Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 43

October 18, 2010

Volume 49, Issue 43

Pages 7817–8045

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: Isomerization-Induced Asymmetric Coordination Chemistry: From Auxiliary Control to Asymmetric Catalysis (Angew. Chem. Int. Ed. 43/2010) (page 7817)

      Dr. Lei Gong, Zhijie Lin, Dr. Klaus Harms and Prof. Dr. Eric Meggers

      Article first published online: 2 AUG 2010 | DOI: 10.1002/anie.201004296

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      Catalytic asymmetric coordination chemistry is made possible by chirality transfer from an organic ligand with sulfur-centered chirality to a chiral-at-metal octahedral ruthenium complex. E. Meggers and co-workers describe in their Communication on page 7955 ff. how (S)-2-(isopropylsulfinyl)phenol and a more electron-rich methoxy derivative are capable of inducing and even catalyzing a chirality-generating transcis isomerization of two 2,3′-bipyridine ligands in the ligand sphere of a ruthenium complex.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Inside Cover: Photocatalytic Aerobic Oxidation of Alcohols on TiO2: The Acceleration Effect of a Brønsted Acid (Angew. Chem. Int. Ed. 43/2010) (page 7818)

      Dr. Qi Wang, Dr. Miao Zhang, Prof. Chuncheng Chen, Prof. Wanhong Ma and Prof. Jincai Zhao

      Article first published online: 7 JUL 2010 | DOI: 10.1002/anie.201003621

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      The acceleration effect of a Brønsted acid was identified in the photocatalytic oxidation of alcohols using TiO2. In their Communication on page 7976 ff., J. Zhao and co-workers show that the acid adsorbed onto the catalyst surface promotes the decomposition of the Ti/H2O2 species to regenerate active sites for the oxidation.

  3. Graphical Abstract

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. You have free access to this content
      Corrigendum: C[BOND]H Bond Functionalization in Water Catalyzed by Carboxylato Ruthenium(II) Systems (page 7833)

      Percia B. Arockiam, Dr. Cédric Fischmeister, Dr. Christian Bruneau and Prof. Pierre H. Dixneuf

      Article first published online: 13 OCT 2010 | DOI: 10.1002/anie.201090139

      This article corrects:

      C[BOND]H Bond Functionalization in Water Catalyzed by Carboxylato Ruthenium(II) Systems1

      Vol. 49, Issue 37, 6629–6632, Article first published online: 28 JUL 2010

    2. You have free access to this content
      Corrigendum: Scavenging Free Radicals To Preserve Enhancement and Extend Relaxation Times in NMR using Dynamic Nuclear Polarization (page 7834)

      Pascal Miéville, Puneet Ahuja, Dr. Riddhiman Sarkar, Dr. Sami Jannin, Dr. Paul R. Vasos, Dr. Sandrine Gerber-Lemaire, Dr. Mor Mishkovsky, Dr. Arnaud Comment, Prof. Rolf Gruetter, Dr. Olivier Ouari, Prof. Paul Tordo and Prof. Geoffrey Bodenhausen

      Article first published online: 13 OCT 2010 | DOI: 10.1002/anie.201090140

      This article corrects:
  5. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
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    1. Neil Branda (page 7840)

      Article first published online: 24 SEP 2010 | DOI: 10.1002/anie.201004905

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      “When I was eighteen I wanted to be older and wiser. In ten years time I will be ten years older but probably no wiser …” This and more about Neil Branda can be found on page 7840.

  7. Book Reviews

    1. Top of page
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    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
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    1. Chiral Amine Synthesis. Methods, Developments and Applications. Edited by Thomas C. Nugent. (page 7841)

      Jacques Royer

      Article first published online: 30 SEP 2010 | DOI: 10.1002/anie.201005721

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      Wiley-VCH, Weinheim 2010. 494 pp., hardcover € 159.00.—ISBN 978-3527325092

    2. Industrial Biotechnology. Sustainable Growth and Economic Success. Edited by Wim Soetaert and Erick J. Vandamme. (pages 7841–7842)

      Rainer Stürmer

      Article first published online: 30 SEP 2010 | DOI: 10.1002/anie.201005629

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      Wiley-VCH, Weinheim 2010. 500 pp., hardcover € 159.00.—ISBN 978-3527314423

  8. Highlights

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

      Putting a Positive Spin on Molecular Bridges (pages 7844–7846)

      Prof. Dr. Dirk M. Guldi

      Article first published online: 27 AUG 2010 | DOI: 10.1002/anie.201002229

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      Getting the message across: Insight into electronic coupling beween electron donors and acceptors connected by molecular bridges (see example) has been achieved by measuring the magnitude of the spin–spin exchange interactions. A kinetic analysis of the magnetic field effects showed that charge transfer in highly π-conjugated bridges is a function of the spin-selective charge-recombination pathways.

