Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 21

May 17, 2013

Volume 52, Issue 21

Pages 5409–5647

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: A High-Valent Heterobimetallic [CuIII(μ-O)2NiIII]2+ Core with Nucleophilic Oxo Groups (Angew. Chem. Int. Ed. 21/2013) (page 5409)

      Subrata Kundu, Florian Felix Pfaff, Enrico Miceli, Dr. Ivelina Zaharieva, Dr. Christian Herwig, Dr. Shenglai Yao, Dr. Erik R. Farquhar, Dr. Uwe Kuhlmann, Dr. Eckhard Bill, Prof. Dr. Peter Hildebrandt, Prof. Dr. Holger Dau, Prof. Dr. Matthias Driess, Prof. Dr. Christian Limberg and Dr. Kallol Ray

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201303268

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      Unlike typical homodinuclear high-valent [M2(μ-O)2]n+ cores, a rare heterobimetallic high-valent CuNi bis(μ-oxo) complex behaves as a nucleophile. In their Communication on page 5622 ff., K. Ray, M. Driess, C. Limberg et al. show that this complex can initiate deformylation of aldehydes, indicating that mixed-metal bis(μ-oxo) cores are viable intermediates in the deformylation of fatty aldehydes by cyanobacterial aldehyde decarbonylase, for which a similar cofactor has been suggested, but not isolated.

    2. You have free access to this content
      Inside Cover: Carbon-Coated CdS Petalous Nanostructures with Enhanced Photostability and Photocatalytic Activity (Angew. Chem. Int. Ed. 21/2013) (page 5410)

      Prof. Yong Hu, Xuehui Gao, Le Yu, Yanrong Wang, Dr. Jiqiang Ning, Prof. Shijie Xu and Prof. Xiong Wen (David) Lou

      Article first published online: 2 MAY 2013 | DOI: 10.1002/anie.201303315

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      Carbon-coated CdS petalous nanostructures have been synthesized through a one-pot solvothermal method, as described by Y. Hu, X. W. Lou, and co-workers in their Communication on page 5636 ff. The carbon nanocoating serves multiple functions, including protection of the CdS surface, enhancement of visible-light absorption, and facilitating the separation of photogenerated charges. As a result, this CdS–C nanohybrid photocatalyst exhibits significantly enhanced photostability and photocatalytic activity.

    3. You have free access to this content
      Inside Back Cover: High-Throughput Screening for Terpene-Synthase-Cyclization Activity and Directed Evolution of a Terpene Synthase (Angew. Chem. Int. Ed. 21/2013) (page 5649)

      Dr. Ryan Lauchli, Dr. Kersten S. Rabe, Karolina Z. Kalbarczyk, Amulya Tata, Dr. Thomas Heel, Rebekah Z. Kitto and Prof. Dr. Frances H. Arnold

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201303270

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      Active terpene synthase mutants are generally identified by using lower-throughput GC-based methods. In their Communication on page 5571 ff., F. H. Arnold and co-workers describe a terpene synthase substrate that enables cyclization activity to be screened in a high-throughput manner. The screening protocol allows the identification of active mutants by the brilliant purple color that these mutants generate in the assay.

    4. You have free access to this content
      Back Cover: Chemotactic Behavior of Catalytic Motors in Microfluidic Channels (Angew. Chem. Int. Ed. 21/2013) (page 5650)

      Dr. Larysa Baraban, Dr. Stefan M. Harazim, Dr. Samuel Sanchez and Prof. Dr. Oliver G. Schmidt

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201303430

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      When man-made self-powered micromotors swim in a gradient of chemical fuel, they experience a chemical attraction towards the fuel and deviate from their otherwise random motion. As S. Sanchez et al. describe in their Communication on page 5552 ff., self-propelled microjets and microparticles change their trajectory when hydrogen peroxide fuel is added to the solution in which they navigate, a response similar to the chemotactic behavior of some living organisms. (The authors thank Dr. Träger for designing the image.)

