Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

September 19, 2011

Volume 50, Issue 39

Pages 8993–9211

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Magneto-Chiral Dichroism of Organic Compounds (Angew. Chem. Int. Ed. 39/2011) (page 8993)

      Yuichi Kitagawa, Prof. Dr. Hiroshi Segawa and Prof. Dr. Kazuyuki Ishii

      Article first published online: 3 AUG 2011 | DOI: 10.1002/anie.201104744

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      The homochirality of life is still an unsolved mystery. Magneto-chiral dichroism (MChD, the dependence of the absorbance of a chiral molecule on the direction of a magnetic field) has attracted attention as a plausible way to explain this puzzle. Several examples of MChD of metal compounds are known, but MChD of biological organic compounds has not been reported. In their Communication on page 9133 ff., K. Ishii et al. describe the first observation of MChD in organic compounds by using porphyrin J-aggregates.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Brightly Tricolored Mechanochromic Luminescence from a Single-Luminophore Liquid Crystal: Reversible Writing and Erasing of Images (Angew. Chem. Int. Ed. 39/2011) (page 8994)

      Dr. Yoshimitsu Sagara and Prof. Takashi Kato

      Article first published online: 8 AUG 2011 | DOI: 10.1002/anie.201104920

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      A mechano- and thermoresponsive luminescent liquid-crystalline material that has a single luminophore group and shows three distinct colors of reddish-orange, yellow, and green is described by Y. Sagara and T. Kato in their Communication on page 9128 ff. Mechanically induced isothermal and thermal phase transitions accompany the switching of the nanostructures formed by the liquid crystal and lead to a change in the intermolecular interactions.

  3. Back Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Back Cover: DNA-Linked Nanoparticle Building Blocks for Programmable Matter (Angew. Chem. Int. Ed. 39/2011) (page 9212)

      Prof. Jin-Woo Kim, Dr. Jeong-Hwan Kim and Prof. Russell Deaton

      Article first published online: 7 SEP 2011 | DOI: 10.1002/anie.201104958

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      Assembly of nanostructures by using DNA has the potential to realize new materials. In their Communication on page 9185 ff., J.-W. Kim et al. introduce a simple and sustainable strategy to place DNA linkers at 90° or 180° angles on nanoparticles, thus producing a nanoscale building block that allows control of the nanoassembly geometry. The picture depicts the iterative process of DNA attachment at maximal separation resulting in DNA linkers at well-defined orientations. (Artwork by Min Kim.)

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Graphical Abstract: Angew. Chem. Int. Ed. 39/2011 (pages 8997–9007)

      Article first published online: 15 SEP 2011 | DOI: 10.1002/anie.201190080

  5. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Masayuki Inoue (page 9016)

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201103732

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      “What I look for first in a publication is architecturally beautiful structures. My favorite piece of research is R. B. Woodward's total synthesis of reserpine …” This and more about Masayuki Inoue can be found on page 9016.

  7. Book Review

    1. Top of page
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    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Handbook of Fluorescence Spectroscopy and Imaging. From Ensemble to Single Molecules. Edited by Markus Sauer, Johan Hofkens and Jörg Enderlein. (pages 9017–9018)

      Marcia Levitus

      Article first published online: 31 AUG 2011 | DOI: 10.1002/anie.201104398

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      Wiley-VCH, Weinheim, 2011. 282 pp., hardcover, € 109.00.—ISBN 978-3527316694

  8. Highlights

    1. Top of page
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    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Silicon Chemistry

      Low-Valent Silicon in Formally Antiaromatic Four-Membered Ring Systems (pages 9020–9022)

      Prof. Dr. Peter Jutzi

      Article first published online: 14 JUL 2011 | DOI: 10.1002/anie.201103254

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      The fundamental question of how silicon handles antiaromaticity in four-membered ring systems has been answered by the synthesis and characterization of the first tetrasilacyclobutadiene Si4Ar4 (1) and by the first dimeric silaisonitrile Si2(NAr′)2 (2). Compound 1 is best described by the charge-separated resonance structure 1′ and 2 by a structure with π-type lone pairs at the nitrogen atoms and vacant π orbitals at the silicon atoms.

