Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 11

March 10, 2014

Volume 53, Issue 11

Pages 2779–3032

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Tuning Ground States of Bis(triarylamine) Dications: From a Closed-Shell Singlet to a Diradicaloid with an Excited Triplet State (Angew. Chem. Int. Ed. 11/2014) (page 2779)

      Yuanting Su, Dr. Xingyong Wang, Xin Zheng, Dr. Zaichao Zhang, Prof. You Song, Yunxia Sui, Prof. Yizhi Li and Prof. Xinping Wang

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201401085

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      Tuning the ground states … … of bis(triphenylamine)benzedine bipolarons through substituent effects is described by X. Wang et al. in their Communication on page 2857 ff. The ground-state structures of three bis(triphenylamine) dications, isolated by using weakly coordinating anions, were tunable through the donor substituents at the para positions of the triphenylamines. This gave rise to closed-shell singlets and a new and stable diradicaloid structure motif with an excited triplet state in the solid state.

    2. You have free access to this content
      Inside Cover: Inhibition of Heme Uptake in Pseudomonas aeruginosa by its Hemophore (HasAp) Bound to Synthetic Metal Complexes (Angew. Chem. Int. Ed. 11/2014) (page 2780)

      Chikako Shirataki, Dr. Osami Shoji, Mitsuyoshi Terada, Prof. Dr. Shin-ichi Ozaki, Dr. Hiroshi Sugimoto, Prof. Dr. Yoshitsugu Shiro and Prof. Dr. Yoshihito Watanabe

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201401090

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      The secreted heme acquisition protein of P. aeruginosa (HasAp), which is shaped like a fish, was found to be able to capture various synthetic iron complexes, such as iron–salophen and iron–phthalocyanine. In their Communication on page 2862 ff., O. Shoji, Y. Watanabe, and co-workers demonstrate the effect of HasAp bound to these unnatural iron complexes on the growth of P. aeruginosa and show that HasAp bound to iron–phthalocyanine inhibits HasAp-mediated iron acquisition.

    3. You have free access to this content
      Inside Back Cover: Lability-Controlled Syntheses of Heterometallic Clusters (Angew. Chem. Int. Ed. 11/2014) (page 3033)

      Dr. Graham N. Newton, Dr. Kiyotaka Mitsumoto, Rong-Jia Wei, Fumichika Iijima, Dr. Takuya Shiga, Prof. Dr. Hiroyuki Nishikawa and Prof. Dr. Hiroki Oshio

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201401079

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      Pick your product from identical reaction mixtures. H. Oshio and co-workers show in their Communication on page 2941 ff., that different heterometallic cyanide-bridged clusters could be selected by controlling the lability of the reaction intermediates though thermally induced electron-transfer-coupled spin transition (ETCST). The Cover Picture shows the assembly of simple building blocks into ETCST-active square intermediates, from which [Fe8Co6] and [Fe8Co4] species were selectively formed.

    4. You have free access to this content
      Back Cover: Polynuclear SmIII Polyamidoamine-Based Dendrimer: A Single Probe for Combined Visible and Near-Infrared Live-Cell Imaging (Angew. Chem. Int. Ed. 11/2014) (page 3034)

      Dr. Alexandra Foucault-Collet, Dr. Chad M. Shade, Iuliia Nazarenko, Prof. Dr. Stéphane Petoud and Dr. Svetlana V. Eliseeva

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201401089

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      Two types of emission under a single excitation wavelength are found for a polynuclear SmIII polyamidoamine-based dendrimer. S. V. Eliseeva, S. Petoud et al. show in their Communication on page 2927 ff. that it emits in the visible and in the near-infrared ranges. The dendrimer proved to be non-cytotoxic, able to be taken up by cells, and capable of performing interchangeably in the visible or near-infrared domains in a proof-of-principle live cell imaging experiment.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Not All Research Is Equal (pages 2782–2783)

      Prof. Adam Heller

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310269

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: Probing the Intracellular Glutathione Redox Potential by In-Cell NMR Spectroscopy (page 2797)

      Dr. Steve Y. Rhieu, Dr. Aaron A. Urbas, Dr. Daniel W. Bearden, Dr. John P. Marino, Dr. Katrice A. Lippa and Dr. Vytas Reipa

      Version of Record online: 6 MAR 2014 | DOI: 10.1002/anie.201401007

      This article corrects:

      Probing the Intracellular Glutathione Redox Potential by In-Cell NMR Spectroscopy1

      Vol. 53, Issue 2, 447–450, Version of Record online: 29 NOV 2013

  5. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Gernot Frenking (pages 2804–2805)

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/anie.201309701

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      “My greatest achievement has been exchanging the engine of a VW Beetle on a remote countryside road in Denmark, only equipped with a simple toolbox and the book Now I Help Myself. My worst nightmare is sitting in the Festspielhaus in Bayreuth and suffering a Wagner opera …” This and more about Gernot Frenking can be found on page 2804.