    2. Liquid Crystals

      From Nanostructured Liquid Crystals to Polymer-Based Electrolytes (pages 7847–7848)

      Prof. Dr. Takashi Kato

      Article first published online: 2 AUG 2010 | DOI: 10.1002/anie.201000707

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      Self-organized channels: Molecular assembly of ionic liquid crystals has led to the formation of self-organized 1D, 2D, and 3D ionic channels. Liquid-crystal-based, mechanically stable electrolyte films have been obtained by the formation of a covalent bond network by in situ cross-linking of polymerizable nanostructured ionic liquid crystals (see picture).

  9. Minireview

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
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    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
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    1. Nanostructure Analysis

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      Imaging of Self-Assembled Structures: Interpretation of TEM and Cryo-TEM Images (pages 7850–7858)

      Dr. Heiner Friedrich, Dr. Peter M. Frederik, Prof. Dr. Gijsbertus de With and Dr. Nico A. J. M. Sommerdijk

      Article first published online: 6 SEP 2010 | DOI: 10.1002/anie.201001493

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      Get the picture: Transmission electron microscopy (TEM) is a frequently used analytical method for the direct imaging of solution-borne nanostructures. This Minireview provides an analysis of the TEM workflow from sample preparation to acquisition and interpretation of electron micrographs. This should provide a framework for the application of (cryo)-TEM as a powerful and reliable tool for the analysis of colloidal and self-assembled structures with nanoscopic dimensions.

  10. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
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    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
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    1. Homogeneous Catalysis

      Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis—The Effect of a Highly Delocalized Counteranion (pages 7860–7888)

      Dr. Sylvain Antoniotti, Prof. Dr. Vincent Dalla and Dr. Elisabet Duñach

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.200906407

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      Worth its salt: The triflimidate anion, by virtue of its highly delocalized charge and steric hindrance, enhances the electrophilic character of the metal center and, therefore, its Lewis acidity. In most cases, triflimidate catalysts are superior to triflates or other salts.

  11. Communications

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
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    11. Review
    12. Communications
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    1. Discrete Cationic Complexes

      Well-Defined Cationic Methallyl α-Keto-β-Diimine Complexes of Nickel (pages 7890–7894)

      Jason D. Azoulay, Zachary A. Koretz, Guang Wu and Prof. Dr. Guillermo C. Bazan

      Article first published online: 25 AUG 2010 | DOI: 10.1002/anie.201003125

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      Complex considerations: The synthesis and characterization of a discrete cationic nickel–methallyl complex (see structure: Ni green, N blue, O red) provided insight into the propagating sites generated by using α-keto-β-diimine–nickel olefin-polymerization catalysts. The addition of Al(C6F5)3 led to carbonyl coordination to aluminum, further depletion of the electron density at the nickel center, and a substantial increase in reactivity towards ethylene.

    2. Cycloaddition

      Catalytic Asymmetric exo′-Selective [3+2] Cycloaddition of Iminoesters with Nitroalkenes (pages 7895–7898)

      Prof. Dr. Takayoshi Arai, Naota Yokoyama, Asami Mishiro and Dr. Hiroyasu Sato

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201004098

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      Under control: A chiral imidazoline–aminophenol/Ni(OAc)2 complex promotes the first catalytic asymmetric exo′-selective [3+2] cycloaddition of iminoesters and nitroalkenes. Thermodynamic control over the stepwise Michael/Mannich cyclization steps gives the adducts in up to 99 % ee.