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
  3. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. You have free access to this content
      Corrigendum: Efficient Assembly of Iminodicarboxamides by a “Truly” Four-Component Reaction (page 5425)

      Kareem Khoury, Dr. Mantosh K. Sinha, Dr. Tadamichi Nagashima, Eberhardt Herdtweck and Prof. Alexander Dömling

      Article first published online: 10 MAY 2013 | DOI: 10.1002/anie.201301832

      This article corrects:

      Efficient Assembly of Iminodicarboxamides by a “Truly” Four-Component Reaction1

      Vol. 51, Issue 41, 10280–10283, Article first published online: 11 SEP 2012

    2. You have free access to this content
      Corrigendum: Synthesis of ortho-Acylphenols through the Palladium-Catalyzed Ketone-Directed Hydroxylation of Arenes (page 5425)

      Dr. Fanyang Mo, Louis J. Trzepkowski and Prof. Dr. Guangbin Dong

      Article first published online: 10 MAY 2013 | DOI: 10.1002/anie.201303140

      This article corrects:

      Synthesis of ortho-Acylphenols through the Palladium-Catalyzed Ketone-Directed Hydroxylation of Arenes1

      Vol. 51, Issue 52, 13075–13079, Article first published online: 19 NOV 2012

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Licheng Sun (page 5434)

      Article first published online: 25 FEB 2013 | DOI: 10.1002/anie.201209482

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      “My worst nightmare is transcontinental travel for more than 36 hours. My favorite piece of research is CO2 activation …” This and more about Licheng Sun can be found on page 5434.

  6. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Applications of Transition Metal Catalysis in Drug Discovery and Development. An Industrial Perspective. Edited by Matthew L. Crawley and Barry M. Trost. (page 5435)

      Jonathan Medlock and Werner Bonrath

      Article first published online: 19 APR 2013 | DOI: 10.1002/anie.201302033

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      John Wiley & Sons, Hoboken, 2012. 376 pp., hardcover, € 80.40.—ISBN 978-0470631324

  7. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Nanostructures

      Of Graphs and Graphenes: Molecular Design and Chemical Studies of Aromatic Compounds (pages 5436–5438)

      Prof. Kim K. Baldridge and Prof. Jay S. Siegel

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201300625

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      All things graphene: Within the graph of graphene one finds subgraphs for a myriad of novel aromatic hydrocarbons. For example, defining the vertices of a C3 subgraph within graphene evokes higher-order structures simply by changing the length of the ring fusion links. Analogously, the C6 transformation yields coronene and kekulene (see scheme).

    2. Promiscuous Biocatalysis

      Enzyme Promiscuity: Using a P450 Enzyme as a Carbene Transfer Catalyst (pages 5439–5440)

      Dr. Dipl. Ing. Gheorghe-Doru Roiban and Prof. Dr. Manfred T. Reetz

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201301083

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      How about this for a change: The promiscuous enzyme cytochrome P450-BM3 catalyzes the cyclopropanation of olefins, sometimes with high stereoselectivity (see scheme). The highlighted paper demonstrates that it is possible to design unusual enzyme promiscuity.

  8. Correspondence

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Antitumor Agents (1)

      The Cytotoxicity of Duocarmycin Analogues is Mediated through Alkylation of DNA, not Aldehyde Dehydrogenase 1: A Comment (pages 5442–5446)

      Dr. Moana Tercel, Sarah P. McManaway, Dr. Euphemia Leung, H. D. Sarath Liyanage, Dr. Guo-Liang Lu and Dr. Frederik B. Pruijn

      Article first published online: 24 APR 2013 | DOI: 10.1002/anie.201208373

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      The answer lies in the DNA: Recent claims that the alkylation of a particular protein contributes to the cytotoxicity of the duocarmycins could not be substantiated. The evidence, like the fluorescent signal derived from a clickable analogue, points instead to a reaction occurring in the nucleus.

    2. Antitumor Agents (2)

      Duocarmycin Analogues without a DNA-Binding Indole Unit Associate with Aldehyde Dehydrogenase 1A1 and not DNA: A Reply (pages 5447–5449)

      Prof. Dr. Lutz F. Tietze and Prof. Dr. Stephan A. Sieber

      Article first published online: 24 APR 2013 | DOI: 10.1002/anie.201301923

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      An open question: Activity-based protein profiling using seco-CBI derivative 1, containing a DNA-binding indole unit, showed that besides binding to DNA, compound 1 also interacts with aldehyde dehydrogenase 1. However, for CBI compounds without an indole unit, the origin of their cytotoxicity has not been identified, yet.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Proteasome Inhibitors

      Synthesis and Pharmacology of Proteasome Inhibitors (pages 5450–5488)

      Dr. Andreas Rentsch, Dr. Dirk Landsberg, Dr. Tobias Brodmann, Dr. Leila Bülow, Dr. Anna-Katharina Girbig and Prof. Dr. Markus Kalesse

      Article first published online: 25 MAR 2013 | DOI: 10.1002/anie.201207900

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      The ubiquitin–proteasome system controls fundamental processes such as cell cycle regulation, DNA repair, apoptosis, and immune and inflammatory responses, as well as hereditary disorders such as cystic fibrosis. This Review covers the synthesis of the most important proteasome inhibitors as well as their mode of action and clinical development.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    1. Fluorescence

