Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 39

September 23, 2013

Volume 52, Issue 39

Pages 10127–10387

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Reviews
    10. Communications
    1. You have free access to this content
      Cover Picture: Polymer-Based Muscle Expansion and Contraction (Angew. Chem. Int. Ed. 39/2013) (page 10127)

      Dr. Molla R. Islam, Xue Li, Keady Smyth and Prof. Dr. Michael J. Serpe

      Version of Record online: 15 AUG 2013 | DOI: 10.1002/anie.201306440

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      Humidity-responsive polymer-based muscles were fabricated by exploiting charged microgel and polyelectrolyte interactions as is shown by M. J. Serpe and co-workers in their Communication on page 10330 ff. Favorable interactions between microgels and polyelectrolytes and microgels and a flexible substrate allow the substrate to bend in a manner that depends on environmental humidity. The resulting actuator, or muscle, is able to lift many times its mass in a reproducible manner.

    2. You have free access to this content
      Inside Cover: A Tailored Microenvironment for Catalytic Biomass Conversion in Inorganic–Organic Nanoreactors (Angew. Chem. Int. Ed. 39/2013) (page 10128)

      Ricardo Alamillo, Dr. Anthony J. Crisci, Dr. Jean Marcel R. Gallo, Prof. Susannah L. Scott and Prof. James A. Dumesic

      Version of Record online: 15 AUG 2013 | DOI: 10.1002/anie.201306524

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      The highly selective conversion of biomass-derived fructose into 5-hydroxymethylfurfural (HMF) can be achieved through the use of a tailored nanocomposite catalyst. In their Communication on page 10349 ff., S. L. Scott, J. A. Dumesic, et al. describe a simple and effective method for manipulating the reaction microenvironment, through the confinement of polymers within a mesoporous catalyst, to control the fructose tautomer distribution and consequentially the HMF selectivity.

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      Inside Back Cover: Detection of Individual Vapors and Their Mixtures Using a Selectivity-Tunable Three-Dimensional Network of Plasmonic Nanoparticles (Angew. Chem. Int. Ed. 39/2013) (page 10389)

      Dr. Radislav A. Potyrailo, Michael Larsen and Orrie Riccobono

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201307183

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      Detection selectivity remains the key challenge for the development of vapor sensors that limits their applications in complex environments. In their Communication on page 10360 ff., R. A. Potyrailo et al. describe the detection of individual vapors and their mixtures by using only a single sensing film formed from a three-dimensional network of plasmonic nanoparticles. The tunable selectivity is achieved within a single multivariable sensor.

    4. You have free access to this content
      Back Cover: Ligand-Induced Conformational Changes of the Multidrug Resistance Transporter EmrE Probed by Oriented Solid-State NMR Spectroscopy (Angew. Chem. Int. Ed. 39/2013) (page 10390)

      Dr. Anindita Gayen, James R. Banigan and Prof. Nathaniel J. Traaseth

      Version of Record online: 20 AUG 2013 | DOI: 10.1002/anie.201306525

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      Oriented solid-state NMR spectra in aligned bicelles with respect to the magnetic field (B0) were used to determine the asymmetric tilt angles of the membrane transporter EmrE. In their Communication on page 10321 ff., N. J. Traaseth and co-workers show that ligand-free EmrE forms antiparallel dimers with different monomer tilt angles relative to the lipid bilayer. Using this approach, subtle ligand-induced conformational changes within the apo structure were also detected.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Reviews
    10. Communications
    1. 50 Years Ago ... (page 10144)

      Version of Record online: 19 SEP 2013 | DOI: 10.1002/anie.201306147

      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
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    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Reviews
    10. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Reviews
    10. Communications
    1. Gautam R. Desiraju (pages 10152–10153)

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201302516

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      “Chemistry is fun because it is an assault on the senses! My favorite quote is ‘To strive, to seek, to find, and not to yield’ from Tennyson's poem ‘Ulysses’ …” This and more about Gautam R. Desiraju can be found on page 10152.

  6. News

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    8. Book Review
    9. Reviews
    10. Communications
  7. Book Review

    1. Top of page
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    1. Carbohydrates—Tools for Stereoselective Synthesis. Edited by Mike Martin Kwabena Boysen. (page 10156)

      George A. O'Doherty

      Version of Record online: 22 AUG 2013 | DOI: 10.1002/anie.201305971

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      Wiley-VCH, Weinheim, 2013. 377 pp., hardcover, € 139.00.—ISBN 978-3527323791

  8. Reviews

    1. Top of page
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    4. Flashback
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    7. News
    8. Book Review
    9. Reviews
    10. Communications
    1. Quantum Electrodynamics

      Controlling Photons in a Box and Exploring the Quantum to Classical Boundary (Nobel Lecture) (pages 10158–10178)

      Prof. Serge Haroche

      Version of Record online: 20 AUG 2013 | DOI: 10.1002/anie.201302971

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      Photons trapped in a superconducting cavity constitute an ideal system to realize some of the thought experiments imagined by the founding fathers of quantum physics. Physics laureate S. Haroche gives a personal account of the experiments performed with this “photon box” at the Ecole Normale Supérieure.

