Angewandte Chemie International Edition

Cover image for Vol. 48 Issue 47

November 9, 2009

Volume 48, Issue 47

Pages 8797–8999

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Fast Prediction of Selectivity in Heterogeneous Catalysis from Extended Brønsted–Evans–Polanyi Relations: A Theoretical Insight (Angew. Chem. Int. Ed. 47/2009) (page 8797)

      David Loffreda, Françoise Delbecq, Fabienne Vigné and Philippe Sautet

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200905266

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      Brønsted–Evans–Polanyi relations are famous in heterogeneous catalysis for their fast prediction of activation barriers with the sole knowledge of the reaction enthalpies. This model has now been extended by D. Loffreda et al. to the hydrogenation of unsaturated aldehydes on platinum. In their Communication on page 8978 ff., they describe on the basis of density functional theory calculations a linear relation connecting the activation barrier with the stability of the initial precursor state.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Label-Free Chemical Imaging of Catalytic Solids by Coherent Anti-Stokes Raman Scattering and Synchrotron-Based Infrared Microscopy (Angew. Chem. Int. Ed. 47/2009) (page 8798)

      Marianne H. F. Kox, Katrin F. Domke, James P. R. Day, Gianluca Rago, Eli Stavitski, Mischa Bonn and Bert M. Weckhuysen

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200905606

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      The catalytic conversion of thiophene derivatives on individual zeolite ZSM-5 crystals was studied by using a combination of multiplex coherent anti-Stokes Raman scattering (CARS) and synchrotron-based IR microscopy. In their Communication on page 8990 ff., B. M. Weckhuysen et al. show how label-free chemical imaging of reactant/reaction products can be achieved with high spatial resolution. Vibrational bands in the CARS and IR spectra evidenced interaction of thiophenes with the zeolite framework, followed by ring opening.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
  5. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Susumu Kitagawa (pages 8818–8820)

      Article first published online: 5 OCT 2009 | DOI: 10.1002/anie.200904270

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      “When I was eighteen I wanted to be an architect. The biggest challenge facing scientists is to prepare organic compounds such as amino acids from air …” This and more about Susumu Kitagawa can be found on page 8818.

  6. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Bioinorganic Photochemistry. By Grażyna Stochel, Małgorzata Brindell, Wojciech Macyk, Zofia Stasicka and Konrad Szaciłowski. (page 8821)

      Günther Knör

      Article first published online: 5 NOV 2009 | DOI: 10.1002/anie.200904873

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      John Wiley & Sons, Hoboken 2009. 398 pp., hardcover € 115.00.—ISBN 978-1405161725

    2. Molecular Chemistry of Sol–Gel Derived Nanomaterials. Edited by Robert J. P. Corriu and Nquyen Trong Anh. (pages 8822–8823)

      Galo J. A. A. Soler-Illia

      Article first published online: 5 NOV 2009 | DOI: 10.1002/anie.200904371

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      John Wiley & Sons, Hoboken 2009. 200 pp., hardcover € 99.90.—ISBN 978-0470721179

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Time-Resolved Spectroscopy

      The Renaissance and Promise of Electron Energy-Loss Spectroscopy (pages 8824–8826)

      Sir John Meurig Thomas

      Article first published online: 14 OCT 2009 | DOI: 10.1002/anie.200904052

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      Less than the twinkling of an eye: EELS time resolution has now been improved by ten orders of magnitude, making possible the observation of transitory changes in electron distribution as exemplified for the laser-induced compression of graphite towards diamond (see picture).

    2. Synthetic Methods

      Highly Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions and Z-Selective Ring-Opening Metathesis Polymerization (pages 8827–8831)

      Armando Córdova and Ramon Rios

      Article first published online: 16 OCT 2009 | DOI: 10.1002/anie.200903409

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      Stopping the gap: A notable shortcoming in olefin metathesis chemistry was the lack of methods for the selective synthesis of Z alkenes. A breakthrough has now been achieved by the employment of a new type of chiral Mo complex (see scheme; TBS=tert-butyldimethylsilyl, X=Cl, Br, I). The first examples of the titled reactions are discussed.

