Hierarchically-structured metalloprotein composite coatings biofabricated from co-existing condensed liquid phases

Complex hierarchical structure governs emergent properties in biopolymeric materials; yet, the material processing involved remains poorly understood. Here, we investigated the multi-scale structure and composition of the mussel byssus cuticle before, during and after formation to gain insight into the processing of this hard, yet extensible metal cross-linked protein composite. Our findings reveal that the granular substructure crucial to the cuticle’s function as a wear-resistant coating of an extensible polymer fiber is pre-organized in condensed liquid phase secretory vesicles. These are phase-separated into DOPA-rich proto-granules enveloped in a sulfur-rich proto-matrix which fuses during secretion, forming the sub-structure of the cuticle. Metal ions are added subsequently in a site-specific way, with iron contained in the sulfur-rich matrix and vanadium coordinated by DOPA-catechol in the granule. We posit that this hierarchical structure self-organizes via phase separation of specific amphiphilic proteins within secretory vesicles, resulting in a meso-scale structuring that governs cuticle function

High-Pressure Speed of Sound Measurements of trans-1-Chloro-3,3,3-trifluoropropene (R1233zd(E)) in Liquid Region for Temperature from (273.15 to 353.15) K

This paper presents speed of sound measurements of liquid trans-1-chloro-3,3,3-trifluoropropene (R1233zd­(E)) along six isotherms over the temperature range from (273.15 to 353.15) K for pressures up to 35 MPa by means of the double pulse–echo method. The expanded uncertainty of the speed of sound measurements at a confidence level of 95% is 0.1%. The experimental results were compared with predictions from the state-of-the-art Fundamental Helmholtz Energy equation of state [Mondéjar, M.E.; McLinden, M.O.; Lemmon, E.W., Thermodynamic Properties of trans-1-Chloro-3,3,3-trifluoropropene (R1233zd­(E)): Vapor Pressure, (p,ρ,T) Behavior, and Speed of Sound Measurements, and Equation of State. J. Chem. Eng. Data, 2015, 60, 2477–2489]

High resolution chemical stratigraphies of atmospheric depositions from a 4 m depth snow pit at dome C (East Antarctica)

In this work, we present chemical stratigraphies of two sampling lines collected within a 4 m depth snow pit dug in Dome C during the Antarctic summer Campaign 2017/2018, 12 years after the last reported snow pit. The first sampling line was analyzed for nine anionic and cationic species using Ion Chromatography (IC); the second sampling line was analyzed for seven major elements in an innovative way with Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after sample pre-concentration, allowing the study of deposition processes of new markers especially related to crustal source. This coupled analysis, besides confirming previous studies, allowed us to investigate the depositions of the last decades at Dome C, enriching the number of the detected chemical markers, and yielding these two techniques complementary for the study of different markers in this kind of matrix. As a result of the dating, the snow layers analyzed covered the last 50 years of snow depositions. The assessment of the accumulation rate, estimated about 9 cm yr−1, was accomplished only for the period 1992–2016, as the eruption of 1992 constituted the only tie-point found in nssSO42− depth profile. Na, the reliable sea salt marker, together with Mg and Sr, mainly arose from marine sources, whereas Ca, Al and Fe originated from crustal inputs. Post-depositional processes occurred on Cl− as well as on NO3− and methanesulfonic acid (MSA); compared to the latter, Cl− had a more gradual decrease, reporting a threshold at 2.5 m for the post-depositional process completion. For NO3− and MSA, instead, the threshold was shallower, at about 1 m depth, with a loss of 87% for NO3− and of 50% for MSA

Benchmark of the GETTHEM Vacuum Vessel Pressure Suppression System (VVPSS) model for a helium-cooled EU DEMO blanket

In the nuclear field, the correct evaluation of the effects of design-basis accidents is fundamental to correctly design the countermeasures needed to preserve the integrity of the containment barriers and to confine the ra-dioactive material. Therefore, both in fission and in fusion, notwithstanding the different amounts of radioac-tive materials, the availability of models that can predict the accidental transients is crucial. Here we describe the model recently developed to analyse an in-vessel Loss-Of-Coolant-Accident in the EU DEMO fusion reactor, and implemented in the GETTHEM code. In particular, we focus on the release of coolant inside the Vacuum Vessel (VV) following a break in the breeding blanket cooling loop, considering a helium-cooled blanket solution. The model of the VV pressure suppression system is calibrated and bench-marked exploiting results from the validated CONSEN code by ENEA

