Angewandte Chemie International Edition

Cover image for Vol. 50 Issue 52

December 23, 2011

Volume 50, Issue 52

Pages 12367–12659

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. Cover Picture: Soluble Heteropolyniobates from the Bottom of Group IA (Angew. Chem. Int. Ed. 52/2011) (page 12367)

      Dr. Yu Hou, Dr. May Nyman and Dr. Mark A. Rodriguez

      Article first published online: 4 OCT 2011 | DOI: 10.1002/anie.201106642

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      Polyoxoniobates (PONb) differ from nearly all other polyanionic clusters in their unusual solubility behavior. In their Communication on page 12 514 ff., M. Nyman and co-workers show that the Cs salts of PONb are the most soluble and the Li salts the least. The opposite trend holds for other polyoxometalates and anionic clusters, owing to factors such as the strong inner-sphere complexation ability of large alkali-metal ions. The excellent solubility of the Rb and Cs heteropolyniobates offers a unique system for aqueous ion-association studies.

  2. Inside Cover

    1. Top of page
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    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. Inside Cover: Silver Nanocrystals with Concave Surfaces and Their Optical and Surface-Enhanced Raman Scattering Properties (Angew. Chem. Int. Ed. 52/2011) (page 12368)

      Xiaohu Xia, Dr. Jie Zeng, Brenden McDearmon, Yiqun Zheng, Dr. Qingge Li and Prof. Younan Xia

      Article first published online: 28 SEP 2011 | DOI: 10.1002/anie.201106647

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      A seed-mediated growth method has been used to synthesize silver nanocrystals enclosed by concave surfaces and thus high-index facets in aqueous solution. Y. Xia and co-workers report in their Communication on page 12 542 ff. that controlling the growth habit of silver cubic seeds leads to concave silver nanocrystals that act as surface-enhanced Raman-scattering substrates with stronger signal enhancements than conventional silver nanocrystals of a similar size but enclosed by flat faces.

  3. Back Cover

    1. Top of page
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    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
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    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. Back Cover: A Stable Cation of a CSi3P Five-Membered Ring with a Weakly Coordinating Chloride Anion (Angew. Chem. Int. Ed. 52/2011) (page 12660)

      Dr. Sakya S. Sen, Jakob Hey, Maria Eckhardt, Dr. Regine Herbst-Irmer, Eric Maedl, Prof. Dr. Ricardo A. Mata, Prof. Dr. Herbert W. Roesky, Prof. Dr. Manfred Scheer and Prof. Dr. Dietmar Stalke

      Article first published online: 19 OCT 2011 | DOI: 10.1002/anie.201107036

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      Reaching for the stars Although the cyclopentadienyl cation is still synthetically out of reach, the isoelectronic replacement of most of the carbon atoms by elements from the lithosphere, such as silicon and phosphorus, makes a heavier congener accessible. In their Communication on page 12 510 ff., H. W. Roesky, M. Scheer, D. Stalke, and co-workers show how the anti-aromatic five-membered CSi3P ring is stabilized. Picture of planet Earth courtesy of NASA, 1972 (Image ID: AS17-148-22727) and picture of Globular Cluster Messier 15 courtesy of ESA/Hubble and NASA, 2011.

  4. Editorial

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    5. Editorial
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    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. You have free access to this content
      Editorial: Fundamental Research Needs Excellent Scientists and its Own Space (pages 12370–12371)

      Dr. Daniela Kneißl and Prof. Dr. Helmut Schwarz

      Article first published online: 8 DEC 2011 | DOI: 10.1002/anie.201108152

      Corrected by:

      Corrigendum: Corrigendum: Editorial: Fundamental Research Needs Excellent Scientists and its Own Space

      Vol. 51, Issue 8, 1750, Article first published online: 14 FEB 2012

  5. Graphical Abstract

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    12. Essay
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    14. Communications
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 52/2011 (pages 12373–12386)

      Article first published online: 21 DEC 2011 | DOI: 10.1002/anie.201190109

  6. News

    1. Top of page
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    5. Editorial
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    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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  7. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. Rhett Kempe (page 12396)

      Article first published online: 8 NOV 2011 | DOI: 10.1002/anie.201106369

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      “When I was eight(een) I wanted to be a boat builder/yacht maker. My favorite drink is whisky (Islay) …” This and more about Rhett Kempe can be found on page 12396.