  8. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cooperative Catalysis

      Neutral Tridentate PNP Ligands and Their Hybrid Analogues: Versatile Non-Innocent Scaffolds for Homogeneous Catalysis (pages 8832–8846)

      Jarl Ivar van der Vlugt and Joost N. H. Reek

      Article first published online: 15 OCT 2009 | DOI: 10.1002/anie.200903193

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      A helping hand! The rich coordination chemistry, versatile reactivity, and the non-innocent behavior of specific ligand structures has led to an increase in the popularity of the chemistry of lutidine-based tridentate ligands that contain phosphorus side groups (see picture). These ligands can participate in cooperative catalysis, which provides possibilities for carrying out previously unknown organic transformations.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Glycobiology

      Glycosphingolipids—Nature, Function, and Pharmacological Modulation (pages 8848–8869)

      Tom Wennekes, Richard J. B. H. N. van den Berg, Rolf G. Boot, Gijsbert A. van der Marel, Herman S. Overkleeft and Johannes M. F. G. Aerts

      Article first published online: 27 OCT 2009 | DOI: 10.1002/anie.200902620

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      Solving the Sphinx's riddle: Glycosphingolipids, such as glucosylceramide, are components of the cellular membrane and are involved in many (patho)physiological processes. As such, they are the subject of intensive research aimed at elucidating their role in the structural integrity of the cell membrane, their participation in recognition and signaling events, and in particular their involvement in processes that are at the basis of human disease (see picture).

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Fluorescence Microscopy

      DNA Origami as a Nanoscopic Ruler for Super-Resolution Microscopy (pages 8870–8873)

      Christian Steinhauer, Ralf Jungmann, Thomas L. Sobey, Friedrich C. Simmel and Philip Tinnefeld

      Article first published online: 14 OCT 2009 | DOI: 10.1002/anie.200903308

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      Resolving the distances: Rectangular DNA origami labeled with fluorophores at specific positions has been used as a nanoscopic ruler. Super-resolution microscopy based on the subsequent localization of single molecules enables two fluorophores at a distance of about 90 nm to be optically resolved. This combination of subdiffraction imaging and DNA nanotechnology opens up new avenues for studying nanostructures and their dynamics.

    2. Catalyst Immobilization

      Reusable Catalysts Based on Dendrimers Trapped in Poly(p-xylylene) Nanotubes (pages 8874–8877)

      Jean-Pierre Lindner, Caren Röben, Armido Studer, Michael Stasiak, Ramona Ronge, Andreas Greiner and Hans-Joachim Wendorff

      Article first published online: 23 OCT 2009 | DOI: 10.1002/anie.200903448

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      Catalysts in a bottle are readily prepared by coelectrospinning of PAMAM dendrimers and poly(ethylene oxide) (PEO). The nanofibers thus obtained can be coated with poly(p-xylylene) by chemical vapor deposition. Removal of the core PEO fibers by extraction with water results in PAMAM dendrimers entrapped in the tubes (see picture). The entrapped dendrimers show a high catalytic activity as reusable organocatalysts.

    3. Nanomaterials

      Nanoscale Tungsten Trioxide Synthesized by In Situ Twin Polymerization (pages 8878–8881)

      Falko Böttger-Hiller, Ralf Lungwitz, Andreas Seifert, Michael Hietschold, Maik Schlesinger, Michael Mehring and Stefan Spange

      Article first published online: 20 OCT 2009 | DOI: 10.1002/anie.200903636

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      Step aside, sol–gel! Nanoscale tungsten oxide with large BET surface area is available through the presented in situ twin polymerization method. In only one process step, nanostructured hybrid materials are synthesized from WCl6 and cationic polymerizable aryl methanols. This procedure forms a bridge between the non-aqueous sol–gel process and twin polymerization and opens new perspectives for the synthesis of various nanostructured metals oxides.