Seguimiento en H-alfa de dos zonas activas del Sol en el mes de febrero de 1986

En el marco de la puesta en marcha de una rutina de la observación de la actividad solar en luz blanca y en la línea H-alfa del hidrógeno, se muestran los resultados durante el mes de febrero de 1986. Los trabajos fueron realizados con un telescopio refractor de 2250 mm de distancia focal y 150 mm de abertura, usando un filtro monocromador centrado en la línea H-alfa con un ancho de banda de 0.25 Å. Una de las regiones activas (longitud 201,1°, latitud -6.0°) fue fotografiada durante su arribo al limbo (días 11 y 12 de febrero) pudiéndose observar la aparición de un "flare" del tipo Sb del día 11 con su máximo brilo a las 1831 TU. Las imágenes (proyectadas sobre el limbo) obtenidas de esta zona con diferentes tiempos de exposición permiten apreciar su estructura tridimensional. Las fotografías obtenidas en luz blanca del grupo de manchas asociado (de estructura irregular) muestran el lugar de desarrollo de "flare" como una zona de rápida evolución (fuerte desorden magnético).Asociación Argentina de Astronomí

EXAFS and XANES structural characterization of bimetallic AuPd vapor derived catalysts

Using an innovative procedure known as metal vapor synthesis (MVS) to prepare bimetallic catalysts, starting from Au and Pd vapors, [AuPd] co-evaporated and [Au][Pd] separately evaporated bimetallic catalysts were achieved. After being tested, the catalytic activity and selectivity of the [AuPd] catalyst turned out to be higher than the [Au][Pd] ones. Using EXAFS spectroscopy it was shown that, in the [AuPd] samples, small bimetallic AuPd nanoparticles were present, having an Au rich core surrounded by an AuPd alloyed shell while in the [Au][Pd] sample there was the presence of monometallic Au and Pd nanoparticles showing some alloying only in the boundary regions. The EXAFS results were also qualitatively conrmed by the XANES spectra

Three-dimensional structural interrelations between cells, extracellular matrix and mineral in normally mineralizing Aavian leg tendon

The spatial-temporal relationship between cells, extracellular matrices, and mineral deposits is fundamental for an improved understanding of mineralization mechanisms in vertebrate tissues. By utilizing focused ion beam-scanning electron microscopy with serial surface imaging, normally mineralizing avian tendons have been studied with nanometer resolution in three dimensions with volumes exceeding tens of micrometers in range. These parameters are necessary to yield sufficiently fine ultrastructural details while providing a comprehensive overview of the interrelationships between the tissue structural constituents. Investigation reveals a complex lacuno-canalicular network in highly mineralized tendon regions, where ∼100 nm diameter canaliculi emanating from cell (tenocyte) lacunae surround extracellular collagen fibril bundles. Canaliculi are linked to smaller channels of ∼40 nm diameter, occupying spaces between fibrils. Close to the tendon mineralization front, calcium-rich deposits appear between the fibrils and, with time, mineral propagates along and within them. These close associations between tenocytes, tenocyte lacunae, canaliculi, small channels, collagen, and mineral suggest a concept for the mineralization process, where ions and/or mineral precursors may be transported through spaces between fibrils before they crystallize along the surface of and within the fibrils

Realisation of an optical pressure standard by a multi-reflection interferometric technique

A novel realization of an optical pressure standard, alternative to Fabry-Perot cavity-based techniques, is presented. It is based on the measurement of the refractive index of a gas through an unbalanced homodyne interferometer, designed to have one of its two arms formed by a multi reflection double mirror assembly to establish an unbalance length larger than 6 m in a compact setup. The paper illustrates the most important steps concerning its realization: the estimate of the pressure-induced deformation of the interferometer, the temperature control at millikelvin level and the measurement in vacuum of the unbalance of the interferometer. The evaluation of the uncertainty of the realized optical pressure standard currently demonstrated to fulfill the main goal of having the ability to measure pressure with a relative uncertainty of 10 ppm at 100 kPa

Voltammetric Study for the Determination of Diclofenac in Aqueous Solutions Using Electro-Activated Carbon Electrodes

Diclofenac (DCF) is a nonsteroidal anti-inflammatory drug to treat pain and inflammatory diseases. The high consumption of the drug leads to a significant change in the ecosystem. With the aim of optimizing a fast screening analysis for DCF detection on many samples with a sensitive and cheap procedure, we considered electrochemical methods using carbon-based electrodes as sensors. The electrochemical behavior of the DCF was studied on glassy carbon electrodes (GCE) and on screen-printed carbon electrodes (SPCEs) from two different suppliers after an anodic activation. The surface of the SPCEs was analyzed by scanning electron microscope (SEM) and Energy Dispersive Spectrometry (EDS). On all the activated electrodes, the voltammetric procedure (Differential Pulse Voltammetry) for the determination of DCF was optimized by the Experimental Design method, and the linearity range of the response, as well as the calibration and limit parameters (limits of detection—LoD; limit of quantification—LoQ), were defined. Analyses on SPCEs were performed both by immersing the electrode in the solution and by deposing a drop of solution on the electrode. DCF signals are stabilized by the polishing process and enhanced by the anodic activation and acid pH. The electrochemical response of DCF is not reversible, and its by-products tend to be adsorbed on the surfaces, particularly on GCE. The lowest limit parameters were obtained using the GCE (LoD = 1.6 µg L−1) and the SPCE, having the smallest surface, immersed in solution (LoD = 7 µg L−1)