A simulational and theoretical study of the spherical electrical double layer for a size-asymmetric electrolyte: the case of big coions

Monte Carlo simulations of a spherical macroion, surrounded by a size-asymmetric electrolyte in the primitive model, were performed. We considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice the size of counterions), for several surface charge densities of the macrosphere. The radial distribution functions, electrostatic potential at the Helmholtz surfaces, and integrated charge are reported. We compare these simulational data with original results obtained from the Ornstein-Zernike integral equation, supplemented by the hypernetted chain/hypernetted chain (HNC/HNC) and hypernetted chain/mean spherical approximation (HNC/MSA) closures, and with the corresponding calculations using the modified Gouy-Chapman and unequal-radius modified Gouy-Chapman theories. The HNC/HNC and HNC/MSA integral equations formalisms show good concordance with Monte Carlo "experiments", whereas the notable limitations of point-ion approaches are evidenced. Most importantly, the simulations confirm our previous theoretical predictions of the non-dominance of the counterions in the size-asymmetric spherical electrical double layer [J. Chem. Phys. 123, 034703 (2005)], the appearance of anomalous curvatures at the outer Helmholtz plane and the enhancement of charge reversal and screening at high colloidal surface charge densities due to the ionic size asymmetry.Comment: 11 pages, 7 figure

Electronic localization at mesoscopic length scales: different definitions of localization and contact effects in a heuristic DNA model

In this work we investigate the electronic transport along model DNA molecules using an effective tight-binding approach that includes the backbone on site energies. The localization length and participation number are examined as a function of system size, energy dependence, and the contact coupling between the leads and the DNA molecule. On one hand, the transition from an diffusive regime to a localized regime for short systems is identified, suggesting the necessity of a further length scale revealing the system borders sensibility. On the other hand, we show that the lenght localization and participation number, do not depended of system size and contact coupling in the thermodynamic limit. Finally we discuss possible length dependent origins for the large discrepancies among experimental results for the electronic transport in DNA sample

The K2-ESPRINT Project. I. Discovery of the Disintegrating Rocky Planet K2-22b with a Cometary Head and Leading Tail

We present the discovery of a transiting exoplanet candidate in the K2 Field-1 with an orbital period of 9.1457 hr: K2-22b. The highly variable transit depths, ranging from $\sim$0\% to 1.3\%, are suggestive of a planet that is disintegrating via the emission of dusty effluents. We characterize the host star as an M-dwarf with $T_{\rm eff} \simeq 3800$ K. We have obtained ground-based transit measurements with several 1-m class telescopes and with the GTC. These observations (1) improve the transit ephemeris; (2) confirm the variable nature of the transit depths; (3) indicate variations in the transit shapes; and (4) demonstrate clearly that at least on one occasion the transit depths were significantly wavelength dependent. The latter three effects tend to indicate extinction of starlight by dust rather than by any combination of solid bodies. The K2 observations yield a folded light curve with lower time resolution but with substantially better statistical precision compared with the ground-based observations. We detect a significant "bump" just after the transit egress, and a less significant bump just prior to transit ingress. We interpret these bumps in the context of a planet that is not only likely streaming a dust tail behind it, but also has a more prominent leading dust trail that precedes it. This effect is modeled in terms of dust grains that can escape to beyond the planet's Hill sphere and effectively undergo `Roche lobe overflow,' even though the planet's surface is likely underfilling its Roche lobe by a factor of 2.Comment: 22 pages, 16 figures. Final version accepted to Ap

Far beyond the Sun: II. Probing the stellar magnetism of the young Sun {\iota} Horologii from the photosphere to its corona

A comprehensive multi-wavelength campaign has been carried out to probe stellar activity and variability in the young Sun-like star $\iota$-Horologii. We present the results from long-term spectropolarimetric monitoring of the system by using the ultra-stable spectropolarimeter/velocimeter HARPS at the ESO 3.6-m telescope. Additionally, we included high-precision photometry from the NASA Transiting Exoplanet Survey Satellite (TESS) and observations in the far- and near-ultraviolet spectral regions using the STIS instrument on the NASA/ESA Hubble Space Telescope (HST). The high-quality dataset allows a robust characterisation of the star's rotation period, as well as a probe of the variability using a range of spectroscopic and photometric activity proxies. By analyzing the gradient of the power spectra (GPS) of the TESS lightcurves we constrained the faculae-to-spot driver ratio ($\rm S_{fac}/S_{spot}$) to 0.510$\pm$0.023, which indicates that the stellar surface is spot dominated during the time of the observations. We compared the photospheric activity properties derived from the GPS method with a magnetic field map of the star derived using Zeeman-Doppler imaging (ZDI) from simultaneous spectropolarimetric data for the first time. Different stellar activity proxies enable a more complete interpretation of the observed variability. For example, we observed enhanced emission in the HST transition line diagnostics C IV and C III, suggesting a flaring event. From the analysis of TESS data acquired simultaneously with the HST data, we investigate the photometric variability at the precise moment that the emission increased and derive correlations between different observables, probing the star from its photosphere to its corona