    2. Colloidal Spheres

      Can Carbon Spheres Be Created through the Stöber Method? (pages 9023–9025)

      Prof. An-Hui Lu, Guang-Ping Hao and Qiang Sun

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103514

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      The Stöber method is an authoritative approach for the synthesis of monodisperse colloidal silica spheres; this method has now been extended to the synthesisis of monodisperse resorcinol-formaldehyde resin polymer and carbon spheres.

  9. Review

    1. Top of page
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    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    12. Preview
    1. Biomimetic Materials

      Modular Design in Natural and Biomimetic Soft Materials (pages 9026–9057)

      Dr. Aaron M. Kushner and Prof. Dr. Zhibin Guan

      Article first published online: 5 SEP 2011 | DOI: 10.1002/anie.201006496

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      Nature's bounty: Recent advances in analytical and synthetic tools are facilitating the development of materials inspired by nature. This Review highlights the history and the state-of-the-art in the quest to understand the molecular mechanisms behind nature's most remarkable peptide-based materials, as well as the attempts to apply that understanding to design biomimetic materials.

  10. Communications

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

      You have full text access to this OnlineOpen article
      Label-Free Detection of Single-Base Mismatches in DNA by Surface-Enhanced Raman Spectroscopy (pages 9058–9061)

      Evanthia Papadopoulou and Dr. Steven E. J. Bell

      Article first published online: 19 JUL 2011 | DOI: 10.1002/anie.201102776

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      Singles only: DNA sequences can be induced to spontaneously adsorb to the surfaces of Ag colloids through their nucleotide side chains (see picture). The SERS spectra of these nonspecifically bound strands are sufficiently reproducible that they can be used to identify single-base mismatches in short (25-mer and 23-mer) strands. Subtracting the spectra of different DNA sequences results in difference spectra that contain features corresponding to the exchanged nucleotides.

    2. Ruthenium Catalysis

      Ruthenium-Catalyzed Coupling of Oxabenzonorbornadienes with Alkynes Bearing a Propargylic Oxygen Atom: Access to Stereodefined Benzonorcaradienes (pages 9062–9065)

      Dr. Alphonse Tenaglia, Sylvain Marc, Laurent Giordano and Innocenzo De Riggi

      Article first published online: 19 AUG 2011 | DOI: 10.1002/anie.201104589

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      Stereodefined: The title reaction provides an atom-economic route to benzonorcaradienes. The diastereoselectivity of the coupling relies upon the structure of the alkene; unsubstituted bicyclic alkenes afforded exclusively exo-benzonorcaradienes (see scheme) whereas the bicyclic alkenes with substituents at the bridgehead positions resulted in endo-benzonorcaradienes.

    3. Layered Compounds

      Copper Hydroxide Ethanedisulfonate: A Cationic Inorganic Layered Material for High-Capacity Anion Exchange (pages 9066–9070)

      Honghan Fei and Prof. Scott R. J. Oliver

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201104200

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      Cationic layers: Copper hydroxide ethanedisulfonate consists of cationic sheets (see structure of a [Cu4(OH)6]2+ layer; Cu green, O red, H white) with ethanedisulfonate as extraframework counteranion. This material shows excellent anion exchange properties for both organics and metal oxo anion pollutants, with over five times higher adsorption capacity for permanganate than hydrotalcite.

    4. Metal Oxides

      Enabling the Anodic Growth of Highly Ordered V2O5 Nanoporous/Nanotubular Structures (pages 9071–9075)

      Dr. Yang Yang, Sergiu P. Albu, Dr. Doohun Kim and Prof. Dr. Patrik Schmuki

      Article first published online: 26 AUG 2011 | DOI: 10.1002/anie.201104029

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      Vanadium oxide layers with homogeneous nanoporous nanotubular morphology (see picture) were successfully fabricated by direct anodization of vanadium in fluoride electrolytes such as [TiF6]2− or [BF4]. The pore size and layer thickness can easily be controlled by tailoring the electrochemical conditions. Such nanotubular or porous structures are promising for the fabrication of lithium-ion insertion electrodes.

