Tunable Aryl Alkyl Ionic Liquid Supported Synthesis of Platinum Nanoparticles and Their Catalytic Activity in the Hydrogen Evolution Reaction and in Hydrosilylation.

Tunable aryl alkyl ionic liquids (TAAILs) are ionic liquids (ILs) with a 1-aryl-3-alkylimidazolium cation having differently substituted aryl groups. Herein, nine TAAILs with the bis(trifluoromethylsulfonyl)imide anion are utilized in combination with and without ethylene glycol (EG) as reaction media for the rapid microwave synthesis of platinum nanoparticles (Pt-NPs). TAAILs allow the synthesis of small NPs and are efficient solvents for microwave absorption. Transmission electron microscopy (TEM) shows that small primary NPs with sizes of 2 nm to 5 nm are obtained in TAAILs and EG/TAAIL mixtures. The Pt-NPs feature excellent activity as electrocatalysts in the hydrogen evolution reaction (HER) under acidic conditions, with an overpotential at a current density of 10 mA cm-2 as low as 32 mV vs the reversible hydrogen electrode (RHE), which is significantly lower than the standard Pt/C 20% with 42 mV. Pt-NPs obtained in TAAILs also achieved quantitative conversion in the hydrosilylation reaction of phenylacetylene with triethylsilane after just 5 min at 200 °C.

The Facile Deposition of Pt Nanoparticles on Reduced Graphite Oxide in Tunable Aryl Alkyl Ionic Liquids for ORR Catalysts.

In this study, we present the facile formation of platinum nanoparticles (Pt-NPs) on reduced graphite oxide (rGO) (Pt-NP@rGO) by microwave-induced heating of the organometallic precursor ((MeCp)PtMe3 in different tunable aryl alkyl ionic liquids (TAAIL). In the absence of rGO, transmission electron microscopy (TEM) reveals the formation of dense aggregates of Pt-NPs, with primary particle sizes of 2 to 6 nm. In contrast, in the Pt-NP@rGO samples, Pt-NPs are homogeneously distributed on the rGO, without any aggregation. Pt-NP@rGO samples are used as electrode materials for oxygen reduction reaction (ORR), which was assessed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrochemical surface area (ECSA) and mass-specific activity (MA) increase up to twofold, compared with standard Pt/C 60%, making Pt-NP@rGO a competitive material for ORR.

A Highly-Efficient Oxygen Evolution Electrocatalyst Derived from a Metal-Organic Framework and Ketjenblack Carbon Material.

The composite of the metal-organic framework (MOF) Ni(Fe)-MOF-74 and the highly conductive carbon material ketjenblack (KB) could be easily obtained from the in-situ MOF synthesis in a one-step solvothermal reaction. The composite material features a remarkable electrochemical oxygen evolution reaction (OER) performance where the overpotential at 10 mA/cm2 and the current density at 1.7 VRHE are recorded as 0.274 VRHE and 650 mA/cm2 , respectively, in 1 mol/L KOH. In particular, the activation of nickel-iron clusters from the MOF under an applied anodic bias steadily boosts the OER performance. Although Ni(Fe)-MOF-74 goes through some structural modification during the electrochemical measurements, the stabilized and optimized composite material shows excellent OER performance. This simple strategy to design highly-efficient electrocatalysts, utilizing readily available precursors and carbon materials, will leverage the use of diverse metal-organic complexes into electrode fabrication with a high energy conversion efficiency.

Quantum confinement of the Dirac surface states in topological-insulator nanowires.

