Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 31

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, Zeitschrift für Chemie

  1. Communications

    1. DNA Rotaxane Shuttles

      Logic Gating by Macrocycle Displacement Using a Double-Stranded DNA [3]Rotaxane Shuttle

      Finn Lohmann, Johannes Weigandt, Dr. Julián Valero and Prof. Michael Famulok

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405447

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      Shuttling on a DNA track: A cascade macrocycle-displacement and -dethreading reaction triggered by light and toehold release oligodeoxynucleotides is used to assemble a logic AND gate on a double-stranded DNA [3]rotaxane. Such structures may find applications in nanoengineering, DNA computing, and even nanomedicine.

    2. Difluoroalkylation

      Synthesis of α,α-Difluoromethylene Alkynes by Palladium-Catalyzed gem-Difluoropropargylation of Aryl and Alkenyl Boron Reagents

      Yan-Bo Yu, Guo-Zhen He and Prof. Dr. Xingang Zhang

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405204

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      gem-Difluoropropargylation: A palladium-catalyzed gem-difluoropropargylation of aryl and alkenyl boronic acids and boronates with gem-difluoropropargyl bromides has been developed (see Scheme). This cross-coupling process represents an attractive approach for the synthesis of complex fluorinated molecules, in particular for drug discovery and development.

    3. Iodine Adsorption

      Adsorption of I2 by Macrocyclic Polyazadithiophenolato Complexes Mediated by Charge-Transfer Interactions

      Matthias Golecki, Norman Beyer, Dr. Gunther Steinfeld, Dr. Vasile Lozan, Dr. Sergei Voitekhovich, Dr. Muhamed Sehabi, Dr. Jens Möllmer, Prof. Dr. Hans-Jörg Krüger and Prof. Dr. Berthold Kersting

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405199

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      Seeing I to I: The macrocyclic complex [Ni2(L)(OAc)]ClO4 (1) adsorbs up to 17 molar equivalents (>270 wt %) of iodine, although it does not exhibit permanent porosity. IR and crystallographic studies reveal that two I2 molecules are captured by means of thiophenolate[RIGHTWARDS ARROW]I2 charge-transfer interactions, which enable the diffusion and sorption of further I2 molecules in a polyiodide-like network.

    4. Nanocapsules

      Chemical Sealing of Nanotubes: A Case Study on Sb2S3

      Suresh Sarkar, Amit K. Guria, Biplab K. Patra and Dr. Narayan Pradhan

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405148

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      Access denied! Binary Sb2S3 nanotubes were sealed with ternary AgSbS2 semiconductors by simply annealing the nanotubes in the presence of Ag0 particles (see structures). In this way, unique dumbbell-shaped hollow nanocapsules were formed.

    5. Small-Molecule Activation

      Tuning Lanthanide Reactivity Towards Small Molecules with Electron-Rich Siloxide Ligands

      Julie Andrez, Dr. Jacques Pécaut, Pierre-Alain Bayle and Dr. Marinella Mazzanti

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405031

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      Yb and Eu can do it! The sterically demanding and electron-rich coordination environment of EuII and YbII in homoleptic siloxide complexes leads to the reduction of azobenzene, carbon disulfide, and carbon dioxide, and the ready release of the reduction products.

    6. Organocatalyis

      Catalytic Asymmetric Torgov Cyclization: A Concise Total Synthesis of (+)-Estrone

      Dr. Sébastien Prévost, Dr. Nathalie Dupré, Markus Leutzsch, Dr. Qinggang Wang, Dr. Vijay Wakchaure and Prof. Dr. Benjamin List

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201404909

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      A short circuit: An asymmetric Torgov cyclization, catalyzed by a novel, highly Brønsted acidic dinitro-substituted disulfonimide, is described. The reaction delivers the Torgov diene and various analogues with excellent yields and enantioselectivity. The method was applied in a very short synthesis of (+)-estrone.