    2. Quantum Mechanics

      Superposition, Entanglement, and Raising Schrödinger’s Cat (Nobel Lecture) (pages 10179–10189)

      Dr. David J. Wineland

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201303404

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      Experimental control of quantum systems has been pursued widely since the invention of quantum mechanics. Today, we can in fact experiment with individual quantum systems, deterministically preparing superpositions and entanglements. In his Nobel lecture, D. J. Wineland gives an overview of this research which has led to the Nobel prize in physics in 2012.

  9. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
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    6. Author Profile
    7. News
    8. Book Review
    9. Reviews
    10. Communications
    1. Agostic Isomers

      Isolation of Two Agostic Isomers of an Organometallic Cation: Different Structures and Colors (pages 10190–10194)

      Dr. Edwin F. van der Eide, Dr. Ping Yang and Dr. R. Morris Bullock

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/anie.201305032

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      Two of a kind: Two agostic isomers of [CpMo(CO)2(PiPr3)]+ B(C6F5)4 have been isolated. Both were characterized in the solid state by X-ray crystallography and spectroscopic techniques, and also by DFT calculations. Significantly different LUMO energies cause the difference in color (blue versus orange, see picture) of these isomers.

    2. Proton Catalysis

      Trifluoromethanesulfonic Acid Catalyzed Synergetic Oxidative/[3+2] Cyclization of Quinones with Olefins (pages 10195–10198)

      Lingkui Meng, Guanghui Zhang, Dr. Chao Liu, Kun Wu and Prof. Aiwen Lei

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305885

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      The proton did it! Tetrahydrobenzodifurans have been synthesized through the trifluoromethanesulfonic acid (HOTf) catalyzed direct oxidative C[BOND]H functionalization of benzoquinone with olefins. A variety of substituents were found to be tolerated, and a synergetic oxidative/[3+2] cyclization mechanism was proposed based on the experimental results.

    3. Germanium Complexes

      Activation of H2 by a Multiply Bonded Amido–Digermyne: Evidence for the Formation of a Hydrido–Germylene (pages 10199–10203)

      Terrance J. Hadlington, Markus Hermann, Jiaye Li, Prof. Dr. Gernot Frenking and Prof. Cameron Jones

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305689

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      The long and the short of it. The first amido–digermyne to possess a short Ge–Ge multiple bond, [LGeGeL], has been prepared and shown to activate H2 below 0 °C, thereby yielding the hydrido–digermene, [L(H)Ge[DOUBLE BOND]Ge(H)L]. This possesses a very long Ge[DOUBLE BOND]Ge bond. Spectroscopic and theoretical data indicate that the dimer dissociates in solution to give the two-coordinate hydrido–germylene, [:Ge(H)(L)]. L=N(Ar)(SiiPr3), Ar=2,6-[C(H)Ph2]2-4-iPrC6H2.

    4. Natural Product Synthesis

      Dearomatizing Conjugate Addition to Quinolinyl Amidines for the Synthesis of Dehaloperophoramidine through Tandem Arylation and Allylation (pages 10204–10207)

      Takayuki Ishida, Hideo Ikota, Kei Kurahashi, Dr. Chihiro Tsukano and Prof. Dr. Yoshiji Takemoto

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201305581

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      Dehaloperophoramidine, the dehalogenated analogue of the marine hexacyclic alkaloid perophoramidine was synthesized. The intramolecular nucleophilic dearomatizing arylation of aminoquinoline initiated by a lithium–iodine exchange and the subsequent direct allylation of the resultant azaenolate afforded a pentacyclic bisamidine compound bearing two contiguous all-carbon quaternary centers in good yield with excellent diastereoselectivity.

    5. Crystal Polymorphs

      Using Magnetic Levitation to Separate Mixtures of Crystal Polymorphs (pages 10208–10211)

      Dr. Manza B. J. Atkinson, Dr. David K. Bwambok, Dr. Jie Chen, Dr. Prashant D. Chopade, Dr. Martin M. Thuo, Dr. Charles R. Mace, Dr. Katherine A. Mirica, Ashok A. Kumar, Prof. Dr. Allan S. Myerson and Prof. Dr. George M. Whitesides

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305549

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      Magnetic levitation (MagLev) provides a simple method for the separation of crystal polymorphs that differ in density (Δρ) by greater than 0.001 g cm−3. Density-based separations of multiple crystalline forms were shown for four organic compounds: 5-methyl-2-[(2-nitro- phenyl)amino]-3-thiophenecarbonitrile, sulfathiazole, carbamazepine, and trans- cinnamic acid.

    6. Peptide Cyclization

      Synthesis of Constrained Head-to-Tail Cyclic Tetrapeptides by an Imine-Induced Ring-Closing/Contraction Strategy (pages 10212–10215)

      Dr. Clarence T. T. Wong, Hiu Yung Lam, Dr. Tao Song, Prof. Dr. Guanhua Chen and Prof. Dr. Xuechen Li

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304773

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      Making heads or tails of it: A strategy involving a head-to-tail imine-captured ring closure followed by ring contraction was used to synthesize otherwise difficult cyclic tetrapeptides. Compared with the direct lactamization process, the estimated activation energies for the cyclic imine formation and the ring contraction were lowered by 7.3 and 7.6 kcal mol−1, respectively, which enables cyclization.