    3. Supramolecular Cross-Linking

      Supramolecular Cross-Linking of [60]Fullerene-Tagged Polyphenylacetylene by the Host–Guest Interaction of Calix[5]arene and [60]Fullerene (pages 7899–7903)

      Prof. Dr. Takeharu Haino, Eri Hirai, Prof. Dr. Yoshihisa Fujiwara and Kouki Kashihara

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201004074

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      Hand in hand: A polyphenylacetylene with C60 moieties can be cross-linked by a homoditopic tetrakiscalix[5]arene host by formation of a specific supramolecular complex (see picture). This noncovalent interaction leads to an increase of the molecular weight of the polymer and produces morphological changes upon addition of the host.

    4. Drug Release Systems

      A Temperature-Sensitive Drug Release System Based on Phase-Change Materials (pages 7904–7908)

      Dr. Sung-Wook Choi, Yu Zhang and Prof. Younan Xia

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201004057

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      Melting away: Phase-change materials (PCMs) are used to encapsulate colloidal particles with FITC-dextran to demonstrate a new temperature-sensitive drug release system. As the temperature is increased to the melting point of the PCM, the particles leach out, followed by release of FITC-dextran. The initiation and rate of release can be manipulated by using different combinations of materials for the PCM and colloidal particles.

    5. Molecular Electronics

      Reticulated Heterojunctions for Photovoltaic Devices (pages 7909–7912)

      Dr. Alon A. Gorodetsky, Chien-Yang Chiu, Dr. Theanne Schiros, Dr. Matteo Palma, Marshall Cox, Zhang Jia, Wesley Sattler, Prof. Ioannis Kymissis, Dr. Michael Steigerwald and Prof. Colin Nuckolls

      Article first published online: 16 SEP 2010 | DOI: 10.1002/anie.201004055

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      An organic semiconductor device is formed by the self-assembly on a transparent electrode surface. The donor (see picture; dibenzotetrathienocoronene, yellow layer) deposits as supramolecular cables, and the acceptor (C60, orange) subsequently infiltrates this network. This network provides a donor–acceptor interface that is interwoven at the nanoscale. When incorporated into a solar cell, the active layer provides large increases in power conversion efficiencies.

    6. Gold Clusters

      Formation of Gold(I) Edge Oxide at Flat Gold Nanoclusters on an Ultrathin MgO Film under Ambient Conditions (pages 7913–7916)

      Dr. Pentti Frondelius, Prof. Dr. Hannu Häkkinen and Dr. Karoliina Honkala

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201003851

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      Edgy oxide: DFT calculations predict the spontaneous formation of a stable one-dimensional edge oxide at the perimeter of a gold cluster on a silver-supported ultrathin MgO film under ambient conditions. The formation of the gold(I) edge oxide is relevant for CO oxidation reactions. Au yellow, gray; Mg green; O red.

    7. Nanoparticles

      Programmed Nanoparticle Aggregation Using Molecular Beacons (pages 7917–7919)

      Jonathan F. Lovell, Honglin Jin, Kenneth K. Ng and Prof. Gang Zheng

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201003846

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      Out in the open: Hydrophobically modified molecular beacons were inserted into lipid nanoparticles. Upon addition of the target DNA to a solution of the lipid nanoparticles, irreversible nanoparticle aggregation occurred (see picture). This aggregation phenomenon results from the opening of the molecular beacons.

    8. DNA Structures

      A Geometric Approach to the Crystallographic Solution of Nonconventional DNA Structures: Helical Superstructures of d(CGATAT) (pages 7920–7922)

      Iñaki Martínez de Ilarduya, Dr. Daniela De Luchi, Prof. Dr. Juan A. Subirana, Dr. J. Lourdes Campos and Prof. Dr. Isabel Usón

      Article first published online: 16 SEP 2010 | DOI: 10.1002/anie.201003647

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      Thinking outside the box: A geometrical approach for the molecular-replacement solution of DNA crystal structures has been applied to solve the superstructures formed by d(CGATAT). Both B- and Z-form duplexes are stacked and form a complex set of intercrossed helical structures of unique topology.