      Building Fluorescent DNA Nanodevices on Target Living Cell Surfaces (pages 5490–5496)

      Guizhi Zhu, Shengfeng Zhang, Prof. Dr. Erqun Song, Jing Zheng, Rong Hu, Prof. Dr. Xiaohong Fang and Prof. Dr. Weihong Tan

      Article first published online: 18 APR 2013 | DOI: 10.1002/anie.201301439

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      DNA nanotrain: Anchoring of preformed fluorescent DNA nanodevices (NDs; see picture) and in situ self-assembly of fluorescent DNA NDs on target living cell surfaces are reported. The in situ self-assembly of the nanodevice was further shown on surfaces of living cells in cell mixtures. These DNA NDs exhibited fluorescence emission and underwent fluorescence resonance energy transfer (FRET) on living cell surfaces.

    2. Protein Transduction

      Collagen-like Cell-Penetrating Peptides (pages 5497–5500)

      Dr. Chisato M. Yamazaki, Dr. Ikuhiko Nakase, Hiroyuki Endo, Saya Kishimoto, Yoshihiro Mashiyama, Dr. Ryo Masuda, Prof. Shiroh Futaki and Prof. Takaki Koide

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201301266

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      Arginine-rich heterotrimeric collagen-like peptides were prepared, and their cellular uptake efficiency was evaluated. The spatial arrangement of the Arg residues (blue in picture) on the triple-helix surface significantly affected the efficacy of the cellular uptake. The collagen-like triple-helical conformation provides these cell-penetrating peptides with a high resistance to proteases. O=L-4-hydroxyproline.

    3. Zeolite Analogues

      A Gallogermanate Zeolite with Eleven-Membered-Ring Channels (pages 5501–5503)

      Yan Xu, Dr. Yi Li, Dr. Yide Han, Dr. Xiaowei Song and Prof. Jihong Yu

      Article first published online: 9 APR 2013 | DOI: 10.1002/anie.201300846

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      Ring the change: The gallogermanate zeolite |(Ni(C3H10N2)3)36Ni4.7|[Ga81.4Ge206.6O576], which has three-dimensional intersecting 11-membered-ring channels (see picture, left), was synthesized. It has the lowest framework density of all known oxide zeolites and features pairs of chiral [312.43.62.116] cavities, induced by chiral [Ni(1,2-PDA)3]2+ cations formed in situ (see picture, right). 1,2-PDA=1,2-diaminopropane.

    4. Molecular Recognition

      Dynamic Molecular Recognition in Solid State for Separating Mixtures of Isomeric Dicarboxylic Acids (pages 5504–5508)

      Dr. Krunoslav Užarević, Dr. Ivan Halasz, Dr. Ivica Đilović, Nikola Bregović, Dr. Mirta Rubčić, Prof. Dubravka Matković-Čalogović and Prof. Vladislav Tomišić

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201301032

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      Flexible even if constrained: A polyamine host recognizes dicarboxylic acids in solution and in the solid state, with the highest selectivity towards maleic acid, binding it from mixtures with up to five other dicarboxylic acids, including fumaric acid (see picture). Recognition using mechanochemistry is a dynamic process involving intermediate phases, resulting in the same selectivity as achieved by crystallization from solution.

    5. Biosensors

      Monovalent Streptavidin that Senses Oligonucleotides (pages 5509–5512)

      Dr. Steven K. Taylor, Jingxian Wang, Natasa Kostic and Prof. Dr. Milan N. Stojanovic

      Article first published online: 19 APR 2013 | DOI: 10.1002/anie.201209948

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      Only one place available: Monovalent streptavidin is prepared in a one-step process based on a trisbiotinylated oligonucleotide that blocks three of streptavidin's four biotin-binding sites. The complex is highly sensitive to single-base differences: perfectly matched oligonucleotides trigger dissociation of the biotin–streptavidin interaction at higher rates than strands with single-base mismatches.

    6. Organic Semiconductors

      Tetraazabenzodifluoranthene Diimides: Building Blocks for Solution-Processable n-Type Organic Semiconductors (pages 5513–5517)

      Dr. Haiyan Li, Dr. Felix Sunjoo Kim, Guoqiang Ren, Emily C. Hollenbeck, Dr. Selvam Subramaniyan and Prof. Dr. Samson A. Jenekhe

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201210085

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      11-Ring heterocyclic diimides were synthesized and found to be planar and to exhibit a slipped face-to-face π stacking. Variation of the substituents tunes the electronic structure and properties. In n-channel organic field-effect transistors, the new organic semiconductors have a high electron mobility. When they were used as acceptor material in polymer solar cells, a power conversion efficiency of 1.8 % was obtained.