  8. News

    1. Top of page
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    5. Editorial
    6. Graphical Abstract
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    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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  9. Book Reviews

    1. Top of page
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    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. DNA. A Graphic Guide to the Molecule that Shook the World. By Israel Rosenfield, Edward Ziff and Borin van Loon. (page 12398)

      Daniel Summerer

      Article first published online: 3 NOV 2011 | DOI: 10.1002/anie.201105791

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      Columbia University Press, New York, 2011. 272 pp., softcover, $ 19.95.—ISBN 978-0231142717

    2. Letters to a Young Chemist. Edited by Abhik Ghosh. (pages 12398–12399)

      Christian Hartinger

      Article first published online: 23 NOV 2011 | DOI: 10.1002/anie.201106202

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      John Wiley & Sons, Hoboken, 2011. 320 pp., softcover, $ 34.90.—ISBN 978-0470390436

  10. Highlights

    1. Top of page
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    3. Inside Cover
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    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
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    10. Book Reviews
    11. Highlights
    12. Essay
    13. Review
    14. Communications
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    1. RNA Aptamers

      Plug and Play with RNA (pages 12400–12401)

      Prof. Dr. Günter Mayer, Dipl.-Biol. Sabine Lennarz, Dipl.-Lebensmittelchem. Falk Rohrbach and M. Sc. Fabian Tolle

      Article first published online: 15 NOV 2011 | DOI: 10.1002/anie.201106636

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      Retooling RNA: RNA aptamers are high-affinity ligands that can be assembled with other structures to yield multivalent molecules. These properties have been addressed in two recent studies: One describes a GFP-like RNA reporter used to study the dynamics of endogenous RNA; the other study reports on an aptamer-templated assembly of multi-enzyme complexes in bacteria for the controlled production of secondary molecules (see picture).

    2. Chirality

      Magnetochiral Effects in Amphiphilic Porphyrin J-Aggregates (pages 12402–12404)

      Prof. Dr. Josep M. Ribó

      Article first published online: 15 NOV 2011 | DOI: 10.1002/anie.201105031

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      The detection of magnetochiral dichroism (MChD; CD: circular dichroism) in a suspension of J-aggregate particles of an achiral amphiphilic nonmetalated porphyrin renews the interest for porphyrins in supramolecular chemistry and reinforces the concept that novel advanced materials can be obtained through self-assembly and auto-organization processes (see picture).

  11. Essay

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    12. Essay
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    14. Communications
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    1. Fast DNA Sequencing

      Decoding Genomes at High Speed: Implications for Science and Medicine (pages 12406–12410)

      Prof. Shankar Balasubramanian

      Article first published online: 5 DEC 2011 | DOI: 10.1002/anie.201106707

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      At warp speed: The speed and cost of sequencing DNA has undergone tremendous improvement based on Solexa sequencing. This technique arose from basic curiosity-driven research and unexpected outcomes, rather than from ideas that were strategically driven. The whole-genome sequencing of individuals now possible may one day transform the way medical disorders are classified, diagnosed, and treated.

  12. Review

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    12. Essay
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    14. Communications
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    1. Biogenesis

      Etiology of Potentially Primordial Biomolecular Structures: From Vitamin B12 to the Nucleic Acids and an Inquiry into the Chemistry of Life’s Origin: A Retrospective (pages 12412–12472)

      Prof. Albert Eschenmoser

      Article first published online: 7 DEC 2011 | DOI: 10.1002/anie.201103672

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      The quest for the etiology of a biomolecular structure acquires special significance when the questions asked refer to molecules, the existence of which are fundamental to life, and in particular to the origin of life. In a search for the chemistry of the emergence of life, one needs to pay strict heed to molecular guides—nucleic acids, proteins, cofactors—that all carry a message, which is our job to decipher.

  13. Communications

    1. Top of page
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    1. Chirality

      Circularly Polarized Luminescence of Rhodamine B in a Supramolecular Chiral Medium Formed by a Vortex Flow (pages 12474–12477)

      Dr. Kunihiko Okano, Makoto Taguchi, Prof. Dr. Michiya Fujiki and Prof. Dr. Takashi Yamashita

      Article first published online: 28 SEP 2011 | DOI: 10.1002/anie.201104708

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      Sucked into the vortex: Hydrogels with embedded Rhodamine B dye showed stir-induced circularly polarized luminescence (CPL; see picture), the sense of which can be controlled by switching the stir direction from clockwise (CW) to counterclockwise (CCW) with slow cooling from the sol to gel states. The chiral alignment of the dye was erased by heating the sample above the gel–sol transition temperature.

    2. Nanofabrication

      Facile Fabrication of Metallic Nanostructures by Tunable Cracking and Transfer Printing (pages 12478–12482)

      Juan Zhu, Mianqi Xue, Dan Zhao, Prof. Meining Zhang, Dr. Lian Duan, Prof. Yong Qiu and Prof. Tingbing Cao

      Article first published online: 3 NOV 2011 | DOI: 10.1002/anie.201106490

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      You crack me up: A topographically patterned PDMS stamp was coated with thin metal film and swelled under organic vapor to induce the tunable cracking of the brittle film into metallic nanostructures (see SEM images, scale bars 1 μm). UV/Vis spectra, OLED efficiency, and SERS spectra demonstrate the fine controllability of the metallic nanostructures, the well-ordered and highly regulable surface plasmons, and the facile fabrication process.

