Synthesis, studies and fuel cell performance of “core–shell” electrocatalysts for oxygen reduction reaction based on a PtNix carbon nitride “shell” and a pyrolyzed polyketone nanoball “core”

This report describes a new class of "core-shell" electrocatalysts for oxygen reduction reaction (ORR) processes for application in Proton Exchange Membrane Fuel Cells (PEMFCs). The electrocatalysts are obtained by supporting a "shell" consisting of PtNix alloy nanoparticles embedded into a carbon nitride matrix (indicated as PtNix-CN) on a "core" of pyrolyzed polyketone nanoballs, labeled 'STp'. ST(p)s are obtained by the sulfonation and pyrolysis of a precursor consisting of XC-72R carbon nanoparticles wrapped by polyketone (PK) fibers. The ST(p)s are extensively characterized in terms of the chemical composition, thermal stability, degree of graphitization and morphology. The "core-shell" ORR electrocatalysts are prepared by the pyrolysis of precursors obtained impregnating the STp "cores" with a zeolitic inorganic-organic polymer electrolyte (Z-IOPE) plastic material. The electrochemical performance of the electrocatalysts in the ORR is tested "in situ" by single fuel cell tests. The interplay between the chemical composition, the degree of graphitization of both PtNix-CN "shell" and STpS "cores", the morphology of the electrocatalysts and the fuel cell performance is elucidated. The most crucial preparation parameters for the optimization of the various features affecting the fuel cell performance of this promising class of ORR electrocatalysts are identified

A Positron Implantation Profile Estimation Approach for the PALS Study of Battery Materials

Positron annihilation spectroscopy is a powerful probe to investigate the interfaces in materials relevant for energy storage such as Li-ion batteries. The key to the interpretation of the results is the positron implantation profile, which is a spatial function related to the characteristics of the materials forming the battery. We provide models for the positron implantation profile in a cathode of a Li-ion battery coin cell. These models are the basis for a reliable visualization of multilayer geometries and their interfaces in thin cathodes of lithium-ion batteries

Evaluation of electrospun spinel-type high-entropy (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4, (Cr0.2Mn0.2Fe0.2Co0.2Zn0.2)3O4 and (Cr0.2Mn0.2Fe0.2Ni0.2Zn0.2)3O4 oxide nanofibers as electrocatalysts for oxygen evolution in alkaline medium

Electrochemical water splitting is a promising sustainable-energy technology, but the slow kinetics of the oxygen evolution reaction represents a limitation for its broad market penetration. Spinel-structured transition metal (TM) oxides have shown great potential as a sustainable alternative to precious metal-based electrocatalysts. High-entropy oxides (HEOs) with multiple TM-cation sites lend themselves to engineering of the octahedral redox-active centres to enhance the catalyst reactivity. This work focuses on the preparation of electrospun spinel-type HEO nanofibers (NFs), based on equimolar (Cr,Mn,Fe,Co,Ni), (Cr,Mn,Fe,Co,Zn) and (Cr,Mn,Fe,Ni,Zn) combinations, and their evaluation as electrocatalysts in alkaline medium together with (Cr,Mn,Fe,Co,Ni) HEO nanoparticles (NPs) prepared via the sol-gel method. (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4 NFs and NPs (Tafel slopes: 49.1 and 51.3 mV dec−1, respectively) outperform both (Cr0.2Mn0.2Fe0.2Co0.2Zn0.2)3O4 and (Cr0.2Mn0.2Fe0.2Ni0.2Zn0.2)3O4 NFs (62.5 and 59.6 mV dec−1, respectively) and IrO2 reference electrocatalyst (52.9 mV dec−1). The higher concentration of oxygen vacancies on their surface and the higher occupation of octahedral sites by redox-active Co2+ and Ni2+ centres are responsible for their behaviour. The present electrospun HEO NFs have great potential as ink-jet printable electrocatalysts

Further characterization of agmatine binding to mitochondrial membranes: involvement of imidazoline I2 receptor.