  7. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  8. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Der Schattensammler. Die allerletzte Autobiografie. By Carl Djerassi. (page 2808)

      Dirk Trauner

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/anie.201400152

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      Translated by Ursula-Maria Mössner. Haymon Verlag, Innsbruck-Wien, 2013. 544 pp., hardcover, € 24.90.—ISBN 978-3852187204

  9. Highlight

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Fluorocarbon Coordination

      Fluorocarbons Modulate the Coordination Sphere of f-Element Complexes (pages 2810–2811)

      Prof. Santiago Alvarez and Dr. Babil Menjón

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201310916

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      Weak yet influential: Fluorocarbons, the least coordinating of all halocarbons, establish secondary coordinative interactions with f elements. These interactions affect the stereochemistry of the complexes and provide examples of coordination polyhedra along distortion paths not seen before (see graphic).

  10. Minireview

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Perovskite Solar Cells

      Perovskite as Light Harvester: A Game Changer in Photovoltaics (pages 2812–2824)

      Dr. Samrana Kazim, Dr. Mohammad Khaja Nazeeruddin, Prof. Michael Grätzel and Dr. Shahzada Ahmad

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201308719

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      Wonder material: The use of perovskites as light absorber in photovoltaic cells has revolutionized the field. Light-to-electricity conversion efficiencies of 15 % have already been achieved, and even without additional hole transport layers efficiencies up to 8 % can be measured. The unique combination of high extinction coefficient along with their ambipolar nature gives perovskites an advantage over quantum-dot- and dye-sensitized solar cells.

  11. Review

    1. Top of page
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    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Dearomatization by Coordination

      Structure and Reactivity of Late Transition Metal η3-Benzyl Complexes (pages 2826–2851)

      Prof. Dr. Barry M. Trost and Dr. Lara C. Czabaniuk

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201305972

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      Transition metals bound to benzyl fragments exhibit a variety of binding patterns, including higher order hapticities with dearomatized arenes. Guided by these first discoveries, η3-benzyl species have been proposed as catalytic intermediates. The synthesis of these complexes and catalytic reactions likely to proceed though the dearomatized intermediate from the past 50 years are discussed.

  12. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Chemical Imaging of Materials

      Assessing Chemical Heterogeneity at the Nanoscale in Mixed-Ligand Metal–Organic Frameworks with the PTIR Technique (pages 2852–2856)

      Dr. Aaron M. Katzenmeyer, Dr. Jerome Canivet, Glenn Holland, Dr. David Farrusseng and Dr. Andrea Centrone

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201309295

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      Beaming with confidence: Mixed-linker metal–organic frameworks with either a homogeneous or a heterogeneous distribution of linkers were synthesized and characterized by PTIR, a novel technique that combines the lateral resolution of AFM with the chemical specificity of IR spectroscopy. By measuring the instantaneous thermal expansion following the absorption of IR light in the sample (see picture), an AFM tip maps the local chemical composition of these materials.

    2. Electronic Structures

      Tuning Ground States of Bis(triarylamine) Dications: From a Closed-Shell Singlet to a Diradicaloid with an Excited Triplet State (pages 2857–2861)

      Yuanting Su, Dr. Xingyong Wang, Xin Zheng, Dr. Zaichao Zhang, Prof. You Song, Yunxia Sui, Prof. Yizhi Li and Prof. Xinping Wang

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/anie.201309458

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      Getting excited: The ground-state electronic structures of three bis(triarylamine) dications (R=H, Me, OMe), which were isolated using weakly coordinating anions and investigated experimentally and theoretically, were tunable by substituent effects. The work provides a new and stable diradicaloid structure motif with an excited triplet state. CS=closed-shell singlet, OS=open-shell singlet, T=excited triplet.