    5. Gold Catalysis

      Gold(I)-Catalyzed Synthesis of Benzoxocines by an 8-endo-dig Cyclization (pages 9076–9080)

      Dipl.-Chem. Kathrin Wittstein, Dr. Kamal Kumar and Prof. Dr. Herbert Waldmann

      Article first published online: 22 AUG 2011 | DOI: 10.1002/anie.201103832

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      A golden dig! Gold-catalyzed direct access to functionalized 2H-1-benzoxocines, eight-membered-ring ethers, is described. This unprecedented synthesis of benzoxocines occurs by an 8-endo-dig cyclization of the 1,7-enyne substrates.

    6. C[BOND]H Fluorination

      Palladium(II)-Catalyzed Selective Monofluorination of Benzoic Acids Using a Practical Auxiliary: A Weak-Coordination Approach (pages 9081–9084)

      Kelvin S. L. Chan, Masayuki Wasa, Dr. Xisheng Wang and Prof. Dr. Jin-Quan Yu

      Article first published online: 11 JUL 2011 | DOI: 10.1002/anie.201102985

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      Finally, a choice! A highly selective palladium(II)-catalyzed ortho-monofluorination reaction has been achieved for the first time through a weak coordination (see scheme; Ar=2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl). Simple modification of this protocol allows for a choice between mono- and difluorination. The mono- and difluorinated benzoic acid derivatives are valuable in the pharmaceutical and agrochemical industries.

    7. Synthetic Methods

      Synthesis of Trifluoroethyl-Substituted Ketones from Aldehydes and Cyclohexanones (pages 9085–9088)

      Bill Morandi and Prof. Dr. Erick M. Carreira

      Article first published online: 26 AUG 2011 | DOI: 10.1002/anie.201103526

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      A trifluoromethylated symphony! A new transformation involving trifluoromethyl diazomethane generated in situ has been developed that allows direct access to trifluoroethyl ketone derivatives from aldehyde and cyclohexanone compounds (see scheme).

    8. Multicatalytic Reactions

      Domino Rhodium-Catalyzed Alkyne Arylation/Palladium-Catalyzed N Arylation: A Mechanistic Investigation (pages 9089–9092)

      Jane Panteleev, Lei Zhang and Prof. Dr. Mark Lautens

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103692

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      It takes two to tango: A domino multicatalytic synthesis of dihydroquinolines is realized, wherein the products of a rhodium-catalyzed arylation of alkynes are cyclized by a palladium-promoted C[BOND]N cross-coupling (see scheme). The combination of catalysts with potentially exchangeable ligands is remarkable as each metal–ligand combination affords specific reactivity and selectivity.

    9. Polymer Architectures

      Rotaxane-Based Mechanically Linked Block Copolymers (pages 9093–9096)

      Dr. Guillaume De Bo, Dr. Julien De Winter, Dr. Pascal Gerbaux and Prof. Charles-André Fustin

      Article first published online: 18 AUG 2011 | DOI: 10.1002/anie.201103716

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      We just clicked: A convergent approach consisting of two successive copper(I)-catalyzed azide–alkyne cycloaddition “click” reactions leads to a diblock copolymer in which the two blocks are linked by a rotaxane-type mechanical bond (see scheme). Rotaxane formation is templated by a square-planar PdII complex.

