Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

June 3, 2013

Volume 52, Issue 23

Pages 5887–6110

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Exploring the Mechanism of IR–UV Double-Resonance for Quantitative Spectroscopy of Protonated Polypeptides and Proteins (Angew. Chem. Int. Ed. 23/2013) (page 5887)

      Natalia S. Nagornova, Thomas R. Rizzo and Oleg V. Boyarkin

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201303560

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      Determination of the 3D structures … of large molecules challenges spectroscopy to perform better. In their Communication on page 6002 ff. O. V. Boyarkin et al. use IR–UV double-resonance cold-ion spectroscopy for conformational assignment of the electronic spectra of a protonated decapeptide and for measurements of absolute absorption cross-sections of vibrational transitions in this species. The limitations of the IR–UV double-resonance approach are illustrated by measuring the gas-phase IR spectrum of a cold, protonated intact protein.

    2. You have free access to this content
      Inside Cover: Improving Hydrothermal Carbonization by Using Poly(ionic liquid)s (Angew. Chem. Int. Ed. 23/2013) (page 5888)

      Pengfei Zhang, Dr. Jiayin Yuan, Dr. Tim-Patrick Fellinger, Prof.Dr. Markus Antonietti, Prof. Dr. Haoran Li and Prof. Dr. Yong Wang

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/anie.201303272

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      Sugars can be directly … … transformed into porous nitrogen-doped carbon materials in the presence of poly(ionic liquid)s. In their Communication on page 6028 ff., J. Yuan, Y. Wang, and co-workers describe the application of this method to synthesize carbon particles 20–50 nm in size and also to synthesize, in one step, nitrogen-doped carbon materials embedded with core–shell Au–Pd nanoparticles.

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      Inside Back Cover: On the Structures of 55-Atom Transition-Metal Clusters and Their Relationship to the Crystalline Bulk (Angew. Chem. Int. Ed. 23/2013) (page 6111)

      Dr. Thomas Rapps, Prof. Dr. Reinhart Ahlrichs, Eugen Waldt, Prof. Dr. Manfred M. Kappes and Dr. Detlef Schooss

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201303643

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      Homonuclear 55-atom … … transition-metal clusters of the 3d and 4d elements show a correlation between the cluster structure type (atomic symbol, bottom right corner) and the bulk lattice morphology (top left corner). This link is found by gas-phase electron diffraction and DFT calculations. In their Communication on page 6102 ff., D. Schooss et al. also describe how the cluster structure types differ in maximum atomic coordination numbers in analogy to the coordination numbers in the bulk lattices.

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      Back Cover: Indeno[2,1-b]fluorene: A 20-π-Electron Hydrocarbon with Very Low-Energy Light Absorption (Angew. Chem. Int. Ed. 23/2013) (page 6112)

      Dr. Akihiro Shimizu, Dr. Ryohei Kishi, Prof. Masayoshi Nakano, Dr. Daisuke Shiomi, Prof. Kazunobu Sato, Prof. Takeji Takui, Dr. Ichiro Hisaki, Prof. Mikiji Miyata and Prof. Yoshito Tobe

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201303391

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      10,12-dimesitylindeno[2,1-b]fluorene … … exhibits a very-low-energy light-absorption band that extends to 2000 nm, despite its small conjugation space of only 20 π electrons. This first example of a meta-quinodimethane embedded in an indenofluorene framework is presented by Y. Tobe and co-workers in their Communication on page 6076 ff. The unusual absorption behavior is attributed to the moderate singlet biradical character and the small π-conjugation space of the hydrocarbon.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    1. 50 Years Ago ... (page 5902)

      Version of Record online: 30 MAY 2013 | DOI: 10.1002/anie.201303275

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    1. Christian Griesinger (pages 5912–5913)

      Version of Record online: 13 MAY 2013 | DOI: 10.1002/anie.201207942

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      “My favorite book is Doktor Faustus. The natural talent I would like to be gifted with being able to improvise on the piano. …” This and more about Christian Griesinger can be found on page 5912.