    7. Heterogeneous Catalysis

      High-Pressure Scanning Tunneling Microscopy of a Silver Surface during Catalytic Formation of Ethylene Oxide (pages 5518–5521)

      Sebastian Böcklein, Prof. Dr. Sebastian Günther and Prof. Dr. Joost Wintterlin

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201210209

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      The active state of a catalyst: A high-pressure scanning tunneling microscope (STM) was used to bridge the pressure gap for the Ag-catalyzed ethylene epoxidation. An active oxygen species on an Ag(111) single crystal was characterized under ultrahigh vacuum conditions. The same species was identified with STM in an ethylene/oxygen mixture (see picture). In the STM cell the formation of ethylene oxide was detected.

    8. Protein Translation

      Suppression of Gene Expression by G-Quadruplexes in Open Reading Frames Depends on G-Quadruplex Stability (pages 5522–5526)

      Tamaki Endoh, Yu Kawasaki and Prof. Naoki Sugimoto

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300058

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      Suppressing the urge to translate: Sequences with the potential to form G-quadruplexes were identified in the open reading frames of E. coli genes. These sequences were found to form parallel G-quadruplexes and to suppress translation (see picture) of the mRNAs into proteins both in vitro and in cells.

    9. Dye-Sensitized Solar Cells

      Stable Dye-Sensitized Solar Cell Electrolytes Based on Cobalt(II)/(III) Complexes of a Hexadentate Pyridyl Ligand (pages 5527–5531)

      Muhammad K. Kashif, Dr. Michael Nippe, Noel. W. Duffy, Dr. Craig M. Forsyth, Prof. Dr. Christopher J. Chang, Prof. Dr. Jeffrey R. Long, Prof. Dr. Leone Spiccia and Prof. Dr. Udo Bach

      Article first published online: 18 APR 2013 | DOI: 10.1002/anie.201300070

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      Energy conversion: A cobalt redox mediator, [Co(bpyPY4)]2+/3+, based on a hexadentate polypyridyl ligand, was developed. Dye-sensitized solar cells (DSCs) made with this redox mediator showed improved stability and slightly higher efficiencies compared to [Co(bpy)3]2+/3+-based devices. Long-term stability evaluation of DSCs based on [Co(bpyPY4)]2+/3+ revealed excellent stability under full irradiation conditions (see picture).

    10. Imine Generation

      Acid-Catalyzed In Situ Generation of Less Accessible or Unprecedented N-Boc Imines from N-Boc Aminals (pages 5532–5534)

      Dr. Taichi Kano, Taiga Yurino, Daisuke Asakawa and Prof. Keiji Maruoka

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300231

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      Crafty aminals: The in situ generation of hitherto unattainable alkynyl-substituted N-Boc-protected imines was realized by the acid-catalyzed elimination of tert-butyl carbamate from N-Boc aminals. A wide variety of N-Boc imines can be generated, which can then be utilized for subsequent carbon–carbon bond-forming reactions, such as Mannich-type reactions.

    11. Carbon Electrodes

      Bioinspired Wafer-Scale Production of Highly Stretchable Carbon Films for Transparent Conductive Electrodes (pages 5535–5538)

      Dr. Rongjin Li, Khaled Parvez, Felix Hinkel, Prof. Dr. Xinliang Feng and Prof. Dr. Klaus Müllen

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201300312

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      Carbon-based films: Dopamine was used as the precursor for the facile yet controllable production of a highly stretchable transparent conductive film (see picture). The film synthesized is transparent and can reversibly withstand mechanical deformations (such as being stretched to 20 % for 100 cycles).

    12. Mesoporous Materials

      Large Increase in the Second-Order Nonlinear Optical Activity of a Hemicyanine-Incorporating Zeolite Film (pages 5539–5543)

      Dr. Tung Cao Thanh Pham, Prof. Dr. Hyun Sung Kim and Prof. Dr. Kyung Byung Yoon

      Article first published online: 18 APR 2013 | DOI: 10.1002/anie.201300326

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      Nonlinear optics: A hemicyanine-incorporating silicalite-1 film with second-order nonlinear optical properties supported on a glass plate was prepared. For the nonlinear optical properties of this material the number of hemicyanine dye moleclues included in the zeolite channels is important. Defects arising from Si deficiency along the channels prohibit the diffusion of the dyes into the interior of the zeolite film (see picture).