    10. Synthetic Methods

      Catalytic and Direct Oxyphosphorylation of Alkenes with Dioxygen and H-Phosphonates Leading to β-Ketophosphonates (pages 9097–9099)

      Wei Wei and Prof. Dr. Jian-Xin Ji

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201100219

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      Direct access: The title reaction has been developed under mild reaction conditions (see scheme; DMSO=dimethyl sulfoxide). This reaction can be effectively scaled up and offers not only a green and attractive approach to β-ketophosphonates, but also a useful example of direct incorporation of an oxygen atom from dioxygen into organic frameworks.

    11. Inhibitors

      Targeting Histone Lysine Demethylases by Truncating the Histone 3 Tail to Obtain Selective Substrate-Based Inhibitors (pages 9100–9103)

      Brian Lohse, Anders L. Nielsen, Jan B. L. Kristensen, Charlotte Helgstrand, Paul A. C. Cloos, Lars Olsen, Michael Gajhede, Rasmus P. Clausen and Jesper L. Kristensen

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201101849

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      How low can you go? The natural substrate for the epigenetic regulators PHF8, JmjD2A, and JmjD2C (lysine demethylases), a peptide consisting of 39 amino acid residues, can be truncated to 14, 8, and 4 amino acids, respectively, while maintaining catalytic activity (see picture). Inhibitors were prepared by attaching small molecules to the truncated substrates. Selective inhibition of JmjD2C over JmjD2A and PHF8 was possible.

    12. Asymmetric Catalysis

      N-Heterocyclic Carbene Catalysis: Enantioselective Formal [2+2] Cycloaddition of Ketenes and N-Sulfinylanilines (pages 9104–9107)

      Teng-Yue Jian, Dr. Lin He, Cen Tang and Prof. Dr. Song Ye

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201102488

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      Sultam of swing: Both enantiomers of 1,2-thiazetidin-3-one oxides were obtained in very good yields with excellent enantioselectivities when using N-heterocyclic carbene catalysts (see scheme; M.S.=molecular sieves, TBS=tert-butyldimethylsilyl). The products were easily converted into 3-oxo-β-sultams, α-mercapto amides, and β-mercapto amines through oxidation or reduction.

    13. Protein Labeling

      Tyrosine-Targeted Spin Labeling and EPR Spectroscopy: An Alternative Strategy for Studying Structural Transitions in Proteins (pages 9108–9111)

      Magali Lorenzi, Carine Puppo, Dr. Régine Lebrun, Sabrina Lignon, Dr. Valérie Roubaud, Dr. Marlène Martinho, Dr. Elisabetta Mileo, Prof. Paul Tordo, Prof. Sylvain R. A. Marque, Dr. Brigitte Gontero, Prof. Bruno Guigliarelli and Dr. Valérie Belle

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201102539

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      Keeping tabs on tyrosine: A three-component Mannich-type reaction extends the scope of site-directed spin labeling by selectively labeling the unique tyrosine residue of CP12 protein (see picture), as was confirmed by mass spectrometry. EPR spectroscopy of the labeled protein showed a very high mobility of the probe, which remained very mobile after complex formation with GAPDH.

    14. Total Synthesis

      Enantioselective Synthesis of (−)-Exiguolide by Iterative Stereoselective Dioxinone-Directed Prins Cyclizations (pages 9112–9115)

      Erika A. Crane, Dr. Thomas P. Zabawa, Rebecca L. Farmer and Prof. Dr. Karl A. Scheidt

      Article first published online: 17 AUG 2011 | DOI: 10.1002/anie.201102790

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      Three become one: The title compound can be prepared in 26 steps by employing a unified Prins cyclization strategy to construct both tetrahydropyran rings (see scheme). The route combines two similar dioxinone fragments and one aldehyde component to generate the core structure. (−)-Exiguolide selectively inhibits the growth of A549 cancer cells at low concentrations; the triene side chain and the Z-enoate geometry are both necessary for this cytotoxicity.