    3. Luminescent Materials

      A Cocrystal Strategy to Tune the Luminescent Properties of Stilbene-Type Organic Solid-State Materials (pages 12483–12486)

      Dongpeng Yan, Dr. Amit Delori, Dr. Gareth O. Lloyd, Dr. Tomislav Friščić, Dr. Graeme M. Day, Prof. William Jones, Prof. Jun Lu, Prof. Min Wei, Prof. David G. Evans and Prof. Xue Duan

      Article first published online: 7 NOV 2011 | DOI: 10.1002/anie.201106391

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      The one- and two-photon luminescence of stilbene-type solid-state materials can be tuned and controlled from blue to yellow color by a supramolecular cocrystal method.

    4. Biosensors

      Two-Temperature Hybridization for Microarray Detection of Label-Free MicroRNAs with Attomole Detection and Superior Specificity (pages 12487–12490)

      Jeong Min Lee and Prof. Dr. Yongwon Jung

      Article first published online: 9 NOV 2011 | DOI: 10.1002/anie.201105605

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      Two is better than one: Two short locked nucleic acid based probes were used to collectively capture and detect microRNAs by a simple two-temperature hybridization process. Intact microRNAs were directly measured down to attomolar concentrations with a high specificity and nearly four orders of magnitude of dynamic range. Single base mismatches in the microRNAs were potently discriminated from the perfectly matched targets.

    5. Conducting Materials

      Stepwise Sequential Redox Potential Modulation Possible on a Single Platform (pages 12491–12495)

      Ariadna Pepiol, Prof. Francesc Teixidor, Prof. Reijo Sillanpää, Marius Lupu and Prof. Clara Viñas

      Article first published online: 3 NOV 2011 | DOI: 10.1002/anie.201105668

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      Step by step: The cluster [3,3′-Co(1,2-C2B9H11)2] is an excellent platform for making a stepwise tunable redox potential system by dehydroiodination. With the addition of up to eight iodine substituents (purple; see picture), there is a fall in the E1/2(CoIII/CoII) value from −1.80 V to −0.68 V (vs. Fc+/Fc; Fc=ferrocene). A practical application of this tunability has been observed in the growth of polypyrrole.

    6. Asymmetric Catalysis

      Taming the Friedel–Crafts Reaction: Organocatalytic Approach to Optically Active 2,3-Dihydrobenzofurans (pages 12496–12500)

      Dr. Łukasz Albrecht, Lars Krogager Ransborg, Vibeke Lauridsen, Mette Overgaard, Dr. Theo Zweifel and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 7 NOV 2011 | DOI: 10.1002/anie.201105819

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      Fine-tuning: Three types of optically active trans-2,3-disubstituted-2,3-dihydrobenzofurans having three contiguous stereogenic centers can be efficiently accessed by one-pot reaction cascades (see scheme; TMS=trimethylsilyl). High substitution diversity of the final products can be achieved from the same common precursors by fine-tuning of their reactivity through simple structural modifications.

    7. Olefin Isomerization

      (E)- and (Z)-β-Borylallylsilanes by Alkyne Silaboration Followed by Regio- and Stereoselective Double-Bond Migration (pages 12501–12504)

      Dr. Toshimichi Ohmura, Kazuyuki Oshima and Prof. Dr. Michinori Suginome

      Article first published online: 9 NOV 2011 | DOI: 10.1002/anie.201106077

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      Double take: β-Borylallylsilanes have been synthesized by the regioselective silaboration of terminal alkynes followed by palladium-catalyzed double-bond migration of the resulting β-borylalkenylsilanes (see scheme). The stereoselectivity of the double-bond migration can be controlled by additives, thus leading to the stereocomplementary synthesis of (E)- and (Z)-β-borylallylsilanes.

    8. Bio-nanotechnology

      Multifunctional Mesoporous Composite Nanocapsules for Highly Efficient MRI-Guided High-Intensity Focused Ultrasound Cancer Surgery (pages 12505–12509)

      Dr. Yu Chen, Prof. Dr. Hangrong Chen, Dr. Yang Sun, Prof. Dr. Yuanyi Zheng, Prof. Dr. Deping Zeng, Prof. Dr. Faqi Li, Dr. Shengjian Zhang, Dr. Xia Wang, Dr. Kun Zhang, Dr. Ming Ma, Dr. Qianjun He, Dr. Linlin Zhang and Prof. Dr. Jianlin Shi

      Article first published online: 10 NOV 2011 | DOI: 10.1002/anie.201106180

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      Bloodless surgical knife: Nano-biotechnology has been introduced into imaging-guided high-intensity focused ultrasound (HIFU) cancer surgery by adopting engineered multifunctional manganese-based mesoporous composite nanocapsules as the contrast agents for T1-weighted magnetic resonance imaging (MRI) and simultaneously as synergistic agents for MRI-guided HIFU cancer surgery.