  6. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    1. Efficient Preparations of Fluorine Compounds. Edited by Herbert W. Roesky. (page 5914)

      Peer Kirsch

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201303020

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      John Wiley & Sons, Hoboken, 2012. 480 pp., hardcover, € 109.00.—ISBN 978-1118078563

  7. Highlights

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

      Computational Studies and Experimental Results—An Example of Excellent Teamwork in Studying Carbocyclization (pages 5916–5918)

      M. Sc. Indre Thiel and Dr. Marko Hapke

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201302496

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      In silico veritas? Maybe not the whole truth, but very helpful suggestions and guidelines for the experimental work can be deduced from computational studies on Rh-catalyzed [3+2+1] cycloaddition reactions for the construction of cis-fused bicyclohexenones from alkylidenecyclopropanes and carbon monoxide.

    2. C[BOND]C and C[BOND]N Coupling

      Ambient-Light-Mediated Copper-Catalyzed C[BOND]C and C[BOND]N Bond Formation (pages 5919–5921)

      Ing. Michal Majek and Prof. Dr. Axel Jacobi von Wangelin

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201301843

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      Bringing to light: The rediscovery of visible light as an abundant energy source for organic reactions has most recently brought copper-catalyzed coupling reactions to the center of attention. This Highlight summarizes the most significant advancements in the field of C[BOND]C and C[BOND]N coupling reactions in which covalent copper–substrate complexes are photo-activated.

  8. Correspondence

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

      Critical Comments on “One Molecule, Two Atoms, Three Views, Four Bonds?” (pages 5922–5925)

      Prof. Gernot Frenking and Markus Hermann

      Version of Record online: 29 APR 2013 | DOI: 10.1002/anie.201301485

      The arguments that are given in the original trialogue in favor of a quadruply bonded C2, in which the bond is claimed to be stronger than that in HC[TRIPLE BOND]CH, are judged invalid by the authors of this Correspondence. They also disagree with some statements about the stability of molecules and the virtue of chemical research beyond synthetic chemistry.

    2. A Response to the Critical Comments on “One Molecule, Two Atoms, Three Views, Four Bonds?” (pages 5926–5928)

      Dr. David Danovich, Prof. Sason Shaik, Prof. Henry S. Rzepa and Prof. Roald Hoffmann

      Version of Record online: 29 APR 2013 | DOI: 10.1002/anie.201302350

      The criticism expressed by Frenking and Hermann on the notion of quadruple bonding in C2 is answered using hard facts. Both experimental and computational data gauge the strength of the fourth bond as 16 kcal mol−1. The authors agree that chemical research goes profitably beyond “synthetic” chemistry.

  9. Minireview

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

      Light-Induced Click Reactions (pages 5930–5938)

      Dr. Mehmet Atilla Tasdelen and Prof. Dr. Yusuf Yagci

      Version of Record online: 7 MAY 2013 | DOI: 10.1002/anie.201208741

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      Shine a light: Owing to their ease of implementation and the availability of inexpensive light sources, light-induced click reactions (see picture) have become a powerful methodology for the synthesis of materials and the modification of biomaterials. Fundamental aspects of these reactions and their application in surface and materials science, as well as their potential in the study of biomolecular systems are highlighted.

  10. Review

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

      Nanoscale Chemical Imaging Using Tip-Enhanced Raman Spectroscopy: A Critical Review (pages 5940–5954)

      Thomas Schmid, Lothar Opilik, Carolin Blum and Renato Zenobi

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201203849

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      Getting to the point: Tip-enhanced Raman spectroscopy (TERS) combines the chemical information of Raman spectroscopy experiments with a high signal enhancement and high spatial resolution. The current status of the technique is described together with the shortcomings and pitfalls that have to be considered for spectroscopic imaging by TERS.

  11. Communications

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

      Photothermally Activated Hybrid Films for Quantitative Confined Release of Chemical Species (pages 5956–5960)

      Dr. Paolo Matteini, Dr. Francesca Tatini, Dr. Lapo Luconi, Dr. Fulvio Ratto, Dr. Francesca Rossi, Dr. Giuliano Giambastiani and Prof. Roberto Pini

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201207986

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      Illuminating films of a porous chitosan matrix containing gold nanorods and thermosensitive micelles loaded with a chemical stimulates local photothermal conversion of the gold nanorods. The heat produced activates the ejection of the chemical from the micelles (see scheme), and causes the transient permeabilization of adjacent cell membranes, resulting in a selective cellular uptake of the released chemical with control over spatiotemporal parameters and dosage.