    4. Template Catalysis

      4-exo Cyclizations by Template Catalysis (pages 8882–8885)

      Andreas Gansäuer, Dennis Worgull, Karsten Knebel, Inga Huth and Gregor Schnakenburg

      Article first published online: 23 OCT 2009 | DOI: 10.1002/anie.200904428

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      Small rings through large templates: A two-point binding of the substrate radicals to cationic titanocene templates is essential for the success of otherwise impossible 4-exo cyclizations (see scheme; Bn=benzyl). The cyclobutanes are obtained in high stereoselectivity and can be additionally functionalized in a straightforward manner.

    5. Single-Molecule Studies

      Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction (pages 8886–8890)

      David Vonlanthen, Artem Mishchenko, Mark Elbing, Markus Neuburger, Thomas Wandlowski and Marcel Mayor

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200903946

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      Stepwise regulation of the molecular conductance was observed in a series of eight biphenyldithiols with fixed torsion angles between the phenyl rings. These compounds were synthesized and their single-molecule conductance was investigated in an STM junction. A cos2 dependence was found between the interplane torsion angle and the single-molecule conductivity (see plot).

    6. Natural Product Synthesis

      Total Synthesis of Piperazimycin A: A Cytotoxic Cyclic Hexadepsipeptide (pages 8891–8895)

      Wenhua Li, Jiangang Gan and Dawei Ma

      Article first published online: 16 OCT 2009 | DOI: 10.1002/anie.200904603

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      Pied piper: The first total synthesis of the title compound 1, a potent cytotoxic natural product has been achieved. The key elements include an efficient synthesis of the difficult-to-install (R,S)-γClPip/(S,S)-γOHPip dipeptide fragment as well as macrocyclization by an SN2 reaction of an N-2-chloroacetyl moiety with a carboxylate anion.

    7. Chemical Ligation

      Phenylthiomethyl Glycosides: Convenient Synthons for the Formation of Azidomethyl and Glycosylmethyl Glycosides and Their Derivatives (pages 8896–8899)

      David Crich and Fan Yang

      Article first published online: 23 OCT 2009 | DOI: 10.1002/anie.200904168

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      Without a trace: Phenylthiomethyl glycosides, which are prepared by glycosylation of phenylthiomethanol, serve as precursors to the hitherto unknown azidomethyl glycosides and then to the N-glycosylmethyl 1,4- and 1,5-substituted triazoles (see scheme; Bz=benzoyl). The azidomethyl glycosides are also readily converted into amidomethyl glycosides by the traceless Staudinger reaction.

    8. Silicon Chemistry

      Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate (pages 8900–8904)

      Ryo Ishimoto, Keigo Kamata  and Noritaka Mizuno 

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200904694

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      Silanol synthesis: Divacant lacunary polyoxotungstate (nBu4N+)4[γ-SiW10O34(H2O)2] (I) is an efficient homogeneous catalyst for highly selective oxidation of organosilanes to silanols with 30–60 % aqueous H2O2. Various kinds of silanes 1 containing aryl, alkyl, alkenyl, alkynyl, and alkoxy groups are chemoselectively converted into the corresponding silanols 2 in high yields with only one equivalent of aqueous H2O2 with respect to the substrate.

    9. Natural Product Synthesis

      Total Synthesis of Zoanthenol (pages 8905–8908)

      Yu Takahashi, Fumihiko Yoshimura, Keiji Tanino and Masaaki Miyashita

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200904537

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      Reaching home plate: The first total synthesis of zoanthenol, an aromatic member of the zoanthamine alkaloid family with potent anti-platelet activity for human platelet aggregation, has been achieved using an intermediate in the total synthesis of norzoanthamine. The key step involves a Brønsted acid-promoted isoaromatization in the AB ring system to install the crucial aromatic ring.