    13. Hybrid Materials

      Ligand-Directed Control over Crystal Structures of Inorganic–Organic Frameworks and Formation of Solid Solutions (pages 5544–5547)

      Hamish H.-M. Yeung, Dr. Wei Li, Dr. Paul J. Saines, Dr. Thomas K. J. Köster, Prof. Clare P. Grey and Prof. Anthony K. Cheetham

      Article first published online: 26 MAR 2013 | DOI: 10.1002/anie.201300440

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      Grounded in fact: Inorganic–organic frameworks with 3D Li–O–Li connectivity can form solid solutions through mechanochemical synthesis. High-resolution synchrotron powder X-ray diffraction and cross-polarization solid-state NMR spectroscopy demonstrate complete ligand mixing in the resulting binary and ternary systems (see picture for trends in unit cell volume (V) of the ternary system {Li2(suc)x(mal)y(met)z}n).

    14. Solid-State Photopolymerization

      Tunable Plastic Films of a Crystalline Polymer by Single-Crystal-to-Single-Crystal Photopolymerization of a Diene: Self-Templating and Shock-Absorbing Two-Dimensional Hydrogen-Bonding Layers (pages 5548–5551)

      Mousumi Garai, Dr. Ramkinkar Santra and Prof. Kumar Biradha

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201300690

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      Film review: Two amide-containing bisolefin monomers undergo solid-state polymerization (see example) through a [2+2] reaction in a single-crystal-to-single-crystal fashion. The transformation was favored by the self-templating and shock-absorbing nature of hydrogen-bonding layers. The pyridine-containing polymers were soluble and useful for making plastic films with considerable tensile strengths.

    15. Micromotors

      Chemotactic Behavior of Catalytic Motors in Microfluidic Channels (pages 5552–5556)

      Dr. Larysa Baraban, Dr. Stefan M. Harazim, Dr. Samuel Sanchez and Prof. Dr. Oliver G. Schmidt

      Article first published online: 24 APR 2013 | DOI: 10.1002/anie.201301460

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      Chemotaxis in practice: Two different artificial catalytic micromotors (tubular and spherical, see scheme) show chemotactic behavior in microfluidic channels demonstrating that catalytic micromotors can sense the gradient of chemical fuel in their environment and be directed towards desired locations.

    16. Asymmetric Synthesis

      Cinchona Alkaloid Amide/Copper(II) Catalyzed Diastereo- and Enantioselective Vinylogous Mannich Reaction of Ketimines with Siloxyfurans (pages 5557–5560)

      Masashi Hayashi, Masahide Sano, Prof. Dr. Yasuhiro Funahashi and Prof. Dr. Shuichi Nakamura

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201301917

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      Managing the Mannich: The first enantioselective vinylogous Mannich reaction of siloxyfurans with ketimines derived from unactivated ketones has been developed. Excellent yields and enantioselectivities were obtained using a new class of readily accessible cinchona alkaloid amide/Cu(OAc)2 catalysts on a range of substrates.

    17. Synthetic Methods

      Palladium-Catalyzed Selective Anti-Markovnikov Oxidation of Allylic Esters (pages 5561–5565)

      Jia Jia Dong, Dr. Martín Fañanás-Mastral, Dr. Paul L. Alsters, Dr. Wesley R. Browne and Prof. Dr. Ben L. Feringa

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201301809

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      An aldol alternative: The palladium(II)-catalyzed anti-Markovnikov oxidation of allylic esters to aldehydes at room temperature provides a viable alternative to valuable cross aldol products. High regioselectivity towards the aldehyde product was achieved using the ester protecting group for the allylic alcohol. Rapid isomerization and the much higher rate of oxidation of the branched isomer result in the same product forming from both linear and branched allylic esters.

    18. Organocatalysis

      Highly Enantioselective Construction of 3-Hydroxy Oxindoles through a Decarboxylative Aldol Addition of Trifluoromethyl α-Fluorinated gem-Diols to N-Benzyl Isatins (pages 5566–5570)

      Dr. Ibrayim Saidalimu, Dr. Xiang Fang, Dr. Xiao-Peng He, Jing Liang, Dr. Xueyan Yang and Prof. Fanhong Wu

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201301443

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      An organocatalytic asymmetric direct aldol addition reaction that involves cleavage of a carbon–carbon bond through the release of trifluoroacetate was developed. The protocol is wide in scope, generating the desired oxindoles of biological interest in nearly quantitative yields (up to 99 %) with excellent enantioselectivities (up to 98 % ee) and diastereoselectivities (up to 99:1 d.r.).