    2. Synthetic Methods

      Highly Atom-Efficient Oxidation of Electron-Deficient Internal Olefins to Ketones Using a Palladium Catalyst (pages 5961–5964)

      Dr. Takato Mitsudome, Syuhei Yoshida, Dr. Tomoo Mizugaki, Prof. Dr. Koichiro Jitsukawa and Prof. Dr. Kiyotomi Kaneda

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301611

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      A 100 % atom-efficient synthesis of ketones from electron-deficient internal olefins was achieved using O2 as a “green” oxidant (see scheme, DMA=N,N-dimethylacetamide, EWG=electron-withdrawing group). Various electron-deficient olefins were oxidized to the corresponding ketones with over 99 % selectivity and without the formation of olefin isomers or their oxidized products.

    3. Ultrabright Nanoparticles

      Prevention of Self-Quenching in Fluorescent Silica Nanoparticles by Efficient Energy Transfer (pages 5965–5968)

      Dr. Damiano Genovese, Dr. Sara Bonacchi, Dr. Riccardo Juris, Prof. Marco Montalti, Prof. Luca Prodi, Dr. Enrico Rampazzo and Prof. Nelsi Zaccheroni

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301155

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      Stars that shine bright: A high local dye concentration in doped silica-based core–shell nanoparticles causes self-quenching and spectral broadening (top images). This phenomenon jeopardizes the potential advantages of heavily doped systems. Förster resonance energy transfer (FRET) to an acceptor co-included in the silica led to ultrabright nanoparticles (bottom images) with a preselected narrow-band emission and a pseudo-Stokes shift of 129 nm.

    4. Electron Microscopy

      Direct Atomic-Resolution Observation of Two Phases in the Li1.2Mn0.567Ni0.166Co0.067O2 Cathode Material for Lithium-Ion Batteries (pages 5969–5973)

      Dr. Haijun Yu, Dr. Ryo Ishikawa, Dr. Yeong-Gi So, Dr. Naoya Shibata, Prof. Tetsuichi Kudo, Prof. Haoshen Zhou and Prof. Yuichi Ikuhara

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301236

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      About phase: The coexistence of rhombohedral LiTMO2 (TM=Ni, Co, or Mn) and monoclinic Li2MnO3-like structures inside Li1.2Mn0.567Ni0.166Co0.067O2 is revealed directly at atomic resolution. The hetero-interface along the [001]rh/[103]mon zone axis direction is demonstrated, indicating the two-phase nature of these lithium-rich cathode materials (green Li, blue Mn, red O, cyan TM).

    5. Protein Photocontrol

      Different Photochemical Events of a Genetically Encoded Phenyl Azide Define and Modulate GFP Fluorescence (pages 5974–5977)

      Samuel C. Reddington, Dr. Pierre J. Rizkallah, Dr. Peter D. Watson, Rachel Pearson, Dr. Eric M. Tippmann and Dr. D. Dafydd Jones

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201301490

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      Expanding the genetic code opens new avenues to modulate protein function in real time. By genetically incorporating photoreactive phenyl azide, the fluorescent properties of green fluorescent protein (GFP) can be modulated by light. Depending on the residue in GFP programmed to incorporate the phenyl azide, different effects on function and photochemical pathways are observed.

    6. Zintl Phases

      LiBSi2: A Tetrahedral Semiconductor Framework from Boron and Silicon Atoms Bearing Lithium Atoms in the Channels (pages 5978–5982)

      Michael Zeilinger, Prof. Dr. Leo van Wüllen, Daryn Benson, Verina F. Kranak, Sumit Konar, Prof. Dr. Thomas F. Fässler and Prof. Dr. Ulrich Häussermann

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301540

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      Silicon swallows up boron: The novel open tetrahedral framework structure (OTF) of the Zintl phase LiBSi2 was made by applying high pressure to a mixture of LiB and elemental silicon. The compound represents a new topology in the B-Si net (called tum), which hosts Li atoms in the channels (see picture). LiBSi2 is the first example where B and Si atoms form an ordered common framework structure with B engaged exclusively in heteronuclear B[BOND]Si contacts.

    7. Heterogeneous Catalysis

      You have full text access to this OnlineOpen article
      Correlating Metal Poisoning with Zeolite Deactivation in an Individual Catalyst Particle by Chemical and Phase-Sensitive X-ray Microscopy (pages 5983–5987)

      Dr. Javier Ruiz-Martínez, Dr. Andrew M. Beale, Dr. Upakul Deka, Dr. Mathew G. O'Brien, Dr. Paul D. Quinn, Dr. J. Fred W. Mosselmans and Prof. Dr. Bert M. Weckhuysen

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201210030

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      Fluid catalytic cracking (FCC) is the main conversion process used in oil refineries. An X-ray microscopy method is used to show that metal poisoning and related structural changes in the zeolite active material lead to a non-uniform core–shell deactivation of FCC catalyst particles. The study links the detrimental effect of V and Ni poisoning with zeolite destruction and dealumination in a spatial manner within a single FCC catalyst particle.