    10. NONOates as Nitroxyl Donors

      Mechanistic Studies on the Reaction between R2N-NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R2N-NONOates to Cobalt(III) Centers (pages 8909–8913)

      Hanaa A. Hassanin, Luciana Hannibal, Donald W. Jacobsen, Mohamed F. El-Shahat, Mohamed S. A. Hamza and Nicola E. Brasch

      Article first published online: 22 OCT 2009 | DOI: 10.1002/anie.200904360

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      Tales of the unexpected: Transfer of a nitroxyl group from R2N-NONOates to aquacobalamin to form nitroxylcobalamin does not proceed via H+-catalyzed R2N-NONOate decomposition, but instead occurs via a probable NONOate-cobalamin intermediate (see scheme; r.d.s.=rate-determining step).

    11. Synthetic Methods

      Isothiourea-Catalyzed Enantioselective Carboxy Group Transfer (pages 8914–8918)

      Caroline Joannesse, Craig P. Johnston, Carmen Concellón, Carmen Simal, Douglas Philp and Andrew D. Smith

      Article first published online: 15 OCT 2009 | DOI: 10.1002/anie.200904333

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      Transferable skills: Enantiomerically pure isothioureas promote the O- to C-carboxyl group transfer of oxazolyl carbonates with excellent levels of enantiocontrol (see scheme). The origin of the enantioselectivity of this process was probed mechanistically and rationalized computationally.

    12. Nanostructures

      Systematic Metal Variation and Solvent and Hydrogen-Gas Storage in Supramolecular Nanoballs (pages 8919–8922)

      Martin B. Duriska, Suzanne M. Neville, Jinzhen Lu, Simon S. Iremonger, John F. Boas, Cameron J. Kepert and Stuart R. Batten

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200903863

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      Play ball! A family of discrete metallo-supramolecular nanoballs (see picture) containing different divalent metals is produced by self-assembly. These species have porous structures, similar to metal–organic frameworks. Stepwise desolvation results in bare metal sites which can be functionalized with organic molecules; the interball cavities show high affinity for hydrogen gas.

    13. Tandem Reactions

      Enantioselective One-Pot Organocatalytic Michael Addition/Gold-Catalyzed Tandem Acetalization/Cyclization (pages 8923–8926)

      Sébastien Belot, Kim A. Vogt, Céline Besnard, Norbert Krause and Alexandre Alexakis

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200903905

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      Au-rganocatalytic reaction: A one-pot process consisting of a Michael addition to a nitroenyne and a subsequent acetalization/cyclization is reported (see scheme; TMS=trimethylsilyl), which results in the formation of nitro-substituted tetrahydrofuranyl ethers with high diastereo- and enantioselectivities. Organocatalysis and gold catalysis are compatible and complementary in a one-pot process.

    14. Multiferroic Materials

      Super High Threshold Percolative Ferroelectric/Ferrimagnetic Composite Ceramics with Outstanding Permittivity and Initial Permeability (pages 8927–8930)

      Hui Zheng, Yanling Dong, Xin Wang, Wenjian Weng, Gaorong Han, Ning Ma and Piyi Du

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200904269

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      Some good percs: Ferroelectric/ferrimagnetic composite ceramics with percolation thresholds of 0.85–0.95 were obtained by an in situ sol–gel process that leads to enwrapping and separation of the conductive ferrite by a ferroelectric phase, e.g. BaTiO3. Such a super high threshold leads to a sharp increase in permittivity (ε) and initial permeability (μi) with increasing ferrite fraction (see graph; NZFO=Ni0.5Zn0.5Fe2O4).