Multivariate Modelling of Pedestrian Fatality Risk Through on the Spot Accident Investigation

Pedestrians are the most vulnerable users of public roads and represent one of the largest groups of road casualties; their death rate around the world due to vehicle-pedestrian collisions is high and tending to rise. In Spain, as in other countries of the European Union, steps have been taken to reduce the number and consequences of such accidents, with encouraging results in recent years. A key to countering this concern is the accident research activity that has obtained remarkable achievements in different fields, especially when multidisciplinary approaches are taken. This paper describes the development of a multivariate model that is able to detect the most influential parameters on the consequences of vehicle-pedestrian collision and to quantify their impact on pedestrian fatality risk. First, an accident database containing detailed information and parameters of vehicle-pedestrian collisions in Madrid has been developed. The accidents were investigated on the spot by INSIA accident investigation teams and analyzed using advanced reconstruction techniques. The model was then developed with two components: (1) a classification tree that characterizes and selects the explanatory variables, identifying their interactions, and (2) a binary logistic regression to quantify the influence of each variable and interaction resulting from the classification tree. The whole model represents an important tool for identifying, quantifying and predicting the potential impact of measures aimed at reducing injuries in vehicle-pedestrian collisions

Obtaining protoanemonin through selective oxidation of Dfructose and 5-(hydroxymethyl) furfural in a self-catalysed reaction

Although different ways of converting 5- (hydroxymethyl)furfural (1) to various substrates with high value have been sought, few transformations have obtained building blocks that can be very useful in the area of fine chemistry. Herein, we report the synthesis of protoanemonin (5-methylenefuran-2(5H)- one) from D-fructose via compound (1), a versatile γalkylidenebutenolide, using an efficient self-catalysed process with formic acid, with high reaction performance and selectivity (up to 94% yield and 98% conversion from (1), while 28% yield from Dfructose). This efficient and simple operational process involved a two-phase aqueous-organic system between chlorinated solvents (CHxCly) and hydrogen peroxide as the initial oxidizing agent. The reaction presents a key cleavage in the 5-hydroxymethyl moiety of (1), due to the Baeyer-Villiger oxidation (BVO) process that generates formic acid in situ. Ultimately, DFF and HMF were successfully obtained in 80% and 98% yield, respectively, starting from D-fructose and using Preyssler heteropolyacids as Brønsted acid catalysts under an atmosphere of oxygen in the absence of hydrogen peroxide.Fil: Martínez, José J.. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Páez, Luis A.. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Gutiérrez, Luisa F.. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Pardo Cuervo, Oscar H.. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Rojas, Hugo A.. Universidad Pedagógica y Tecnológica de Colombia; ColombiaFil: Romanelli, Gustavo Pablo. Facultad de Ciencias Agrarias y Forestales, Universidad Nacional de la Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Portilla, Jaime. Universidad de Los Andes, Colombia; ColombiaFil: Castillo, Juan Carlos. Universidad Pedagógica y Tecnológica de Colombia; Colombia. Universidad de los Andes; ColombiaFil: Gamboa Becerra, Diana Paola. Universidad Pedagógica y Tecnológica de Colombia; Colombi

Randomized phase II trial of FOLFIRI-panitumumab compared with FOLFIRI alone in patients with RAS wild-type circulating tumor DNA metastatic colorectal cancer beyond progression to first-line FOLFOX-panitumumab : the BEYOND study (GEMCAD 17-01)

Altres ajuts: Fundació la Marató de TV3 (201330.10); Fundacion Olga Torres (Modalitat A. 2019/2020); Spanish Association Against Cancer (AECC, PROYE19040POST_001).Purpose: Panitumumab plus FOLFOX (P-FOLFOX) is standard first-line treatment for RAS wild-type (WT) metastatic colorectal cancer. The value of panitumumab rechallenge is currently unknown. We assessed addition of panitumumab to FOLFIRI (P-FOLFIRI) beyond progression to P-FOLFOX in patients with no RAS mutations in liquid biopsy (LB). Methods: In this randomized phase II trial, patients were assigned (3:2 ratio) to second-line P-FOLFIRI (arm A) or FOLFIRI alone (arm B). LB for circulating tumor DNA analysis was collected at study entry and at disease progression. Primary endpoint was 6-month progression-free survival. Two-stage Simon design required 85 patients to be included (EudraCT 2017-004519-38). Results: Between February 2019 and November 2020, 49 patients were screened (16 RAS mutations in LB detected) and 31 included (18 assigned to arm A and 13 to arm B). The study was prematurely closed due to inadequate recruitment. Serious adverse events were more frequent in arm A (44% vs. 23%). Overall response rate was 33% (arm A) vs. 7.7% (arm B). Six-month progression-free survival rate was 66.7% (arm A) and 38.5% (arm B). Median progression-free survival was 11.0 months (arm A) and 4.0 months (arm B) (hazard ratio, 0.58). At disease progression, RAS or BRAF mutations in LB were found in 4/11 patients (36%) in arm A and 2/10 (20%) in arm B. Conclusions: The BEYOND study suggests a meaningful benefit of P-FOLFIRI beyond progression to P-FOLFOX in metastatic colorectal cancer patients with WT RAS status selected by LB. This strategy deserves further investigation