    8. Photoresponsive Polymers

      Liquid-Crystalline Polymer and Block Copolymer Domain Alignment Controlled by Free-Surface Segregation (pages 5988–5991)

      Kei Fukuhara, Yasuyoshi Fujii, Yuki Nagashima, Dr. Mitsuo Hara, Prof. Shusaku Nagano and Prof. Takahiro Seki

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300560

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      An orientational change from homeotropic to planar of liquid crystal (LC) mesogens and the microphase separation (MPS) domains is attained by the segregated skin layer at the free surface. This allows for an efficient in-plane photoalignment of the cylindrical domains. The surface segregation strategy is very simple and is therefore expected to open up new possibilities for the orientation control of various types of LC materials.

    9. Carbocycles

      Dibenzopentalenes from B(C6F5)3-Induced Cyclization Reactions of 1,2-Bis(phenylethynyl)benzenes (pages 5992–5996)

      Dr. Chao Chen, Dr. Marcel Harhausen, René Liedtke, Kathrin Bussmann, Prof. Aiko Fukazawa, Prof. Shigehiro Yamaguchi, Prof. Jeffrey L. Petersen, Dr. Constantin G. Daniliuc, Dr. Roland Fröhlich, Dr. Gerald Kehr and Prof. Gerhard Erker

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201300871

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      'Lene' and mean: The strong Lewis acid B(C6F5)3 efficiently converts some bis(arylethynyl)benzenes into dibenzopentalenes through a series of Lewis acid induced cyclization reactions at room temperature. Thus the reaction has the potential to be useful in the synthesis of substituted dibenzopentalene derivatives which are difficult to make by conventional means.

    10. Lithium Ion Battery

      Catalyst-free Direct Growth of a Single to a Few Layers of Graphene on a Germanium Nanowire for the Anode Material of a Lithium Battery (pages 5997–6001)

      Hyungki Kim, Yoonkook Son, Chibeom Park, Prof. Dr. Jaephil Cho and Prof. Dr. Hee Cheul Choi

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300896

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      Direct growth of a single to a few layers of graphene on a germanium nanowire (Gr/Ge NW; see picture) was achieved by a metal-catalyst-free chemical vapor deposition (CVD) process. The Gr/Ge NW was used as anode in a lithium ion battery. This material has a specific capacity of 1059 mA h g−1 at 4.0 C, a long cycle life over 200 cycles, and a high capacity retention of 90 %.

    11. Structure Elucidation

      Exploring the Mechanism of IR–UV Double-Resonance for Quantitative Spectroscopy of Protonated Polypeptides and Proteins (pages 6002–6005)

      Natalia S. Nagornova, Thomas R. Rizzo and Oleg V. Boyarkin

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201301656

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      Spectroscopic fingerprint: Infrared–ultraviolet double resonance photodissociation is used for conformational assignment of the electronic spectra of a cold protonated decapeptide (see picture). A mechanism of the IR–UV depletion spectroscopy is proposed and a procedure of using it for measurements of absolute absorption cross-sections of vibrational transitions is elaborated.

    12. Foldamers

      Helical Oligomers of Thiazole-Based γ-Amino Acids: Synthesis and Structural Studies (pages 6006–6010)

      Loïc Mathieu, Dr. Baptiste Legrand, Cheng Deng, Dr. Lubomir Vezenkov, Emmanuel Wenger, Dr. Claude Didierjean, Dr. Muriel Amblard, Dr. Marie-Christine Averlant-Petit, Dr. Nicolas Masurier, Prof. Vincent Lisowski, Prof. Jean Martinez and Dr. Ludovic T. Maillard

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201302106

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      9-Helix: 4-Amino(methyl)-1,3-thiazole-5-carboxylic acids (ATCs) were synthesized as new γ-amino acid building blocks. The structures of various ATC oligomers were analyzed in solution by CD and NMR spectroscopy and in the solid state by X-ray crystallography. The ATC sequences adopted a well-defined 9-helix structure in the solid state and in aprotic and protic organic solvents as well as in aqueous solution.