    19. Directed Evolution

      High-Throughput Screening for Terpene-Synthase-Cyclization Activity and Directed Evolution of a Terpene Synthase (pages 5571–5574)

      Dr. Ryan Lauchli, Dr. Kersten S. Rabe, Karolina Z. Kalbarczyk, Amulya Tata, Dr. Thomas Heel, Rebekah Z. Kitto and Prof. Dr. Frances H. Arnold

      Article first published online: 26 MAR 2013 | DOI: 10.1002/anie.201301362

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      An easy assay: A synthetic substrate enables a colorimetric screen for terpene synthase cyclization activity, thereby facilitating the engineering of these enzymes. By using directed evolution, the thermostability of a sesquiterpene synthase was increased without the loss of other properties. The technique also enabled rapid optimization of conditions for expression and stabilization in lysate of another terpene synthase. PPO=diphosphate.

    20. Heterocycle Synthesis

      Efficient Access to Trifluoromethyl Diarylpyrrolines and their N-Oxides through Enantioselective Conjugate Addition of Nitromethane to β,β-Disubstituted Enones (pages 5575–5579)

      Dr. Hiroyuki Kawai, Zhe Yuan, Takashi Kitayama, Etsuko Tokunaga and Prof. Norio Shibata

      Article first published online: 18 APR 2013 | DOI: 10.1002/anie.201301123

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      The cupreidinium salt 1 catalyzes the highly enantioselective conjugate addition of nitromethane to β-aryl-β-trifluoromethyl aryl enones (2). The biologically important chiral pyrrolines 4 and N-oxide 5, having a trifluoromethylated all-carbon quaternary chiral center, were easily synthesized from the key intermediate (R)-3 in high to excellent yields. M.S.=molecular sieves.

    21. Drug Delivery

      Glucose- and pH-Responsive Controlled Release of Cargo from Protein-Gated Carbohydrate-Functionalized Mesoporous Silica Nanocontainers (pages 5580–5584)

      Shanshan Wu, Xuan Huang and Prof. Dr. Xuezhong Du

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300958

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      Learning to let go: Controlled release of cargo (purple cubes) from lectin (blue squares)-gated nanopores was achieved using mannose (green loops)-functionalized mesoporous silica (see scheme). The protein nanogates could be opened either by decreasing the pH of the buffer or by adding competing glucose (yellow rings) to release the cargo from the pores.

    22. Metal-Free Electrocatalysts

      Molecular Architecture of Cobalt Porphyrin Multilayers on Reduced Graphene Oxide Sheets for High-Performance Oxygen Reduction Reaction (pages 5585–5589)

      Hongjie Tang, Huajie Yin, Jiangyan Wang, Nailiang Yang, Prof. Dan Wang and Prof. Zhiyong Tang

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300711

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      ORR inspiring: Multilayers of Co2+ and porphyrin, fabricated on the surface of reduced graphene oxide sheets (see picture) by a layer-by-layer assembly technique, are potentially cost-effective and high-efficient oxygen reduction reaction (ORR) catalysts. The multilayers have comparable electrocatalytic activity to commercial C/Pt catalysts, but much better methanol tolerance and long-term stability toward ORR.

    23. Protein Nanowires

      Construction of Protein Nanowires through Cucurbit[8]uril-based Highly Specific Host–Guest Interactions: An Approach to the Assembly of Functional Proteins (pages 5590–5593)

      Dr. Chunxi Hou, Jiaxi Li, Linlu Zhao, Dr. Wei Zhang, Dr. Quan Luo, Dr. Zeyuan Dong, Jiayun Xu and Prof. Dr. Junqiu Liu

      Article first published online: 19 APR 2013 | DOI: 10.1002/anie.201300692

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      Getting your proteins in a row: Self-assembled protein nanowires were designed by utilizing highly specific supramolecular interactions of cucurbit[8]uril (CB[8]) and a tripeptide FGG-tag attached on the N-termini of dimeric glutathione S-transferase (GST). With the aid of enzyme simulation, model protein GST was converted into a selenoenzyme glutathione peroxidase mimic, and the CB[8]-induced Se-FGG-GST(Y6C) nanowires demonstrated excellent antioxidative capacity.

    24. Biological Radicals

      Oxidation and Reduction of the 5-(2′-Deoxyuridinyl)methyl Radical (pages 5594–5598)

      Dr. Gengjie Lin and Prof. Lei Li

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201209454

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      Sleeping beauty: The 5-(2′-Deoxyuridinyl)methyl radical 1 is a key intermediate in the thymine oxidative reaction mediated by reactive oxygen species. Evidence is presented that 1 is prone to both oxidation and reduction reactions at the absence of O2. These results question the current paradigm and suggest that the redox chemistry of 1, which has been largely overlooked in the past, may play a major role in determining the fate of 1.