    3. Heme Proteins

      Inhibition of Heme Uptake in Pseudomonas aeruginosa by its Hemophore (HasAp) Bound to Synthetic Metal Complexes (pages 2862–2866)

      Chikako Shirataki, Dr. Osami Shoji, Mitsuyoshi Terada, Prof. Dr. Shin-ichi Ozaki, Dr. Hiroshi Sugimoto, Prof. Dr. Yoshitsugu Shiro and Prof. Dr. Yoshihito Watanabe

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201307889

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      Switching (t)heme: The Pseudomonas aeruginosa hemophore HasAp can bind a variety of synthetic metal complexes such as Fe–salophen (yellow), Fe–phthalocyanine (Fe–Pc; turquoise), and Fe–mesoporphyrin IX (pink). The crystal structures of HasAp bound to these metal complexes showed only small structural perturbations compared to that of heme-bound HasAp. HasAp bound to Fe–Pc inhibits HasAp-mediated heme acquisition in P. aeruginosa.

    4. Nanoscale Critical Phenomena

      Identification of a Critical Intermediate in Galvanic Exchange Reactions by Single-Nanoparticle-Resolved Kinetics (pages 2867–2872)

      Jeremy G. Smith, Qing Yang and Prof. Prashant K. Jain

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201309307

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      No two particles are alike: The probing of galvanic exchange with single-nanoparticle resolution (see picture) revealed a previously unknown critical phenomenon. The formation of a critical void of approximately 20 atomic vacancies in Ag nanoparticles drove rapid spontaneous galvanic exchange, which led to the formation of a Au/Ag nanocage.

    5. Metal–Boron Complexes

      Reactivity of Diruthenium and Dirhodium Analogues of Pentaborane(9): Agostic versus Boratrane Complexes (pages 2873–2877)

      R. S. Anju, Dipak Kumar Roy, Bijan Mondal, K. Yuvaraj, C. Arivazhagan, Koushik Saha, Dr. Babu Varghese and Dr. Sundargopal Ghosh

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310416

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      All in a bind of a different kind: Boron–transition-metal complexes with novel binding modes were synthesized efficiently from diruthenium and dirhodium analogues of pentaborane(9) without the use of preformed boron-containing ligands. The observed binding modes included an agostic interaction, a metalladiborane structure, and a boratrane (see structures IIII). A thioborane with a tantalum center (structure IV) is also described.

    6. Covalent Organic Frameworks

      3D Microporous Base-Functionalized Covalent Organic Frameworks for Size-Selective Catalysis (pages 2878–2882)

      Dr. Qianrong Fang, Dr. Shuang Gu, Jie Zheng, Dr. Zhongbin Zhuang, Prof. Shilun Qiu and Prof. Dr. Yushan Yan

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310500

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      A nifty net: Two novel 3D microporous base-functionalized COFs (BF-COFs, see structure of one framework), were synthesized by the condensation of a tetrahedral alkyl amine with two planar triangular building units, and their catalytic properties were explored in the Knoevenagel condensation reaction. Both BF-COFs showed excellent catalytic activity with high conversion, excellent size selectivity, and good recyclability.

    7. Molecular Recognition

      Folding of Synthetic Homogeneous Glycoproteins in the Presence of a Glycoprotein Folding Sensor Enzyme (pages 2883–2887)

      Dr. Simone Dedola, Dr. Masayuki Izumi, Dr. Yutaka Makimura, Dr. Akira Seko, Dr. Akiko Kanamori, Dr. Masafumi Sakono, Prof. Dr. Yukishige Ito and Prof. Dr. Yasuhiro Kajihara

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309665

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      Folded up: A flexible model to reproduce in vitro folding of a glycoprotein in the presence of UDP-glucose:glycoprotein glucosyltransferase (UGGT) in a mixture containing correctly folded, folding intermediates, and misfolded glycoproteins is described. The data demonstrates that UGGT can re-glucosylate all intermediates, thus indicating that UGGT inspects not only final folded products, but also the glycoprotein folding intermediates.

    8. Mesoporous Materials

      Ultralight Mesoporous Magnetic Frameworks by Interfacial Assembly of Prussian Blue Nanocubes (pages 2888–2892)

      Biao Kong, Jing Tang, Zhangxiong Wu, Jing Wei, Hao Wu, Yongcheng Wang, Prof. Gengfeng Zheng and Prof. Dongyuan Zhao

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201308625

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      Ultralight: A method for the synthesis of three-dimensional iron oxide (3DMI) architectures that feature hierarchically porous frameworks, high surface area (ca. 117 m2 g−1), and ultralow density (ca. 6 mg cm−3) has been developed. These 3DMI materials exhibit high superparamagnetism and tunable hydrophilicity and hydrophobicity, and can be cut and tailored into arbitrary shapes.