    15. Alkaloid Synthesis

      Catalytic Enantioselective Total Synthesis of Hodgkinsine B (pages 9116–9119)

      Robert H. Snell, Dr. Robert L. Woodward and Dr. Michael C. Willis

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103864

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      The power of palladium: The total synthesis of the alkaloid hodgkinsine B has been achieved with just six isolated intermediates and only four chromatographic operations. The route involves a palladium-catalyzed enantioselective desymmetrizing N-allylation of meso- chimonanthine to establish the absolute configuration and elaboration of the desymmetrized core by a diastereoselective palladium-catalyzed α-oxindole arylation.

    16. Trifluoromethylation

      Copper-Catalyzed Trifluoromethylation of Unactivated Olefins (pages 9120–9123)

      Dr. Andrew T. Parsons and Prof. Dr. Stephen L. Buchwald

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201104053

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      Activating the inactive: A copper-catalyzed allylic trifluoromethylation of unactivated terminal olefins proceeds under mild conditions to produce linear allylic trifluoromethylated products with high E/Z selectivity (see scheme). The reaction can be applied to a range of substrates bearing numerous functional groups. Furthermore, the reaction is scalable and amenable to a benchtop setup.

    17. Asymmetric Synthesis

      Enantioselective Michael/Cyclization Reaction Sequence: Scaffold-Inspired Synthesis of Spirooxindoles with Multiple Stereocenters (pages 9124–9127)

      Dr. Yiming Cao, Dr. Xianxing Jiang, Luping Liu, Fangfang Shen, Futing Zhang and Prof. Dr. Rui Wang

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201104216

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      A-spiro-ing: The title reaction of α-isothiocyanato imides and methyleneindolinones has been realized for the first time using 1 as the catalyst. This newly developed synthetic method provides a simple, efficient, and environmentally friendly way to access, in an enantioselective manner, densely functionalized spirooxindoles having three contiguous stereogenic centers.

    18. Materials Chemistry

      Brightly Tricolored Mechanochromic Luminescence from a Single-Luminophore Liquid Crystal: Reversible Writing and Erasing of Images (pages 9128–9132)

      Dr. Yoshimitsu Sagara and Prof. Takashi Kato

      Article first published online: 27 JUL 2011 | DOI: 10.1002/anie.201100914

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      A glowing image: The photoluminescent colors reddish-orange, yellow, and green, are generated from a single liquid-crystalline mixture containing one luminophore (see picture). The colors are easily distinguished by the naked eye and can be reversibly written and erased. Moreover, these luminescent colors can be switched by mechanical and thermal stimuli.

    19. Chirality

      Magneto-Chiral Dichroism of Organic Compounds (pages 9133–9136)

      Yuichi Kitagawa, Prof. Dr. Hiroshi Segawa and Prof. Dr. Kazuyuki Ishii

      Article first published online: 27 JUL 2011 | DOI: 10.1002/anie.201101809

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      Direction decides: Magneto-chiral dichroism describes the dependence of the absorbance of a chiral molecule on the direction of a magnetic field to which it is exposed, and it may help to explain the homochirality of life. This phenomenon was now observed in organic compounds using porphyrin J-aggregates.

    20. In Vivo Electron Transport

      Observation of In Vivo Cytochrome-Based Electron-Transport Dynamics Using Time-Resolved Evanescent Wave Electroabsorption Spectroscopy (pages 9137–9140)

      Toshihiko Shibanuma, Dr. Ryuhei Nakamura, Yuichiro Hirakawa, Prof. Dr. Kazuhito Hashimoto and Prof. Dr. Kazuyuki Ishii

      Article first published online: 2 AUG 2011 | DOI: 10.1002/anie.201101810

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      Morning light: In vivo photodissociation of CO from bacterial c-type cytochromes yields a redox-active Fe2+ form, which can be oxidized at an electrode surface to the Fe3+ form. Reduction by electrons from the metabolic pathway regenerates the Fe2+ form (see picture). Spectroscopic monitoring of this process yields information on the in vivo respiratory electron-transport dynamics.