    9. Singlet Oxygen

      Reversible pH-Regulated Control of Photosensitized Singlet Oxygen Production Using a DNA i-Motif (pages 7923–7925)

      Thomas Tørring, Rasmus Toftegaard, Dr. Jacob Arnbjerg, Prof. Peter R. Ogilby and Prof. Kurt V. Gothelf

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201003612

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      On again, off again: Reversible pH-controlled on-and-off switching of a singlet oxygen sensitizer is achieved when an i-motif DNA sequence is employed to control the proximity of a singlet oxygen sensitizer and a quencher (see picture). At pH values less than 5, the i-motif is stable and the singlet oxygen sensitizer quenched, whereas at pH values above 8 the i-motif is denatured and singlet oxygen production is increased by a factor of 35.

    10. Enediyne Biosynthesis

      Identification of a Nonaketide Product for the Iterative Polyketide Synthase in Biosynthesis of the Nine-Membered Enediyne C-1027 (pages 7926–7928)

      Xiaolei Chen, Dr. Zu-Feng Guo, Pok Man Lai, Prof. Kong Hung Sze and Prof. Zhihong Guo

      Article first published online: 16 SEP 2010 | DOI: 10.1002/anie.201003369

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      Not octa- but nonaketide: The nine-membered enediyne core polyketide synthase SgcE efficiently synthesizes a nonaketide in the absence of any assisting proteins (see scheme), contrary to the suggestion that an octaketide is the product of the synthase under assistance from a thioesterase. This finding redefines the catalytic functions of the polyketide synthase. CoA=coenzyme A.

    11. Solvolysis

      “Organic Aqua Regia”—Powerful Liquids for Dissolving Noble Metals (pages 7929–7932)

      Wei Lin, Rong-Wei Zhang, Seung-Soon Jang, Prof. Ching-Ping Wong and Jung-Il Hong

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201001244

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      The noble prize: Various noble metals can be dissolved in organic solutions with high dissolution rates under mild conditions by using thionyl chloride (SOCl2) and organic solvents/reagents (pyridine, N,N-dimethylformamide, and imidazole). Varying the composition of the solvent and reaction conditions even allows the selective dissolution of noble metals (see picture).

    12. Porous Alumina Membranes

      Dressing in Layers: Layering Surface Functionalities in Nanoporous Aluminum Oxide Membranes (pages 7933–7937)

      Abdul Mutalib Md Jani, Dr. Ivan M. Kempson, Dr. Dusan Losic and Prof. Dr. Nicolas H. Voelcker

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201002504

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      Layers of meaning: Nanoporous anodic aluminum oxide membranes can be fabricated with multilayered surface functionalities. Membranes produced by this technique are chemically robust and mechanically stable, and show selectivity towards the transport of small molecules.

    13. Biosensors

      A General Approach to the Construction of Structure-Switching Reporters from RNA Aptamers (pages 7938–7942)

      Pui Sai Lau, Prof. Dr. Brian K. Coombes and Prof. Dr. Yingfu Li

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201002621

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      Three in one: A three-component, duplex-to-complex structure-switching system is a simple and general strategy for the construction of fluorescent reporters from existing RNA aptamers (see picture). The tagging strategy is attractive as it circumvents the need for the chemical synthesis of modified RNA, and the structure-switching reporters can be used to distinguish targets that have very similar chemical structures.

    14. Diffusion in Nanochannels

      Anomalous Diffusion of Electrically Neutral Molecules in Charged Nanochannels (pages 7943–7947)

      Dr. Wei Chen , Dr. Zeng-Qiang Wu, Prof. Xing-Hua Xia, Prof. Jing-Juan Xu and Prof. Hong-Yuan Chen

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201002711

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      Confined and free diffusion of phenol occur in the electric double layer (EDL) and extra-EDL region in the nanochannels of porous anodic alumina (see picture). The inductive effect of the EDL electric field on the phenol molecules slows their diffusion, but it is negligible in the free-diffusion region. The extent of the two regions depends on EDL thickness, and hence the diffusion flux increases with increasing ionic strength of the electrolyte.

    15. DNA-Controlled Synthesis

      Multistep DNA-Templated Reactions for the Synthesis of Functional Sequence Controlled Oligomers (pages 7948–7951)

      Dr. Mireya L. McKee, Dr. Phillip J. Milnes, Dr. Jonathan Bath, Dr. Eugen Stulz, Prof. Andrew J. Turberfield and Dr. Rachel K. O'Reilly

      Article first published online: 10 SEP 2010 | DOI: 10.1002/anie.201002721

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      Biomimetic: A strand displacement mechanism was designed to permit DNA-templated synthesis of functional oligomers of arbitrary length (see scheme). Key features of the mechanism are that successive coupling reactions take place in near-identical environments and that purification is only necessary in the last synthesis step.