    7. Carbon Nanotubes

      Stable Electron Donor–Acceptor Nanohybrids by Interfacing n-Type TCAQ with p-Type Single-Walled Carbon Nanotubes (pages 10216–10220)

      Dr. Carlos Romero-Nieto, Dr. Raúl García, Dr. María Ángeles Herranz, Dr. Laura Rodríguez-Pérez, Dr. Macarena Sánchez-Navarro, Dr. Javier Rojo, Prof. Dr. Nazario Martín and Prof. Dr. Dirk M. Guldi

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304032

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      Tuning the electronics of nanotubes: Electron-accepting 11,11,12,12-tetracyano-9,10-anthraquinodimethane (TCAQ) nanotweezers endowed with a carboxylic acid-containing dendrimeric moiety form exceptionally stable n-/p-type dispersions with single-walled carbon nanotubes (SWCNTs) in water. Upon photoexcitation, the nanohybrids undergo a less common electron transfer from the SWCNTs to the TCAQ nanotweezers (see picture).

    8. Glycopeptide Foldamers

      Sugar-Modified Foldamers as Conformationally Defined and Biologically Distinct Glycopeptide Mimics (pages 10221–10226)

      Dr. Aloysius Siriwardena, Kiran Kumar Pulukuri, Pancham S. Kandiyal, Dr. Saumya Roy, Dr. Omprakash Bande, Dr. Subhash Ghosh, Dr. José Manuel Garcia Fernández, Dr. Fernando Ariel Martin, Dr. Jean-Marc Ghigo, Dr. Christophe Beloin, Dr. Keigo Ito, Dr. Robert J. Woods, Dr. Ravi Sankar Ampapathi and Dr. Tushar Kanti Chakraborty

      Version of Record online: 13 AUG 2013 | DOI: 10.1002/anie.201304239

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      To fold or not to fold? It is shown that attached sugars play a defining role in the conformations adopted by a pair of novel SAA-derived foldamers in water and that these differences are reflected in the contrasting interactions of these glycofoldamers with various biological targets. C green, O red, N blue, H gray; yellow oval=mannose.

    9. Kinetic Resolution

      Kinetic Resolution of Secondary Alcohols Catalyzed by Chiral Phosphoric Acids (pages 10227–10230)

      Dr. Shingo Harada, Satoru Kuwano, Dr. Yousuke Yamaoka, Prof. Dr. Ken-ichi Yamada and Prof. Dr. Kiyosei Takasu

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304281

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      Acid instead of base: Kinetic resolution of secondary alcohols is realized using chiral Brønsted acid catalyzed acylation instead of the conventional basic conditions. A broad range of functional groups are tolerated, such as aldehydes, carboxylic acids, and enoates. The selectivity factor (s) reaches up to 215 at ambient temperature.

    10. Template Synthesis

      Sodium Ions Template the Formation of Rotaxanes from BPX26C6 and Nonconjugated Amide and Urea Functionalities (pages 10231–10236)

      You-Han Lin, Prof. Chien-Chen Lai, Yi-Hung Liu, Prof. Shie-Ming Peng and Prof. Sheng-Hsien Chiu

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304636

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      Picking up the thread: The macrocycle bis-p-xylyl[26]crown-6 is capable of forming pseudorotaxane-like structures with single, nonconjugated urea or amide moieties when assisted by templating Na+ ions (see example). By using this approach, rotaxanes were synthesized with glycine residues or the repeating unit of nylon-6,6 as key components in the threadlike units.

    11. Guest-Responsive Materials

      Actuated Conformational Switching in a Single Crystal of a Homodithiacalix[4]arene (pages 10237–10240)

      Dr. Joice Thomas, Gunter Reekmans, Prof. Peter Adriaensens, Prof. Luc Van Meervelt, Prof. Mario Smet, Prof. Wouter Maes, Prof. Wim Dehaen and Dr. Liliana Dobrzańska

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201302822

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      Frozen but flexible: The conformational flexibility of calixarene molecules is not only limited to solution. It can also manifest itself in single crystals as a response to the right external stimuli.

    12. Flow Chemistry

      In Situ Generation of Diimide from Hydrazine and Oxygen: Continuous-Flow Transfer Hydrogenation of Olefins (pages 10241–10244)

      Bartholomäus Pieber, Dr. Sabrina Teixeira Martinez, Dr. David Cantillo and Prof. C. Oliver Kappe

      Version of Record online: 14 AUG 2013 | DOI: 10.1002/anie.201303528

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      No catalyst required! A highly efficient, catalyst-free process to generate diimide in situ from hydrazine monohydrate and molecular oxygen for the selective reduction of alkenes has been developed. The use of a gas–liquid segmented flow system allowed safe operating conditions and dramatically enhanced this atom-economical reaction, resulting in short processing times.