    9. Silicon Chemistry

      A Stable Cation of a CSi3P Five-Membered Ring with a Weakly Coordinating Chloride Anion (pages 12510–12513)

      Dr. Sakya S. Sen, Jakob Hey, Maria Eckhardt, Dr. Regine Herbst-Irmer, Eric Maedl, Prof. Dr. Ricardo A. Mata, Prof. Dr. Herbert W. Roesky, Prof. Dr. Manfred Scheer and Prof. Dr. Dietmar Stalke

      Article first published online: 29 SEP 2011 | DOI: 10.1002/anie.201104146

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      Don′t count on counterions: The cyclic five-membered CSi3P cation 1 is synthesized in the reaction of benzamidinato-stabilized chlorosilylene and methyl phosphaalkyne. The presence of four π electrons in 1 means it can be considered as a formal, heavier analogue of the cyclopentadienyl cation. Surprisingly the small counteranion (Cl) does not contribute to the ring stability.

    10. Heteropolyniobates

      Soluble Heteropolyniobates from the Bottom of Group IA (pages 12514–12517)

      Dr. Yu Hou, Dr. May Nyman and Dr. Mark A. Rodriguez

      Article first published online: 7 SEP 2011 | DOI: 10.1002/anie.201104478

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      Surprising solubility: While it is already well known that [Nb6O19]8− salts exhibit an unusual solubility trend, that is, Cs>Rb>K>Na>Li, the heteropolyniobates of Cs and Rb had not yet been crystallized. These very soluble entities have now been obtained from solution by a simple and universal process. New polyoxoniobate geometries are thus unveiled, and the [SiNb12O40]16− Keggin ion is characterized in solution for the first time.

    11. Metal–Organic Frameworks

      Metal–Organic Frameworks with a Three-Dimensional Ordered Macroporous Structure: Dynamic Photonic Materials (pages 12518–12522)

      Yi-nan Wu, Prof. Dr. Fengting Li, Wei Zhu, Jiecheng Cui, Cheng-an Tao, Changxu Lin, Phillip M. Hannam and Prof. Dr. Guangtao Li

      Article first published online: 17 OCT 2011 | DOI: 10.1002/anie.201104597

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      Tuning MOFs: When a metal–organic framework (MOF) with an ordered three-dimensional macroporous structure is integrated into a film, the resulting materials have an additional optical element, which can be used as a general and effective signal transducer. This, in combination with the hierarchical pore structure, makes these films interesting dynamic photonic materials with potential applications in sensors.

    12. Supramolecular Chemistry

      Liquid-Crystalline Hybrid Materials Based on [60]Fullerene and Bent-Core Structures (pages 12523–12528)

      Dr. Jorge Vergara, Dr. Joaquín Barberá, Prof. José Luis Serrano, Prof. M. Blanca Ros, Nerea Sebastián, Prof. Rosario de la Fuente, Dr. David O. López, Dr. Gustavo Fernández, Dr. Luis Sánchez and Prof. Nazario Martín

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201104866

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      What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C60 unit, lamellar polar liquid-crystal phases were induced (see scheme). The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.

    13. Organic Bioelectronics

      Electrochemical Control of Growth Factor Presentation To Steer Neural Stem Cell Differentiation (pages 12529–12533)

      Dr. Anna Herland, Kristin M. Persson, Vanessa Lundin, Prof. Mats Fahlman, Prof. Magnus Berggren, Dr. Edwin W. H. Jager and Dr. Ana I. Teixeira

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201103728

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      Let it grow: The conjugated polymer poly(3,4-ethylenedioxythiophene) (PEDOT) was synthesized with heparin as the counterion to form a cell culture substrate. The surface of PEDOT:heparin in the neutral state associated biologically active growth factors (see picture). Electrochemical in situ oxidation of PEDOT during live cell culture decreased the bioavailability of the growth factor and created an exact onset of neural stem cell differentiation.

    14. Glycosyltransferase Inhibitors

      High-Throughput Screening for Inhibitors of Sialyl- and Fucosyltransferases (pages 12534–12537)

      Cory D. Rillahan, Dr. Steven J. Brown, Amy C. Register, Prof. Hugh Rosen and Prof. James C. Paulson

      Article first published online: 9 NOV 2011 | DOI: 10.1002/anie.201105065

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      Sweet screens: A high-throughput screening platform for identification of inhibitors of sialyl- and fucosyltransferases based on fluorescence polarization (FP) has been developed. An analogue of the natural donor substrate carrying a fluorescent label (green star) is transferred to a glycoprotein acceptor, which results in robust FP (see picture). The screening of 16 000 compounds against different glycosyltransferases has identified various interesting inhibitors.

    15. Proton Transport

      High Proton Conductivity of Water Channels in a Highly Ordered Nanowire (pages 12538–12541)

      H. Wang, X. Xu, N. M. Johnson, N. K. R. Dandala and H.-F. Ji

      Article first published online: 3 NOV 2011 | DOI: 10.1002/anie.201105118

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      A proton-conductive material based on a crystalline assembly of trimesic acid and melamine (TMA⋅M, see picture) is reported. Because of the ordered structure of the assembly, the water-saturated proton conductivity for the TMA⋅M assembly is 5.5 S cm−1, which is the highest proton conductivity measured to date. This exceptionally high conductivity and low-cost fabrication of the material make applications feasible for fuel-cell devices.