    16. Protein Imaging

      Direct Visualization of Protein Association in Living Cells with Complex-Edited Electron Microscopy (pages 7952–7954)

      Dr. Rachel J. Dexter and Prof. Alanna Schepartz

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201003217

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      Good partnership: A novel technique called complex-edited electron microscopy (CE-EM) combines bipartite tetracysteine display with EM and permits high-resolution imaging of discrete protein complexes (A and B in the picture). The strategy facilitates the direct and selective labeling of discrete protein complexes in living cells, followed by imaging with the extraordinary resolution of EM.

    17. Asymmetric Catalysis

      Isomerization-Induced Asymmetric Coordination Chemistry: From Auxiliary Control to Asymmetric Catalysis (pages 7955–7957)

      Dr. Lei Gong, Zhijie Lin, Dr. Klaus Harms and Prof. Dr. Eric Meggers

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201003139

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      Asymmetric generator: Chiral (S)-2-(isopropylsulfinyl)phenol and a more electron-rich methoxy derivative (R=OCH3) are capable of inducing and even catalyzing a chirality-generating transcis isomerization of two 2,2′-bipyridine ligands in an octahedral coordination sphere of a ruthenium complex.

    18. Heterocycle Synthesis

      Cascade Palladium-Catalyzed Direct Intramolecular Arylation/Alkene Isomerization Sequences: Synthesis of Indoles and Benzofurans (pages 7958–7962)

      Myriam Yagoubi, Ana C. F. Cruz, Dr. Paula L. Nichols, Dr. Richard L. Elliott and Dr. Michael C. Willis

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201004097

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      One route, two cycles: A palladium-catalyzed intramolecular direct arylation reaction combined with an isomerization step provided a straightforward synthetic route to both indoles and benzofurans (see scheme). Isolation and functionalization of intermediate alkene isomers allowed the formation of variants having substituents remote from the core.

    19. Cycloaddition

      Stereoselective Synthesis of α-Diazo Oxime Ethers and Their Application in the Synthesis of Highly Substituted Pyrroles through a [3+2] Cycloaddition (pages 7963–7967)

      Emmanuvel Lourdusamy, Lin Yao and Prof. Dr. Cheol-Min Park

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201004073

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      The stereoselective diazo transfer reaction with oxime ethers offers an efficient route to the corresponding α-diazo oxime ethers. The utility of these compounds has been demonstrated by the synthesis of highly substituted pyrroles through a [3+2] cycloaddition of α-oximino carbenoids with enamines (see scheme).

    20. Photochromism

      Controlling Contact Electrification with Photochromic Polymers (pages 7968–7971)

      Dr. Simone Friedle and Prof. Samuel W. Thomas III

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201003985

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      Charge switching: Control of contact electrification was achieved using a combination of photoreactive polymers and light. Upon UV irradiation, polymers substituted with photochromic spiropyrans reversibly switch their rate, and depending on chemical structure, their sign of charging by contact electrification (see picture). Consistent with empirical predictions, these photochromic polymers tended to charge positively upon irradiation with UV light.

    21. Nucleophilic Addition

      Facile Access to Key Reactive Intermediates in the Pd/PR3-Catalyzed Telomerization of 1,3-Butadiene (pages 7972–7975)

      Peter J. C. Hausoul, Dr. Andrei N. Parvulescu, Dr. Martin Lutz, Prof. Dr. Anthony L. Spek, Dr. Pieter C. A. Bruijnincx, Prof. Dr. Bert M. Weckhuysen and Prof. Dr. Robertus J. M. Klein Gebbink

      Article first published online: 10 SEP 2010 | DOI: 10.1002/anie.201003090

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      Found at last: A simple and efficient one-pot synthesis procedure leads to several cationic [Pd(1,2,3,7,8-η5-octa-2,7-dien-1-yl)(PR3)]+ complexes (see structure; Pd pink, O red, P orange), which are the long sought-after key reactive intermediates in the Pd/PR3-catalyzed telomerization of butadiene.

