Structural Landscape and Proton Conduction of Lanthanide 5-(Dihydroxyphosphoryl)isophthalates.

Metal phosphonate-carboxylate compounds represent a promising class of materials for proton conduction applications. This study investigates the structural, thermal, and proton conduction properties of three groups of lanthanide-based compounds derived from 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). The crystal structures, solved from X-ray powder diffraction data, reveal that groups , Ln[OP-CH(COO)(COOH)(HO)] (Ln = La, Pr), and , Ln{[OP-CH(COO)(COOH)](HO)}·2HO (Ln = La, Pr, Eu), exhibit three-dimensional frameworks, while group , Ln[OP-CH(COO)(COOH)(HO)] (Ln = Yb), adopts a layered structure with unbonded carboxylic groups oriented toward the interlayer region.

Influence of Rare-Earth Doping Content and Type on Phase Transformation and Transport Properties in Highly Doped CeO.

Rare-earth doped CeO materials find extensive application in high-temperature energy conversion devices such as solid oxide fuel cells and electrolyzers. However, understanding the complex relationship between structural and electrical properties, particularly concerning rare-earth ionic size and content, remains a subject of ongoing debate, with conflicting published results. In this study, we have conducted comprehensive long-range and local order structural characterization of CeLnO samples ( ≤ 0.

Sex-based Differences in Heart Failure Biomarkers.

Purpose Of Review: Differences in HF biomarker levels by sex may be due to hormonal, genetic, and fat distribution differences. Knowledge of these differences is scarce, and it is not well established whether they may affect their usefulness in the management of HF.

Recent Findings: The different biomarker profiles in women and men have been confirmed in recent studies: in women, markers of cardiac stretch and fibrosis (NP and galectin-3) are higher, whereas in men, higher levels of markers of cardiac injury and inflammation (cTn and sST2) are found.

Real-world cost-effectiveness analysis of NOACs versus VKA for stroke prevention in Spain.

Aims: A Markov model was adapted to assess the real-world cost-effectiveness of rivaroxaban, dabigatran and apixaban. Each of these non-vitamin K antagonist oral anticoagulants was compared with vitamin K antagonist for stroke prevention in patients with non-valvular atrial fibrillation in Spain.

Methods: All inputs were derived from real-world studies: baseline patient characteristics, clinical event rates, as well as persistence rates for the vitamin K antagonist treatment option.

Isolation and Molecular Characterisation of and Genes from Subspecies and , Study of Their Influences on Seedling Root Angles.

Durum wheat ( 2n = 4x = AABB) includes several subspecies with differential characteristics in their root system architecture (RSA). Subspecies has longer and more vertical roots, while subspecies has smaller and shallower roots. The homeologous genes and of both subspecies have been identified and found to differ in their sizes, sequences and the proteins they encode.

Properties and Applications of Metal Phosphates and Pyrophosphates as Proton Conductors.

We review the progress in metal phosphate structural chemistry focused on proton conductivity properties and applications. Attention is paid to structure-property relationships, which ultimately determine the potential use of metal phosphates and derivatives in devices relying on proton conduction. The origin of their conducting properties, including both intrinsic and extrinsic conductivity, is rationalized in terms of distinctive structural features and the presence of specific proton carriers or the factors involved in the formation of extended hydrogen-bond networks.

Exploiting the Multifunctionality of M/Imidazole-Etidronates for Proton Conductivity (Zn) and Electrocatalysis (Co, Ni) toward the HER, OER, and ORR.

This work deals with the synthesis and characterization of one-dimensional (1D) imidazole-containing etidronates, [M(ETID)(Im)]·HO (M = Co and Ni; = 0, 1, 3) and [Zn(ETID)(HO)](Im), as well as the corresponding Co/Ni solid solutions, to evaluate their properties as multipurpose materials for energy conversion processes. Depending on the water content, metal ions in the isostructural Co and Ni derivatives are octahedrally coordinated ( = 3) or consist of octahedral together with dimeric trigonal bipyramidal ( = 1) or square pyramidal ( = 0) environments. The imidazole molecule acts as a ligand (Co, Ni derivatives) or charge-compensating protonated species (Zn derivative).

Structural and proton conductivity studies of fibrous π-TiO(PO)·2HO: application in chitosan-based composite membranes.

Although the fibrous polymorphic modification of titanium phosphate, π-Ti2O(PO4)2·2H2O (π-TiP) has been known for decades, its crystal structure has remained unsolved. Herewith, we report the crystal structure of π-TiP at room temperature, as determined from synchrotron radiation powder X-ray diffraction, and corroborated by 31P solid state NMR and accurate density functional theory calculations. In contrast to the previously reported ρ-TiP polymorph, the as-synthesized hydrated phase crystallizes in the monoclinic system (P21/c, a = 5.