    16. Concave Nanoparticles

      Silver Nanocrystals with Concave Surfaces and Their Optical and Surface-Enhanced Raman Scattering Properties (pages 12542–12546)

      Xiaohu Xia, Dr. Jie Zeng, Brenden McDearmon, Yiqun Zheng, Dr. Qingge Li and Prof. Younan Xia

      Article first published online: 12 SEP 2011 | DOI: 10.1002/anie.201105200

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      Shaped and dimpled: Silver nanocrystals enclosed by concave surfaces and thus high-index facets have been prepared by simply controlling the growth habit of Ag cubic seeds. Four types of concave nanocrystals, including octahedron, cube, octapod, and trisoctahedron, were obtained (see picture).

    17. Perovskite Phases

      BaFeO3: A Ferromagnetic Iron Oxide (pages 12547–12550)

      Dr. Naoaki Hayashi, Takafumi Yamamoto, Prof. Dr. Hiroshi Kageyama, Dr. Masakazu Nishi, Yoshitaka Watanabe, Prof. Dr. Takateru Kawakami, Dr. Yoshitaka Matsushita, Prof. Dr. Atsushi Fujimori and Prof. Dr. Mikio Takano

      Article first published online: 7 NOV 2011 | DOI: 10.1002/anie.201105276

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      Magnetic attraction: The cubic perovskite BaFeO3 (see picture, Ba blue, Fe brown, O white), which is obtained by a low-temperature reaction using ozone as an oxidant, exhibits ferromagnetism with a fairly large moment of 3.5 μB per Fe ion above a small critical field of approximately 0.3 T. This specific ferromagnetism is attributed to the enhancement of O[RIGHTWARDS ARROW]Fe charge transfer that arises from deepening of the Fe4+ d levels.

    18. CO2 Hydrogenation

      Carbon Dioxide Hydrogenation to Formic Acid by Using a Heterogeneous Gold Catalyst (pages 12551–12554)

      Dr. Debora Preti, Dr. Claudio Resta, Dr. Sergio Squarcialupi and Prof. Dr. Giuseppe Fachinetti

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201105481

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      AUROlite, consisting of gold supported on titania (picture shows extrudates in a steel net cage), is a robust catalyst for the production of catalyst-free HCOOH/NEt3 adducts from H2, CO2, and neat NEt3. Pure HCOOH is freed from the adducts by amine exchange.

    19. Microporous Catalysts

      Microporous Aluminoborates with Large Channels: Structural and Catalytic Properties (pages 12555–12558)

      Dr. Tao Yang, Agnieszka Bartoszewicz, Dr. Jing Ju, Dr. Junliang Sun, Dr. Zheng Liu, Prof. Xiaodong Zou, Prof. Yingxia Wang, Prof. Guobao Li, Fuhui Liao, Prof. Belén Martín-Matute and Jianhua Lin

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106310

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      Channel zapping: PKU-1 and newly synthesized PKU-2 (Al2B5O9(OH)3n H2O; see picture) possess microporous structures with 18-ring and 24-ring channels, respectively. They show high reactivity and size selectivity in the cyanosilylation of aldehydes as heterogeneous Lewis acid catalysts. The different channel sizes determine the substrate selectivity. These examples demonstrate the potential of octahedron-based aluminoborate channels in catalysis.

    20. Smart Polymers

      Light-Orchestrated Macromolecular “Accordions”: Reversible Photoinduced Shrinking of Rigid-Rod Polymers (pages 12559–12563)

      Dr. David Bléger, Tobias Liebig, Raphael Thiermann, Prof. Dr. Michael Maskos, Prof. Dr. Jürgen P. Rabe and Prof. Dr. Stefan Hecht

      Article first published online: 24 NOV 2011 | DOI: 10.1002/anie.201106879

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      Light can play: Irradiation causes dramatic changes in the shape of rigid-rod polymers incorporating azobenzene photochromes in the main chain. The embedded photoswitches act as hinges, which upon light-induced isomerization lead to reversible shrinking and stretching of the polymer backbone (see scheme), resembling light-orchestrated macromolecular accordions.

    21. Artificial Channels

      Selective Artificial Transmembrane Channels for Protons by Formation of Water Wires (pages 12564–12568)

      Wen Si, Lei Chen, Xiao-Bo Hu, Gangfeng Tang, Zhenxia Chen, Prof. Jun-Li Hou and Prof. Zhan-Ting Li

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106857

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      Lined up water molecules: Artificial transmembrane channels from pillar[5]arene monomeric and dimeric derivatives have been prepared. Single-channel conductance measurements and isotopeeffect experiments under acidic conditions showed selective proton transport through the channels, which were mediated by water wires formed in the pillar[5]arene backbones (see picture).

    22. Molecular Switches

      pH-Dependent Conformational Switching in 2,6-Benzamidodiphenylacetylenes (pages 12569–12571)

      Ian M. Jones, Dr. Hannah Lingard and Prof. Andrew D. Hamilton

      Article first published online: 15 DEC 2011 | DOI: 10.1002/anie.201106241

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      The conformational equilibrium of a pH-dependent switch based on an intramolecularly H-bonded diphenylacetylene can be predictably biased by using electron-donating or -withdrawing groups (see scheme). Furthermore, protonation of the electron-donating dimethylamino group converts it into an electron-withdrawing dimethylammonium cation with a concomitant switch in conformation.

