Analyzing the catalytic processes of immobilized redox enzymes by vibrational spectroscopies

Analyzing the structure and function of redox enzymes attached to electrodes is a central challenge in many fields of fundamental and applied life science. Electrochemical techniques such as cyclic voltammetry which are routinely used do not provide insight into the molecular structure and reaction mechanisms of the immobilized proteins. Surface-enhanced infrared absorption (SEIRA) and surface-enhanced resonance Raman (SERR) spectroscopy may fill this gap, if nanostructured Au or Ag are used as conductive support materials. In this account, we will first outline the principles of the methodology including a description of the most important strategies for biocompatible protein immobilization. Subsequently, we will critically review SERR and SEIRA spectroscopic approaches to characterize the protein and active site structure of the immobilized enzymes. Special emphasis is laid on the combination of surface-enhanced vibrational spectroscopies with electrochemical methods to analyze equilibria and dynamics of the interfacial redox processes. Finally, we will assess the potential of SERR and SEIRA spectroscopy for in situ investigations on the basis of the first promising studies on human sulfite oxidase and hydrogenases under turnover conditions. Copyright © 2012 Wiley Periodicals, Inc

Sulfide Bridged Covalent Quinoxaline Frameworks for Lithium Organosulfide Batteries

The chelating ability of quinoxaline cores and the redox activity of organosulfide bridges in layered covalent organic frameworks COFs offer dual active sites for reversible lithium Li storage. The designed COFs combining these properties feature disulfide and polysulfide bridged networks showcasing an intriguing Li storage mechanism, which can be considered as a lithium organosulfide Li OrS battery. The experimental computational elucidation of three quinoxaline COFs containing systematically enhanced sulfur atoms in sulfide bridging demonstrates fast kinetics during Li interactions with the quinoxaline core. Meanwhile, bilateral covalent bonding of sulfide bridges to the quinoxaline core enables a redox mediated reversible cleavage of the sulfur amp; 63743;sulfur bond and the formation of covalently anchored lithium sulfide chains or clusters during Li interactions, accompanied by a marked reduction of Li polysulfide Li PS dissolution into the electrolyte, a frequent drawback of lithium sulfur Li S batteries. The electrochemical behavior of model compounds mimicking the sulfide linkages of the COFs and operando Raman studies on the framework structure unravels the reversibility of the profound Li ion organosulfide interactions. Thus, integrating redox active organic framework materials with covalently anchored sulfides enables a stable Li OrS battery mechanism which shows benefits over a typical Li S batter

Relativistic Jets in Active Galactic Nuclei and Microquasars

Collimated outflows (jets) appear to be a ubiquitous phenomenon associated with the accretion of material onto a compact object. Despite this ubiquity, many fundamental physics aspects of jets are still poorly understood and constrained. These include the mechanism of launching and accelerating jets, the connection between these processes and the nature of the accretion flow, and the role of magnetic fields; the physics responsible for the collimation of jets over tens of thousands to even millions of gravitational radii of the central accreting object; the matter content of jets; the location of the region(s) accelerating particles to TeV (possibly even PeV and EeV) energies (as evidenced by (Formula presented.)-ray emission observed from many jet sources) and the physical processes responsible for this particle acceleration; the radiative processes giving rise to the observed multi-wavelength emission; and the topology of magnetic fields and their role in the jet collimation and particle acceleration processes. This chapter reviews the main knowns and unknowns in our current understanding of relativistic jets, in the context of the main model ingredients for Galactic and extragalactic jet sources. It discusses aspects specific to active Galactic nuclei (especially blazars) and microquasars, and then presents a comparative discussion of similarities and differences between them.Fil: Romero, Gustavo Esteban. Provincia de Buenos Aires. Gobernación. Comision de Investigaciones Científicas. Instituto Argentino de Radioastronomía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto Argentino de Radioastronomia; ArgentinaFil: Boettcher, Markus. North-West University; SudáfricaFil: Markoff, Sera. University of Amsterdam; Países BajosFil: Tavecchio, Fabrizio. Osservatorio Astronomico Di Brera; Itali

Characteristics, management, and outcomes of patients with left‐sided infective endocarditis complicated by heart failure: a substudy of the ESC‐EORP EURO‐ENDO (European infective endocarditis) registry

International audienc