    22. Heterogeneous Catalysis

      Photocatalytic Aerobic Oxidation of Alcohols on TiO2: The Acceleration Effect of a Brønsted Acid (pages 7976–7979)

      Dr. Qi Wang, Dr. Miao Zhang, Prof. Chuncheng Chen, Prof. Wanhong Ma and Prof. Jincai Zhao

      Article first published online: 7 JUL 2010 | DOI: 10.1002/anie.201001533

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      Up to speed: Brønsted acids adsorbed onto TiO2 dramatically accelerated the photocatalytic oxidation of alcohols without any loss of selectivity (see scheme). This effect results from the decomposition of the Ti species, having a side-on peroxide, on the TiO2 surface. The decomposition is aided by the Brønsted acid, thereby regenerating the active Ti sites on the surface of the catalyst.

    23. Plasmon-Induced Enhancement

      Silver Nanoparticle Induced Photocurrent Enhancement at WO3 Photoanodes (pages 7980–7983)

      Dr. Renata Solarska, Dr. Agata Królikowska and Prof. Jan Augustyński

      Article first published online: 10 SEP 2010 | DOI: 10.1002/anie.201002173

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      Silver screen: Thin silver nanoparticle layers embedded within a 1 μm thick semiconducting WO3 film on conducting glass substrates enhance optical absorption over a broad wavelength region. The combination of light scattering and nearby electromagnetic-field effects causes a large increase of photocurrents associated with water splitting generated at the WO3 photoanodes under simulated solar light irradiation.

    24. Noncovalent Spin Labeling

      Noncovalent and Site-Directed Spin Labeling of Nucleic Acids (pages 7984–7986)

      Sandip A. Shelke and Prof. Dr. Snorri Th. Sigurdsson

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201002637

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      Spin label parking: The rigid spin label ç (magenta), which is an analogue of cytidine, binds site-specifically to abasic sites in duplex DNAs, through hydrogen bonding to guanine (blue) and π stacking with the flanking base pairs. EPR spectroscopy shows complete binding of ç to the abasic site at low temperatures. This new spin-labeling strategy gives easy access to spin-labeled nucleic acids for structural studies by pulsed EPR techniques.

    25. Mesoporous Materials

      A Low-Concentration Hydrothermal Synthesis of Biocompatible Ordered Mesoporous Carbon Nanospheres with Tunable and Uniform Size (pages 7987–7991)

      Yin Fang, Dong Gu, Ying Zou, Zhangxiong Wu, Prof. Dr. Fuyou Li, Prof. Dr. Renchao Che, Prof. Dr. Yonghui Deng, Prof. Dr. Bo Tu and Prof. Dr. Dongyuan Zhao

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201002849

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      Mesoporous carbon nanoparticles with uniform spherical morphology were fabricated through a low-concentration hydrothermal synthesis route. The diameters can be tuned from 20 to 140 nm by varying the reagent concentration. The highly ordered mesoporous carbon nanospheres with high surface area and large pore volume show low cytotoxicity and can easily penetrate into living cells.

    26. Solar Cells

      Enhanced Photovoltaic Performance of Low-Bandgap Polymers with Deep LUMO Levels (pages 7992–7995)

      Huaxing Zhou, Liqiang Yang, Samuel C. Price, Kelly Jane Knight and Prof. Dr. Wei You

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201003357

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      Mind the gap! Polymers synthesized by replacing the benzene unit in the acceptor 4,7-dithien-2-yl-2,1,3-benzothiadiazole (DTBT) with a π-electron-deficient pyridine unit (DTPyT) show a smaller bandgap than their DTBT counterparts. Power conversion efficiencies of over 6 % are demonstrated in solar cell studies (see picture; PNDT, PQDT, and PBnDT represent dithiophene derivatives as weak donors).