    23. Crystal Growth

      Capillarity Creates Single-Crystal Calcite Nanowires from Amorphous Calcium Carbonate (pages 12572–12577)

      Yi-Yeoun Kim, Nicola B. J. Hetherington, Elizabeth H. Noel, Dr. Roland Kröger, Dr. John M. Charnock, Dr. Hugo K. Christenson and Prof. Fiona C. Meldrum

      Article first published online: 8 NOV 2011 | DOI: 10.1002/anie.201104407

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      Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product.

    24. Synthetic Methods

      Palladium-Catalyzed Oxidative Arylalkylation of Activated Alkenes: Dual C[BOND]H Bond Cleavage of an Arene and Acetonitrile (pages 12578–12581)

      Tao Wu, Xin Mu and Prof. Dr. Guosheng Liu

      Article first published online: 11 NOV 2011 | DOI: 10.1002/anie.201104575

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      Not one but two: The title reaction proceeds through the dual C[BOND]H bond cleavage of both aniline and acetonitrile (see scheme). The reaction affords a variety of cyano-bearing indolinones in excellent yield. Mechanistic studies demonstrate that this reaction involves a fast arylation of the olefin and a rate-determining C[BOND]H activation of the acetonitrile.

    25. Highly Twisted Arenes by Scholl Cyclizations with Unexpected Regioselectivity (pages 12582–12585)

      Anirban Pradhan, Dr. Pierre Dechambenoit, Dr. Harald Bock and Dr. Fabien Durola

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201105105

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      Let's twist! The Scholl reaction with quinquephenyl derivatives has been shown to have an unexpectedly strong preference for forming twisted, helicene aromatic polycycles, instead of their flat counterparts. This tendency is so strong that it will overcome even severe steric hindrance, and the procedure can be used in the efficient synthesis of hexa-tert-butylhexabenzotriphenylene from a simple biaryl starting material (see scheme).

    26. Organocatalysis

      Chiral Brønsted Acid Catalyzed Stereoselective Addition of Azlactones to 3-Vinylindoles for Facile Access to Enantioenriched Tryptophan Derivatives (pages 12586–12590)

      Prof. Dr. Masahiro Terada, Kenichi Moriya, Kyohei Kanomata and Dr. Keiichi Sorimachi

      Article first published online: 28 OCT 2011 | DOI: 10.1002/anie.201105562

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      Syn-gled out: The syn diastereo- and enantioselective addition of azlactones to 3-vinylindoles was accomplished by using a chiral, binapthol-derived, Brønsted acid catalyst (see scheme). This method enables facile access to tryptophan derivatives with adjacent quaternary and tertiary stereogenic centers, which are potentially useful for the synthesis of peptidomimetics.

    27. Silicon Clusters

      Resolving the Different Silicon Clusters in Li12Si7 by 29Si and 6,7Li Solid-State NMR Spectroscopy (pages 12591–12594)

      Dr. Thomas K.-J. Köster, Dr. Elodie Salager, Dr. Andrew J. Morris, Dr. Baris Key, Dr. Vincent Seznec, Dr. Mathieu Morcrette, Prof. Chris J. Pickard and Prof. Clare P. Grey

      Article first published online: 29 NOV 2011 | DOI: 10.1002/anie.201105998

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      Structural signatures: The analysis of Si–Si and Si–Li connectivities by solid-state NMR spectroscopy allows the different types of silicon clusters to be discriminated in the model lithium silicide compound Li12Si7 (see picture, Si clusters red and blue, Li ions gray). The results provide new NMR spectroscopic strategies with which to differentiate and study the structures formed in silicon-based electrode materials.

    28. Synthetic Methods

      Iron-Catalyzed C[BOND]H and C[BOND]C Bond Cleavage: A Direct Approach to Amides from Simple Hydrocarbons (pages 12595–12599)

      Chong Qin, Wang Zhou, Feng Chen, Yang Ou and Dr. Ning Jiao

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106112

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      Something functional: The title reaction proceeds in the presence of azide and water to deliver amides in high yields, and it can be used in a ring-expansion strategy to generate lactams. A mechanism is proposed based on experimental results. This reaction offers a new approach to functionalizing simple and readily available hydrocarbons. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

    29. Water Oxidation

      Effects of a Proximal Base on Water Oxidation and Proton Reduction Catalyzed by Geometric Isomers of [Ru(tpy)(pynap)(OH2)]2+ (pages 12600–12604)

      Dr. Julie L. Boyer, Dr. Dmitry E. Polyansky, Dr. David J. Szalda, Dr. Ruifa Zong, Prof. Randolph P. Thummel and Dr. Etsuko Fujita

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201102648

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      Basic difference: The importance of a pendent base in promoting proton-coupled electron-transfer reactions with low activation barriers has been discussed for H+ reduction or H2 oxidation in acetonitrile. Investigation of the interaction between a base positioned in the second coordination sphere of a complex and a water ligand in water oxidation reactions using geometric isomers of [Ru(tpy)(pynap)(OH2)]2+ (see picture) gave intriguing results.