    13. Asymmetric Catalysis

      Chiral Scandium(III)-Catalyzed Enantioselective α-Arylation of N-Unprotected 3-Substituted Oxindoles with Diaryliodonium Salts (pages 10245–10249)

      Jing Guo, Shunxi Dong, Yulong Zhang, Yulong Kuang, Prof. Dr. Xiaohua Liu, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Version of Record online: 9 SEP 2013 | DOI: 10.1002/anie.201303602

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      Catalytic asymmetric α-arylation of N-unprotected 3-substituted oxindoles with diaryliodonium salts has been realized by a chiral Lewis acid promoted electrophilic addition and aryl-rearrangement process. Single C3-arylated products containing a quaternary carbon center were generated in high enantioselectivity and reactivity.

    14. Copper Complexes

      The X-ray Crystal Structure of a Cuprate–Carbonyl π-Complex (pages 10250–10252)

      Prof. Dr. Steven H. Bertz, Richard A. Hardin, Thomas J. Heavey and Prof. Dr. Craig A. Ogle

      Version of Record online: 13 AUG 2013 | DOI: 10.1002/anie.201303783

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      Why is it π? The first X-ray crystal structure of a cuprate–carbonyl π-complex has been obtained for the intermediate prepared from Me2CuLi and fluorenone (see scheme). It is also the first structure of a π-complex between an organocuprate and a double bond of any kind.

    15. Reaction Intermediates

      Trapping Formaldehyde in the Homogeneous Catalytic Reduction of Carbon Dioxide (pages 10253–10255)

      Dr. Sébastien Bontemps and Dr. Sylviane Sabo-Etienne

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/anie.201304025

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      Formaldehyde detectives: Evidence for the production of formaldehyde during a ruthenium-catalyzed CO2 reduction process, and for its involvement in the formation of the resulting C2 compound, is disclosed. Ultimately, formaldehyde can be recovered by methanol trapping. HBPin=pinacolborane.

    16. Quintuple Bond

      Haloacylation of the Quintuple-Bonded Group VI Metal Amidinate Dimers and Disproportionation of Acyl Groups to Form Carbynes (pages 10256–10260)

      Han-Gung Chen, Hsiang-Wen Hsueh, Ting-Shen Kuo and Prof. Dr. Yi-Chou Tsai

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304750

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      Give me five: Group VI metal quintuple bonds undergo Friedel–Crafts-type haloacylation reactions. Treatment of the quintuple-bonded molybdenum complexes with one equivalent of acyl halides RCOX (R=Me, C6H5, 2-MeC6H4; X=Cl, Br), yields metal–metal quadruple-bonded acyl complexes. Subsequent treatment with a second equivalent of acyl halides causes disproportionation of two acyl groups to give dimolybdenum carbyne carboxylate complexes.

    17. Surface Modification

      Surface Patterning Using Two-Phase Laminar Flow and In Situ Formation of Aryldiazonium Salts (pages 10261–10264)

      Dr. Andrew J. Gross, Dr. Volker Nock, Dr. Matthew I. J. Polson, Prof. Maan M. Alkaisi and Prof. Alison J. Downard

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305024

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      In the reaction zone: Reaction of an aryltriazene with acid generates the corresponding aryldiazonium ion. When this reaction takes place in the mixing zone, at the interface between two streams flowing laminarly and in parallel through a 100 μm microchannel, a submicrometer line of organic film is grafted at the substrate surface.

    18. Asymmetric Catalysis

      Copper-Catalyzed Enantioselective Henry Reaction of Enals and Subsequent Iodocyclization: Stereoselective Construction of Chiral Azatricyclic Frameworks (pages 10265–10269)

      Dr. Yirong Zhou, Yuequan Zhu, Shaobai Yan and Prof. Dr. Yuefa Gong

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201305148

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      In the frame: A cascade sequence combining an asymmetric Henry reaction and a stereoselective intramolecular iodocyclization provides direct access to an enantioenriched tricyclic hexahydrochromeno[4,3-b]pyrrole framework (see scheme). The Henry reaction is catalyzed by copper in the presence of L1.

    19. Molecular Devices

      An Anion-Modulated Three-Way Supramolecular Switch that Selectively Binds Dihydrogen Phosphate, H2PO4 (pages 10270–10274)

      Jesse V. Gavette, Prof. Dr. Nancy S. Mills, Dr. Lev N. Zakharov, Dr. Charles A. Johnson II, Prof. Dr. Darren W. Johnson and Prof. Dr. Michael M. Haley

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201302929

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      An anionic three-way switch: A bipyridyl bis(urea)-based anion receptor that is highly selective for dihydrogen phosphate demonstrates spectroscopically distinct anion-bound conformations toward halides and select oxoanions. 1H NMR studies show the differing anion-induced conformations are reversible allowing this system to function as a three-way molecular switch.