    7. Fingerprints

      Immunological Multimetal Deposition for Rapid Visualization of Sweat Fingerprints

      Yayun He, Linru Xu, Yu Zhu, Qianhui Wei, Prof. Meiqin Zhang and Prof. Bin Su

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201404416

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      With bare eyes: The detection of latent fingerprints and biomolecules that are secreted by human eccrine sweat glands is possible by immunological multimetal deposition (iMMD). In this approach, gold nanoparticles serve as the nucleation sites for autometallographic deposition of silver particles from the silver staining solution and as the carriers of recognition molecules.

    8. Gas-Phase Reactions

      Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl] and [HCCMgCl2] by LiCl and MgCl2

      Dr. George N. Khairallah, Dr. Gabriel da Silva and Prof. Richard A. J. O'Hair

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201404362

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      How do individual salt molecules influence the kinetic basicity of organometallates reacting with water? Addition of LiCl to [HCCLiCl] or [HCCMgCl2] enhances their reactivity towards water by a factor of about two, while addition of MgCl2 to [HCCMgCl2] enhances its reactivity by a factor of about four (see picture). The mechanism of hydration is studied theoretically.

    9. Drug Design | Hot Paper

      Tumor-Targeting of EGFR Inhibitors by Hypoxia-Mediated Activation

      M. Sc. Claudia Karnthaler-Benbakka, M. Sc. Diana Groza, Mag. Kushtrim Kryeziu, Dr. Verena Pichler, Dipl.-Ing. Alexander Roller, Prof. Dr. Walter Berger, Dr. Petra Heffeter and Dr. Christian R. Kowol

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201403936

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      Targeted attack: Receptor tyrosine-kinase inhibitors are essential cancer therapeutics, but therapy is limited by strong adverse effects. A tumor-targeting strategy for epidermal growth factor receptor (EGFR) inhibitors through hypoxia-mediated activation has now been developed. The CoIII-based prodrug showed selective hypoxic activation with release of the active EGFR inhibitor and potent anticancer activity in human xenograft models.

    10. Lithium-Ion Batteries

      Spatiotemporal Changes of the Solid Electrolyte Interphase in Lithium-Ion Batteries Detected by Scanning Electrochemical Microscopy

      M. Sc. Heinz Bülter, M. Sc. Fabian Peters, Dr. Julian Schwenzel and Prof. Dr. Gunther Wittstock

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201403935

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      Actively passivating: Lithium-ion batteries only operate safely if a passivating solid electrolyte interphase (SEI) prevents chemical reactions between strongly reducing lithiated graphite and electrolyte components. Spontaneous local fluctuations of the passivating properties of the SEI are detected by scanning electrochemical microscopy. The direct monitoring of the spatiotemporal dynamics of this critical SEI property offers potential for their optimization.

    11. Graphene Oxide Radicals

      π-Conjugated Carbon Radicals at Graphene Oxide to Initiate Ultrastrong Chemiluminescence

      Liang Yang, Ruilong Zhang, Bianhua Liu, Jianping Wang, Suhua Wang, Dr. Ming-Yong Han and Prof. Zhongping Zhang

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405295

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      GO chemiluminescence: Freshly prepared graphene oxide exhibits a large number of π-conjugated carbon radicals at its π-network plane. These radicals result from the addition of hydroxyl radicals from hydrogen peroxide onto the conjugated double bonds of graphene oxide and can directly initiate a long-lasting visible chemiluminescence of luminol.

    12. High-Resolution Microscopy

      Visualizing the Stoichiometry of Industrial-Style Co-Mo-S Catalysts with Single-Atom Sensitivity

      Yuanyuan Zhu, Quentin M. Ramasse, Michael Brorson, Poul G. Moses, Lars P. Hansen, Christian F. Kisielowski and Stig Helveg

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405690

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      Promoting the edge: The structure of an industrial-style MoS2 nanocatalyst with cobalt promoter atoms is visualized using analytical electron microscopy with single-atom sensitivity. The stoichiometries of the catalytically important MoS2 edge sites were unambiguously revealed atom by atom. These insights should facilitate the optimization of methods for MoS2 nanocatalyst preparation.

  2. Highlights

    1. Proteomics

      From the Human Genome to the Human Proteome

      Dr. Javier Muñoz and Prof. Dr. Albert J. R. Heck

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406545

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      A herculean task: Determining the human proteome sets the ultimate challenge in cell biology as it is thought to consist of more than 1 000 000 proteoforms, in contrast to “only” 20 000 protein-coding genes. Two teams of researchers have now proved the translation of 18 000 proteins (and more than 27 000 isoforms) by mass spectrometry. They obtained important information on the extent of protein translation and alternative splicing.