    30. Cycloaddition

      Lewis Acid Catalyzed Intramolecular [3+2] Cross-Cycloaddition of Donor–Acceptor Cyclopropanes with Carbonyls: A General Strategy for the Construction of Acetal[n.2.1] Skeletons (pages 12605–12609)

      Dr. Siyang Xing, Yan Li, Zhen Li, Chang Liu, Jun Ren and Prof. Zhongwen Wang

      Article first published online: 7 NOV 2011 | DOI: 10.1002/anie.201106368

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      Build a bridge: The first catalytic intramolecular [3+2] cycloaddition of monodonor–monoacceptor cyclopropanes (see scheme) provides a general and efficient strategy for construction of structurally diverse acetal[n.2.1] and 1,4-dioxygen-substituted cyclic skeletons, which are widely distributed in biologically important natural products.

    31. Carbohydrates

      A Unique Bicyclic Monosaccharide from the Bradyrhizobium Lipopolysaccharide and Its Role in the Molecular Interaction with Plants (pages 12610–12612)

      Prof. Dr. Alba Silipo, Dr. Maria R. Leone, Dr. Gitte Erbs, Prof. Rosa Lanzetta, Prof. Michelangelo Parrilli, Prof. Woo-Suk Chang, Prof. Mari-Anne Newman and Prof. Antonio Molinaro

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106548

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      Sugar coat: The nitrogen-fixing soil bacterium Bradyrhizobium sp. BTAi1 is coated with a unique lipopolysaccharide that does not induce innate immune responses in its host plant Aeschynomene indica or in different plant families. The chemical nature of the monosaccharide forming the polymer (see picture) is unprecedented in nature, which helps to avoid “harmful” recognition by its symbiotic host.

    32. Dehydrocoupling of Boranes

      Transition-Metal-Catalyzed Synthesis of Diboranes(4) (pages 12613–12616)

      Prof. Dr. Holger Braunschweig and Frank Guethlein

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201104854

      Thumbnail image of graphical abstract

      The diboranes(4) bis(catecholato)diborane (B2Cat2) and bis(pinacolato)diborane (B2Pin2) are important precursors for organoboronic esters, which are versatile reagents for the formation of carbon–carbon bonds. A new catalytic synthesis for these compounds starts from catecholborane or pinacolborane and gives the dehydrocoupling products B2Cat2 and B2Pin2 with turnover numbers of up to 11 600 (see scheme).

    33. Small-Molecule Stabilization

      Ethenedithione (S[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]S): Trapping and Isomerization in a Cobalt Complex (pages 12617–12620)

      Wolfram W. Seidel, Matthias J. Meel, Stephen R. Hughes, Florian Hupka and Alexander Villinger

      Article first published online: 30 NOV 2011 | DOI: 10.1002/anie.201105055

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      Swing bridge: The triplet species ethenedithione has been generated within the coordination sphere of cobalt, leading to a dinuclear μ-η22-C2S2 complex (see picture: C gray, Co blue, P purple, S yellow). Depending on the solvent, the C2S2 moiety displays a transoid or a cisoid geometry. This isomerization step changes the sign of the magnetic coupling between the cobalt centers.

    34. Enzyme Models

      The Conversion of Nickel-Bound CO into an Acetyl Thioester: Organometallic Chemistry Relevant to the Acetyl Coenzyme A Synthase Active Site (pages 12621–12625)

      Dipl.-Chem. Bettina Horn, Prof. Dr. Christian Limberg, Dr. Christian Herwig and Dr. Stefan Mebs

      Article first published online: 7 NOV 2011 | DOI: 10.1002/anie.201105281

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      When three become one: Within one nickel-based model system, the three reactants CO, MeI, and PhSH have been assembled to yield an acetyl thioester. The reactivity is of relevance for the functioning of the acetyl coenzyme A synthase active site and provides insights into possible binding sequences.

    35. Asymmetric Organocatalysis

      Designing N-Heterocyclic Carbenes: Simultaneous Enhancement of Reactivity and Enantioselectivity in the Asymmetric Hydroacylation of Cyclopropenes (pages 12626–12630)

      Fan Liu, Dr. Xavier Bugaut, Michael Schedler, Dr. Roland Fröhlich and Prof. Dr. Frank Glorius

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106155

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      Faster, higher, stronger! The N-heterocyclic carbene (NHC) catalyzed diastereo- and enantioselective hydroacylation of cyclopropenes affords structurally valuable acylcyclopropanes. A new family of electron-rich, 2,6-dimethoxyphenyl-substituted NHCs induces excellent reactivity and enantioselectivity. Preliminary kinetic studies unambiguously demonstrated the superiority of this family of catalysts over known NHCs in this challenging transformation.