Agmatine, a divalent diamine with two positive charges at physiological pH, is transported into the matrix of liver mitochondria by an energy-dependent mechanism, the driving force of which is the electrical membrane potential. Its binding to mitochondrial membranes is studied by applying a thermodynamic treatment of ligand-receptor interactions on the analyses of Scatchard and Hill. The presence of two mono-coordinated binding sites S(1) and S(2), with a negative influence of S(2) on S(1), has been demonstrated. The calculated binding energy is characteristic for weak interactions. S(1) exhibits a lower binding capacity and higher binding affinity both of about two orders of magnitude than S(2). Experiments with idazoxan, a ligand of the mitochondrial imidazoline receptor I(2), demonstrate that S(1) site is localized on this receptor while S(2) is localized on the transport system. S(1) would act as a sensor of exogenous agmatine concentration, thus modulating the transport of the amine by its binding to S(2)

Quantum view of Li-ion high mobility at carbon-coated cathode interfaces

: Lithium-ion batteries (LIBs) are among the most promising power sources for electric vehicles, portable electronics and smart grids. In LIBs, the cathode is a major bottleneck, with a particular reference to its low electrical conductivity and Li-ion diffusivity. The coating with carbon layers is generally employed to enhance the electrical conductivity and to protect the active material from degradation during operation. Here, we demonstrate that this layer has a primary role in the lithium diffusivity into the cathode nanoparticles. Positron is a useful quantum probe at the electroactive materials/carbon interface to sense the mobility of Li-ion. Broadband electrical spectroscopy demonstrates that only a small number of Li-ions are moving, and that their diffusion strongly depends on the type of carbon additive. Positron annihilation and broadband electrical spectroscopies are crucial complementary tools to investigate the electronic effect of the carbon phase on the cathode performance and Li-ion dynamics in electroactive materials

Positron unveiling high mobility graphene stack interfaces in Li-ion cathodes

Carbon-based coatings in Li-ion battery cathodes improve electron conductivity and enable rapid charging. However, the mechanism is not well understood. Here, we address this question by using positrons as non-destructive probes to investigate nano-interfaces within cathodes. We calculate the positron annihilation lifetime in a graphene stack LiCoO2 heterojunction using an ab initio method with a non-local density approximation to accurately describe the electron-positron correlation. This ideal heterostructure represents the standard carbon-based coating performed on cathode nanoparticles to improve the conduction properties of the cathode. We characterize the interface between LiCoO2 and graphene as a p-type Schottky junction and find positron surface states. The intensity of the lifetime component for these positron surface states serves as a descriptor for positive ion ultra-fast mobility. Consequently, optimizing the carbon layer by enhancing this intensity and by analogizing Li-ion adatoms on graphene layers with positrons at surfaces can improve the design of fast-charging channels.Carbon layers in Li-ion battery cathodes are important for fast charging but the underlying mechanism is still not well understood. Here, ab initio calculations of the positron annihilation lifetime in graphene stack LiCoO2 heterojunction gives insights into ultra-fast ion mobility

Esophageal atresia in newborns: a wide spectrum from the isolated forms to a full VACTERL phenotype?

Background: VATER association was first described in 1972 by Quan and Smith as an acronym which identifies a non-random co-occurrence of Vertebral anomalies, Anal atresia, Tracheoesophageal fistula and/or Esophageal atresia, Radial dysplasia. It is even possible to find out Cardiovascular, Renal and Limb anomalies and the acronym VACTERL was adopted, also, embodying Vascular, as single umbilical artery, and external genitalia anomalies. Methods: Data on patients with esophageal atresia (EA) with or without tracheoesophageal fistula (TEF) admitted in the Neonatal Intensive Care Unit (NICU) between January 2003 and January 2013 were evaluated for the contingent occurrence of typical VACTERL anomalies (VACTERL-type) and non tipical VACTERL anomalies (non-VACTERL-type). The inclusion criterion was the presence of EA with or without TEF plus two or more of the following additional malformations: vertebral defects, anal atresia, cardiovascular defects, renal anomalies and lower limb deformities, like radial dysplasia. Results: Among 52 patients with EA/TEF, 20 (38,4%) had isolated EA and 7 (21,8%) had a recognized etiology such a syndrome and therefore were excluded. Among 32 infants with EA and associated malformations, 15 (46,8%) had VACTERL association. The most common anomalies were congenital heart defects (73,3%), followed by vertebral anomalies (66,6%). Many patients also had additional non-VACTERL-type defects. Single umbilical artery was the most common one followed by nervous system abnormalities and anomalies of toes. Between the groups of infants with VACTERL type and non-VACTERL-type anomalies, there are several overlapping data regarding both the tipically described spectrum and the most frequently reported non-VACTERL-type malformations. Thus, it is possible to differentiate infants with a full phenotype (VACTERL full phenotype) and patients that do not meet all the criteria mentioned above, but with some homologies with the first group (VACTERL partial phenotype). Conclusion: The high frequency of non-VACTERL-type anomalies encountered in full and partial phenotype patients would suggest the need for an extension of the clinical criteria for the diagnosis of VACTERL association and also for pre- and post-operative management and follow-up in the short and long term