      Corrected by:

      Corrigendum: Super High Threshold Percolative Ferroelectric/Ferrimagnetic Composite Ceramics with Outstanding Permittivity and Initial Permeability

      Vol. 49, Issue 12, 2083, Article first published online: 10 MAR 2010

    15. Vinyl Cations

      Facile Generation of a Strained Cyclic Vinyl Cation by Thermal Solvolysis of Cyclopent-1-enyl-λ3-bromanes (pages 8931–8934)

      Kazunori Miyamoto, Motoo Shiro and Masahito Ochiai

      Article first published online: 14 OCT 2009 | DOI: 10.1002/anie.200903368

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      Last of the cyclic vinyl cations: The simple solvolysis of cyclopent-1-enyl-λ3-bromane efficiently generates the highly strained cyclopent-1-enyl cation at room temperature (see scheme). The very high nucleofugality of the aryl-λ3-bromanyl groups are responsible for this unique unimolecular dissociation.

    16. C[BOND]C Coupling

      Rhodium/N-Heterocyclic Carbene Catalyzed Direct Intermolecular Arylation of sp2 and sp3 C[BOND]H Bonds with Chelation Assistance (pages 8935–8939)

      Min Kim, Jaesung Kwak and Sukbok Chang

      Article first published online: 23 OCT 2009 | DOI: 10.1002/anie.200903500

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      Rh-oadies join in: A new rhodium catalyst was developed for the chelation-assisted direct intermolecular arylation using an N-heterocyclic carbene and phosphine ligands (see scheme; IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene). The reaction is operationally simple, proceeds under mild reaction conditions to afford mono- or diarylated products in excellent yields, and is applicable to the arylation at the sp3 or sp2 C[BOND]H bonds of 2-pyridyl-containing aryl, vinyl, or alkyl moieties.

    17. Cluster Ions

      Ion–Molecule Reactions in Helium Nanodroplets Doped with C60 and Water Clusters (pages 8940–8943)

      Stephan Denifl, Fabio Zappa, Ingo Mähr, Filipe Ferreira da Silva, Abid Aleem, Andreas Mauracher, Michael Probst, Jan Urban, Pavel Mach, Arntraud Bacher, Olof Echt, Tilmann D. Märk and Paul Scheier

      Article first published online: 22 OCT 2009 | DOI: 10.1002/anie.200904381

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      Double trouble: The binding between C60+ and (H2O)4 is surprisingly weak in a charged C60–H2O tetramer complex formed in helium nanodroplets (see picture). Doubly charged C602+ intermediates are proposed to form by charge transfer with He+; these intermediates can trigger ion–molecule reactions that may play a role in molecular synthesis in interstellar clouds and solar nebula.

    18. Porous Coordination Polymers

      Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin-Crossover Coordination Polymer (pages 8944–8947)

      Gloria Agustí, Ryo Ohtani, Ko Yoneda, Ana B. Gaspar, Masaaki Ohba, Juan F. Sánchez-Royo, M. Carmen Muñoz, Susumu Kitagawa and José A. Real

      Article first published online: 23 OCT 2009 | DOI: 10.1002/anie.200904379

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      Mixing with the guests: Exposure of the porous spin-crossover framework {Fe(pz)[PtII(CN)4]} to X2 (pz=pyrazine; X2=Cl2, Br2, and I2) leads to incorporation of the halides in the coordinatively unsaturated [PtII(CN)4]2− moieties through oxidative addition, thus affording the mixed-valence series {Fe(pz)[PtII/IV(CN)4(X)]}, which features quite distinct cooperative spin-transition properties.

    19. Asymmetric Catalysis

      Asymmetric Dehydrative Cyclization of ω-Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes (pages 8948–8951)

      Shinji Tanaka, Tomoaki Seki and Masato Kitamura

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200904671

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      New axially chiral ligands and their allyl esters have been designed and synthesized. The combination of these ligands with [CpRu(CH3CN)3]PF6 has realized highly efficient intramolecular dehydrative cylization of ω-hydroxy allyl alcohols, to give α-alkenyl-substituted cyclic ethers with up to greater than 99:1 enantiomeric ratio without activation of the allylic moieties (see scheme; Cp=cyclopentadienyl, naph=naphthyl, py=pyridine).

