Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal−Organic Framework: A Multitechnique Investigation

Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4- yl)ethyne (H2BPE) was expressly designed and synthesized to devise metal−organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl2 aqueous solutions prompts its conversion into HgCl2@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl2-triggered i-Zn-to- HgCl2@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl2 interacts via the mercury atom with the carbon−carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl2@ni-Zn transition in 100−5000 ppm HgCl2 (aq) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl2 is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl2@ni-Zn conversion kinetics at different HgCl2 (aq) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl2 and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and costeffective purification.University of Insubria for partial fundingPrograma Juan de la Cierva Formación (FJC2020-045043-I)MCIN/AEI/10.13039/501100011033European Union NextGenerationEU/PRTR (Grants PID2020- 113608RB-I00 and TED2021-129886B-C41

The Tidal Evolution of Local Group Dwarf Spheroidals

(Abridged) We use N-body simulations to study the evolution of dwarf spheroidal galaxies (dSphs) driven by galactic tides. We adopt a cosmologically-motivated model where dSphs are approximated by a King model embedded within an NFW halo. We find that these NFW-embedded King models are extraordinarily resilient to tides; the stellar density profile still resembles a King model even after losing more than 99% of the stars. As tides strip the galaxy, the stellar luminosity, velocity dispersion, central surface brightness, and core radius decrease monotonically. Remarkably, we find that the evolution of these parameters is solely controlled by the total amount of mass lost from within the luminous radius. Of all parameters, the core radius is the least affected: after losing 99% of the stars, R_c decreases by just a factor of ~2. Interestingly, tides tend to make dSphs more dark-matter dominated because the tightly bound central dark matter ``cusp'' is more resilient to disruption than the ``cored'' King profile. We examine whether the extremely large M/L ratios of the newly-discovered ultra-faint dSphs might have been caused by tidal stripping of once brighter systems. Although dSph tidal evolutionary tracks parallel the observed scaling relations in the luminosity-radius plane, they predict too steep a change in velocity dispersion compared with the observational estimates hitherto reported in the literature. The ultra-faint dwarfs are thus unlikely to be the tidal remnants of systems like Fornax, Draco, or Sagittarius. Despite spanning four decades in luminosity, dSphs appear to inhabit halos of comparable peak circular velocity, lending support to scenarios that envision dwarf spheroidals as able to form only in halos above a certain mass threshold.Comment: 17 pages, 12 figs., accepted by Ap

Diversification of substrate specificities in teleostei Fads2: characterization of Δ4 and Δ6Δ5 desaturases of Chirostoma estor

Currently existing data show that the capability for long-chain PUFA (LC-PUFA) biosynthesis in teleost fish is more diverse than in other vertebrates. Such diversity has been primarily linked to the subfunctionalization that teleostei fatty acyl desaturase (Fads)2 desaturases have undergone during evolution. We previously showed that Chirostoma estor, one of the few representatives of freshwater atherinopsids, had the ability for LC-PUFA biosynthesis from C18 PUFA precursors, in agreement with this species having unusually high contents of DHA. The particular ancestry and pattern of LC-PUFA biosynthesis activity of C. estor make this species an excellent model for study to gain further insight into LC-PUFA biosynthetic abilities among teleosts. The present study aimed to characterize cDNA sequences encoding fatty acyl elongases and desaturases, key genes involved in the LC-PUFA biosynthesis. Results show that C. estor expresses an elongase of very long-chain FA (Elovl)5 elongase and two Fads2 desaturases displaying Δ4 and Δ6/Δ5 specificities, thus allowing us to conclude that these three genes cover all the enzymatic abilities required for LC-PUFA biosynthesis from C18 PUFA. In addition, the specificities of the C. estor Fads2 enabled us to propose potential evolutionary patterns and mechanisms for subfunctionalization of Fads2 among fish lineages

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO3) carbonation (silicate dissolution -> carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.This research was funded by the Spanish Government (grants CGL2015-70642-R, CGL2015-73103-EXP, CTQ2017-84692-R), EU FEDER funding, the University of Granada (“Unidad Científica de Excelencia” UCE-PP2016-05) and the Junta de Andalucía (grant P11-RNM-7550 and Research Group RNM-179). We thank the personnel of the Centro de Instrumentación Científica (CIC) of the University of Granada for their help during TG-DSC, FESEM, -XRD, and ICP-OES analyses