Immunoglobulin free light chains and GAGs mediate multiple myeloma extracellular vesicles uptake and secondary NfkB nuclear traslocation

Multiplemyeloma(MM) is a hematological malignancy caused by a microenviromentally aided persistence of plasmacells in the bone marrow. Monoclonal plasmacells often secrete high amounts of immunoglobulin free light chains(FLCs)that could induce tissue damage. Recently, we showed that FLCs are internalized in endothelial and myocardial cell lines and secreted in extracellular vesicles(EVs). MM serum derived EVs presented phenotypic differences if compared with monoclonal gammopathy of undetermined significance (MGUS)serum derived EVs suggesting their involvement in MM pathogenesis or progression. To investigate the effect of circulating EVs on endothelial and myocardial cells, we purified MM and MGUS serum derived EVs with differential ultracentrifugation protocols and tested their biological activity. We found that MM and MGUS EVs induced different proliferation and internalization rates in endothelial and myocardial cells, thus we tried to find specific targets in MM EVs docking and processing. Pre-treatment of EVs withanti-FLCs antibodies or heparin blocked the MM EVs uptake, highlighting that FLCs and glycosaminoglycans are involved. Indeed, only MM EVs exposure induced a strong nuclear factor kappa B nuclear translocation that was completely abolished afteranti-FLCs antibodies and heparin pre-treatment. The protein tyrosine kinase c-src is present on MM circulating EVs and redistributes to the cell plasma membrane after MM EVs exposure.The anti-FLCs antibodies and heparin pre-treatments were able to block the intracellular redistribution of the c-src kinase and the subsequent c-src kinase containing EVs production. Our results open new insights in EVs cellular biology and in MM therapeutic and diagnostic approaches

Immunoglobulin free light chains and GAGs mediate multiple myeloma extracellular vesicles uptake and secondary NfkB nuclear traslocation

Multiplemyeloma(MM) is a hematological malignancy caused by a microenviromentally aided persistence of plasmacells in the bone marrow. Monoclonal plasmacells often secrete high amounts of immunoglobulin free light chains(FLCs)that could induce tissue damage. Recently, we showed that FLCs are internalized in endothelial and myocardial cell lines and secreted in extracellular vesicles(EVs). MM serum derived EVs presented phenotypic differences if compared with monoclonal gammopathy of undetermined significance (MGUS)serum derived EVs suggesting their involvement in MM pathogenesis or progression. To investigate the effect of circulating EVs on endothelial and myocardial cells, we purified MM and MGUS serum derived EVs with differential ultracentrifugation protocols and tested their biological activity. We found that MM and MGUS EVs induced different proliferation and internalization rates in endothelial and myocardial cells, thus we tried to find specific targets in MM EVs docking and processing. Pre-treatment of EVs withanti-FLCs antibodies or heparin blocked the MM EVs uptake, highlighting that FLCs and glycosaminoglycans are involved. Indeed, only MM EVs exposure induced a strong nuclear factor kappa B nuclear translocation that was completely abolished afteranti-FLCs antibodies and heparin pre-treatment. The protein tyrosine kinase c-src is present on MM circulating EVs and redistributes to the cell plasma membrane after MM EVs exposure.The anti-FLCs antibodies and heparin pre-treatments were able to block the intracellular redistribution of the c-src kinase and the subsequent c-src kinase containing EVs production. Our results open new insights in EVs cellular biology and in MM therapeutic and diagnostic approaches