    2. Supramolecular Polymers

      Effective Integrative Supramolecular Polymerization

      Dr. Qiwei Zhang and Prof.Dr. He Tian

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405025

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      Exercise control: By taking advantage of self-sorting processes among host–guest components, a controlled supramolecular polymerization can be realized, as demonstrated recently with the preparation of a cucurbit[n]uril-based supramolecular polymer. This method may be used for the design of more ordered supramolecular polymers from complex and discrete components.

  3. Cover Pictures

    1. 100 Years of the Max Planck Institut für Kohlenforschung

      Prof. Dr. Benjamin List

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406876

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      Five departments, one common goal: The Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr has for the past 100 years focused above all on chemical catalysis, and this is even more true today. Researchers in heterogeneous, homogeneous, and biocatalysis, organometallic chemistry, organic synthesis, as well as theoretical chemistry are occupied with the catalytic transformation of raw materials and pure compounds with the highest possible chemo-, regio-, and stereoselectivity under conditions that maximize the use of natural resources.

    2. 100 Years of the Max-Planck-Institut für Kohlenforschung

      Prof. Dr. Benjamin List

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406847

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      Some of the most important chemical discoveries of the last 100 years were made at the Max-Planck-Institut für Kohlenforschung (MPI) in Mülheim an der Ruhr, which was founded in 1914—100 years ago—as the Kaiser-Wilhelm-Institut für Kohlenforschung. A look at history illustrates the scientific potential of the Mülheim basic research: in 1925 F. Fischer and H. Tropsch filed a patent for the Fischer–Tropsch synthesis—gasoline from coal. The low-pressure approach to polyethylene was patented in 1953 by K. Ziegler, H. Breil, E. Holzkamp, and H. Martin. Ziegler was awarded the Nobel Prize in 1963 for this work. The decaffeination of coffee by supercritical carbon dioxide was patented in 1970 by K. Zosel. This Issue, starting with an Editorial by B. List (10.1002/anie.201406956), contains contributions from researchers, who during their scientific careers have had a close connection in one way or another with this extraordinary Institution. A summary of the history of the “KoFo-MPI” is given in the Essay by M. Reetz (10.1002/anie.201403217).

    3. Paenilamicin: Structure and Biosynthesis of a Hybrid Nonribosomal Peptide/Polyketide Antibiotic from the Bee Pathogen Paenibacillus larvae

      Sebastian Müller, Dr. Eva Garcia-Gonzalez, Dr. Andi Mainz, Gillian Hertlein, Nina C. Heid, Eva Mösker, Hans van den Elst, Prof. Dr. Herman S. Overkleeft, Priv.-Doz. Dr. Elke Genersch and Prof. Roderich D. Süssmuth

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406846

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      American Foulbrood is a widespread and devastating disease of the honey bee brood caused by the bacterium Paenibacillus larvae. In their Communication (DOI: 10.1002/anie.201404572), R. D. Süssmuth et al. elucidated a fascinating nonribosomal biosynthesis through the isolation and structure elucidation of the antibacterial and antifungal paenilamicins. Furthermore, the examination of the secondary metabolites of P. larvae sheds light on the virulence mechanisms.

  4. Communications

    1. 1,2,3-Triazoles

      An Organocatalytic Azide–Aldehyde [3+2] Cycloaddition: High-Yielding Regioselective Synthesis of 1,4-Disubstituted 1,2,3-Triazoles

      Prof. Dr. Dhevalapally B. Ramachary, Adluri B. Shashank and S. Karthik

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406721

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      Metal-free click: A variety of commercially available aldehydes was used in the metal-free organo-click reaction with aryl azides to obtain 1,4-disubstituted 1,2,3-triazoles. The method constitutes an alternative to previously known metal-catalyzed azide–alkyne cycloaddition reactions (AAC), such as CuAAC, RuAAC, and IrAAC. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene; DMSO=dimethyl sulfoxide.