    25. Fluorescence

      Off/On Fluorescent Chemosensors for Organotin Halides Based on Binuclear Ruthenium Complexes (pages 5599–5603)

      Yufen Niu, Feifei Han, Qian Zhang, Tingwan Xie, Liu Lu, Dr. Shunhua Li and Prof. Haiping Xia

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201209549

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      Fluorescent organotin sensing: Molecular recognition driven by halogen-bonding interactions and the phenomenon of aggregation-induced emission were combined to construct fluorescent chemosensors. Binuclear ruthenium complexes containing multiple isocyanide ligands were synthesized as nonluminescent receptors that emit red fluorescence upon interacting with organotin halides (see picture; QY=quantum yield).

    26. Asymmetric Catalysis

      Catalytic Asymmetric [8+2] Cycloaddition: Synthesis of Cycloheptatriene-Fused Pyrrole Derivatives (pages 5604–5607)

      Mingsheng Xie, Prof. Dr. Xiaohua Liu, Xiaoxia Wu, Yunfei Cai, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 19 APR 2013 | DOI: 10.1002/anie.201209601

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      Add a ring: A catalytic asymmetric [8+2] cycloaddition reaction of azaheptafulvenes with alkylidene malonates was developed. When employing catalytic amounts of a chiral N,N′-dioxide L–NiII complex, the reaction afforded functionalized cycloheptatriene-fused pyrrole derivatives in excellent yields (up to 99 %), diastereoselectivities (>95:5 d.r.), and enantioselectivities (91–97 % ee) under mild conditions.

    27. Heterogeneous Catalysis

      Vibrational Analysis of an Industrial Fe-Based Fischer–Tropsch Catalyst Employing Inelastic Neutron Scattering (pages 5608–5611)

      Dr. Neil G. Hamilton, Dr. Ian P. Silverwood, Robbie Warringham, Dr. Josef Kapitán, Dr. Lutz Hecht, Dr. Paul B. Webb, Prof. Robert P. Tooze, Dr. Stewart F. Parker and Dr. David Lennon

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201210179

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      Inelastic neutron scattering (INS) has been used to obtain the vibrational spectrum of a technical-grade iron-based Fischer–Tropsch catalyst that has been taken from an industrial large-scale unit operation. Whereas previous reports on iron Fischer–Tropsch catalysts highlight the presence of retained carbonaceous species, the INS spectra reveal the additional presence of partially hydrogenated aromatic molecules (see picture).

    28. DNA Separation

      Integrated Bare Narrow Capillary–Hydrodynamic Chromatographic System for Free-Solution DNA Separation at the Single-Molecule Level (pages 5612–5616)

      Zaifang Zhu, Huang Chen, Dr. Wei Wang, Aaron Morgan, Dr. Congying Gu, Prof. Chiyang He, Joann J. Lu and Prof. Shaorong Liu

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300208

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      Turn the volume down: Coupling a high-pressure electroosmotic pump (EOP) and a microfabricated chip-injector with a bare narrow capillary–hydrodynamic chromatographic system (BaNC-HDC), enables samples to be injected at low-picoliter volumes, analytes to be eluted at picoliters per minute, and a wide size range of DNA fragments to be resolved (see picture) rapidly in free solution at the single-molecule level.

    29. Asymmetric Catalysis

      Enantioselective Synthesis of Planar-Chiral Carba-Paracyclophanes: Rhodium-Catalyzed [2+2+2] Cycloaddition of Cyclic Diynes with Terminal Monoynes (pages 5617–5621)

      Tatsuya Araki, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Article first published online: 25 MAR 2013 | DOI: 10.1002/anie.201300696

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      Just ‘plane’ chiral: The high-yielding and highly enantioselective synthesis of carba[10]–[12]paracyclophanes has been achieved with up to 91 % yield and 93 % ee by using the cationic rhodium(I)/(S,S)-bdpp-catalyzed [2+2+2] cycloaddition of cyclic diynes with terminal monoynes under high substrate concentrations. nbd=2,5-norbornadiene, Ns=p-nitrobenzenesulfonyl, Ts=4-toluenesulfonyl.

    30. Bioinorganic Chemistry

      A High-Valent Heterobimetallic [CuIII(μ-O)2NiIII]2+ Core with Nucleophilic Oxo Groups (pages 5622–5626)

      Subrata Kundu, Florian Felix Pfaff, Enrico Miceli, Dr. Ivelina Zaharieva, Dr. Christian Herwig, Dr. Shenglai Yao, Dr. Erik R. Farquhar, Dr. Uwe Kuhlmann, Dr. Eckhard Bill, Prof. Dr. Peter Hildebrandt, Prof. Dr. Holger Dau, Prof. Dr. Matthias Driess, Prof. Dr. Christian Limberg and Dr. Kallol Ray

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201300861

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      Cores and effect: Unlike homobimetallic analogues, the heterobimetallic CuNi bis(μ-oxo) diamond core has nucleophilic oxo groups. A similar heterobimetallic core may, therefore, act as a viable intermediate during the deformylation of fatty aldehydes by cyanobacterial aldehyde decarbonylase.