    21. Structure–Property Relationships

      NaSr3Be3B3O9F4: A Promising Deep-Ultraviolet Nonlinear Optical Material Resulting from the Cooperative Alignment of the [Be3B3O12F]10− Anionic Group (pages 9141–9144)

      Hongwei Huang, Jiyong Yao, Zheshuai Lin, Xiaoyang Wang, Ran He, Wenjiao Yao, Naixia Zhai and Prof. Chuangtian Chen

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103960

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      Structure matters: Owing to the structure and arrangement of the [Be3B3O12F]10− group (see picture, left, Be blue, B olive, F green, O red), the mixed-cation fluorine beryllium borate NaSr3Be3B3O9F4 (right) exhibits a large second harmonic generation effect and a short UV absorption edge. Its crystals show no layering tendency, making it promising for applications in deep-UV nonlinear optics.

    22. DNA Crystal Growth

      Coverage Control of DNA Crystals Grown by Silica Assistance (pages 9145–9149)

      Junwye Lee, Sunho Kim, Junghoon Kim, Dr. Chang-Won Lee, Prof. Yonghan Roh and Prof. Sung Ha Park

      Article first published online: 26 AUG 2011 | DOI: 10.1002/anie.201103604

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      A surface-assisted fabrication scheme enables direct surface coverage control of functionalized DNA nanostructures on centimeter-scaled silica (SiO2) substrates from 0 to 100 % (see picture). Electrostatic interactions between the DNA structures and the surface lead to dramatic topological changes of the structures, thereby creating novel formations of the crystals.

    23. Self-Assembly

      Deconstruction of Capsules Using Chiral Spacers (pages 9150–9153)

      Dr. Yoshihiro Yamauchi, Prof. Dariush Ajami, Ji-Yeon Lee and Prof. Julius Rebek Jr.

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103031

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      Interconvertible host: Extended cavitands and capsules that recognize n-alkanes were generated using N-methyl glycoluril as a chiral spacer. The two host assemblies were interconverted by factors such as temperature, concentration, and guest length (see scheme).

    24. Polyoxometalates

      A Mixed-Valence Manganese Cubane Trapped by Inequivalent Trilacunary Polyoxometalate Ligands (pages 9154–9157)

      Dr. Scott G. Mitchell, Pedro I. Molina, Dr. Sumit Khanra, Dr. Haralampos N. Miras, Dr. Alessandro Prescimone, Dr. Geoffrey J. T. Cooper, Ross S. Winter, Dr. Euan K. Brechin, Dr. De-Liang Long, Prof. Richard J. Cogdell and Prof. Leroy Cronin

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201102727

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      Three's a charm: The title compound (see picture, right, WO6 purple polyhedra, Mn orange and brown, Si green, O red) contains an embedded mixed-valence {Mn5O6} cubane core, which is structurally similar to the active site in photosystem II. Solid-, solution-, and gas-phase studies indicate the presence of three lacunary Keggin fragments, thereby giving insight into the complex solution chemistry of plenary POM fragments.

    25. Materials Science

      Enhancement of Proton Transport by Nanochannels in Comb-Shaped Copoly(arylene ether sulfone)s (pages 9158–9161)

      Dr. Nanwen Li, Dr. Chenyi Wang, So Young Lee, Dr. Chi Hoon Park, Prof. Young Moo Lee and Dr. Michael D. Guiver

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201102057

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      Combed to perfection: Fully aromatic comb-shaped copolymers based on a poly(arylene ether sulfone) (PAES) backbone with highly sulfonated (SA) poly(phenylene oxide) (PPO) graft chains have a nanochannel morphology (see picture) for efficient proton transport. These molecular structures show a dramatic enhancement in proton conductivity under partially hydrated conditions compared with typical hydrocarbon polymer electrolytes.