    20. Anion Binding

      Selective Nitrate Binding in Competitive Hydrogen Bonding Solvents: Do Anion–π Interactions Facilitate Nitrate Selectivity? (pages 10275–10280)

      Michelle M. Watt, Dr. Lev N. Zakharov, Prof. Michael M. Haley and Prof. Darren W. Johnson

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201303881

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      New tripodal urea receptors demonstrate preferential binding of anions over competitive hydrogen bonding solvents. 1H NMR titrations in 10 % [D6]DMSO/CDCl3 show a higher affinity for nitrate over the halides for the fluorinated receptor, which is lost when the fluorine atoms are absent. An anion–π interaction between the nitrate and the π-system of the ethynyl-substituted arene is proposed as the source of this selectivity.

    21. Gold Photochemistry

      Photoinduced Gold(I)–Gold(I) Chemical Bonding in Dicyanoaurate Oligomers (pages 10281–10285)

      Dr. Ganglong Cui, Dr. Xiao-Yan Cao, Prof. Dr. Wei-Hai Fang, Prof. Dr. Michael Dolg and Prof. Dr. Walter Thiel

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305487

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      Not only σ*σ but also σ*π: High-level electronic structure calculations reveal the σ*σ and σ*π bonding patterns for AuI–AuI bonding in excited states and suggest two conformation-dependent photophysical relaxation mechanisms for dicyanoaurate oligomers (n=2–5; see picture) in aqueous solution. These insights into the excited-state electronic structure should also be relevant for other gold complexes with a similar gold scaffold.

    22. Target Identification

      Identification of Malate Dehydrogenase 2 as a Target Protein of the HIF-1 Inhibitor LW6 using Chemical Probes (pages 10286–10289)

      Prof. Kyeong Lee, Dr. Hyun Seung Ban, Ravi Naik, Ye Seul Hong, Seohyun Son, Dr. Bo-Kyung Kim, Dr. Yan Xia, Prof. Kyung Bin Song, Dr. Hong-Sub Lee and Dr. Misun Won

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304987

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      Tracking the target: To identify a protein that binds directly to the HIF-1α inhibitor LW6, a series of new chemical probes were synthesized with a clickable tag and/or a photoactivatable moiety. LW6 was found to be localized to the mitochondria (see picture) and MDH2 was identified as a target protein of LW6. These results indicate that the HIF-1α inhibitory activity of LW6 is a consequence of MDH2 suppression.

    23. Biophysics

      You have full text access to this OnlineOpen article
      Long-Range Distances in Amyloid Fibrils of α-Synuclein from PELDOR Spectroscopy (pages 10290–10294)

      Dr. S. Pornsuwan, K. Giller, Dr. D. Riedel, Dr. S. Becker, Prof. C. Griesinger and Prof. M. Bennati

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304747

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      Distance measurements: Pulsed EPR distance measurements combined with strategic spin labeling provide structural constraints at the molecular level for the fold of α-synuclein in amyloid fibrils (see picture; r=distance). The detection of interstrand distances in fibrils will potentially make it possible to extend these measurements to oligomeric states of these protein families.

    24. Smart Materials

      A Self-Powered Polymeric Material that Responds Autonomously and Continuously to Fleeting Stimuli (pages 10295–10299)

      Matthew S. Baker, Vinita Yadav, Prof. Ayusman Sen and Prof. Scott T. Phillips

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304333

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      Pumped up: Building an autoinductive, self-propagating reaction directly into a polymer has resulted in stimuli-responsive materials that are capable of remembering the presence of a stimulus, even after the stimulus is no longer present. As a proof of concept, a nonmechanical, polymer-based pump has been made that is capable of pumping fluids surrounding the polymer when exposed to a fleeting signal (UV light, see picture).

    25. Surface Chemistry

      Polymerization of Polyanthrylene on a Titanium Dioxide (011)-(2×1) Surface (pages 10300–10303)

      Marek Kolmer, Amir A. Ahmad Zebari, Dr. Jakub S. Prauzner-Bechcicki, Dr. Witold Piskorz, Dr. Filip Zasada, Dr. Szymon Godlewski, Dr. Bartosz Such, Prof. Zbigniew Sojka and Prof. Marek Szymonski

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201303657

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      On-surface polymerization is feasible on semiconducting surfaces. Thermally triggered covalent coupling of 10,10′-dibromo-9,9′-bianthryl molecules on the TiO2(011)-(2×1) surface is demonstrated. The result paves the way for application of the thermally driven on-surface polymerization on semiconducting surfaces and indicates that methods based on such a reaction are more universal than previously thought.

    26. Non-equilibrium Self-Assembly

      The Rate of Energy Dissipation Determines Probabilities of Non-equilibrium Assemblies (pages 10304–10308)

      Dr. Konstantin V. Tretiakov, Prof. Igal Szleifer and Prof. Bartosz A. Grzybowski

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201301386

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      Outside thermodynamic equilibrium, outcomes of self-assembly can be dictated not by energy but by the energy dissipation rate. Remarkably, non-equilibrium self-assembly can lead to both low- and high-dissipation structures. The latter, thermodynamically more wasteful structures are exponentially less probable with increasing dissipation rate. This dependence is quantified in a Boltzmann-like relation for non-equilibrium systems.