Chromosomal studies, pollen morphology and fertility in Dioscorea ayardei (Dioscoreaceae)

Antecedentes y Objetivos: La gran variabilidad de caracteres en Dioscorea dificultan la delimitación de las especies, por lo que estudios complementarios son necesarios para lograr su identificación. Dioscorea ayardei, especie endémica descrita recientemente de las Sierras de Calilegua (Jujuy, Argentina), se diferencia por la particularidad del androceo en sus flores estaminadas, la cual consiste en una estructura navicular con una sola antera en el centro y tres apéndices dendriformes erectos. El objetivo de este trabajo fue realizar un estudio conjunto de sus caracteres cromosómicos y palinológicos, que sumados a los morfológicos aporten información complementaria para su correcta delimitación. Métodos: El material estudiado fue identificado según los métodos clásicos en taxonomía y depositado en el Herbario LIL, de la Fundación Miguel Lillo. Para estudiar la meiosis se seleccionaron al azar botones florales jóvenes, que fueron fijados en Farmer durante 24 horas y conservados en alcohol etílico 70° a -4°C. La tinción de los cromosomas se realizó con hematoxilina propiónica al 2%. La fertilidad de los granos de polen se estimó mediante las técnicas de Mützing y DAPI. Para describir la morfología polínica, el material fue procesado según las técnicas convencionales de acetólisis y polen natural; se tomaron fotos con microscopía óptica (MO) y electrónica de barrido (MEB). Resultados clave: Dioscorea ayardei presentó un número gametofítico n=20II. El comportamiento meiótico fue generalmente regular. Las técnicas para estimar viabilidad y fertilidad del grano de polen revelaron un valor de 90-93% respectivamente. La morfología muestra un grano disulcado de tamaño pequeño (16-24 µm) a mediano (25-30 µm) con tectum microreticulado. Conclusiones: Se reafirma el número cromosómico básico para el género x=10. Dioscorea ayardei es un tetraploide con n=20, de comportamiento meiótico normal que concuerda con la viabilidad potencial del grano de polen. La ornamentación de la exina y el número cromosómico la relaciona con el clado Nuevo Mundo II.Background and Aims: The great variability of characters in Dioscorea makes it difficult to define the species, therefore additional studies are necessary to identify them. Dioscorea ayardei, a recently described endemic species from the Sierras de Calilegua (Jujuy, Argentina), differs by the particularity of the androecium of its staminate flowers which consists of a navicular structure with a single anther in the center and three erect dendriform appendages. The aim of this paper was to carry out an ensemble study of its chromosomal and palynological characters that, added to the morphological ones, provide complementary information for its correct delimitation. Methods: The studied material was identified according to the classic methods in taxonomy and deposited in the LIL Herbarium, of the Fundación Miguel Lillo. For study of meiosis, young flower buds were randomly selected, which were fixed in Farmer for 24 hours and preserved in 70° to -4°C ethyl alcohol. For chromosome staining, 2% propionic hematoxylin was used. Fertility of pollen grains was estimated using the Mützing and DAPI techniques. For the pollen morphology description the material was processed according to the conventional techniques of acetolysis and natural pollen; photographs were taken with light microscope (LM) and scanning electron microscope (SEM). Key results: Dioscorea ayardei presented a gametophytic number n=20II. Meiotic behavior was generally regular. The techniques to estimate viability and fertility of the pollen grain revealed a value of 90-93%, respectively. The morphology showed a small (16-24 µm) to medium (25-30 µm) sized disulcate grain with microreticulate tectum. Conclusions: The basic chromosome number for the genus x=10 is reaffirmed. Dioscorea ayardei is a tetraploid with n=20, with normal meiotic behavior consistent with the potential viability of the pollen grain. The exine ornamentation and chromosome number relates with the New World II clade

Synergistic Degradation Mechanism in Single Crystal Ni-Rich NMC//Graphite Cells

Acknowledgments We acknowledge Diamond Light Source for time on beamline I09 under Proposals SI30201-1 and SI30201-2. This work is supported by the Faraday Institution under Grants FIRG044, FIRG024, and FIRG060.Peer reviewedPublisher PD