Biological Solid-state NMR at ETH Zurich

Solid-state Magnetic Resonance has been greatly developed over the past decade. Higher field spectrometers and other technical developments are expected to lead to further significant improvements

Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy of GNNQQNY Nanocrystals and Amyloid Fibrils

Dynamic nuclear polarization (DNP) utilizes the inherently larger polarization of electrons to enhance the sensitivity of conventional solid-state NMR experiments at low temperature. Recent advances in instrumentation development and sample preparation have transformed this field and have opened up new opportunities for its application to biological systems. Here, we present DNP-enhanced [superscript 13]C–[superscript 13]C and [superscript 15]N–[superscript 13]C correlation experiments on GNNQQNY nanocrystals and amyloid fibrils acquired at 9.4 T and 100 K and demonstrate that DNP can be used to obtain assignments and site-specific structural information very efficiently. We investigate the influence of temperature on the resolution, molecular conformation, structural integrity and dynamics in these two systems. In addition, we assess the low-temperature performance of two commonly used solid-state NMR experiments, proton-driven spin diffusion (PDSD) and transferred echo double resonance (TEDOR), and discuss their potential as tools for measurement of structurally relevant distances at low temperature in combination with DNP.National Institutes of Health (U.S.) (Grant EB002804)National Institutes of Health (U.S.) (Grant EB003151)National Institutes of Health (U.S.) (Grant EB002026

SPITZER survey of dust grain processing in stable discs around binary post-AGB stars

Aims: We investigate the mineralogy and dust processing in the circumbinary discs of binary post-AGB stars using high-resolution TIMMI2 and SPITZER infrared spectra. Methods: We perform a full spectral fitting to the infrared spectra using the most recent opacities of amorphous and crystalline dust species. This allows for the identification of the carriers of the different emission bands. Our fits also constrain the physical properties of different dust species and grain sizes responsible for the observed emission features. Results: In all stars the dust is oxygen-rich: amorphous and crystalline silicate dust species prevail and no features of a carbon-rich component can be found, the exception being EPLyr, where a mixed chemistry of both oxygen- and carbon-rich species is found. Our full spectral fitting indicates a high degree of dust grain processing. The mineralogy of our sample stars shows that the dust is constituted of irregularly shaped and relatively large grains, with typical grain sizes larger than 2 micron. The spectra of nearly all stars show a high degree of crystallinity, where magnesium-rich end members of olivine and pyroxene silicates dominate. Other dust features of e.g. silica or alumina are not present at detectable levels. Temperature estimates from our fitting routine show that a significant fraction of grains must be cool, significantly cooler than the glass temperature. This shows that radial mixing is very efficient is these discs and/or indicates different thermal conditions at grain formation. Our results show that strong grain processing is not limited to young stellar objects and that the physical processes occurring in the discs are very similar to those in protoplanetary discs.Comment: 22pages, 50 figures (in appendix), accepted for A&

Intermolecular Structure Determination of Amyloid Fibrils with 2 Magic-Angle Spinning and Dynamic Nuclear Polarization NMR

We describe magic-angle spinning NMR experiments designed to elucidate the interstrand architecture of amyloid fibrils. Three methods are introduced for this purpose, two being based on the analysis of long-range [superscript 13]C–[superscript 13]C correlation spectra and the third based on the identification of intermolecular interactions in [superscript 13]C–[superscript 15]N spectra. We show, in studies of fibrils formed by the 86-residue SH3 domain of PI3 kinase (PI3-SH3 or PI3K-SH3), that efficient [superscript 13]C–[superscript 13]C correlation spectra display a resonance degeneracy that establishes a parallel, in-register alignment of the proteins in the amyloid fibrils. In addition, this degeneracy can be circumvented to yield direct intermolecular constraints. The [superscript 13]C–[superscript 13]C experiments are corroborated by [superscript 15]N–[superscript 13]C correlation spectra obtained from a mixed [[superscript 15]N,[superscript 12]C]/[[superscript 14]N,[superscript 13]C] sample which directly quantify interstrand distances. Furthermore, when the spectra are recorded with signal enhancement provided by dynamic nuclear polarization (DNP) at 100 K, we demonstrate a dramatic increase (from 23 to 52) in the number of intermolecular [superscript 15]N–[superscript 13]C constraints detectable in the spectra. The increase in the information content is due to the enhanced signal intensities and to the fact that dynamic processes, leading to spectral intensity losses, are quenched at low temperatures. Thus, acquisition of low temperature spectra addresses a problem that is frequently encountered in MAS spectra of proteins. In total, the experiments provide 111 intermolecular [superscript 13]C–[superscript 13]C and [superscript 15]N–[superscript 13]C constraints that establish that the PI3-SH3 protein strands are aligned in a parallel, in-register arrangement within the amyloid fibril.National Institutes of Health (U.S.) (Grant EB-003151)National Institutes of Health (U.S.) (Grant EB-002804)National Institutes of Health (U.S.) (Grant EB-002026