    9. Protein Delivery

      Combinatorially Designed Lipid-like Nanoparticles for Intracellular Delivery of Cytotoxic Protein for Cancer Therapy (pages 2893–2898)

      Dr. Ming Wang, Kyle Alberti, Shuo Sun, Carlos Luis Arellano and Prof. Dr. Qiaobing Xu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311245

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      A protein delivery platform that combines a library of lipid-like nanoparticles and a reversible chemical protein modification approach is presented. With ribonuclease A (RNase A) and saporin as representative cytotoxic proteins, the nanoparticles deliver proteins into cancer cells and inhibit cell proliferation. A representative lipidoid protein nanoparticle formulation inhibits tumor cell proliferation in vitro and suppresses tumor growth.

    10. Pigment Design

      Full-Spectrum Photonic Pigments with Non-iridescent Structural Colors through Colloidal Assembly (pages 2899–2903)

      Dr. Jin-Gyu Park, Prof. Shin-Hyun Kim, Sofia Magkiriadou, Tae Min Choi, Dr. Young-Seok Kim and Prof. Vinothan N. Manoharan

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309306

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      Coloration without colorants: A new colloidal assembly method is presented to fabricate “photonic pigments”: microcapsules with non-iridescent structural colors. These pigments exhibit full-spectrum colors that are viewing angle independent.

    11. Supramolecular Chemistry

      Luminescence Enhancement after Adding Stoppers to Europium(III) Nanozeolite L (pages 2904–2909)

      Peng Li, Prof. Dr. Yige Wang, Prof. Dr. Huanrong Li and Prof. Dr. Gion Calzaferri

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201310485

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      Tales of the unexpected: A surprisingly large increase of the luminescence intensity of Eu3+-β-diketonate complexes inside the channels of nanosized zeolite L was observed after modification with an imidazolium stopper molecule.

    12. Plasmonic Nanocatalysts

      Surfactant-Free Nonaqueous Synthesis of Plasmonic Molybdenum Oxide Nanosheets with Enhanced Catalytic Activity for Hydrogen Generation from Ammonia Borane under Visible Light (pages 2910–2914)

      Hefeng Cheng, Dr. Takashi Kamegawa, Dr. Kohsuke Mori and Prof. Dr. Hiromi Yamashita

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309759

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      Making MoO3-x, and hydrogen too: Well-defined molybdenum oxide nanosheets (MoO3-x) were prepared by a facile surfactant-free nonaqueous process. With strong localized surface plasmon resonances, these MoO3-x nanostructures could be used as highly efficient catalysts, and showed dramatically enhanced activity for hydrogen evolution from ammonia borane under visible-light irradiation.

    13. Surface Topography

      Rapid Generation of Cell Gradients by Utilizing Solely Nanotopographic Interactions on a Bio-Inert Glass Surface (pages 2915–2918)

      Dr. Gao Yang, MSc. Yanhua Cao, Dr. Junbing Fan, Dr. Hongliang Liu, Dr. Feilong Zhang, Dr. Pengchao Zhang, Dr. Chao Huang, Prof. Lei Jiang and Prof. Shutao Wang

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309974

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      Making things stick: A nanotopographic gradient strategy was used to rapidly generate cell gradients on a glass surface solely by the introduction of gradient nanodendritic silica. This approach can generate cell gradients rapidly and without chemical modifications owing to the enhanced topographic interactions between the nanodendritic structures and nanoscaled filopodia of the cells.

    14. Proteomics

      Organelle-Specific Activity-Based Protein Profiling in Living Cells (pages 2919–2922)

      Dr. Susan D. Wiedner, Lindsey N. Anderson, Natalie C. Sadler, William B. Chrisler, Vamsi K. Kodali, Dr. Richard D. Smith and Dr. Aaron T. Wright

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201309135

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      Basic targeting: Organelle-targeted chemoproteomics in live cells is possible through tuning the physicochemical properties of an activity-based probe. A weakly basic amine was used to target an activity-based probe to the lysosome. Analysis of in vivo labeled cells by LC–MS/MS showed good probe specificity for lysosome cysteine proteases. The probe was then used to measure the activity of these proteases during autophagy.