Manganese(II) pyrimidine-4,6-dicarboxylates: Synthetic, structural, magnetic and adsorption insights into the system

A series of manganese(II) coordination polymers containing the bridging ligand pyrimidine-4,6-dicarboxylate (pmdc) have been prepared. The stoichiometries and structural features of these materials, which range from the one-dimensional (1D) chains in {[Mn(\ub5-pmdc)(H2O)3]\ub72H2O}n (1) and {[Mn2(\ub5-pmdc)2(H2O)5]\ub72H2O}n (2) to the two-dimensional layers in {[Mn(\ub53-pmdc)(H2O)]\ub7H2O}n (3) or the three-dimensional porous network in {[Mn(pmdc)] \ub7 2H2O}n (4), are extremely dependent on the synthetic conditions (i.e., temperature and solvent). In spite of the structural diversity of these systems, crystallographic studies revealed that the pmdc ligand typically displays a tetradentate \ub5-(\u3baO,\u3baN:\u3baO\u2032\u2032,\u3baN\u2032) coordination mode with the carboxylate groups almost coplanar with the pyrimidine ring [as in compounds 1 and 2 and compound 5 described below)]. In compound 3, the pmdc moiety adopts a pentadentate \ub53-(\u3baO,\u3baN:\u3baO\u2032\u2032,\u3baN\u2032:\u3baO) coordination mode. The thermal, magnetic, and adsorption properties of these systems were also studied. The results showed that these compounds behave as antiferromagnets as a consequence of ef\ufb01cient magnetic exchange through the pmdc bridges. Compound 4 possesses permanent porosity, as proved by gas sorption data (N2 at 77 K and CO2 at 293 K). Finally, the heteronuclear iron(II)/manganese(II) compound {[FeMn(\ub5-pmdc)2(H2O)5]\ub72H2O}n (5), which is isomorphous to 2, was also prepared and fully characterized

CO2 Adsorption in a Robust Iron(III) Pyrazolate-Based MOF: Molecular-Level Details and Frameworks Dynamics From Powder X-ray Diffraction Adsorption Isotherms

Understanding adsorption processes at the molecular level, with multi-technique approaches, is nowadays at the frontier of porous materials research. In this work it is shown that with a proper data treatment, in situ high-resolution powder X-ray diffraction (HR-PXRD) at variable temperature and gas pressure can reveal atomic details of the accommodation sites, the framework dynamics as well as thermodynamic information (isosteric heat of adsorption) of the CO2 adsorption process in the robust iron(III) pyrazolate-based MOF Fe2(BDP)3 [H2BDP = 1,4-bis(1H-pyrazol-4-yl)benzene]. Highly reliable "HR-PXRD adsorption isotherms" can be constructed from occupancy values of CO2 molecules. The "HR-PXRD adsorption isotherms" accurately match the results of conventional static and dynamic gas sorption experiments and Monte Carlo simulations. These results are indicative of the impact of the molecular-level behavior on the bulk properties of the system under study and of the potential of the presented multi-technique approach to understand adsorption processes in metal-organic frameworks

Validation of models with constant bias: an applied approach

Objective. This paper presents extensions to the statistical validation method based on the procedure of Freese when a model shows constant bias (CB) in its predictions and illustrate the method with data from a new mechanistic model that predict weight gain in cattle. Materials and methods. The extensions were the hypothesis tests and maximum anticipated error for the alternative approach, and the confidence interval for a quantile of the distribution of errors. Results. The model evaluated showed CB, once the CB is removed and with a confidence level of 95%, the magnitude of the error does not exceed 0.575 kg. Therefore, the validated model can be used to predict the daily weight gain of cattle, although it will require an adjustment in its structure based on the presence of CB to increase the accuracy of its forecasts. Conclusions. The confidence interval for the 1-α quantile of the distribution of errors after correcting the constant bias, allows determining the top limit for the magnitude of the error of prediction and use it to evaluate the evolution of the model in the forecasting of the system. The confidence interval approach to validate a model is more informative than the hypothesis tests for the same purpose

Ingresos hospitalarios en niños menores de un año y su relación con la calidad del agua, clases y grupos sociales de la ciudad de Boaco.