The non-trivial topology of three-dimensional topological insulators dictates the appearance of gapless Dirac surface states. Intriguingly, when made into a nanowire, quantum confinement leads to a peculiar gapped Dirac sub-band structure. This gap is useful for, e.g., future Majorana qubits based on TIs. Furthermore, these sub-bands can be manipulated by a magnetic flux and are an ideal platform for generating stable Majorana zero modes, playing a key role in topological quantum computing. However, direct evidence for the Dirac sub-bands in TI nanowires has not been reported so far. Here, using devices fabricated from thin bulk-insulating (Bi1-xSbx)2Te3 nanowires we show that non-equidistant resistance peaks, observed upon gate-tuning the chemical potential across the Dirac point, are the unique signatures of the quantized sub-bands. These TI nanowires open the way to address the topological mesoscopic physics, and eventually the Majorana physics when proximitized by an s-wave superconductor.

Receptor-Mediated In Vivo Targeting of Breast Cancer Cells with 17α-Ethynylestradiol-Conjugated Silica-Coated Gold Nanoparticles.

Efficient therapies for breast cancer remain elusive because of the lack of strategies for targeted transport and receptor-mediated uptake of synthetic drug molecules by cancer cells. Conjugation of nanoparticles (NPs) with active targeting ligands enabling selective molecular recognition of antigens expressed on the surface of cancer cells is promising for localization and treatment of malignant cells. In this study, covalent attachment of synthetic estrogen 17α-ethynylestradiol on the silica (SiO2) shell of silica-gold NPs (SiO2@Au) was undertaken to improve the cancer-targeting ability of the nano-biotags. Chemical and structural analysis of the bioconjugates examined in solution (UV-vis and ξ-potential) and solid state (Fourier transform infrared spectroscopy, X-ray diffractometry, and transmission electron microscopy) confirmed the identity of the carrier particles and surface-bound ligands. The mesoporous silica shell served as a reservoir for anticancer drugs (doxorubicin and quercetin) and to facilitate covalent attachment of receptor molecules by click chemistry protocols. The chemoselective recognition between the nanoconjugates and cell membranes was successfully demonstrated by the accumulation of nanoprobes in the tumor tissue of mice with subcutaneous breast cancer, whereas healthy cells were unaffected. The drug release studies showed sustained release kinetics over several weeks. These findings elaborate the exceptional selectivity and potential of estrogen-coated nano-biolabels in efficient diagnosis and detection of breast cancer cells.

Detection by flow cytometry of anti-neutrophil cytoplasmic antibodies in a novel approach based on neutrophil extracellular traps.

BACKGROUND: Anti-neutrophil-cytoplasmic antibodies (ANCA) are auto-antibodies directed against components of neutrophil granulocytes and may be found in various inflammatory conditions, like small-vessel vasculitis or ulcerative colitis (UC). Routine ANCA screening is performed on ethanol-fixed neutrophils using indirect immunofluorescence technique. Yet, how neutrophil granule proteins become available to immunologic presentation is a matter of debate. In recent years, various studies have shown that neutrophils are able to extrude their chromatin decorated with granular proteins as neutrophil extracelullar traps (NETs). AIM: We hypothesized that (I) ANCA immunoreactivity may be found on NETs and (II) NETs may serve as a useful tool in a novel approach for ANCA detection. METHODS: Sera from patients suffering from either ANCA-associated vasculitis (n = 10), UC (n = 30) or sera from patients without diagnosed ANCA-associated diseases (n = 20), respectively, were subjected to indirect immunofluorescence and a newly developed method to detect ANCA by flow cytometry employing microbead technology. RESULTS: ANCA-related immunofluorescence was readily detectable on ethanol-fixed NETs, establishing NETs as a structure carrying ANCA target antigens. Moreover, we observed that neutrophils form NETs in response to microbeads and stick to the surface of these beads. Using these NET-coated microbeads in flow cytometry, we were capable of reliably detecting p-ANCA, c-ANCA, and a-ANCA in tested patient sera. UC-related complex DNase-1-sensitive ANCA (NET-ANCA) antigens were also detected on NET-coated microbeads. CONCLUSION: NET-coated microbeads may be commercially developed as a novel tool for automated ANCA screening assays using flow cytometry.

High-Flux Carbon Molecular Sieve Membranes for Gas Separation.

