In Memoriam: Albert Hofmann (1906–2008)

Commentary on the life achievements of Albert Hofmann (1906–2008), one of UZH's most honored alumni

Application of Structural Principles to the Design of Triptycene-Based Molecular Gears with Parallel Axes

This perspective discusses the important aspects of the design of molecular gear systems based on triptycene. Molecular systems are categorized into three classes according to the orientation of the gear axes: i) bent (bevel gears), ii) linear, and ii) parallel (spur gears). To date, no examples of molecular gears in which the axes of rotation lie in parallel have been reported; correspondingly, the bulk of this report focuses on the factors one must evaluate to construct such systems

Condensation of Fivefold-Symmetric Molecules in Two Dimensions

We report the formation of a two-dimensional glass by solidification of a two-dimensional gas of fivefold-symmetric molecules on a copper surface upon cooling. Direct observation with scanning tunneling microscopy allows a detailed insight into the implications of a symmetry mismatch between molecular geometry and crystal lattice

Conformations of large macrocycles and ring-in-ring complexes

This work was supported by the Swiss National Science Foundation.A kinetically directed, stepwise approach towards molecular Borromean links enabled the isolation and structural characterization of synthetic intermediates along the way. Here we report the synthesis and crystal structures of three flexible macrocyclic intermediates and a new ring-in-ring complex, anchored together through ruthenium(ii) centers, which contains open terpyridine caps in the inner Ring II. Terpyridines circumvent the conformational cis/trans limitations of bipyridines and the new ring-in-ring complex forms tetrametallic complexes with Zn(ii), Pt(ii) and Ru(iii) metal ions. Analysis of the four macrocyclic structures provides a good foundation for the conformational flexibility in these complexes and demonstrates the robust applicability of the terpyridine design elements towards the engineered synthesis of ring-in-ring topologies.Publisher PDFPeer reviewe

The chemistry of branched condensed phosphates.

Condensed phosphates may exist as linear, cyclic or branched structures. Due to their important role in nature, linear polyphosphates have been well studied. In contrast, branched phosphates (ultraphosphates) remain largely uncharacterised, because they were already described in 1950 as exceedingly unstable in the presence of water, epitomized in the antibranching-rule. This rule lacks experimental backup, since, to the best of our knowledge, no rational synthesis of defined ultraphosphates is known. Consequently, detailed studies of their chemical properties, reactivity and potential biological relevance remain elusive. Here, we introduce a general synthesis of monodisperse ultraphosphates. Hydrolysis half-lives up to days call the antibranching-rule into question. We provide evidence for the interaction of an enzyme with ultraphosphates and discover a rearrangement linearizing the branched structure. Moreover, ultraphosphate can phosphorylate nucleophiles such as amino acids and nucleosides with implications for prebiotic chemistry. Our results provide an entry point into the uncharted territory of branched condensed phosphates

The ACS survey of galactic globular clusters. XI. The three-dimensional orientation of the Sagittarius dwarf spheroidal galaxy and its globular clusters

We use observations from the Hubble Space Telescope Advanced Camera for Surveys (HST/ACS) study of Galactic globular clusters to investigate the spatial distribution of the inner regions of the disrupting Sagittarius dwarf spheroidal galaxy (Sgr). We combine previously published analyses of four Sgr member clusters located near or in the Sgr core (M54, Arp 2, Terzan 7, and Terzan 8) with a new analysis of diffuse Sgr material identified in the background of five low-latitude Galactic bulge clusters (NGC 6624, 6637, 6652, 6681, and 6809) observed as part of the ACS survey. By comparing the bulge cluster color-magnitude diagrams to our previous analysis of the M54/Sgr core, we estimate distances to these background features. The combined data from four Sgr member clusters and five Sgr background features provide nine independent measures of the Sgr distance and, as a group, provide uniformly measured and calibrated probes of different parts of the inner regions of Sgr spanning 20° over the face of the disrupting dwarf. This allows us, for the first time, to constrain the three-dimensional orientation of Sgr's disrupting core and globular cluster system and compare that orientation to the predictions of an N-body model of tidal disruption. The density and distance of Sgr debris are consistent with models that favor a relatively high Sgr core mass and a slightly greater distance (28-30kpc, with a mean of 29.4kpc). Our analysis also suggests that M54 is in the foreground of Sgr by ∼ 2 kpc, projected on the center of the Sgr dSph. While this would imply a remarkable alignment of the cluster and the Sgr nucleus along the line of sight, we cannot identify any systematic effect in our analysis that would falsely create the measured 2kpc separation. Finally, we find that the cluster Terzan 7 has the most discrepant distance (25kpc) among the four Sgr core clusters, which may suggest a different dynamical history than the other Sgr core clusters

The ACS Survey of Galactic Globular Clusters. I. Overview and Clusters Without Previous HST Photometry

We present the first results of a large ACS Survey of Galactic globular clusters. This Hubble Space Telescope (HST) Treasury project is designed to obtain photometry with S/N > ~10 for main sequence stars with masses > ~0.2Msun in a sample of globulars using the Advanced Camera for Surveys (ACS) Wide Field Channel. Here we focus on clusters without previous HST imaging data. These include NGC 5466, 6779, 5053, 6144, Palomar 2, E 3, Lynga 7, Palomar 1, and NGC 6366. Our CMDs extend reliably from the horizontal branch to as much as seven magnitudes fainter than the main sequence turnoff and represent the deepest CMDs published to-date for these clusters. Using fiducial sequences for three standard clusters (M92, NGC 6752, and 47 Tuc) with well-known metallicities and distances, we perform main sequence fitting on the target clusters in order to obtain estimates of their distances and reddenings. These comparisons along with fitting the cluster main sequences to theoretical isochrones yield ages for the target clusters. We find that the majority of the clusters have ages that are consistent with the standard clusters at their metallicities. The exceptions are E 3 which appears ~2 Gyr younger than 47 Tuc, and Pal 1, which could be as much as 8 Gyr younger than 47 Tuc.Comment: 22 pages, 29 figures, accepted for publication in The Astronomical Journal, April 2007. High resolution version available at http://www.astro.ufl.edu/~ata/GC_Treasury/Web_Page/publications.htm

Dominant inhibition of Fas ligand-mediated apoptosis due to a heterozygous mutation associated with autoimmune lymphoproliferative syndrome (ALPS) Type Ib

<p>Abstract</p> <p>Background:</p> <p>Autoimmune lymphoproliferative syndrome (ALPS) is a disorder of lymphocyte homeostasis and immunological tolerance due primarily to genetic defects in Fas (CD95/APO-1; <it>TNFRSF6</it>), a cell surface receptor that regulates apoptosis and its signaling apparatus.</p> <p>Methods:</p> <p>Fas ligand gene mutations from ALPS patients were identified through cDNA and genomic DNA sequencing. Molecular and biochemical assessment of these mutant Fas ligand proteins were carried out by expressing the mutant FasL cDNA in mammalian cells and analysis its effects on Fas-mediated programmed cell death.</p> <p>Results:</p> <p>We found an ALPS patient that harbored a heterozygous A530G mutation in the FasL gene that replaced Arg with Gly at position 156 in the protein's extracellular Fas-binding region. This produced a dominant-interfering FasL protein that bound to the wild-type FasL protein and prevented it from effectively inducing apoptosis.</p> <p>Conclusion:</p> <p>Our data explain how a naturally occurring heterozygous human FasL mutation can dominantly interfere with normal FasL apoptotic function and lead to an ALPS phenotype, designated Type Ib.</p