Se estudió la relación entre ingresos hospitalarios en niños menores de 1 año, calidad del agua que consumían y las clases y grupos sociales a que pertenecían, para este efecto se revisaron los expedientes de todos los ingresos pediátricos efectuados entre el 1 de agosto de 1981 y el 31 de julio de 1983, tomados de los registros médicos del hospital José Nieborowski de la ciudad de Boaco, de los cuales se escogieron a todos los menores de 1 año con dirección urbana en la ciudad mencionada. El universo de estudio quedó constituído por 132 ingresos de éstos, 96 ingresaron por enfermedades de transmisión hídrica y 36 por otras causas. A todos se les aplicó una ficha en donde se recogieron los datos generales del ingreso, además se encuestó a sus familiares para determinar la calidad del agua consumida, la clase o grupo social a que pertenecían, la escolaridad y educación sanitaria de las madres. Los resultados obtenidos se plasmaron en tablas donde se establecieron las relaciones entre ingresos hospitalarios de niños menores de 1 año por enfermedades de transmisión hídricas y por otras causas, con la edad, sexo, fuentes de abastecimiento de agua en la vivienda, clases y grupos sociales, número de miembros en el núcleo familiar, ingreso económico familiar mensual, escolaridad y educación sanitaria de las madres. Las conclusiones más importantes a que nos llevó el estudio son: de los ingresos estudiados ninguno consumía agua de buena calidad; el abastecimiento de agua que resultó ser el mayor factor predisponente para la ocurrencia de enfermedades de transmisión hídrica en relación a las de otras causas, fue el grupo de otras fuentes. El 80.3 porciento de todos los ingresos correspondían a trabajadores de servicio y obreros. Existe una relación inversamente proporcional entre ingresos económicos familiares e ingresos hospitalarios en general. Se recomienda implementar charlas orientadas a mejorar el nivel de educación sanitaria de las madres tanto en consulta externa como en hospitalización, además mantener e incrementar la divulgación de la educación popular en salud. El proyecto de construcción de la planta de tratamiento en el Acueducto de Boaco planeado por INAA se agilice. Ejercer control sobre el expendio ambulatorio agua, tanto las condiciones de la fuente como realizando exámenes bacteriológico periódicos

The PAndAS Field of Streams: stellar structures in the Milky Way halo toward Andromeda and Triangulum

We reveal the highly structured nature of the Milky Way stellar halo within the footprint of the PAndAS photometric survey from blue main sequence and main sequence turn-off stars. We map no fewer than five stellar structures within a heliocentric range of ~5 to 30 kpc. Some of these are known (the Monoceros Ring, the Pisces/Triangulum globular cluster stream), but we also uncover three well-defined stellar structures that could be, at least partly, responsible for the so-called Triangulum/Andromeda and Triangulum/Andromeda 2 features. In particular, we trace a new faint stellar stream located at a heliocentric distance of ~17 kpc. With a surface brightness of \Sigma_V ~ 32-32.5 mag/arcsec^2, it follows an orbit that is almost parallel to the Galactic plane north of M31 and has so far eluded surveys of the Milky Way halo as these tend to steer away from regions dominated by the Galactic disk. Investigating our follow-up spectroscopic observations of PAndAS, we serendipitously uncover a radial velocity signature from stars that have colors and magnitudes compatible with the stream. From the velocity of eight likely member stars, we show that this stellar structure is dynamically cold, with an unresolved velocity dispersion that is lower than 7.1 km/s at the 90-percent confidence level. Along with the width of the stream (300-650 pc), its dynamics points to a dwarf-galaxy-accretion origin. The numerous stellar structures we can map in the Milky Way stellar halo between 5 and 30 kpc and their varying morphology is a testament to the complex nature of the stellar halo at these intermediate distances.Comment: 11 pages, 8 figures, accepted for publication in the ApJ, Figure 3 is the money plo