    26. Polymer Self-Assembly

      Molecular Self-Assembly of a Homopolymer: An Alternative To Fabricate Drug-Delivery Platforms for Cancer Therapy (pages 9162–9166)

      Jinyao Liu, Prof. Dr. Wei Huang, Yan Pang, Ping Huang, Prof. Dr. Xinyuan Zhu, Prof. Dr. Yongfeng Zhou and Prof. Dr. Deyue Yan

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201102280

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      The best of both worlds: A novel amphiphilic homopolymer synthesized from a monomer consisting of a hydrophobic group (see picture, red) and a hydrophilic moiety (green) self-assembles in aqueous solution. The resulting micelles have a multi-core/shell structure and exhibit smart redox-responsive properties, thus providing a favorable drug delivery platform for cancer therapy.

    27. Dual-Modality Imaging Agents

      Sequential SPECT and Optical Imaging of Experimental Models of Prostate Cancer with a Dual Modality Inhibitor of the Prostate-Specific Membrane Antigen (pages 9167–9170)

      Dr. Sangeeta Ray Banerjee, Mrudula Pullambhatla, Dr. Youngjoo Byun, Dr. Sridhar Nimmagadda, Dr. Catherine A. Foss, Gilbert Green, James J. Fox, Dr. Shawn E. Lupold, Dr. Ronnie C. Mease and Prof.Dr. Martin G. Pomper

      Article first published online: 22 AUG 2011 | DOI: 10.1002/anie.201102872

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      One reagent for two techniques: Compound [111In]1 provides a platform for sequential radionuclide and optical imaging of prostate cancer through targeting of the prostate-specific membrane antigen. Because the same subject can be dual-imaged after one injection of the agent, these findings support rapid clinical translation.

    28. Synthetic Methods

      Highly Enantioselective and Efficient Asymmetric Epoxidation Catalysts: Inorganic Nanosheets Modified with α-Amino Acids as Ligands (pages 9171–9176)

      Jiuzhao Wang, Liwei Zhao, Huimin Shi and Prof. Jing He

      Article first published online: 26 AUG 2011 | DOI: 10.1002/anie.201103713

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      Layered catalyst: The attachment of α-amino acid ligands to inorganic nanosheets for use as ligands to vanadium, resulted in a catalyst that enhanced the enantioselectivity of the epoxidation of allylic alcohols (see picture) . The catalyst can be colloidized, allowing for the catalytic reactions to be carried out under pseudo-homogeneous reaction conditions and also the catalysts to be directly recycled by simple liquid/liquid separation.

    29. Natural Product Synthesis

      A Synthetic Study of Atropurpuran: Construction of a Pentacyclic Framework by an Intramolecular Reverse-Electron-Demand Diels–Alder Reaction (pages 9177–9179)

      Dr. Takahiro Suzuki, Aya Sasaki, Naoki Egashira and Prof. Dr. Susumu Kobayashi

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103950

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      Masked talent: A tetracyclo[5.3.3.04,9.04,12]tridecane skeleton can be accessed by an intramolecular reverse-electron-demand Diels–Alder (REDDA) reaction of masked ortho-benzoquinone (MOB; see scheme). This reaction gives access to the pentacyclic framework of atropurpuran, and also enables the construction of other anti-Bredt and cage-like complex molecules.

    30. Chemoselective Reduction

      Selective Catalytic Monoreduction of Phthalimides and Imidazolidine-2,4-diones (pages 9180–9184)

      Shoubhik Das, Dr. Daniele Addis, Leif R. Knöpke, Dr. Ursula Bentrup, Dr. Kathrin Junge, Prof. Dr. Angelika Brückner and Prof. Dr. Matthias Beller

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201104226

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      Fluoride's new role: Selective and efficient monoreductions of imides can be achieved with polymethylhydrosiloxane (PMHS) and tetra-n-butylammonium fluoride (TBAF) as catalyst (see scheme). The system is characterized by good chemoselectivity, operational simplicity, and functional-group tolerance; a concise mechanistic proposal was possible from in situ spectroscopic investigations.