    15. Gold Nanoclusters

      A Chiral Gold Nanocluster Au20 Protected by Tetradentate Phosphine Ligands (pages 2923–2926)

      Xian-Kai Wan, Shang-Fu Yuan, Zhi-Wei Lin and Prof. Dr. Quan-Ming Wang

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201308599

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      Gold with a twist: A chiral Au20 nanocluster has been prepared by the reduction of a gold(I)–tetraphosphine complex. The C3 Au20 core can be viewed as the combination of an icosahedral Au13 (see picture, orange) and a helical Y-shaped Au7 motif (green). This is the first structural determination of a gold nanocluster containing an intrinsic chiral inorganic core.

    16. Combined Vis and NIR imaging

      Polynuclear SmIII Polyamidoamine-Based Dendrimer: A Single Probe for Combined Visible and Near-Infrared Live-Cell Imaging (pages 2927–2930)

      Dr. Alexandra Foucault-Collet, Dr. Chad M. Shade, Iuliia Nazarenko, Prof. Dr. Stéphane Petoud and Dr. Svetlana V. Eliseeva

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/anie.201311028

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      The good samarium: As a proof-of-principle, a generation-3 polyamidoamine dendrimer functionalized with thirty-two 2,3-naphthalimide moieties and incorporating eight SmIII ions is used as a bioprobe for combined visible and near-infrared imaging.

    17. Controlled Peptide Folding

      Total Synthesis of Human Hepcidin through Regioselective Disulfide-Bond Formation by using the Safety-Catch Cysteine Protecting Group 4,4′-Dimethylsulfinylbenzhydryl (pages 2931–2934)

      Zoltan Dekan, Dr. Mehdi Mobli, Dr. Michael W. Pennington, Dr. Eileen Fung, Dr. Elizabeta Nemeth and Prof. Paul F. Alewood

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310103

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      Safety first: Native hepcidin, which contains four disulfide bonds, and an earlier proposed disulfide-bond isomer were synthesized with full regiocontrol by employing the safety-catch thiol protecting group 4,4′-dimethylsulfinylbenzhydryl (Msbh). With the synthetically confirmed connectivity, a high-resolution NMR structure of native hepcidin could be obtained. The Msbh group expands the scope of strategies for the regioselective synthesis of disulfide-rich molecules.

    18. Nanoparticle Photocatalysts

      Viable Photocatalysts under Solar-Spectrum Irradiation: Nonplasmonic Metal Nanoparticles (pages 2935–2940)

      Dr. Sarina Sarina, Prof. Dr. Huai-Yong Zhu, Qi Xiao, Prof. Esa Jaatinen, Prof. Jianfeng Jia, Yiming Huang, Prof. Zhanfeng Zheng and Prof. Haishun Wu

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201308145

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      An effective energy boost: Electrons in nonplasmonic transition-metal nanoparticles absorb light energy by interband absorption (see picture) and drive a wide range of well-established organic reactions with high efficiency at ambient temperatures.

    19. Self-Assembly

      Lability-Controlled Syntheses of Heterometallic Clusters (pages 2941–2944)

      Dr. Graham N. Newton, Dr. Kiyotaka Mitsumoto, Rong-Jia Wei, Fumichika Iijima, Dr. Takuya Shiga, Prof. Dr. Hiroyuki Nishikawa and Prof. Dr. Hiroki Oshio

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309374

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      Spin offs: A bulky bidentate ligand stabilizes a [Fe8Co6] cluster. Changing the ligand's electronic state by derivatization with one or two methoxy groups gave a homologous [Fe8Co6] species and a [Fe8Co4] complex, respectively. Reactions at low temperature allowed the isolation of the [Fe8Co4] cluster with all three ligands through a solution-state electron-transfer-coupled spin transition (ETCST) which acts as a self-assembly directing process.

    20. Functionalized Mesoporous Films

      Electrochemically Assisted Generation of Highly Ordered Azide-Functionalized Mesoporous Silica for Oriented Hybrid Films (pages 2945–2950)

      Dr. Neus Vilà, Dr. Jaafar Ghanbaja, Dr. Emmanuel Aubert and Dr. Alain Walcarius

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309447

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      A combination of click chemistry with electrochemically assisted self-assembly enables highly ordered and vertically aligned mesoporous silica films to be generated. These can be derivatized with a variety of organic functional groups that remain active and easily accessible upon immobilization in the oriented matrix.

    21. Photocatalysis

      Monolayer HNb3O8 for Selective Photocatalytic Oxidation of Benzylic Alcohols with Visible Light Response (pages 2951–2955)

      Dr. Shijing Liang, Linrui Wen, Dr. Sen Lin, Dr. Jinhong Bi, Prof. Pingyun Feng, Prof. Xianzhi Fu and Prof. Ling Wu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311280

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      One layer is enough: Surface complexes between monolayer HNb3O8 and reactants help to remove the bandgap limitation for visible light photocatalysis. This catalyst exhibited exceptional performance for the selective oxidation of alcohols. This research provides proof-of-concept for the rational fabrication of visible light photocatalysts.