    31. Heterogeneous Catalysis

      Heterogeneously Catalyzed Aerobic Cross-Dehydrogenative Coupling of Terminal Alkynes and Monohydrosilanes by Gold Supported on OMS-2 (pages 5627–5630)

      Dr. Kazuya Yamaguchi, Dr. Ye Wang, Takamichi Oishi, Dr. Yoshiyuki Kuroda and Prof. Dr. Noritaka Mizuno

      Article first published online: 16 APR 2013 | DOI: 10.1002/anie.201300988

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      Cross-dehydrogenative coupling of various terminal alkynes and monohydrosilanes efficiently proceeded in the presence of gold supported on OMS-2 (Au/OMS-2) using O2 as a terminal oxidant, affording the corresponding alkynylsilanes in moderate to high yields (see picture). The observed catalysis was truly heterogeneous, and the catalyst could be reused at least ten times without a significant loss of its high catalytic performance.

    32. Energy Conversion

      Exceptional Dendrimer-Based Mimics of Diiron Hydrogenase for the Photochemical Production of Hydrogen (pages 5631–5635)

      Dr. Tianjun Yu, Dr. Yi Zeng, Dr. Jinping Chen, Dr. Ying-Ying Li, Prof. Dr. Guoqiang Yang and Prof. Dr. Yi Li

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201301289

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      A three-component homogeneous catalyst system has been prepared with an IrIII complex as the photosensitizer, artificial hydrogenases bearing a diiron core and dendritic frameworks as the proton reduction catalyst, and triethylamine as the sacrificial electron donor. An initial turnover frequency of over 7240 h−1 and a quantum yield of up to 28 % were determined for the photocatalytic evolution of hydrogen.

    33. Cadmium Sulfide Nanoparticles

      Carbon-Coated CdS Petalous Nanostructures with Enhanced Photostability and Photocatalytic Activity (pages 5636–5639)

      Prof. Yong Hu, Xuehui Gao, Le Yu, Yanrong Wang, Dr. Jiqiang Ning, Prof. Shijie Xu and Prof. Xiong Wen (David) Lou

      Article first published online: 5 APR 2013 | DOI: 10.1002/anie.201301709

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      More than just skin deep: Carbon-coated CdS petalous particles have been synthesized through a one-pot solvothermal method. The carbon nanocoating serves multiple functions, including protection of the CdS surface, enhancement of visible light absorption, and facilitating the separation of photogenerated charges. As a result, this CdS-C nanohybrid photocatalyst exhibits significantly enhanced photostability and photocatalytic activity.

    34. Main-Group Chemistry

      Phosphastannirane: A Phosphorus/Tin(II) Lewis Pair that Undergoes Alkyne and Alkene Addition (pages 5640–5643)

      Sarah Freitag, Jens Henning, Dr. Hartmut Schubert and Prof. Dr. Lars Wesemann

      Article first published online: 15 APR 2013 | DOI: 10.1002/anie.201301153

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      Bermuda triangle: The first molecule containing a cyclic three-membered Sn[BOND]C[BOND]P ring has been synthesized and characterized. This SnII[BOND]P Lewis pair reacts at room temperature with alkynes and pentene to give the five-membered cyclic addition products. In the case of pentene, this reaction is reversible at room temperature. Trip=2,4,6-iPr3C6H2.

    35. Main-Group Elements

      Stabilization of a Two-Coordinate [GeCl]+ Cation by Simultaneous σ and π Donation from a Monodentate Carbodiphosphorane (pages 5644–5647)

      Dr. Shabana Khan, Dr. Gopinadhanpillai Gopakumar, Prof. Dr. Walter Thiel and Dr. Manuel Alcarazo

      Article first published online: 12 APR 2013 | DOI: 10.1002/anie.201300677

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      Give me four: The synthesis, structure, and reactivity of [GeCl]+ and [SnCl]+ cations bearing a carbodiphosphorane as ancillary ligand are presented. In the Ge compound, simultaneous σ and π donation from the carbodiphosphorane to Ge is observed (see HOMO (left) and HOMO−1 (right); C black, H white, P orange, Cl green, Ge purple (not visible)), whereas only the σ dative component is present in the Sn analogue.

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