    27. NMR Spectroscopy

      Crosslinked Poly(ethylene oxide) as a Versatile Alignment Medium for the Measurement of Residual Anisotropic NMR Parameters (pages 10309–10312)

      Christian Merle, Dr. Grit Kummerlöwe, Dr. J. Christoph Freudenberger, Dr. Felix Halbach, Wolfgang Stöwer, Dr. Christoph Lierse v. Gostomski, Dr. Johannes Höpfner, Timo Beskers, Prof. Dr. Manfred Wilhelm and Prof. Dr. Burkhard Luy

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201301929

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      A universal alignment medium for the measurement of anisotropic NMR parameters that can be used for almost any type of sample would be highly useful for structure analysis in solution. Cross-linked poly(ethylene oxide) with incredible solvent and solute compatibility range provides this medium. The picture shows residual 15N chemical shift anisotropies (RCSAs) of 15N-labeled ubiquitin.

    28. Silylium Cations

      Synthesis of a Silylium Zwitterion (pages 10313–10315)

      Rodrigo Ramírez-Contreras, Dr. Nattamai Bhuvanesh, Dr. Jia Zhou and Prof. Oleg V. Ozerov

      Version of Record online: 8 AUG 2013 | DOI: 10.1002/anie.201302082

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      A zwitterionic construction has been synthesized that covalently links a trialkylsilylium cation and a weakly coordinating carborane anion in one neutral molecule (see X-ray structure; Si green, C gray, B orange, Cl red). The silylium character of this molecule is supported by DFT calculations (see LUMO), 29Si CP/MAS NMR spectroscopy, and reactivity.

    29. Metal–Organic Frameworks

      A Water Stable Metal–Organic Framework with Optimal Features for CO2 Capture (pages 10316–10320)

      Prof. Qingyuan Yang, Dr. Sébastien Vaesen, Florence Ragon, Dr. Andrew D. Wiersum, Dong Wu, Dr. Ana Lago, Dr. Thomas Devic, Dr. Charlotte Martineau, Dr. Francis Taulelle, Dr. Philip L. Llewellyn, Dr. Hervé Jobic, Prof. Chongli Zhong, Dr. Christian Serre, Prof. Guy De Weireld and Prof. Guillaume Maurin

      Version of Record online: 20 JUN 2013 | DOI: 10.1002/anie.201302682

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      One flue over the cuckoo's nest: A novel porous Zr-based MOF combining a high chemical stability, easy “green” synthesis and scalability is prepared. This material incorporating carboxylic functions on its organic linkers has thermodynamically and kinetically very promising properties for CO2 capture from post-combustion flue gas under real working conditions.

    30. Membrane Proteins

      Ligand-Induced Conformational Changes of the Multidrug Resistance Transporter EmrE Probed by Oriented Solid-State NMR Spectroscopy (pages 10321–10324)

      Dr. Anindita Gayen, James R. Banigan and Prof. Nathaniel J. Traaseth

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201303091

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      An EmrE-ging market: Oriented solid-state NMR spectroscopy and biochemical cross-linking experiments were used to show that the ligand-free membrane protein transporter EmrE forms anti-parallel dimers with different monomer tilt angles relative to the lipid bilayer. In addition, subtle conformational changes were detected upon drug binding that emphasize the need for an atomic-resolution structure.

    31. Biosensors

      Semiconducting Polymer Nanoprobe for In Vivo Imaging of Reactive Oxygen and Nitrogen Species (pages 10325–10329)

      Dr. Kanyi Pu, Dr. Adam J. Shuhendler and Prof. Jianghong Rao

      Version of Record online: 13 AUG 2013 | DOI: 10.1002/anie.201303420

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      Semiconducting polymer nanoparticles are used as a free-radical inert and light-harvesting nanoplatform for in vivo molecular imaging of reactive oxygen and nitrogen species (RONS). This nanoprobe permits detection of RONS in the microenvironment of spontaneous bacterial infection (see picture; FRET=fluorescence resonance energy transfer).

    32. Polymer Actuation

      Polymer-Based Muscle Expansion and Contraction (pages 10330–10333)

      Dr. Molla R. Islam, Xue Li, Keady Smyth and Prof. Dr. Michael J. Serpe

      Version of Record online: 4 JUL 2013 | DOI: 10.1002/anie.201303475

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      Weight lifting: A polymer-based device capable of lifting many times its own mass was fabricated by drying a solution of the polycation poly(diallyldimethyl ammonium chloride) (pDADMAC) on a surface coated with charged poly(N-isopropylacrylamide)-based microgels. Upon drying of the pDADMAC solution on the microgel-modified surface, it bends. Flexible surfaces then curl up into scroll-like structures, which can be opened up at high humidity.