    2. Electrochemistry

      [FeFe] Hydrogenase: Protonation of {2Fe3S} Systems and Formation of Super-reduced Hydride States

      Aušra Jablonskytė, Dr. Joseph A. Wright, Dr. Shirley A. Fairhurst, Dr. Lee R. Webster and Prof. Christopher J. Pickett

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406210

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      Out of thin layers: The synthesis and crystallographic characterization of a complex possessing a well-defined {2Fe3S(μ-H)} core gives access to a paramagnetic bridging hydride with retention of the core geometry. The chemistry of this 35-electron species within the confines of a thin-layer FTIR spectro-electrochemistry cell provides evidence for an unprecedented super-reduced FeI(μ-H)FeI intermediate (see scheme).

    3. Metal Nitrides

      Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide

      Peter A. Cleaves, Dr. David M. King, Dr. Christos E. Kefalidis, Prof. Laurent Maron, Dr. Floriana Tuna, Prof. Eric J. L. McInnes, Dr. Jonathan McMaster, Dr. William Lewis, Prof. Alexander J. Blake and Prof. Stephen T. Liddle

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406203

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      Exploiting U: A reductive f-block carbonylation of terminal uranium(V) and uranium(VI) nitrides affords cyanates, which can be retained at uranium or expelled. This method effects denitrification and the closure of a remarkably simple synthetic cycle for the conversion of azide to nitride to cyanate, exploiting a two-electron UIII/V redox couple.

    4. Molecular Devices

      Sequential Logic Operations with a Molecular Keypad Lock with Four Inputs and Dual Fluorescence Outputs

      Dr. Xiong-Jie Jiang and Prof. Dennis K. P. Ng

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406002

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      A coumarin–rhodamine conjugate serves as a ratiometric and highly selective fluorescent sensor for Hg2+ ions. Its metal-responsive spectral properties were utilized to construct an advanced molecular keypad lock with a high security level.

    5. Heterocycles

      Catalytic Methylation of C[BOND]H Bonds Using CO2 and H2

      Dr. Yuehui Li, Tao Yan, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201405779

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      Capturing: Carbon dioxide in the presence of H2 is shown to be an efficient methylating reagent for carbon nucleophiles such as 2-substituted indoles, pyrroles, and electron-rich arenes. Experimental data support the formal capture of formaldehyde. acac=acetylacetonate, triphos=1,1,1-tris(diphenylphosphinomethyl)ethane.

    6. Natural Products | Hot Paper

      Paenilamicin: Structure and Biosynthesis of a Hybrid Nonribosomal Peptide/Polyketide Antibiotic from the Bee Pathogen Paenibacillus larvae

      Sebastian Müller, Dr. Eva Garcia-Gonzalez, Dr. Andi Mainz, Gillian Hertlein, Nina C. Heid, Eva Mösker, Hans van den Elst, Prof. Dr. Herman S. Overkleeft, Priv.-Doz. Dr. Elke Genersch and Prof.Dr. Roderich D. Süssmuth

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201404572

      Thumbnail image of graphical abstract

      The bee all and end all? American Foulbrood, which is caused by the bacterium Paenibacillus larvae, is a widespread and devastating disease of the honey bee brood. Through the isolation and structure elucidation of the antibacterial and antifungal paenilamicins, we deciphered a fascinating nonribosomal biosynthesis. The study of the secondary metabolites of P. larvae sheds light on the virulence mechanisms of this serious disease.

  5. Cover Pictures

    1. Ultra-Low-Field NMR Relaxation and Diffusion Measurements Using an Optical Magnetometer

      Paul J. Ganssle, Hyun D. Shin, Dr. Scott J. Seltzer, Dr. Vikram S. Bajaj, Dr. Micah P. Ledbetter, Prof. Dmitry Budker, Dr. Svenja Knappe, Dr. John Kitching and Prof. Alexander Pines

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406156

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      An optical magnetometer used for making ultra-low-field NMR measurements of relaxation and diffusion has the chemical sensitivity required to distinguish between hydrocarbons and water in Earth′s magnetic field (0.5 G). P. J. Ganssle, A. Pines et al. describe in their Communication (10.1002/anie.201403416) this important proof-of-concept for the commercial applicability of these robust, portable NMR sensors, particularly in the context of oil-well logging.