    13. Click Chemistry

      Plasmon Resonance Scattering Spectroscopy at the Single-Nanoparticle Level: Real-Time Monitoring of a Click Reaction (pages 6011–6014)

      Lei Shi, Chao Jing, Dr. Wei Ma, Dr. Da-Wei Li, Jonathan E. Halls, Prof. Frank Marken and Prof. Yi-Tao Long

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301930

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      A method based on plasmon resonance Rayleigh scattering (PRRS) spectroscopy and dark-field microscopy (DFM) was established for the real-time monitoring of a click reaction at the single-nanoparticle level. Click reactions on the surface of single gold nanoparticles (GNPs) result in interparticle coupling, which leads to a red-shift of the λmaxλmax=43 nm) in the PRRS spectra and a color change of the single gold nanoparticles in DFM (from green to orange).

    14. Total Synthesis

      General Entry to Aspidosperma Alkaloids: Enantioselective Total Synthesis of (−)-Aspidophytine (pages 6015–6018)

      Rongwen Yang and Prof. Dr. Fayang G. Qiu

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201302442

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      A general approach toward the asymmetric total synthesis of various aspidosperma alkaloids includes the combination of a C[BOND]H bond activation with a Heck-type coupling, and the stereo-controlled formation of piperidine and pyrrolidine rings as key steps. The feasibility of this approach was demonstrated with the total synthesis of aspidophytine in 18 steps from 4,4-disubstituted cyclohexanedione and 2,3-dimethoxyaniline (see scheme).

    15. Crystal Coalescence

      Preservation of Lattice Orientation in Coalescing Imperfectly Aligned Gold Nanowires by a Zipper Mechanism (pages 6019–6023)

      Jun Xu, Yawen Wang, Xiaoying Qi, Cuicui Liu, Jiating He, Prof. Hua Zhang and Prof. Hongyu Chen

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301271

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      Parallel-stacked gold nanowires (NWs) in a ring conformation are induced to coalesce, forming solid seamless rings. The axial lattice orientation of the original Au NWs is preserved in the coalesced rings (see picture; scale bars 2 nm, insets 50 nm). A zipper mechanism is proposed to reconcile the three major events in coalescing nanocrystals: ligand loss, lattice alignment, and coalescence.

    16. Fluorinated Compounds

      Manganese-Catalyzed Oxidative Benzylic C–H Fluorination by Fluoride Ions (pages 6024–6027)

      Wei Liu and Prof. John T. Groves

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301097

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      An efficient protocol for the selective fluorination of benzylic C[BOND]H bonds is described. The process is catalyzed by manganese salen complexes and uses nucleophilic fluorine sources, such as triethylamine trihydrofluoride and KF. Reaction rates are sufficiently high (30 min) to allow adoption for the incorporation of 18F fluoride sources for PET imaging applications.

    17. Nanomaterials

      Improving Hydrothermal Carbonization by Using Poly(ionic liquid)s (pages 6028–6032)

      Pengfei Zhang, Dr. Jiayin Yuan, Dr. Tim-Patrick Fellinger, Prof.Dr. Markus Antonietti, Prof. Dr. Haoran Li and Prof. Dr. Yong Wang

      Version of Record online: 16 APR 2013 | DOI: 10.1002/anie.201301069

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      Pores for thought: Porous nitrogen-doped carbon materials (HTC Carbon with PILs) composed of spherical nanoparticles, and also those with Au–Pd core–shell nanoparticles embedded (Au–Pd@N-Carbon) were synthesized. These materials can be prepared from sugars by hydrothermal carbonization (160–200 °C) in the presence of poly(ionic liquid)s (PILs), which act as a stabilizer, pore-generating agent, and nitrogen source.

    18. Synthetic Methods

      Rhodium(III)-Catalyzed Redox-Neutral Coupling of N-Phenoxyacetamides and Alkynes with Tunable Selectivity (pages 6033–6037)

      Prof. Guixia Liu, Yangyang Shen, Zhi Zhou and Prof. Xiyan Lu

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300881

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      Give it a tweak: A novel oxidizing directing group was developed for a rhodium(III)-catalyzed C[BOND]H functionalization of N-phenoxyacetamides with alkynes. A small change in the reaction conditions leads to either ortho-hydroxyphenyl-substituted enamides or cyclization to deliver benzofurans with high selectivity (see scheme; Cp*=C5Me5).