    22. Asymmetric Catalysis

      Highly Chemo-, Regio-, and Enantioselective Rhodium-Catalyzed Cross-Cyclotrimerization of Two Different Alkynes with Alkenes (pages 2956–2959)

      Jun Hara, Mana Ishida, Masayuki Kobayashi, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201310336

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      Cross-training: It has been established that a cationic rhodium(I)/(R)-tol-binap complex catalyzes the cross-cyclotrimerization of silylacetylenes, di-tert-butyl acetylenedicarboxylates, and acrylamides with excellent chemo-, regio-, and enantioselectivities. Unsymmetrical alkynoates can also be employed in place of di-tert-butyl acetylenedicarboxylate for this process, but with a reduced chemoselectivity. cod=cyclo-1,5-octadiene.

    23. Prodrugs

      A Bis(dipyridophenazine)(2-(2-pyridyl)pyrimidine-4-carboxylic acid)ruthenium(II) Complex with Anticancer Action upon Photodeprotection (pages 2960–2963)

      Dr. Tanmaya Joshi, Vanessa Pierroz, Cristina Mari, Lea Gemperle, Priv.-Doz. Dr. Stefano Ferrari and Prof. Dr. Gilles Gasser

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309576

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      Light, ruthenium, anticancer action! Modifying substitutionally inert [Ru(dppz)2(CppH)]2+ to become a 3-(4,5-dimethoxy-2-nitrophenyl)-2-butyl ester renders it inactive to both cancerous (HeLa and U2OS) and non-cancerous (MRC-5) cells. Cytotoxic effects of the complex can be unleashed upon illumination. CppH=2-(2-pyridyl)pyrimidine-4-carboxylic acid; dppz=dipyrido[3,2-a:2′,3′-c]phenazine.

    24. Phosphine Catalysis

      Phosphine-Catalyzed Enantioselective γ-Addition of 3-Substituted Oxindoles to 2,3-Butadienoates and 2-Butynoates: Use of Prochiral Nucleophiles (pages 2964–2968)

      Tianli Wang, Weijun Yao, Fangrui Zhong, Guo Hao Pang and Prof. Dr. Yixin Lu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201307757

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      Oxindoles and allenoates: The phosphine-catalyzed γ-addition of allenoates to oxindoles enabled the synthesis of oxindole derivatives that bear an all-carbon quaternary stereogenic center at the 3-position in high yields and with excellent enantioselectivity. The synthetic potential of the addition products was demonstrated by the formal total synthesis of two natural products.

    25. Hypergolic Ionic Liquids

      Borohydride Ionic Liquids and Borane/Ionic-Liquid Solutions as Hypergolic Fuels with Superior Low Ignition-Delay Times (pages 2969–2972)

      Songqing Li, Prof. Dr. Haixiang Gao and Prof. Dr. Jean'ne M. Shreeve

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201309044

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      No more delay: Boron hydrides show marked potential in accelerating the ignition of hypergolic liquid fuels. The borohydride-based ionic liquids (IL) 1 and 2 were investigated along with borane additives. IL 1 exhibited the shortest ignition-delay time of any known hypergolic ILs, and the triethylamine–borane complex is the most efficient hypergolic additive examined to date.

    26. Porphyrin Sensitizers

      Molecular Engineering of Push–Pull Porphyrin Dyes for Highly Efficient Dye-Sensitized Solar Cells: The Role of Benzene Spacers (pages 2973–2977)

      Aswani Yella, Chi-Lun Mai, Shaik M. Zakeeruddin, Shu-Nung Chang, Chi-Hung Hsieh, Chen-Yu Yeh and Michael Grätzel

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309343

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      Not just to fill a gap: Porphyrins are promising sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. The incorporation of a 2,1,3-benzothiadiazole moiety in a donor–acceptor zinc porphyrin as a π-conjugated linker between the anchoring group and the chromophore (see structure) broadened the absorption spectra to fill the valley between the Soret and Q bands and led to efficient power conversion.