Carbonaceous molecules in the oxygen-rich circumstellar environment of binary post-AGB stars: C_{60} fullerenes and polycyclic aromatic hydrocarbons

Context. The circumstellar environment of evolved stars is generally rich in molecular gas and dust. Typically, the entire environment is either oxygen-rich or carbon-rich, depending on the evolution of the central star. Aims. In this paper we discuss three evolved disc sources with evidence of atypical emission lines in their infrared spectra. The stars were taken from a larger sample of post-AGB binaries for which we have Spitzer infrared spectra, characterised by the presence of a stable oxygen-rich circumbinary disc. Our previous studies have shown that the infrared spectra of post-AGB disc sources are dominated by silicate dust emission, often with an extremely high crystallinity fraction. However, the three sources described here are selected because they show a peculiar molecular chemistry. Methods. Using Spitzer infrared spectroscopy, we study in detail the peculiar mineralogy of the three sample stars. Using the observed emission features, we identify the different observed dust, molecular and gas species. Results. The infrared spectra show emission features due to various oxygen-rich dust components, as well as CO2 gas. All three sources show the strong infrared bands generally ascribed to polycyclic aromatic hydrocarbons. Furthermore, two sample sources show C60 fullerene bands. Conclusions. Even though the majority of post-AGB disc sources are dominated by silicate dust in their circumstellar environment, we do find evidence that, for some sources at least, additional processing must occur to explain the presence of large carbonaceous molecules. There is evidence that some of these sources are still oxygen-rich, which makes the detection of these molecules even more surprising.Comment: Accepted for publication in Astronomy and Astrophysics, 10 pages, 7 figure

Geospatial Information Research: State of the Art, Case Studies and Future Perspectives

Geospatial information science (GI science) is concerned with the development and application of geodetic and information science methods for modeling, acquiring, sharing, managing, exploring, analyzing, synthesizing, visualizing, and evaluating data on spatio-temporal phenomena related to the Earth. As an interdisciplinary scientific discipline, it focuses on developing and adapting information technologies to understand processes on the Earth and human-place interactions, to detect and predict trends and patterns in the observed data, and to support decision making. The authors – members of DGK, the Geoinformatics division, as part of the Committee on Geodesy of the Bavarian Academy of Sciences and Humanities, representing geodetic research and university teaching in Germany – have prepared this paper as a means to point out future research questions and directions in geospatial information science. For the different facets of geospatial information science, the state of art is presented and underlined with mostly own case studies. The paper thus illustrates which contributions the German GI community makes and which research perspectives arise in geospatial information science. The paper further demonstrates that GI science, with its expertise in data acquisition and interpretation, information modeling and management, integration, decision support, visualization, and dissemination, can help solve many of the grand challenges facing society today and in the future

Locating the post-national activist:Migration rights, civil society and the practice of post-nationalism

Theorists of post-nationalism examine the (re)configuration of national identity, membership and rights. Yet while normative scholarship has conceptualized post-nationalism as an ongoing practice of discursive contestation over the role of national group membership in liberal democratic societies, more empirical studies have tended to overlook these features to predominantly focus instead on top-down legal and political institution-building as evidence of post-nationalism. In this article I argue in favour of an empirical conceptualization of post-nationalism which more effectively captures micro-level practices of discursive contestation. Specifically I posit that post-national activists, or actors engaging in post-national practices of contestation from within the state, are a key focus of analysis for scholars of post-nationalism. I develop this claim through the analysis of data collected with individuals working on civil society campaigns for migration rights in Europe, Australia and the USA who–I demonstrate–embody many of the characteristics of the post-national activist