    19. Cascade Reactions

      Catalytic Generation and Selective Heterocoupling of Two Electron-Rich Alkenes (pages 6038–6042)

      Alicia Galván, Dr. Jonás Calleja, Prof. Dr. Francisco J. Fañanás and Prof. Félix Rodríguez

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201209870

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      Complex heterocyclic products were synthesized from simple alkynamine and alkynol derivatives in a double cycloisomerization/heterodimerization cascade reaction (see scheme). The reaction includes the heterocoupling reaction of two different electron-rich alkenes and leads to the formation of four new bonds and three stereocenters (two of them quaternary).

    20. Direct Amination

      Directed Amination of Non-Acidic Arene C[BOND]H Bonds by a Copper–Silver Catalytic System (pages 6043–6046)

      Ly Dieu Tran, James Roane and Prof. Dr. Olafs Daugulis

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300135

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      Amine meets arene: A method for direct amination of β-C(sp2)[BOND]H bonds of benzoic acid derivatives and γ-C(sp2)[BOND]H bonds of benzylamine derivatives has been developed. The reaction is catalyzed by Cu(OAc)2 and a Ag2CO3 cocatalyst, and shows high generality and functional-group tolerance, as well as providing a straightforward means for the preparation of ortho-aminobenzoic acid derivatives.

    21. Crystal Structure Analysis

      The Absolute Configuration of (+)- and (−)-erythro-Mefloquine (pages 6047–6049)

      Dr. Michael Müller, M. Sc. Claudia M. Orben, Dr. Nina Schützenmeister, Dipl.-Chem. Manuel Schmidt, Dr. Andrei Leonov, Prof. Dr. Uwe M. Reinscheid, Dr. Birger Dittrich and Prof. Dr. Christian Griesinger

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300258

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      The controversy over the absolute configuration of (+)-erythro-mefloquine, the less psychosis-causing enantiomer of the anti-malarial drug Lariam, has been resolved by Mosher ester crystallization. The configuration determined previously by physical methods (see scheme) is correct, whereas the configuration determined by three enantioselective syntheses is wrong.

    22. Asymmetric Catalysis

      A Palladium/Chiral Amine Co-catalyzed Enantioselective Dynamic Cascade Reaction: Synthesis of Polysubstituted Carbocycles with a Quaternary Carbon Stereocenter (pages 6050–6054)

      Dr. Guangning Ma, Samson Afewerki, Luca Deiana, Carlos Palo-Nieto, Leifeng Liu, Junliang Sun, Prof. Dr. Ismail Ibrahem and Prof. Dr. Armando Córdova

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201300559

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      Polysubstituted 5- and 6-membered carbocycles were synthesized by the title reaction. The one-pot dynamic relay process generates four new stereocenters, including a quaternary carbon center, in a highly enantioselective fashion (99.5:0.5[RIGHTWARDS ARROW]99:0.5 e.r.) by using a simple combination of palladium and chiral amine co-catalysts.

    23. Aptamer Microarray

      Development of a MALDI-TOF MS Strategy for the High-Throughput Analysis of Biomarkers: On-Target Aptamer Immobilization and Laser-Accelerated Proteolysis (pages 6055–6058)

      Xueyang Zhang, Shaochun Zhu, Ya Xiong, Prof. Dr. Chunhui Deng and Prof. Dr. Xiangmin Zhang

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300566

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      An aptamer-based strategy was developed for the high-throughput analysis of protein biomarkers, such as lysozyme, by on-target MALDI-TOF MS. The aptamers were immobilized on the target plate through formation of covalent bonds with a stable and porous gold layer. An infrared laser was subsequently applied for fast proteolysis (see picture). High sensitivities were observed both in standard solutions and human urine.

    24. Bioinorganic Chemistry

      Platinum(IV) Prodrugs with Haloacetato Ligands in the Axial Positions can Undergo Hydrolysis under Biologically Relevant Conditions (pages 6059–6062)

      Dr. Ezequiel Wexselblatt, Dr. Eylon Yavin and Prof. Dan Gibson

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/anie.201300640

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      Losing ligands rapidly: PtIV complexes with haloacetato ligands can hydrolyze rapidly under biological conditions (pH 7 and 37 °C, see scheme) and the rate increases with increasing pH value. Possible mechanisms for this hydrolysis are examined using H218O and ESI-MS analysis.