Carbon membranes have great potential for highly selective and cost-efficient gas separation. Carbon is chemically stable and it is relative cheap. The controlled carbonization of a polymer coating on a porous ceramic support provides a 3D carbon material with molecular sieving permeation performance. The carbonization of the polymer blend gives turbostratic carbon domains of randomly stacked together sp2 hybridized carbon sheets as well as sp3 hybridized amorphous carbon. In the evaluation of the carbon molecular sieve membrane, hydrogen could be separated from propane with a selectivity of 10 000 with a hydrogen permeance of 5 m3 (STP)/(m2 hbar). Furthermore, by a post-synthesis oxidative treatment, the permeation fluxes are increased by widening the pores, and the molecular sieve carbon membrane is transformed from a molecular sieve carbon into a selective surface flow carbon membrane with adsorption controlled performance and becomes selective for carbon dioxide.

Influence of the Ba2+/Sr2+ content and oxygen vacancies on the stability of cubic Ba(x)Sr(1-x)Co(0.75)Fe(0.25)O(3-δ).

We present a theoretical and experimental study on the influence of the Ba/Sr and Co/Fe ratios as well as the oxygen-non-stoichiometry on the stability of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). Thin-layer depositions are analysed by looking at TEM images and EDX spectra. Bond-analytical calculations are performed to explain the stability difference between hexagonal and cubic BSCF. Finally, annealing experiments analysed using XRD give an insight into the differences of phase-fraction growth with respect to the Ba/Sr ratio.

Engineering microstructure and redox properties in the mixed conductor Ce(0.9)Pr(0.1)O(2-δ) + Co 2 mol%.

10% Praseodymium doped ceria exhibits a combination of mixed ionic and electronic conductivity, redox catalytic properties and chemical compatibility with water and carbon dioxide at high temperatures. Minor additions of cobalt oxide have been demonstrated to act as a sintering aid as well as an effective promoter of the electronic conduction. However, an excess of sintering temperature causes cobalt aggregation into the grain boundaries as inferred from FE-SEM/EDX and TEM analysis. The redox behaviour of the materials was studied by means of temperature programmed desorption (TPD) and reduction (TPR). This work shows the systematic study of sintering conditions in order to understand the evolution of the material microstructure, grain boundaries and the role of cobalt in this complex system. The final purpose of the work is to improve both electronic and oxygen ion transport properties for their potential application as oxygen-transport membranes and solid oxide fuel cell components. The sample sintered at 1000 °C exhibited the highest total conductivity at high temperatures, which is principally related to the improvement in the electronic conductivity through the grain boundary network.

Enhanced H2 separation through mixed proton-electron conducting membranes based on La5.5 W0.8 M0.2 O11.25-δ.

La(5.5) WO11.25-δ is a proton-conducting oxide that shows high protonic conductivity, sufficient electronic conductivity, and stability in moist CO2 environments. However, the H2 flows achieved to date when using La(5.5) WO11.25-δ membranes are still below the threshold for practical application in industrial processes. With the aim of improving the H2 flow obtained with this material, La(5.5) WO11.25-δ was doped in the W position by using Re and Mo; the chosen stoichiometry was La(5.5) W0.8 M0.2 O11.25-δ . This work presents the electrochemical characterization of these two compounds under reducing conditions, the H2 separation properties, as well as the influence of the H2 concentration in the feed stream, degree of humidification, and operating temperature. Doping with both Re and Mo enabled the magnitude of H2 permeation to be enhanced, reaching unrivaled values of up to 0.095 mL min(-1) cm(-2) at 700 °C for a La(5.5) W0.8 Re0.2 O11.25-δ membrane (760 µm thick). The spent membranes were investigated by using XRD, SEM, and TEM on focused-ion beam lamellas. Furthermore, the stability in CO2 -rich and H2 S-containing atmospheres was evaluated, and the compounds were shown to be stable in the atmospheres studied.