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111.
Alejandra Medrano-Banda Dr. Alfonso Crespo-Yapur Dr. Miguel Ángel Velasco-Soto Dr. Marcelo Videa 《ChemistryOpen》2022,11(2):e202100241
The synthesis of hybrid platinum materials is fundamental to enable alkaline water electrolysis for cost-effective H2 generation. In this work, we have used a galvanostatic method to co-deposit PtNi films onto polycrystalline gold. The surface concentrations of Ni (ΓNi) and Pt (ΓPt) were calculated from electrochemical measurements; the ΓPt/ΓNi ratio and electrocatalytic activity of these materials towards hydrogen evolution reaction (HER) in 1 M KOH show a strong dependence on the current density pulse applied during the electrodeposition. Analysis of the Tafel parameters hints that, on these deposits, HER proceeds through a Volmer-Heyrovsky mechanism. The galvanostatically deposited PtNi layers present a high current output per Pt gram, 3199 A gPt−1, which is significantly larger compared to other PtNi-based materials obtained by more extended and more complex synthesis methods. 相似文献
112.
Felipe J. Llanes-Estrada Tim Van Cauteren Ángel P. Martín 《The European Physical Journal C - Particles and Fields》2007,51(4):945-952
We study the multiple solutions of the truncated propagator Dyson–Schwinger equation for a simple fermion theory with Yukawa
coupling to a scalar field. Upon increasing the coupling constant g, other parameters being fixed, more than one non-perturbative
solution breaking chiral symmetry becomes possible and we find these numerically. These “recurrences” appear as a mechanism
to generate different fermion generations as quanta of the same fundamental field in an interacting field theory, without
assuming any composite structure. The number of recurrences or flavors is reduced to the question of the value of the Yukawa
coupling, and it has no special profound significance in the standard model. The resulting mass function can have one or more
nodes and the measurement that potentially detects them can be thought of as a collider-based test of the virtual dispersion
relation for the charged lepton member of each family. This requires the three independent measurements of the charged lepton’s energy,
three-momentum and off-shellness. We illustrate how this can be achieved for the (more difficult) case of the tau lepton.
PACS 12.15.Ff; 11.30.Rd 相似文献
113.
Ricard López-Coll Rubén Álvarez-Yebra Dr. Ferran Feixas Dr. Agustí Lledó 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10099-10106
The conformational equilibria and guest exchange process of a resorcin[4]arene derived self-folding cavitand receptor have been characterized in detail by molecular dynamics simulations (MD) and 1H EXSY NMR experiments. A multi-timescale strategy for exploring the fluxional behaviour of this system has been constructed, exploiting conventional MD and accelerated MD (aMD) techniques. The use of aMD allows the reconstruction of the folding/unfolding process of the receptor by sampling high-energy barrier processes unattainable by conventional MD simulations. We obtained MD trajectories sampling events occurring at different timescales from ns to s: 1) rearrangement of the directional hydrogen bond seam stabilizing the receptor, 2) folding/unfolding of the structure transiting partially open intermediates, and 3) guest departure from different folding stages. Most remarkably, reweighing of the biased aMD simulations provided kinetic barriers that are in very good agreement with those determined experimentally by 1H NMR. These results constitute the first comprehensive characterization of the complex dynamic features of cavitand receptors. Our approach emerges as a valuable rational design tool for synthetic host-guest systems 相似文献
114.
Dr. Tatiana Suárez-Rodríguez Prof. Dr. Ángel L. Suárez-Sobrino Prof. Dr. Alfredo Ballesteros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(51):13079-13084
Gold(I)-catalyzed formal [4+2] cycloaddition of O-aryl ynol ethers 1 and enol ethers 2 is described. This intermolecular reaction between two electron-rich unsaturated systems takes place, under mild conditions, in the presence of 5 mol% [IPrAu(CH3CN)]SbF6 as catalyst giving chromene derivatives with good yields. The cycloaddition is completely regio- and stereoselective, as well as versatile for both reactives. Silyl enol ethers can also react in the same way and under the same reaction conditions with quantitative yields. A plausible mechanism through a selective addition of the enol ether to the alkyne gold activated complex followed by an intramolecular aromatic electrophilic substitution is proposed. Several experimental results support the presence of a cationic oxonium intermediate prior to the aromatic substitution. The reaction represents a new entry to the chromene core. 相似文献
115.