    33. Controlled Release

      Turning Coacervates into Biohybrid Glass: Core/Shell Capsules Formed by Silica Precipitation in Protein/Polysaccharide Scaffolds (pages 10334–10338)

      Dr. Philipp Erni, Gregory Dardelle, Matthew Sillick, Dr. Kenneth Wong, Pascal Beaussoubre and Dr. Wolfgang Fieber

      Version of Record online: 23 JUL 2013 | DOI: 10.1002/anie.201303489

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      In case of emergency, break glass: Biohybrid core/shell capsules (see picture) suitable for encapsulation of volatile molecules can be formed through precipitation of amorphous silica in a protein/polyanion coacervate scaffold. The coacervate molds the final shape and structure of the capsule shell and provides an acidic microenvironment to locally induce hydrolysis and condensation of liquid silica precursors.

    34. Bioinorganic Chemistry

      Single Glutamate to Aspartate Mutation Makes Ferric Uptake Regulator (Fur) as Sensitive to H2O2 as Peroxide Resistance Regulator (PerR) (pages 10339–10343)

      Aubérie Parent, Christelle Caux-Thang, Dr. Luca Signor, Dr. Martin Clémancey, Dr. Ramakrishnan Sethu, Dr. Geneviève Blondin, Dr. Pascale Maldivi, Dr. Victor Duarte and Dr. Jean-Marc Latour

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304021

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      Let the Fur fly: Mutation of a single glutamate into an aspartate was shown to make the Fe sensor Fur as reactive to H2O2 as the peroxide sensor PerR. In vivo and in vitro peroxide sensitivities of a series of PerR and Fur Asp/Glu mutants were studied by mass spectrometry. A combination of Mössbauer spectroscopy analyses and DFT calculations gave a structural rationale for this behavior.

    35. Metal Heterostructures

      Anisotropic Overgrowth of Metal Heterostructures Induced by a Site-Selective Silica Coating (pages 10344–10348)

      Dr. Feng Wang, Dr. Si Cheng, Dr. Zhihong Bao and Prof. Jianfang Wang

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304364

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      More than skin deep: A selective silica coating on the ends and side of gold nanorods enables the successful selective overgrowth of palladium, gold, platinum, and silver on these surfaces. As a result, eight types of unprecedented metal homo- and heterostructures are produced.

    36. Hybrid Nanoreactors

      A Tailored Microenvironment for Catalytic Biomass Conversion in Inorganic–Organic Nanoreactors (pages 10349–10351)

      Ricardo Alamillo, Dr. Anthony J. Crisci, Dr. Jean Marcel R. Gallo, Prof. Susannah L. Scott and Prof. James A. Dumesic

      Version of Record online: 1 AUG 2013 | DOI: 10.1002/anie.201304693

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      Building a better dehydrator: A nanocomposite catalyst was designed and synthesized expressly for the dehydration of fructose to the platform chemical, 5-hydroxymethylfurfural (HMF). When poly(vinylpyrrolidone) is intercalated and cross-linked inside the acid-functionalized mesopores of silica, the fructose tautomer equilibrium favors HMF production.

    37. Phosphine-Free Hydrogenation

      Asymmetric Hydrogenation of Ketones with H2 and Ruthenium Catalysts Containing Chiral Tetradentate S2N2 Ligands (pages 10352–10355)

      Ruth Patchett, Iris Magpantay, Dr. Lionel Saudan, Dr. Christoph Schotes, Prof. Dr. Antonio Mezzetti and Dr. Francesco Santoro

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201304844

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      Getting more for less: In the presence of H2 and a base, air- and moisture-tolerant RuII complexes catalyze the hydrogenation of ketones and aldehydes with excellent activity and chemoselectivity, and with enantioselectivity of up to 95 % under mild conditions. The ratio of substrate to catalyst can be lowered to 106:1. The reactions tolerate scale-up and can be carried out with almost no solvent. A base-free method is available for base-sensitive substrates.

    38. Atomic Force Microscopy

      Single-Molecule Analysis of the Recognition Forces Underlying Nucleo-Cytoplasmic Transport (pages 10356–10359)

      Dr. Martina Rangl, Prof. Andreas Ebner, Justin Yamada, Dr. Christian Rankl, Prof. Robert Tampé, Prof. Hermann J. Gruber, Prof. Michael Rexach and Prof. Peter Hinterdorfer

      Version of Record online: 5 SEP 2013 | DOI: 10.1002/anie.201305359

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      Transport forces: To move molecules across the nuclear envelope they have to overcome the selective barrier of the nuclear pore which is formed by nucleoporins (nups) with FG repeats. The molecules are chaperoned by shuttling receptors that interact with FG nups thereby passing the barrier using an unresolved mechanism. This process is explored by single-molecule force spectroscopy (see picture).

    39. Multivariable Sensors

      Detection of Individual Vapors and Their Mixtures Using a Selectivity-Tunable Three-Dimensional Network of Plasmonic Nanoparticles (pages 10360–10364)

      Dr. Radislav A. Potyrailo, Michael Larsen and Orrie Riccobono

      Version of Record online: 12 AUG 2013 | DOI: 10.1002/anie.201305303

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      Sensor selectivity: Selective detection of individual vapors and their mixtures is achieved by using a single three-dimensional networked film of organothiol-functionalized plasmonic nanoparticles (see picture). This approach gives a new perspective for sensing, where tunable selectivity is achieved within a single sensing film, rather than from an array of separate conventional sensors.