    20. Small-Molecule Inhibitors

      Cortistatin A is a High-Affinity Ligand of Protein Kinases ROCK, CDK8, and CDK11 (pages 8952–8957)

      Victor J. Cee, David Y.-K. Chen, Matthew R. Lee and K. C. Nicolaou

      Article first published online: 20 OCT 2009 | DOI: 10.1002/anie.200904778

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      Antiproliferative alkaloid: Cortistatin A is a high-affinity ligand for a small set of protein kinases including Rho-associated, coiled-coil-containing protein kinase (ROCK), cyclin-dependent kinase 8 (CDK8), and cyclin-dependent kinase 11 (CDK11). Models of cortistatin A bound to a crystallographic structure of ROCK (see picture) and a homology model of CDK8 are presented.

    21. Lipid Bilayers

      Structure of Cholesterol/Lipid Ordered Domains in Monolayers and Single Hydrated Bilayers (pages 8958–8961)

      Roy Ziblat, Kristian Kjaer, Leslie Leiserowitz and Lia Addadi

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200903847

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      Interacting leaflets: Grazing-incidence X-ray diffraction measurements are performed on single hydrated lipid bilayers. Comparison between the structure of a monolayer composed of sphingomyelin, cholesterol, and phosphocholine (36:54:10) with that of a bilayer of the same composition (see picture) shows differences in structure and phase behavior, because of the formation of bilayer-thick cholesterol crystals.

    22. Self-Assembly

      Supramolecular Amphiphiles Based on a Water-Soluble Charge-Transfer Complex: Fabrication of Ultralong Nanofibers with Tunable Straightness (pages 8962–8965)

      Chao Wang, Yinsheng Guo, Yapei Wang, Huaping Xu, Ruji Wang and Xi Zhang

      Article first published online: 19 OCT 2009 | DOI: 10.1002/anie.200903897

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      From curly to straight: The formation of a charge-transfer complex is driven by the combination of Coulombic attraction and charge transfer interactions. The charge-transfer complex which is obtained from a supramolecular amphiphile (see picture) is water-soluble and forms ultralong nanofibers, the straightness of which can be modulated by changing the pH of the reaction solution.

    23. Art Conservation

      Nanoscience for Art Conservation: Oil-in-Water Microemulsions Embedded in a Polymeric Network for the Cleaning of Works of Art (pages 8966–8969)

      Emiliano Carretti, Emiliano Fratini, Debora Berti, Luigi Dei and Piero Baglioni

      Article first published online: 15 OCT 2009 | DOI: 10.1002/anie.200904244

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      As good as new: Oil-in-water nanocontainers within an aqueous polymer network were effective for the low-impact selective cleaning of painted and gilded surfaces. Interactions with the polymer (black in the schematic illustration) did not alter the structure of the microemulsion nanodroplets (light blue and red) significantly. A photograph of an equilibrated mixture of the microemulsion and the polymer is shown.

    24. Cancer Diagnosis

      Three-Dimensional Nanostructured Substrates toward Efficient Capture of Circulating Tumor Cells (pages 8970–8973)

      Shutao Wang, Hao Wang, Jing Jiao, Kuan-Ju Chen, Gwen E. Owens, Ken-ichiro Kamei, Jing Sun, David J. Sherman, Christian P. Behrenbruch, Hong Wu and Hsian-Rong Tseng

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200901668

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      A grabby substrate: A 3D nanostructured substrate, namely, a silicon-nanopillar (SiNP) array coated with epithelial-cell adhesion-molecule antibody (anti-EpCAM), shows enhanced local topographic interactions between nanoscale cell-surface components and the substrates surface, resulting in enhanced cell-capture efficiency when employed to isolate viable cancer cells from whole-blood samples (see schematic and SEM image of a captured cancer cell).