    27. Asymmetric Catalysis

      Enantioselective Palladium-Catalyzed Insertion of α-Aryl-α-diazoacetates into the O[BOND]H Bonds of Phenols (pages 2978–2981)

      Xiu-Lan Xie, Prof. Shou-Fei Zhu, Jun-Xia Guo, Yan Cai and Prof. Qi-Lin Zhou

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309820

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      Things and Ar–OHs: A palladium-catalyzed asymmetric O[BOND]H insertion of α-aryl-α-diazoacetates into phenols was developed. As well as giving high yields and excellent enantioselectivity, this reaction exhibits a broad substrate scope under mild reaction conditions, thus providing an efficient method for the preparation of synthetically useful optically active α-aryl-α-aryloxyacetates.

    28. Coordination Chemistry

      Elevated Catalytic Activity of Ruthenium(II)–Porphyrin-Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N-Heterocyclic Carbene Ligands (pages 2982–2987)

      Ka-Ho Chan, Dr. Xiangguo Guan, Dr. Vanessa Kar-Yan Lo and Prof. Dr. Chi-Ming Che

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309888

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      Por complexes, working like crazy: Bis(N-heterocyclic carbene) (NHC) ruthenium(II) porphyrin (Por) complexes showed unprecedentedly high catalytic activity toward alkene cyclopropanation (see scheme; TOF/TON=turnover frequency/number), carbene C[BOND]H, S[BOND]H, N[BOND]H, and O[BOND]H insertion, alkene aziridination, and nitrene C[BOND]H insertion. Highly enantioselective carbene and nitrene C[BOND]H insertion and addition to C[DOUBLE BOND]C bonds was also possible.

    29. Natural Product Synthesis

      Total Synthesis of the Isodon Diterpene Sculponeatin N (pages 2988–2991)

      Dr. Benjamin J. Moritz, Dr. Daniel J. Mack, Liuchuan Tong and Prof. Regan J. Thomson

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310060

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      Sculpting sculponeatin: The total synthesis of sculponeatin N, a bioactive polycyclic diterpene isolated from Isodon sculponeatus, is reported. Key features of the synthesis include diastereoselective Nazarov and ring-closing metathesis reactions, and highly efficient formation of the bicyclo[3.2.1]octane ring system by a reductive radical cyclization.

    30. Triphyrins(n.1.1)

      Synthesis and Switching the Aromatic Character of Oxatriphyrins(2.1.1) (pages 2992–2996)

      Dr. Miłosz Pawlicki, Karolina Hurej, Dr. Ludmiła Szterenberg and Prof. Lechosław Latos-Grażyński

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310129

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      Going for a spin: The precisely crafted thiophene-fused oxatriphyrins(2.1.1) show an aromatic character consistent with 14 π or 18 π delocalization pathways. The aromaticity is strongly dependent on a thiophene incorporation mode and can be switched to anti-aromatic (16 π electrons) or non-aromatic by reduction with a zinc amalgam. Both reduced structures are stable as boron(III) complexes.

    31. Synthetic Methods

      Asymmetric Vinylogous Diels–Alder Reactions Catalyzed by a Chiral Phosphoric Acid (pages 2997–3000)

      Xu Tian, Dr. Nora Hofmann and Prof. Dr. Paolo Melchiorre

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201310487

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      Further and further: A vinylogous Diels–Alder reaction that is catalyzed by a commercially available chiral phosphoric acid has been developed. A range of structurally diverse complex tetrahydrocarbazoles were obtained in high chemical yields and with excellent stereoselectivity. It was thus demonstrated that the synthetic utility of the Diels–Alder reaction can be extended to include a vinylogous reactivity space.

    32. C[BOND]C Activation

      Highly Enantioselective Rhodium(I)-Catalyzed Activation of Enantiotopic Cyclobutanone C[BOND]C Bonds (pages 3001–3005)

      Laetitia Souillart, Dr. Evelyne Parker and Prof. Dr. Nicolai Cramer

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311009

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      All in (cyclobutan)one: The enantioselective direct C[BOND]C activation of cyclobutanones was achieved by using chiral rhodium(I) catalysts. The intermediate rhodacyclopentanone reacts with a wide variety of tethered olefins to deliver complex bicyclic ketones in high yield. Despite operating at 130 °C, the process is characterized by outstanding enantioselectivity with the e.r. generally greater than 99.5:0.5.