    31. Self-Assembly

      DNA-Linked Nanoparticle Building Blocks for Programmable Matter (pages 9185–9190)

      Prof. Jin-Woo Kim, Dr. Jeong-Hwan Kim and Prof. Russell Deaton

      Article first published online: 2 SEP 2011 | DOI: 10.1002/anie.201102342

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      One step at a time: DNA linkers were placed at defined locations and in defined 3D orientations on a colloidal nanoparticle. Because the implemented ligand-replacement strategy was carried out sequentially, DNA linkers maximally segregated, producing a nanoparticle with linkers at 90 or 180° angles (see picture). These building blocks should enable assembly of anisotropic nanostructures with precisely designed geometry and complex functionality.

    32. Iron–Sulfur Clusters

      The Complete Characterization of a Reduced Biomimetic [2 Fe-2 S] Cluster (pages 9191–9194)

      Antonia Albers, Dr. Serhiy Demeshko, Dr. Sebastian Dechert, Dr. Eckhard Bill, Dr. Eberhard Bothe and Prof. Dr. Franc Meyer

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201100727

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      Cores and effect: A biomimetic [2 Fe-2 S] cluster is characterized crystallographically in both the [FeIIIFeIII] and the mixed-valent [FeIIIFeII] forms—the [2 Fe-2 S] cores show only minor geometric differences. The reduced form has an S=1/2 ground state and the unpaired electron is partially delocalized over the cluster core. The experimental effective coupling constant predicts the position of the intervalence charge transfer band in the IR regime.

    33. Superconductors

      Superconductivity up to 35 K in the Iron Platinum Arsenides (CaFe1−xPtxAs)10Pt4−yAs8 with Layered Structures (pages 9195–9199)

      Catrin Löhnert, Tobias Stürzer, Dr. Marcus Tegel, Rainer Frankovsky, Gina Friederichs and Prof. Dr. Dirk Johrendt

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201104436

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      The family of iron arsenide superconductors is expanded by the new iron platinum compounds (CaFe1−xPtxAs10)Pt4−yAs8 with novel crystal structures. Layers of FeAs4/4 tetrahedra and of nearly planar PtAs4/2 squares with (As2)4− dumbbells are stacked in different ways, resulting in polytypes with triclinic or tetragonal symmetry. Superconductivity up to 35 K is induced either by Pt doping of the Fe site or by electron transfer from PtAs to FeAs layers.

    34. Post-Translational Modification

      Efficient Synthesis and Applications of Peptides containing Adenylylated Tyrosine Residues (pages 9200–9204)

      Cornelis Smit, Julia Blümer, Martijn F. Eerland, Michael F. Albers, Matthias P. Müller, Prof. Dr. Roger S. Goody, Dr. Aymelt Itzen and Dr. Christian Hedberg

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201103203

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      The enzyme DrrA of the human pathogen Legionella pneumophila adenylylates specifically a tyrosine of the GTPase Rab1. An efficient synthesis route using Fmoc solid phase peptide synthesis led to Tyr-adenylylated peptides and allowed the generation of mono-selective polyclonal antibodies against this post-translational modification.

    35. Organozinc Reagents

      Preparation of Solid Salt-Stabilized Functionalized Organozinc Compounds and their Application to Cross-Coupling and Carbonyl Addition Reactions (pages 9205–9209)

      MSc. Sebastian Bernhardt, Dr. Georg Manolikakes, MSc. Thomas Kunz and Prof. Dr. Paul Knochel

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201104291

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      Powdered organozinc reagents: Various aryl and heteroaryl bromides as well as benzylic chlorides react with Mg and Zn(OPiv)2⋅2 LiCl (OPiv=pivalate) to provide solid organozinc reagents after solvent evaporation. These powders can be stored at room temperature under argon for months and can be manipulated in air for a short time. They undergo smooth Negishi cross-coupling and carbonyl addition reactions (see scheme).

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      Preview: Angew. Chem. Int. Ed. 40/2011 (page 9211)

      Article first published online: 15 SEP 2011 | DOI: 10.1002/anie.201190081

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