    27. Electron Transfer in Dipeptides

      Intramolecular Electron Transfer in the Photooxidized Peptides Tyrosine–Histidine and Histidine–Tyrosine: A Time-Resolved CIDNP Study (pages 7996–7999)

      Dr. Olga B. Morozova and Dr. Alexandra V. Yurkovskaya

      Article first published online: 16 SEP 2010 | DOI: 10.1002/anie.201003780

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      Invisible to other methods, reactions of the histidyl radical could be followed by NMR spectroscopic detection of the histidine signal through the use of time-resolved chemically induced dynamic nuclear polarization (CIDNP). CIDNP decay of the His signal during photooxidation of the peptides His-Tyr and Tyr-His pointed to electron transfer from the tyrosine residue to the histidyl radical (see scheme for Tyr-His).

    28. Subphthalocyanines

      Subazaphenalenephthalocyanine: A Subphthalocyanine Analogue Bearing a Six-Membered Ring Unit (pages 8000–8003)

      Hua Zhu, Dr. Soji Shimizu and Prof. Dr. Nagao Kobayashi

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201003929

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      At the core: A novel core-modified subphthalocyanine analogue has been synthesized (see structure; Cl green, red O, blue N). This molecule comprises a six-membered ring unit in place of a five-membered ring unit and exhibits unique spectroscopic (see plot) and electrochemical properties originating from the azaphenalene-containing 14π-electron conjugation system.

    29. Anodic Cyclization

      Intramolecular Anodic Olefin Coupling Reactions: Use of the Reaction Rate To Control Substrate/Product Selectivity (pages 8004–8007)

      Hai-Chao Xu and Prof. Dr. Kevin D. Moeller

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201003924

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      Look out—it's a trap! The anodic coupling of olefins with amine trapping groups to form proline and pipecolic acid derivatives with a quaternary α carbon atom (see scheme) was successful despite the significantly lower oxidation potential of the product relative to that of either functional group in the substrate: owing to the very fast cyclization, the oxidation potential of the substrate is lower than that of the product. Ts=p-toluenesulfonyl.

    30. Vanadium Azides

      The Syntheses and Structure of the Vanadium(IV) and Vanadium(V) Binary Azides V(N3)4, [V(N3)6]2−, and [V(N3)6] (pages 8008–8012)

      Dr. Ralf Haiges, Dr. Jerry A. Boatz and Prof. Dr. Karl O. Christe

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.200906537

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      Shock-sensitive and highly explosive V(N3)4 was prepared from VF4 and Me3SiN3 by fluoride–azide exchange. Salts of the [V(N3)6]2− anion (see picture) were obtained by treatment of the neutral tetraazide with ionic azides. Vanadium(V) azide, the only binary vanadium(V) compound known apart from VF5, VF6, and V2O5, was successfully prepared from the VF6 anion.

    31. Silicon Azides

      Neutral Lewis Base Adducts of Silicon Tetraazide (pages 8013–8016)

      Dr. Peter Portius, Prof. Dr. Alexander C. Filippou, Dr. Gregor Schnakenburg, Dr. Martin Davis and Prof. Dr. Klaus-Dieter Wehrstedt

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201001826

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      Highly energetic and still stable: The first base adducts of silicon tetraazide, Si(N3)4(L2) (L2=bipyridine, 1,10-phenanthroline), were prepared and fully characterized (picture: the ball and stick model of the adduct with L2=2,2'-bipyridine in front of its FTIR spectrum; dark gray C, white H, light gray Si, blue N). The highly energetic compounds combine a remarkable thermal stability, with a high reactive nitrogen content (up to 48 %) and convenient accessibility.

    32. Bismuth Azides

      Binary Bismuth(III) Azides: Bi(N3)3 , [Bi(N3)4], and [Bi(N3)6]3− (pages 8017–8020)

      Dr. Alexander Villinger and Prof. Dr. Axel Schulz

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201002179

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      Nitrogen finally meets bismuth: The synthesis of binary bismuth(III) azides BiIII(N3)3, [BiIII(N3)4], and [BiIII(N3)6]3− along with their characterization is presented for the first time and closes a chapter in main group chemistry. Bi(N3)3⋅THF qualifies as a good precursor for the generation of binary BiN owing to its low shock and heat sensitivity, in contrast to pure, highly sensitive Bi(N3)3.