    25. Nanostructures

      Plasmonic and Catalytic AuPd Nanowheels for the Efficient Conversion of Light into Chemical Energy (pages 6063–6067)

      Xiaoqing Huang, Yongjia Li, Yu Chen, Hailong Zhou, Prof. Xiangfeng Duan and Prof. Yu Huang

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301096

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      Reinventing the wheel: Bimetallic AuPd nanowheels (see picture), a freestanding form of 2D AuPd nanostructures, were synthesized in a one-pot process. The well-defined and tunable surface plasmon resonance displayed by these nanowheels was exploited in a unique catalytic process in which light energy was used to drive catalytic reactions, such as the Suzuki coupling, with much higher efficiency than that of the conventional heating process.

    26. Glycosylation

      Direct Synthesis of β-N-Glycosides by the Reductive Glycosylation of Azides with Protected and Native Carbohydrate Donors (pages 6068–6071)

      Dr. Jianbin Zheng, Dr. Kaveri Balan Urkalan and Dr. Seth B. Herzon

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301264

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      A simple and straightforward method for the stereocontrolled synthesis of β-linked N-glycosides uses alkyl and aryl azides as the nitrogen source. The N-glycosides are formed in high yields and with high β selectivities (typically >70 % yield, >15:1 β:α selectivity). This approach is also amenable to the synthesis of N-glycosylated amino acids and peptides (see example, Fmoc=9-fluorenylmethoxycarbonyl).

    27. Synthetic Methods

      Iridium-Catalyzed Enantioselective Hydrogenation of Unsaturated Heterocyclic Acids (pages 6072–6075)

      Dr. Song Song, Prof. Shou-Fei Zhu, Liu-Yang Pu and Prof. Qi-Lin Zhou

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301341

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      Spiral binding: A highly enantioselective hydrogenation of unsaturated heterocyclic acids has been developed by using chiral iridium/spirophosphino oxazoline catalysts (see scheme; BArF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Boc=tert-butoxycarbonyl). This reaction provided an efficient method for the preparation of optically active heterocyclic acids with excellent enantioselectivities.

    28. Polycyclic Hydrocarbons

      Indeno[2,1-b]fluorene: A 20-π-Electron Hydrocarbon with Very Low-Energy Light Absorption (pages 6076–6079)

      Dr. Akihiro Shimizu, Dr. Ryohei Kishi, Prof. Masayoshi Nakano, Dr. Daisuke Shiomi, Prof. Kazunobu Sato, Prof. Takeji Takui, Dr. Ichiro Hisaki, Prof. Mikiji Miyata and Prof. Yoshito Tobe

      Version of Record online: 29 APR 2013 | DOI: 10.1002/anie.201302091

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      Smaller can be better: The first example of meta-quinodimethane embedded in an indenofluorene framework has been synthesized. 10,12-Dimesitylindeno[2,1-b]fluorene exhibits extremely low-energy light absorption, despite the small conjugation space of the molecule, which consists of only 20 π electrons.

    29. Pyrrole Alkylation

      Palladium-Catalyzed Direct C[BOND]H Alkylation of Electron-Deficient Pyrrole Derivatives (pages 6080–6083)

      Dr. Lei Jiao and Prof. Dr. Thorsten Bach

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301154

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      The apparent and the real: What looks like a Friedel–Crafts alkylation reaction of electron-deficient pyrroles is actually a PdII-catalyzed, norbornene-mediated C[BOND]H activation reaction, in which the alkylation of the pyrrole core occurs by reductive elimination. As well as ethyl-1H-pyrrole-2-carboxylate (see scheme), several other 2,3-disubstituted pyrroles underwent the selective C5 alkylation in good yield.

    30. Carbohydrate Biosensors

      Mechanical Carbohydrate Sensors Based on Soft Hydrogel Particles (pages 6084–6087)

      Daniel Pussak, Daniela Ponader, Simone Mosca, Salomé Vargas Ruiz, Dr. Laura Hartmann and Dr. Stephan Schmidt

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300469

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      Elastic sensors: A simple method is presented for the measurement of specific biomolecular interactions with soft colloidal hydrogel particles (SCPs) as sensors. Carbohydrate/lectin interactions (see picture; green: carbohydrate molecules) were studied by optical detection of the mechanical deformation of the particles on a lectin surface. The affinity of various carbohydrate inhibitors could also be readily determined.

