Patients with chronic kidney disease (CKD) have an increased risk of premature mortality, mainly due to cardiovascular causes. The association between hemodialysis and accelerated atherosclerosis has ...long been described. The ankle-brachial index (ABI) is a surrogate marker of atherosclerosis and recent studies indicate its utility as a predictor of future cardiovascular disease and all-cause mortality. The clinical implications of ABI cut-points are not well defined in patients with CKD. Echocardiography is the most widely used imaging method for cardiac evaluation. Structural and functional myocardial abnormalities are common in patients with CKD due to pressure and volume overload as well as non-hemodynamic factors associated with CKD. Our study aimed to identify markers of subclinical cardiovascular risk assessed using ABI and 2D and 3D echocardiographic parameters evaluating left ventricular (LV) structure and function in patients with end-stage renal disease (ESRD) (patients undergoing dialysis), patients after kidney transplantation and non-ESRD patients (control). In ESRD, particularly in hemodialysis patients, changes in cardiac structure, rather than function, seems to be more pronounced. 3D echocardiography appears to be more sensitive than 2D echocardiography in the assessment of myocardial structure and function in CKD patients. Particularly 3D derived end-diastolic volume and 3D derived LV mass indexed for body surface appears to deteriorate in dialyzed and transplanted patients. In 2D echocardiography, myocardial mass represented by left ventricular mass/body surface area index (LVMI) appears to be a more sensitive marker of cardiac structural changes, compared to relative wall thickness (RWT), left ventricle and diastolic diameter index (LVEDDI) and left atrial volume index (LAVI). We observed a generally favorable impact of kidney transplantation on cardiac structure and function; however, the differences were non-significant. The improvement seems to be more pronounced in cardiac function parameters, peak early diastolic velocity/average peak early diastolic velocity of mitral valve annulus (E/e´), 3D left ventricle ejection fraction (LV EF) and global longitudinal strain (GLS). We conclude that ABI is not an appropriate screening test to determine the cardiovascular risk in patients with ESRD.
Many of the studies on the entropy‐stabilized oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O have been heavily application‐based. Previous works have studied effects of cation stoichiometry on the entropy‐driven ...reaction to form a single phase, but a fundamental exploration of the effects of anion stoichiometry and/or redox chemistry on electrical properties is lacking. Using near‐edge X‐ray absorption fine structure (NEXAFS) and electrical measurements, we show that oxidizing thin film samples of (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O affects primarily the valence of Co, leaving the other cations in this high‐entropy system unchanged. This oxidation increases electrical conduction in these thin films, which occurs via small polaron hopping mediated by the Co valence shift from 2+ to a mixed 2+/3+ state. In parallel, we show that bulk samples sintered in an oxygen‐rich atmosphere have a lower activation energy for electrical conduction than those equilibrated in a nitrogen (reducing) atmosphere. Combining feasible defect compensation scenarios with electrical impedance measurements and NEXAFS data, we propose a self‐consistent interpretation of Co redox‐mediated small polaron conduction as the dominant method of charge transfer in this system.
Introducing heterovalent cations at the octahedral sites of halide perovskites can substantially change their optoelectronic properties. Yet, in most cases, only small amounts of such metals can be ...incorporated as impurities into the three-dimensional lattice. Here, we exploit the greater structural flexibility of the two-dimensional (2D) perovskite framework to place three distinct stoichiometric cations in the octahedral sites. The new layered perovskites AI4Cu II (Cu I In III ) 0.5 Cl 8 ( 1 , A = organic cation) may be derived from a Cu I –In III double perovskite by replacing half of the octahedral metal sites with Cu 2+ . Electron paramagnetic resonance and X-ray absorption spectroscopy confirm the presence of Cu 2+ in 1 . Crystallographic studies demonstrate that 1 represents an averaging of the Cu I –In III double perovskite and Cu II single perovskite structures. However, whereas the highly insulating Cu I –In III and Cu II perovskites are colorless and yellow, respectively, 1 is black, with substantially higher electronic conductivity than that of either endmember. We trace these emergent properties in 1 to intervalence charge transfer between the mixed-valence Cu centers. We further propose a tiling model to describe how the Cu + , Cu 2+ , and In 3+ coordination spheres can pack most favorably into a 2D perovskite lattice, which explains the unusual 1 : 2 : 1 ratio of these cations found in 1 . Magnetic susceptibility data of 1 further corroborate this packing model. The emergence of enhanced visible light absorption and electronic conductivity in 1 demonstrates the importance of devising strategies for increasing the compositional complexity of halide perovskites.
Metathesis reactions are widely used in synthetic chemistry. While state-of-the-art organic metathesis involves highly controlled processes where specific bonds are broken and formed, inorganic ...metathesis reactions are often extremely exothermic and, consequently, poorly controlled. Ternary nitrides offer a technologically relevant platform for expanding synthetic control of inorganic metathesis reactions. Here, we show that energy-controlled metathesis reactions involving a heterovalent exchange are possible in inorganic nitrides. We synthesized Zn3WN4 by swapping Zn2+ and Li+ between Li6WN4 and ZnX2 (X = Br, Cl, F) precursors. The in situ synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the ZnX2 melting point and that product purity is inversely correlated with the reaction's exothermicity. Therefore, careful choice of the halide counterion (i.e., ZnBr2) allows the synthesis to proceed in a swift but controlled manner at a surprisingly low temperature for an inorganic nitride (300 °C). High resolution synchrotron powder X-ray diffraction and diffuse reflectance spectroscopy confirm the synthesis of a cation-ordered Zn3WN4 semiconducting material. We hypothesize that this synthesis strategy is generalizable because many Li–M–N phases are known (where M is a metal) and could therefore serve as precursors for metathesis reactions targeting new ternary nitrides. This work expands the synthetic control of inorganic metathesis reactions in a way that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials.
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