    33. Natural Products

      A Short Formal Total Synthesis of Strychnine with a Samarium Diiodide Induced Cascade Reaction as the Key Step (pages 8021–8025)

      Dipl.-Chem. Christine Beemelmanns and Prof. Dr. Hans-Ulrich Reissig

      Article first published online: 16 SEP 2010 | DOI: 10.1002/anie.201003320

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      Brevity is the soul of wit! The power of SmI2-induced cyclizations has been demonstrated by the shortest formal total synthesis of (±)-strychnine to date, which features a new cascade reaction. Only one protective-group transformation is required. The ketyl–aryl coupling/acylation cascade also efficiently proceeds with other indole derivatives with excellent diastereoselectivities.

    34. Biocatalysis

      Probing the Active Site of an O2-Tolerant NAD+-Reducing [NiFe]-Hydrogenase from Ralstonia eutropha H16 by In Situ EPR and FTIR Spectroscopy (pages 8026–8029)

      Marius Horch, Lars Lauterbach, Dr. Miguel Saggu, Prof. Peter Hildebrandt, Dr. Friedhelm Lendzian, Prof. Robert Bittl, Dr. Oliver Lenz and Dr. Ingo Zebger

      Article first published online: 20 SEP 2010 | DOI: 10.1002/anie.201002197

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      A clear picture: In situ EPR and FTIR spectroscopic studies on the soluble, NAD+-reducing [NiFe]-hydrogenase of Ralstonia eutropha reveal that the catalytic site resides predominantly in the intermediate Nia-C state within whole cells. This state, can either be reversibly oxidized to a “Nir-B”-like state or further reduced to various Nia-SR species. The data suggest that the iron center in the active site contains a standard set (one CO and two CN) of inorganic ligands.

    35. Telluronic Acids

      A Well-Defined Dinuclear Telluronic Acid [RTe(μ-O)(OH)3]2 (pages 8030–8032)

      Prof. Dr. Jens Beckmann, Dipl.-Chem. Jens Bolsinger, Dipl.-Chem. Pamela Finke and Dr. Malte Hesse

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201002545

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      Two for Te: The ditelluronic acid 3 is the first heavy congener of sulfonic and selenonic acids and is obtained by the O2 oxidation of the tellurinate 2 in the presence of [18]crown-6. Compound 2 is prepared by the reaction of the ditellurinic acid 1 with NaH. The direct oxidation of 1 to 3 using strong oxidants, such as H2O2, KMnO4, and NaIO4 failed.

    36. Bioinorganic Chemistry

      Catalytic Hydrogen Evolution from Mononuclear Iron(II) Carbonyl Complexes as Minimal Functional Models of the [FeFe] Hydrogenase Active Site (pages 8033–8036)

      Dr. Sandeep Kaur-Ghumaan, Dr. Lennart Schwartz, Dr. Reiner Lomoth, Dr. Matthias Stein and Dr. Sascha Ott

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201002719

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      How much iron does it take? Mononuclear complexes [FeII(3,6-R2bdt)(CO)2(PMe3)2] (bdt=1,2-C6H4(S)2; R=H, Cl) can be reversibly protonated at the sulfur ligands, can catalyze the electrochemical reduction of protons, and are thus minimal functional models of the [FeFe] hydrogenases (see scheme). DFT calculations show that cleavage of an Fe[BOND]S bond leads to the generation of a free coordination site, which is crucial for the formation of hydrides that are key intermediates in the generation of hydrogen.

    37. Surface Chemistry

      Anomalous Surface Compositions of Stoichiometric Mixed Oxide Compounds (pages 8037–8041)

      Dr. Sergiy V. Merzlikin, Dr. Nikolay N. Tolkachev, Dr. Laura E. Briand, Dr. Thomas Strunskus, Prof. Dr. Christof Wöll, Prof. Israel E. Wachs and Prof. Dr. Wolfgang Grünert

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201001804

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      Coated: Surface analytical studies (including low-energy ion scattering (LEIS)) show that the outer surface of bulk, stoichiometric mixed vanadates and molybdates can be strongly enriched with VOx or MoOx species. Such surface reconstruction even in the calcined initial state has implications for the discussion of catalytic and other materials properties.

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      Preview: Angew. Chem. Int. Ed. 44/2010 (page 8045)

      Article first published online: 13 OCT 2010 | DOI: 10.1002/anie.201090141

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