Multiplexed Determination of Amino‐Terminal Pro‐B‐Type Natriuretic Peptide and C‐Reactive Protein Cardiac Biomarkers in Human Serum at a Disposable Electrochemical Magnetoimmunosensor
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Berta Esteban‐Fernández de Ávila Vanessa Escamilla‐Gómez Valentina Lanzone Susana Campuzano María Pedrero Dario Compagnone José M. Pingarrón 《Electroanalysis》2014,26(2):254-261
A rapid magnetoimmunosensor for the simultaneous determination of two cardiac biomarkers, amino‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP) and C‐reactive protein (CRP), in human serum is described. Specific capture antibodies were covalently immobilized onto carboxylic acid‐modified magnetic beads. The quantification of NT‐proBNP and CRP was performed by using indirect competitive and sandwich configurations, respectively, and horseradish peroxidase‐labeled tracers. The use of dual screen‐printed carbon electrodes allowed the achievement of simultaneous independent amperometric readout for each cardiac biomarker. The developed methodology showed very low limits of detection (0.47 ng mL?1). An international standard for CRP serum spiked with NT‐proBNP was analyzed to evaluate the usefulness of the magnetoimmunosensor. 相似文献
116.
D. Ramírez K. Álvarez G. Riveros M. Tejos M. G. Lobos 《Journal of Solid State Electrochemistry》2014,18(10):2869-2884
This study was focused in the electrodeposition of both compact and nanostructured extrinsic n-type doped ZnO films, which was achieved with aluminum, gallium, and indium. These elements were directly added into a Zn(II) rich electrolyte with molecular oxygen acting as an oxide precursor in aqueous perchlorate media. This way, the use of nitrate ions, whose by-products are accumulated in the aqueous electrolyte, and chloride ions, an electrically active element in ZnO, was therefore avoided. Speciation diagrams, conditional solubility diagrams and a potentiodynamic study were used to explain the way in which extrinsic n-type ZnO can be prepared by electrochemical deposition. Relatively compact films with a highly preferred orientation along the c-axis were suitable for impedance measurements, thus allowing the measurement of their doping levels. Al- and Ga-doped lamellar nanostructures were successfully prepared when the nature of the anion was changed from perchlorate to sulfate. Under specific conditions, the structure of these films changed from opened and isolated nanosheets to interconnected ones. Morphological, optical, and crystallographic properties of these films were also analyzed. Results and discussion presented here should provide a better understanding toward the study of alternative materials in fields such as photovoltaics and photocatalysis. 相似文献
117.
118.
Ángela Martínez‐Peragón Dr. Delia Miguel Rocío Jurado Dr. José Justicia Prof. José M. Álvarez‐Pez Dr. Juan M. Cuerva Dr. Luis Crovetto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(2):447-455
9‐Alkyl xanthenones with different aliphatic pendant groups have been easily prepared by means of nucleophilic addition of the corresponding Grignard derivative to a tert‐butyldimethylsilyl ether (TBDMS)‐protected 3,6‐dihydroxy‐xanthenone. The photophysical behavior of the new dyes has been explored by using absorption, steady‐state‐, and time‐resolved fluorescence measurements. We determined the equilibrium constants, visible spectral characteristics, fluorescence quantum yield, and decay times. Remarkably, they retain similar fluorescent properties of fluorescein including the characteristic phosphate‐mediated excited‐state proton‐transfer (ESPT) reaction. 6‐Hydroxy‐9‐isopropyl‐3H‐xanthen‐3‐one ( 5 ) was investigated in living cells; it presented a good permeability and efficient accumulation inside the cytosol. For the first time, we reported that the requirement of an aryl group at C‐9 is no longer needed and new fluorescent sensors can be therefore easily developed. 相似文献
119.
Coordination Chemistry of Cyclopropenylidene‐Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes
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Ágnes Kozma Tobias Deden Dr. Javier Carreras Christian Wille Dr. Jekaterina Petuškova Jörg Rust Dr. Manuel Alcarazo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2208-2214
A straightforward synthesis of cyclopropenylidene‐stabilized phosphenium cations 1 a – g through the reaction of [(iPr2N)2C3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite‐type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a – g still act as two‐electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the Ccarbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of PtII complexes was tested; all of the cationic phosphines accelerated the prototype 6‐endo‐dig cyclization of 2‐ethynyl‐1,1′‐biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A. 相似文献
120.
A Silver Bite: Crystalline Heterometallic Architectures Based on Ag–π Interactions with a Bis‐Dipyrrin Zinc Helicate
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Hervé Ruffin Dr. Stéphane A. Baudron Dr. Domingo Salazar‐Mendoza Prof. Mir Wais Hosseini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2449-2453
An unprecedented mode of assembly of helical motives and AgI ions in the crystalline state is described. The combination of a ZnII helicate based on a 2,2′‐bisdpm bearing peripheral benzonitrile moieties with AgX salts, leads to the formation of a tetranuclear core containing Ag–π interactions. Depending on the coordinating ability of the X? anion and the solvents used, the tetranuclear complex self‐assembles into coordination polymers of varying dimensionality. From the sequence of coordination events (Ag–π or Ag–peripheral site), one may envisage two possible construction scenarios. However, the Ag–π as primary event seems reasonable owing to the rather weak binding propensity of the nitrile group and the chelating nature of the π‐clefts. 相似文献