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The beamline optics and endstations at branch B of the Versatile Soft X-ray (VerSoX) beamline B07 at Diamond Light Source are described. B07-B provides medium-flux X-rays in the range 45-2200â eV from a bending magnet source, giving access to local electronic structure for atoms of all elements from Li to Y. It has an endstation for high-throughput X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) measurements under ultrahigh-vacuum (UHV) conditions. B07-B has a second endstation dedicated to NEXAFS at pressures from UHV to ambient pressure (1â atm). The combination of these endstations permits studies of a wide range of interfaces and materials. The beamline and endstation designs are discussed in detail, as well as their performance and the commissioning process.
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Vanadium redox flow battery (VRFB) electrodes face challenges related to their long-term operation. We investigated different electrode treatments mimicking the aging processes during operation, including thermal activation, aging, soaking, and storing. Several characterization techniques were used to deepen the understanding of the treatment of carbon felts. Synchrotron X-ray imaging, electrochemical impedance spectroscopy (EIS) with the distribution of relaxation times analysis, and dynamic vapor sorption (DVS) revealed differences between the wettability of felts. The bulk saturation after electrolyte injection into the carbon felts significantly differed from 8 % to 96 %. DVS revealed differences in the sorption/desorption behavior of carbon felt ranging from a slight change of 0.8â wt % to over 100â wt %. Additionally, the interactions between the water vapor and the sample change from type V to type H2. After treatment, morphology changes were observed by atomic force microscopy and scanning electron microscopy. Cyclic voltammetry and EIS were used to probe the electrochemical performance, revealing different catalytic activities and transport-related impedances for the treated samples. These investigations are crucial for understanding the effects of treatments on the performance and optimizing materials for long-term operation.
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NEMO is a ubiquitin-binding protein which regulates canonical NF-κB pathway activation in innate immune signaling, cell death regulation and host-pathogen interactions. Here we identify an NF-κB-independent function of NEMO in proteostasis regulation by promoting autophagosomal clearance of protein aggregates. NEMO-deficient cells accumulate misfolded proteins upon proteotoxic stress and are vulnerable to proteostasis challenges. Moreover, a patient with a mutation in the NEMO-encoding IKBKG gene resulting in defective binding of NEMO to linear ubiquitin chains, developed a widespread mixed brain proteinopathy, including α-synuclein, tau and TDP-43 pathology. NEMO amplifies linear ubiquitylation at α-synuclein aggregates and promotes the local concentration of p62 into foci. In vitro, NEMO lowers the threshold concentrations required for ubiquitin-dependent phase transition of p62. In summary, NEMO reshapes the aggregate surface for efficient autophagosomal clearance by providing a mobile phase at the aggregate interphase favoring co-condensation with p62.
Assuntos
Quinase I-kappa B , NF-kappa B , Humanos , NF-kappa B/metabolismo , Quinase I-kappa B/genética , Quinase I-kappa B/metabolismo , alfa-Sinucleína/genética , Ubiquitina/metabolismo , Autofagia/genéticaRESUMO
Cobalt iron containing layered double hydroxides (LDHs) and spinels are promising catalysts for the electrochemical oxygen evolution reaction (OER). Towards development of better performing catalysts, the precise tuning of mesostructural features such as pore size is desirable, but often hard to achieve. Herein, a computer-controlled microemulsion-assisted co-precipitation (MACP) method at constant pH is established and compared to conventional co-precipitation. With MACP, the particle growth is limited and through variation of the constant pH during synthesis the pore size of the as-prepared catalysts is controlled, generating materials for the systematic investigation of confinement effects during OER. At a threshold pore size, overpotential increased significantly. Electrochemical impedance spectroscopy (EIS) indicated a change in OER mechanism, involving the oxygen release step. It is assumed that in smaller pores the critical radius for gas bubble formation is not met and therefore a smaller charge-transfer resistance is observed for medium frequencies.
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Water is an integral component in electrochemistry, in the generation of the electric double layer, and in the propagation of the interfacial electric fields into the solution; however, probing the molecular-level structure of interfacial water near functioning electrode surfaces remains challenging. Due to the surface-specificity, sum-frequency-generation (SFG) spectroscopy offers an opportunity to investigate the structure of water near working electrochemical interfaces but probing the hydrogen-bonded structure of water at this buried electrode-electrolyte interface was thought to be impossible. Propagating the laser beams through the solvent leads to a large attenuation of the infrared light due to the absorption of water, and interrogating the interface by sending the laser beams through the electrode normally obscures the SFG spectra due to the large nonlinear response of conduction band electrons. Here, we show that the latter limitation is removed when the gold layer is thin. To demonstrate this, we prepared Au gradient films on CaF2 with a thickness between 0 and 8 nm. SFG spectra of the Au gradient films in contact with H2O and D2O demonstrate that resonant water SFG spectra can be obtained using Au films with a thickness of â¼2 nm or less. The measured spectra are distinctively different from the frequency-dependent Fresnel factors of the interface, suggesting that the features we observe in the OH stretching region indeed do not arise from the nonresonant response of the Au films. With the newfound ability to probe interfacial solvent structure at electrode/aqueous interfaces, we hope to provide insights into more efficient electrolyte composition and electrode design.
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Although the term 'confinement' regularly appears in electrochemical literature, elevated by continuous progression in the research of nanomaterials and nanostructures, up until today the various aspects of confinement considered in electrochemistry are rather scattered individual contributions outside the established disciplines in this field. Thanks to a number of highly original publications and the growing appreciation of confinement as an overarching link between different exciting new research strategies, 'electrochemistry under confinement' is the process of forming a research discipline of its own. To aid the development a coherent terminology and joint basic concepts, as crucial factors for this transformation, this review provides an overview on the different effects on electrochemical processes known to date that can be caused by confinement. It also suggests where boundaries to other effects, such as nano-effects could be drawn. To conceptualize the vast amount of research activities revolving around the main concepts of confinement, we define six types of confinement and select two of them to discuss the state of the art and anticipated future developments in more detail. The first type concerns nanochannel environments and their applications for electrodeposition and for electrochemical sensing. The second type covers the rather newly emerging field of colloidal single entity confinement in electrochemistry. In these contexts, we will for instance address the influence of confinement on the mass transport and electric field distributions and will link the associated changes in local species concentration or in the local driving force to altered reaction kinetics and product selectivity. Highlighting pioneering works and exciting recent developments, this educational review does not only aim at surveying and categorizing the state-of-the-art, but seeks to specifically point out future perspectives in the field of confinement-controlled electrochemistry.
Assuntos
Nanoestruturas , Eletroquímica , Nanoestruturas/químicaRESUMO
To understand corrosion, energy storage, (electro)catalysis, etc., obtaining chemical information on the solid-liquid interface is crucial but remains extremely challenging. Here, X-ray absorption spectroscopy (XAS) is used to study the solid-liquid interface between TiO2 and H2O. A thin film (6.7 nm) of TiO2 is deposited on an X-ray-transparent SiNx window, acting as the working electrode in a three-electrode flow cell. The spectra are collected based on the electron emission resulting from the decay of the X-ray-induced core-hole-excited atoms, which we show is sensitive to the solid-liquid interface within a few nm. The drain currents measured at the working and counter electrodes are identical but of opposite sign. With this method, we found that the water layer next to anatase is spectroscopically similar to ice. This result highlights the potential of electron-yield XAS to obtain chemical and structural information with a high sensitivity for the species at the electrode-electrolyte interface.