    31. Nanomaterials

      Twin Polymerization at Spherical Hard Templates: An Approach to Size-Adjustable Carbon Hollow Spheres with Micro- or Mesoporous Shells (pages 6088–6091)

      Falko Böttger-Hiller, Patrick Kempe, Dr. Gerhard Cox, Dr. Alexander Panchenko, Dr. Nicole Janssen, Dr. Albrecht Petzold, Prof. Dr. Thomas Thurn-Albrecht, Lars Borchardt, Dr. Marcus Rose, Prof. Dr. Stefan Kaskel, Colin Georgi, Prof. Dr. Heinrich Lang and Prof. Dr. Stefan Spange

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201209849

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      Kitset hollow spheres: The combination of twin polymerization with hard templates makes hollow carbon spheres (HCSs) with tailored properties easily accessible. The thickness and pore texture of the HCS shells and also the diameter of the spherical cavity can be varied. The application potential of synthesized HCS is substantiated by an excellent cycling stability of lithium–sulfur batteries.

    32. Nonclassical Silane Complexes

      A Unifying Bonding Concept for Metal Hydrosilane Complexes (pages 6092–6096)

      Prof. Dr. Wolfgang Scherer, M. Sc. Petra Meixner, Dr. José Enrique Barquera-Lozada, Dipl.-Phys. Christoph Hauf, Dr. Andreas Obenhuber, Dr. Andreas Brück, Dr. David J. Wolstenholme, Prof. Dr. Klaus Ruhland, Dr. Dirk Leusser and Prof. Dr. Dietmar Stalke

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201210224

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      Experimental and theoretical charge density studies and molecular orbital analyses suggest that the complexes [Cp2Ti(PMe3)SiH2Ph2] (1) and [Cp2Ti(PMe3)SiHCl3] (2) display virtually the same electronic structures. No evidence for a significant interligand hypervalent interaction could be identified for 2. A bonding concept for transition-metal hydrosilane complexes aims to identify the true key parameters for a selective activation of the individual M[BOND]Si and Si[BOND]H bonds.

    33. Methane Activation

      Isomer-Selective Thermal Activation of Methane in the Gas Phase by [HMO]+ and [M(OH)]+ (M=Ti and V) (pages 6097–6101)

      Dr. Robert Kretschmer, Dr. Maria Schlangen and Prof. Dr. Helmut Schwarz

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201300900

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      Methane scrabble: To have the right elements is sometimes just not sufficient, as shown by [M(OH)]+ (M=Ti, V), which do not react with methane. However, reshuffling of the “tiles” to [HMO]+ changes the reactions behavior completely, leading to the first example of C[BOND]H bond activation of methane by an early first-row transition-metal cation.

    34. Cluster Structures

      On the Structures of 55-Atom Transition-Metal Clusters and Their Relationship to the Crystalline Bulk (pages 6102–6105)

      Dr. Thomas Rapps, Prof. Dr. Reinhart Ahlrichs, Eugen Waldt, Prof. Dr. Manfred M. Kappes and Dr. Detlef Schooss

      Version of Record online: 9 MAY 2013 | DOI: 10.1002/anie.201302165

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      Correlation of cluster and bulk structure: Electron-diffraction measurements of homonuclear 55-atom transition-metal cluster anions covering essentially all 3d and 4d elements show only four main structure families. Elements with the same bulk lattice morphology generally have a common cluster structure type. The cluster structure types differ in maximum atomic coordination numbers in analogy to the coordination numbers in the corresponding bulk lattices.

    35. Antitumor Vaccines

      Self-Adjuvanting Synthetic Antitumor Vaccines from MUC1 Glycopeptides Conjugated to T-Cell Epitopes from Tetanus Toxoid (pages 6106–6110)

      Dr. Hui Cai, Mei-Sha Chen, Zhan-Yi Sun, Prof. Dr. Yu-Fen Zhao, Prof. Dr. Horst Kunz and Prof. Dr. Yan-Mei Li

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201300390

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      The T-helper epitope peptide P30 (green in the scheme) from tetanus toxoid was used as the immunostimulant in MUC1 glycopeptide antitumor vaccines and apparently also acts as a built-in adjuvant. P30-conjugated glycopeptide vaccines containing three glycans in the immunodominant motifs PDTRP and GSTAP induced much stronger immune responses and complement dependent cytotoxicity mediated killing of tumor cells when applied in plain PBS solution without complete Freund's adjuvant.

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