    33. Fullerene Chemistry

      Regioselective Electrosynthesis of Rare 1,2,3,16-Functionalized [60]Fullerene Derivatives (pages 3006–3010)

      Yang Xiao, Dr. San-E Zhu, Ding-Jia Liu, Dr. Mitsuaki Suzuki, Prof. Dr. Xing Lu and Prof. Dr. Guan-Wu Wang

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201310565

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      Exercizing control: The highly regioselective reaction of dianionic fullerene species, generated by electroreduction of a fulleroindoline, with benzyl bromide or ethyl bromoacetate affords the rare 1,2,3,16-adducts of C60 (see scheme). Intriguingly, either one or two alkyl groups can be selectively introduced onto the fullerene surface in the absence or presence of sodium hydride. The high regioselectivity is governed by both the charge distribution and steric factors.

    34. Natural Product Biosynthesis

      Heterologous Reconstitution of Ikarugamycin Biosynthesis in E. coli (pages 3011–3014)

      M.Sc. Janine Antosch, Dipl.-Chem. Françoise Schaefers and Dr. Tobias A. M. Gulder

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310641

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      Small cluster, big molecule: Polycyclic tetramate macrolactams (PTMs) are a family of structurally diverse, bioactive natural products. Valuable insight into the compact biosynthesis of PTMs has been obtained by heterologous expression of the newly identified ikarugamycin biosynthetic gene cluster in E. coli. The heterologous production of PTMs with the established method will allow many cryptic PTM gene clusters to be chemically unlocked in the future.

    35. Noble 2D Materials

      Two Dimensional Materials Beyond MoS2: Noble-Transition-Metal Dichalcogenides (pages 3015–3018)

      Dr. Pere Miró, Mahdi Ghorbani-Asl and Prof. Dr. Thomas Heine

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309280

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      Show you're metal: The structure and electronic structure of layered noble-transition-metal dichalcogenides MX2 with metals M (Pt and Pd) and chalcogenides X (S, Se, and Te) have been investigated with periodic density functional theory calculations. The MS2 monolayers are indirect band-gap semiconductors whereas the MSe2 and MTe2 analogues show a significant decrease in their band-gaps and can even become semimetallic or metallic materials.

    36. Spin-Crossover Films

      Iron(II) Spin-Crossover Complexes in Ultrathin Films: Electronic Structure and Spin-State Switching by Visible and Vacuum-UV Light (pages 3019–3023)

      E. Ludwig, H. Naggert, Dr. M. Kalläne, S. Rohlf, E. Kröger, Dr. A. Bannwarth, A. Quer, Dr. K. Rossnagel, Prof. Dr. L. Kipp and Prof. Dr. F. Tuczek

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201307968

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      Spin-state switching in ultrathin films of a FeII spin crossover complex deposited on Au(111) is achieved by irradiation with visible and vacuum-UV light. The electronic structure of the complex is determined by UPS, which allows the thermal as well as light-induced transition between the high-spin (HS) and the low-spin (LS) form to be monitored.

    37. Covalent Protein Modification

      N-Terminal Protein Modification by Substrate-Activated Reverse Proteolysis (pages 3024–3028)

      Dr. Sandra Liebscher, Dr. Michael Schöpfel, Dr. Tobias Aumüller, Ariunkhur Sharkhuukhen, Dr. Andreas Pech, Dr. Eva Höss, Dr. Christoph Parthier, Dr. Günther Jahreis, Prof. Dr. Milton T. Stubbs and Prof. Dr. Frank Bordusa

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201307736

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      Trypsiligase catalyzes the selective modification of proteins with the substrate-mimetic 4-guanidino phenyl ester (OGp). Modification proceeds with quantitative product yields under native (aqueous) conditions. The variant possesses a disordered zymogen-like activation domain, effectively suppressing the hydrolysis reaction, which is converted to an active conformation in the presence of appropriate substrates.

    38. Main-Group Compounds

      Probing the Zintl–Klemm Concept: A Combined Experimental and Theoretical Charge Density Study of the Zintl Phase CaSi (pages 3029–3032)

      M.Sc. Iryna M. Kurylyshyn, Prof. Dr. Thomas F. Fässler, M.Sc. Andreas Fischer, Dipl.-Phys. Christoph Hauf, Dr. Georg Eickerling, Dipl.-Phys. Manuel Presnitz and Prof. Dr. Wolfgang Scherer

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201308888

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      Over-Zintl-ified? The nature of chemical bonding in the Zintl phase CaSi has been analyzed by experimental and theoretical charge density analyses. The presence of covalent Si[BOND]Si interactions supports this fundamental bonding concept. Now however, clear experimental evidence is provided that the cation–polyanion interaction cannot be solely described as purely ionic, a potential explanation of the unexpected metallic behavior.

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