Phase Transformation Dynamics in Sulfate-Loaded Lanthanide Triphosphonates. Proton Conductivity and Application as Fillers in PEMFCs.

Phase transformation dynamics and proton conduction properties are reported for cationic layer-featured coordination polymers derived from the combination of lanthanide ions (Ln) with nitrilo-tris(methylenephosphonic acid) (HNMP) in the presence of sulfate ions. Two families of materials are isolated and structurally characterized, i.e.

NH/HO-mediated proton conductivity and photocatalytic behaviour of Fe(ii)-hydroxyphosphonoacetate and M(ii)-substituted derivatives.

Synthesis redesign and derivatisation of Fe(ii)-hydroxyphosphonoacetate, incorporating different ammonia loads and M(ii) isomorphic substitutions (M = Mn, Co and Zn), have been implemented. The NH adsorption led to materials with enhanced proton conductivity, up to ∼10 S cm, although it caused a progressive amorphization. The Pair Distribution Function (PDF) analysis for this material confirmed the loss of crystallinity but the local order appeared to be maintained.

Clinical profile and management of rivaroxaban in patients with atrial fibrillation in routine practice in Spain: data from six nationwide studies.

Aims: To analyze the clinical profile and management of patients with nonvalvular atrial fibrillation taking rivaroxaban in routine practice in Spain.

Methods: Clinical data from the observational studies HEROIC (cardiology and hematology; n=1,727), EMIR (cardiology; n=1,493), BRONCE-AP (primary care; n=133), SILVER-AP (primary care; n=457), ALADIN (internal medicine and neurology; n=249), and ESPARTA (internal medicine; n=110) of patients taking rivaroxaban were analyzed. The clinical profile was compared with those of the XANTUS and ROCKET-AF studies.

Phosphonate Decomposition-Induced Polyoxomolybdate Dumbbell-Type Cluster Formation: Structural Analysis, Proton Conduction, and Catalytic Sulfoxide Reduction.

The reaction of MoO with a number of phosphonic acids [bis(phosphonomethyl)glycine, -hydroxyphosphonoacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, phenylphosphonic acid, aminotris(methylene phosphonic acid), and 1,2-ethylenediphosphonic acid] under oxidizing (HO) hydrothermal conditions at low pH leads to rupture of the P-C bond, release of orthophosphate ions, and generation of the octanuclear, phosphate-bridged, polyoxometalate molybdenum cluster (NH)[Mo(OH)O(μ-PO)](HO) (). This cluster has been fully characterized and its structure determined. It was studied as a proton conductor, giving moderate values of σ = 2.

Relationship between the Structure and Transport Properties in the CeLaO System.

La-doped CeO materials have been widely investigated for potential applications in different high-temperature electrochemical devices, such as fuel cells and ceramic membranes for hydrogen production. However, the crystal structure is still controversial, and different models based on fluorite, pyrochlore, and/or type-C structures have been considered, depending on the lanthanum content and synthesis method used. In this work, an exhaustive structural analysis of the CeLaO system (0.

A Self-Folding Polymer Film Based on Swelling Metal-Organic Frameworks.

Herein, we exploit the well-known swelling behaviour of metal-organic frameworks (MOFs) to create a self-folding polymer film. Namely, we show that incorporating crystals of the flexible MOF MIL-88A into a polyvinylidene difluoride (PVDF) matrix affords a polymer composite film that undergoes reversible shape transformations upon exposure to polar solvents and vapours. Since the self-folding properties of this film correlate directly with the swelling properties of the MIL-88A crystals, it selectively bends to certain solvents and its degree of folding can be controlled by controlling the relative humidity.

Three-Component Copper-Phosphonate-Auxiliary Ligand Systems: Proton Conductors and Efficient Catalysts in Mild Oxidative Functionalization of Cycloalkanes.

The synthesis, structural characterization, topological analysis, proton conductivity, and catalytic properties are reported of two Cu(II)-based compounds, namely a dinuclear Cu(II) complex [Cu(μ-VPA)(phen)(HO)]·8HO (1) (HVPA = vinylphosphonic acid, phen = 1,10-phenanthroline) and a 1D coordination polymer [Cu(μ-SO)(phen)(HO)] (2). Their structural features and H-bonding interactions were investigated in detail, showing that the metal-organic structures of 1 and 2 are extended by multiple hydrogen bonds to more complex 2D or 1D H-bonded architectures with the kgd [Shubnikov plane net (3.6.

Zinc(ii), cobalt(ii) and manganese(ii) networks with phosphoserine ligand: synthesis, crystal structures and magnetic and proton conductivity properties.