    25. Drug Delivery

      Layer-by-Layer Platform Technology for Small-Molecule Delivery (pages 8974–8977)

      Renée C. Smith, Mariawy Riollano, Amy Leung and Paula T. Hammond

      Article first published online: 21 OCT 2009 | DOI: 10.1002/anie.200902782

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      Flexible delivery vehicle: Layer-by-layer assembly and supramolecular chemistry were used to create an ultrathin-film platform technology for small-molecule delivery using a hydrolytically degradable polyion (see picture, blue waves) and a polymeric cyclodextrin (see picture, red cups).

    26. Heterogeneous Catalysis

      Fast Prediction of Selectivity in Heterogeneous Catalysis from Extended Brønsted–Evans–Polanyi Relations: A Theoretical Insight (pages 8978–8980)

      David Loffreda, Françoise Delbecq, Fabienne Vigné and Philippe Sautet

      Article first published online: 19 SEP 2009 | DOI: 10.1002/anie.200902800

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      Figuring it out: Linear relations are found when the energies of the transition states (equation image) are plotted against those of the precursor states (equation image) for the hydrogenation of unsaturated aldehydes on platinum (see picture, FS=final state). This relation allows a quick and accurate determination of the energy barriers of the reaction when changing the chemical environment of the reactive center.

    27. Solar Cells

      Optical Fiber/Nanowire Hybrid Structures for Efficient Three-Dimensional Dye-Sensitized Solar Cells (pages 8981–8985)

      Benjamin Weintraub, Yaguang Wei and Zhong Lin Wang

      Article first published online: 22 OCT 2009 | DOI: 10.1002/anie.200904492

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      Wired up: The energy conversion efficiency of three-dimensional dye-sensitized solar cells (DSSCs) in a hybrid structure that integrates optical fibers and nanowire arrays is greater than that of a two-dimensional device. Internal axial illumination enhances the energy conversion efficiency of a rectangular fiber-based hybrid structure (see picture) by a factor of up to six compared to light illumination normal to the fiber axis from outside the device.

    28. Rotaxanes

      A Rigid Helical Peptide Axle for a [2]Rotaxane Molecular Machine (pages 8986–8989)

      Alessandro Moretto, Ileana Menegazzo, Marco Crisma, Elizabeth J. Shotton, Harriott Nowell, Stefano Mammi and Claudio Toniolo

      Article first published online: 22 OCT 2009 | DOI: 10.1002/anie.200904749

      Thumbnail image of graphical abstract

      Spinning around? A series of peptido[2]rotaxanes have been designed which contain a rigid helix as a significant part of their axle. One such rotaxane has been used to construct a reversible molecular device, in which, by virtue of the size of the inner cavity of the wheel relative to the outer diameter of the peptide helix, a rotation of the wheel might occur concomitantly with its translation along the axle (see picture).

    29. Heterogeneous Catalysis

      Label-Free Chemical Imaging of Catalytic Solids by Coherent Anti-Stokes Raman Scattering and Synchrotron-Based Infrared Microscopy (pages 8990–8994)

      Marianne H. F. Kox, Katrin F. Domke, James P. R. Day, Gianluca Rago, Eli Stavitski, Mischa Bonn and Bert M. Weckhuysen

      Article first published online: 12 OCT 2009 | DOI: 10.1002/anie.200904282

      Thumbnail image of graphical abstract

      Take a look inside: The combination of coherent anti-Stokes Raman scattering and synchrotron-based IR microscopy during the catalytic conversion of thiophene derivatives on zeolite crystals yields space- and time-resolved chemically specific information without the need for labeling (see picture). The thiophene reactant is mostly present in the center of the crystal, and the product is aligned within the straight pores of the zeolites.

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      Preview: Angew. Chem. Int. Ed. 48/2009 (page 8999)

      Article first published online: 5 NOV 2009 | DOI: 10.1002/anie.200990239

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