispersion of Co2-MOF in an alcoholic solution of Nafion gives rise to a composite (Co2-MOF@Nafion) with great resistance to hydrolysis in aqueous media and good adherence to graphite electrodes. In fact, it exhibits high electrocatalytic activity and robustness for the oxygen evolution reaction (OER), with a turnover frequency number value superior to those reported for similar electrocatalysts. Overall, this work has provided the basis for the rational design of new cobalt OER catalysts and related materials employing well-defined metal clusters as directing agents of the MOF structure

Performance of the upgraded PreProcessor of the ATLAS Level-1 Calorimeter Trigger

Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, los autores pertenecientes a la UAM y el nombre del grupo de colaboración, si lo hubiereThe PreProcessor of the ATLAS Level-1 Calorimeter Trigger prepares the analogue trigger signals sent from the ATLAS calorimeters by digitising, synchronising, and calibrating them to reconstruct transverse energy deposits, which are then used in further processing to identify event features. During the first long shutdown of the LHC from 2013 to 2014, the central components of the PreProcessor, the Multichip Modules, were replaced by upgraded versions that feature modern ADC and FPGA technology to ensure optimal performance in the high pile-up environment of LHC Run 2. This paper describes the features of the new Multichip Modules along with the improvements to the signal processing achieve

Measurements of the production cross-section for a Z boson in association with b-jets in proton-proton collisions at √s = 13 TeV with the ATLAS detector

Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, los autores pertenecientes a la UAM y el nombre del grupo de colaboración, si lo hubiereThis paper presents a measurement of the production cross-section of a Z boson in association with b-jets, in proton-proton collisions at s = 13 TeV with the ATLAS experiment at the Large Hadron Collider using data corresponding to an integrated luminosity of 35.6 fb−1. Inclusive and differential cross-sections are measured for events containing a Z boson decaying into electrons or muons and produced in association with at least one or at least two b-jets with transverse momentum pT> 20 GeV and rapidity |y| < 2.5. Predictions from several Monte Carlo generators based on leading-order (LO) or next-to-leading-order (NLO) matrix elements interfaced with a parton-shower simulation and testing different flavour schemes for the choice of initial-state partons are compared with measured cross-sections. The 5-flavour number scheme predictions at NLO accuracy agree better with data than 4-flavour number scheme ones. The 4-flavour number scheme predictions underestimate data in events with at least one b-je

Performance of the ATLAS muon triggers in Run 2

Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, los autores pertenecientes a la UAM y el nombre del grupo de colaboración, si lo hubiereThe performance of the ATLAS muon trigger system is evaluated with proton-proton (pp) and heavy-ion (HI) collision data collected in Run 2 during 2015-2018 at the Large Hadron Collider. It is primarily evaluated using events containing a pair of muons from the decay of Z bosons to cover the intermediate momentum range between 26 GeV and 100 GeV. Overall, the efficiency of the single-muon triggers is about 68% in the barrel region and 85% in the endcap region. The pT range for efficiency determination is extended by using muons from decays of Jψ mesons, W bosons, and top quarks. The performance in HI collision data is measured and shows good agreement with the results obtained in pp collisions. The muon trigger shows uniform and stable performance in good agreement with the prediction of a detailed simulation. Dedicated multi-muon triggers with kinematic selections provide the backbone to beauty, quarkonia, and low-mass physics studies. The design, evolution and performance of these triggers are discussed in detai

ATLAS data quality operations and performance for 2015-2018 data-taking

Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, los autores pertenecientes a la UAM y el nombre del grupo de colaboración, si lo hubiereThe ATLAS detector at the Large Hadron Collider reads out particle collision data from over 100 million electronic channels at a rate of approximately 100 kHz, with a recording rate for physics events of approximately 1 kHz. Before being certified for physics analysis at computer centres worldwide, the data must be scrutinised to ensure they are clean from any hardware or software related issues that may compromise their integrity. Prompt identification of these issues permits fast action to investigate, correct and potentially prevent future such problems that could render the data unusable. This is achieved through the monitoring of detector-level quantities and reconstructed collision event characteristics at key stages of the data processing chain. This paper presents the monitoring and assessment procedures in place at ATLAS during 2015-2018 data-taking. Through the continuous improvement of operational procedures, ATLAS achieved a high data quality efficiency, with 95.6% of the recorded proton-proton collision data collected at s=13 TeV certified for physics analysi