A series of zinc(ii), cobalt(ii) and manganese(ii) coordination networks with phosphoserine ligand (HPSer) are synthesized and characterized. Whereas in compounds 1 and 2 with the general formula [M(HPser)] [M = Zn (1) and Co (2)], the metal(ii) ion presents a tetrahedral geometry, in [Co(HPSer)(HO)] (3) and [Mn(HPSer)(HO)] (4), the metal(ii) ions are in a distorted octahedral geometry. The 3D frameworks are formed by inorganic layers built up from MO or MO polyhedra and phosphate groups.

Influence of Proton Conducting Cations on the Structure and Properties of 2D Anilate-Based Magnets.

The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (MeNH)[MnCr(BrAn)]·2HO (1), (EtNH)[MnCr(BrAn)] (2), (EtNH)[MnCr(ClAn)] (3), and [(Et)(i-Pr)NH][MnCr(BrAn)]·(CHCl)·(HO) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by MeNH, EtNH, or EtNH cations.

Luminescent and Proton Conducting Lanthanide Coordination Networks Based On a Zwitterionic Tripodal Triphosphonate.

The synthesis, structural characterization, luminescence properties, and proton conduction performance of a new family of isostructural cationic 2D layered compounds are reported. These have the general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La(3+), Pr(3+), Sm(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), Ho(3+), H6NMP = nitrilotris(methylphosphonic acid)], and contain Cl(-) as the counterion. In the case of Ce(3+), a 1D derivative, [Ce2(H3NMP)2(H2O)4]·4.

Single-crystal and humidity-controlled powder diffraction study of the breathing effect in a metal-organic framework upon water adsorption/desorption.

Herein we report a study on water adsorption/desorption-triggered single-crystal to single-crystal transformations in a MOF, by single-crystal and humidity-controlled powder X-ray diffraction and water-sorption measurements. We identified a gate-opening effect at a relative humidity of 85% upon water adsorption, and a gate-closure effect at a relative humidity of 55 to 77% upon water desorption. This reversible breathing effect between the "open" and the "closed" structures of the MOF involves the cleavage and formation of several coordination bonds.

The number of risk factors is the strongest predictor of prostate cancer mortality: multi-institutional outcomes of an extreme-risk prostate cancer cohort.

Purpose: To report treatment outcomes in a cohort of extreme-risk prostate cancer patients and identify a subgroup of patients with worse prognosis.

Materials And Methods: Extreme-risk prostate cancer patients were defined as patients with at least one extreme-risk factor: stage cT3b-cT4, Gleason score 9-10 or PSA > 50 ng/ml; or patients with 2 or more high-risk factors: stage cT2c-cT3a, Gleason 8 and PSA > 20 ng/ml. Overall survival (OS), cause-specific survival (CSS), clinical-free survival (CFS), and biochemical non-evidence of disease (bNED) survival are the four outcomes of interest in a population of 1341 patients.

Modeling of biomass fractionation in a lab-scale biorefinery: Solubilization of hemicellulose and cellulose from holm oak wood using subcritical water.

Lignocellulose fractionation is a key biorefinery process that need to be understood. In this work, a comprehensive study on hydrothermal-fractionation of holm oak in a semi-continuous system was conducted. The aim was to develop a physicochemical model in order to reproduce the role of temperature and water flow over the products composition.

Guest molecule-responsive functional calcium phosphonate frameworks for tuned proton conductivity.

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca(2+) ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPhtA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels.

Proton conductors based on alkaline-earth substituted La(28-x)W(4+x)O(54+3x/2).

Lanthanum tungstates, "La6WO12", are mixed ion proton-electronic conductors with very interesting properties for technological applications and better phase stability compared to alkaline earth perovskites. A new series of compounds La(27.04-x)M(x)W(4.

Structural variability in multifunctional metal xylenediaminetetraphosphonate hybrids.

Two new families of divalent metal hybrid derivatives from the aromatic tetraphosphonic acids 1,4- and 1,3-bis(aminomethyl)benzene-N,N'-bis(methylenephosphonic acid), (H2O3PCH2)2-N-CH2C6H4CH2-N(CH2PO3H2)2 (designated herein as p-H8L and m-H8L) have been synthesized by crystallization at room temperature and hydrothermal conditions. The crystal structures of M[(HO3PCH2)2N(H)CH2C6H4CH2N(H)(CH2PO3H)2(H2O)2]·2H2O (M = Mg, Co, and Zn), M-(p-H6L), and M[(HO3PCH2)2N(H)CH2C6H4CH2N(H)(CH2PO3H)2]·nH2O (M = Ca, Mg, Co, and Zn and n = 1-1.5), M-(m-H6L), were solved ab initio by synchrotron powder diffraction data using the direct methods and subsequently refined using the Rietveld method.