    36. Asymmetric Catalysis

      Catalytic Asymmetric Diastereodivergent Deracemization (pages 12631–12635)

      Dr. Marco Luparia, Maria Teresa Oliveira, Dr. Davide Audisio, Dr. Frédéric Frébault, Dr. Richard Goddard and Dr. Nuno Maulide

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201106321

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      Your wish is my command: Deracemization is a powerful strategy wherein a racemate is converted into a 100 % yield of a single enantiopure product. A new concept in catalytic deracemization is presented, in which a racemate with n stereogenic elements can be selectively converted into each one of 2m (m=number of chiral centers of the product) different enantiopure products, by simple tuning of the reaction conditions.

    37. Silylium Ions

      A New Synthesis of Triarylsilylium Ions and Their Application in Dihydrogen Activation (pages 12636–12638)

      André Schäfer, Matti Reißmann, Dr. Annemarie Schäfer, Wolfgang Saak, Detlev Haase and Prof. Dr. Thomas Müller

      Article first published online: 9 NOV 2011 | DOI: 10.1002/anie.201106582

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      Well-shuffled: An unexpected substituent distribution reaction via alkyldiarylsilylium ions leads to a distribution of substituents. Starting from alkyldiaryl silanes, this reaction provides a facile synthetic approach to sterically highly hindered triarylsilylium ions. These silylium ions can be applied in dihydrogen activation reactions.

    38. Dispersion Interactions

      Steric Crowding Can Stabilize a Labile Molecule: Solving the Hexaphenylethane Riddle (pages 12639–12642)

      Prof. Dr. Stefan Grimme and Prof. Dr. Peter R. Schreiner

      Article first published online: 24 OCT 2011 | DOI: 10.1002/anie.201103615

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      12 not so angry men: Hexaphenylethane is unstable, a phenomenon traditionally attributed to steric repulsion between the six phenyl rings. However, adding 12 bulky tert-butyl groups, one to each of the 12 meta positions, gives a stabile ethane derivative (see space-filling model and potential energy curve for the dissociation of the central C[BOND]C bond). This unexpected stabilization is shown to result from attractive dispersion interactions between the substituents.

    39. Single-Molecule Kinetics

      Signal-Pair Correlation Analysis of Single-Molecule Trajectories (pages 12643–12646)

      Dr. Armin Hoffmann and Prof. Dr. Michael T. Woodside

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201104033

      Thumbnail image of graphical abstract

      There you go: How to get kinetic information from trajectories of single biomolecules? A method based on correlating signal ranges (here for a three-state DNA hairpin with F=folded, I= intermediate, and U=unfolded state) is reported and shows how to get the kinetic scheme and the corresponding rates, even for states with low occupancy or very short lifetime, states which overlap because of noise, and systems with very similar or very different rates.

    40. Photoinduced Electron Transfer

      Unexpected Electron Transfer in Cryptochrome Identified by Time-Resolved EPR Spectroscopy (pages 12647–12651)

      Dr. Till Biskup, Dr. Kenichi Hitomi, Prof. Dr. Elizabeth D. Getzoff, Sebastian Krapf, Prof. Dr. Thorsten Koslowski, Dr. Erik Schleicher and Prof. Dr. Stefan Weber

      Article first published online: 15 NOV 2011 | DOI: 10.1002/anie.201104321

      Thumbnail image of graphical abstract

      Subtle differences in the local sequence and conformation of amino acids can result in diversity and specificity in electron transfer (ET) in proteins, despite structural conservation of the redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of the ET partners, and thus the stabilization of the charge-separated states, contribute substantially.

    41. Pericyclic Reactions

      Electronic Bond-to-Bond Fluxes in Pericyclic Reactions: Synchronous or Asynchronous? (pages 12652–12654)

      Timm Bredtmann and Prof. Dr. Jörn Manz

      Article first published online: 4 NOV 2011 | DOI: 10.1002/anie.201104465

      Thumbnail image of graphical abstract

      One at a time or all at once? Electronic fluxes during a pericyclic reaction in the electronic ground state—exemplified for the degenerate Cope rearrangement of semibullvalene—may proceed either synchronously or asynchronously. Quantum simulations show that the mechanism is determined by the preparation of the reactants, for example, synchronous at cryogenic temperatures (tunneling) but asynchronous when induced by selective laser pulses (with energy over the barrier).

    42. Protein Cross-Linking

      A FlAsH-Based Cross-Linker to Study Protein Interactions in Living Cells (pages 12655–12658)

      Dr. Anna Rutkowska, Dr. Christian H. Haering and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 16 NOV 2011 | DOI: 10.1002/anie.201106404

      Thumbnail image of graphical abstract

      As you like it: xCrAsH, a dimeric derivative of the arsenical compound FlAsH, enables the highly specific, covalent cross-linking of two proteins containing a 12 amino acid peptide tag. This inducible and (by addition of dithiols) reversible system can be used to detect and manipulate protein–protein interactions both in vitro and in living cells (see picture).

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      Article first published online: 21 DEC 2011 | DOI: 10.1002/anie.201190110

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