    40. Sodium Cyclopentadienide

      Strong Intermolecular Interactions Shaping a Small Piano-Stool Complex (pages 10365–10369)

      Dipl.-Chem. Jakob Hey, Dr. Diego M. Andrada, Dipl.-Chem. Reent Michel, Prof. Dr. Ricardo A. Mata and Prof. Dr. Dietmar Stalke

      Version of Record online: 8 AUG 2013 | DOI: 10.1002/anie.201304498

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      The smallest piano stool [CpNa(NH3)3] is not a stand-alone unit in the solid state but is largely shaped by strong intermolecular N[BOND]H⋅⋅⋅π interactions. Small but important structural features, such as the bending of the C[BOND]H bonds inwards to the sodium atom that was confirmed by experimental charge density investigations, could only be reproduced by quantum mechanical calculations that included a lattice of more than 300 units.

    41. Poly(A) Duplex

      Structure of the Parallel Duplex of Poly(A) RNA: Evaluation of a 50 Year-Old Prediction (pages 10370–10373)

      Nozhat Safaee, Dr. Anne M. Noronha, Dmitry Rodionov, Dr. Guennadi Kozlov, Prof. Christopher J. Wilds, Prof. George M. Sheldrick and Prof. Kalle Gehring

      Version of Record online: 27 JUN 2013 | DOI: 10.1002/anie.201303461

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      The other double helix: The molecular structure of double-stranded poly(rA) was predicted in 1961, but it has only now been confirmed. The crystal structure of the parallel double helix of (rA)11 obtained at physiological pH was solved using ab initio direct methods and refined to 1.0 Å resolution. The crystals have bound ammonium ions that are complexed by the RNA phosphates and adenine N1 atoms (see section of the structure).

    42. Model Heme Complexes

      Binding of O2 and CO to Metal Porphyrin Anions in the Gas Phase (pages 10374–10377)

      Dr. Tatjana Karpuschkin, Prof. Dr. Manfred M. Kappes and Priv.-Doz. Dr. Oliver Hampe

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201303200

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      The binding energies of O2 and CO to iron(II) and manganese(II) porphyrin anions has been determined in the gas phase. Low-pressure ion–molecule equilibria have been measured in a cryogenically cooled trap of an FT-ICR mass spectrometer, and binding energies of (40.8±1.3) kJ mol−1 and (66.3±2.6) kJ mol−1 have been obtained for oxygen and carbon monoxide, respectively, with a heme-analogue FeII porphyrin complex.

    43. Protein Aggregation

      Selectively N-Methylated Soluble IAPP Mimics as Potent IAPP Receptor Agonists and Nanomolar Inhibitors of Cytotoxic Self-Assembly of Both IAPP and Aβ40 (pages 10378–10383)

      Dr. Li-Mei Yan, Dr. Aleksandra Velkova, Dipl.-Chem. Marianna Tatarek-Nossol, Prof. Dr. Gerhard Rammes, Dr. Andrei Sibaev, Dr. Erika Andreetto, Dipl.-Ing. Michael Kracklauer, Dipl.-Biochem. Maria Bakou, Dipl.-Chem. Eleni Malideli, Prof. Dr. Burkhard Göke, Prof. Dr. Jörg Schirra, Prof. Dr. Martin Storr and Prof. Dr. Aphrodite Kapurniotu

      Version of Record online: 19 AUG 2013 | DOI: 10.1002/anie.201302840

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      The selective incorporation of N-methyl groups in the highly amyloidogenic and cytotoxic sequence of the type 2 diabetes islet amyloid polypeptide (IAPP) generates a unique class of soluble and nontoxic IAPP mimics. These polypeptides combine potent IAPP receptor agonism with nanomolar-affinity inhibitory potential on the amyloid formation and cell-damaging effects of both IAPP and the Alzheimer's β-amyloid peptide (Aβ40).

    44. Medicinal Chemistry

      Structural Analysis of Phenothiazine Derivatives as Allosteric Inhibitors of the MALT1 Paracaspase (pages 10384–10387)

      Florian Schlauderer, Dr. Katja Lammens, Daniel Nagel, Dr. Michelle Vincendeau, Dr. Andrea C. Eitelhuber, Dr. Steven H. L. Verhelst, Dale Kling, Al Chrusciel, Prof. Dr. Jürgen Ruland, Dr. Daniel Krappmann and Prof. Karl-Peter Hopfner

      Version of Record online: 14 AUG 2013 | DOI: 10.1002/anie.201304290

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      Second site: In the crystal structure of human MALT1casp-Ig3 (mucosa-associated lymphoid tissue lymphoma translocation protein 1) in complex with the tricyclic phenothiazine derivative thioridazine (violet in the picture), the inhibitor is bound in a hydrophobic pocket far from the active site. This explains the action of phenothiazine derivatives as noncompetitive, reversible inhibitors.

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