  6. Communications

    1. Active Sites in Sn-β

      NMR Signatures of the Active Sites in Sn-β Zeolite

      Patrick Wolf, Maxence Valla, Dr. Aaron J. Rossini, Dr. Aleix Comas-Vives, Dr. Francisco Núñez-Zarur, Prof. Dr. Bernard Malaman, Dr. Anne Lesage, Prof. Dr. Lyndon Emsley, Prof. Dr. Christophe Copéret and Prof. Dr. Ive Hermans

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201403905

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      Open and closed: The Sn-β zeolite spectroscopic signatures obtained from 119Sn Mössbauer and DNP-SENS NMR spectroscopy combined with DFT calculations on a T site model indicate that the active sites correspond to two types of octahedral SnIV sites: one with two water molecules coordinated to the framework Sn atom (closed site) and one where an Sn-O-Si bridge was opened by one of the water molecules (open site).

  7. Reviews

    1. Theta Defensins

      The Chemistry and Biology of Theta Defensins

      Anne C. Conibear and Prof. David J. Craik

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201402167

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      Climbing up the ladder: Theta defensins are the only known cyclic backbone peptides from mammals and are characterized by the cyclic cystine ladder motif. They have promising applications as antimicrobials and peptide drug scaffolds, but little is known about their distribution in primate species or biosynthesis from two gene products. The Review discusses the progress in understanding the chemistry and biology of theta defensins and highlights remaining challenges and questions.

  8. Communications

    1. 3D Printed Reactors

      3D Printed High-Throughput Hydrothermal Reactionware for Discovery, Optimization, and Scale-Up

      Dr. Philip J. Kitson, Ross J. Marshall, Dr. Deliang Long, Dr. Ross S. Forgan and Prof. Leroy Cronin

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201402654

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      Form and function: Sealed, monolithic reactors suitable for use in hydrothermal synthesis are digitally designed and realized using 3D printing techniques. The utility of these reactors is shown by the fabrication of high-throughput-array reactors which were used to discover two new coordination polymers, and to optimize and scale up the synthesis of one of these.

    2. Natural Products

      Annulation Approach to Doubly Linked (A-type) Oligocatechins: Syntheses of (+)-Procyanidin A2 and (+)-Cinnamtannin B1

      Yuji Ito, Prof. Dr. Ken Ohmori and Prof. Dr. Keisuke Suzuki

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201405600

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      Sweet oligocatechins: The first stereoselective and high-yielding syntheses of doubly linked (A-type) procyanidins, (+)-procyanidin A2 and (+)-cinnamtannin B1, have been achieved by exploiting dual activation of the electrophilic flavan units at C2 and C4, thus allowing catechin annulation with nucleophilic flavan units in a regio- and stereoselective manner.

  9. Highlights

    1. Protein Bioconjugation

      Cysteine-Selective Reactions for Antibody Conjugation

      Pedro M. S. D. Cal, Dr. Gonçalo J. L. Bernardes and Dr. Pedro M. P. Gois

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201405702

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      Moving tracks from maleimide: New site-selective protein modification reactions at cysteine have been developed. Unlike conventional maleimide conjugation, which results in a labile thioether succinimide, the new bioconjugation reactions result in stable conjugates and provide opportunities to develop a new generation of homogeneous, stable, and therapeutically useful conjugates.

  10. Communications

    1. Single-Electron-Transfer Catalysis

      Oxidative Catalysis Using the Stoichiometric Oxidant as a Reagent: An Efficient Strategy for Single-Electron-Transfer-Induced Tandem Anion–Radical Reactions

      Ing. František Kafka, Ing. Martin Holan, M.Sc. Denisa Hidasová, Dr. Radek Pohl, Dr. Ivana Císařová, Dr. Blanka Klepetářová and Dr. Ullrich Jahn

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201403776

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      Making waste a functionality: Oxidative electron-transfer-mediated anion–radical transformations are rendered catalytic by employing a 2,2,6,6-tetramethyl-N-oxopiperidinium salt and ferrocene. The method provides an asymmetric approach to highly functionalized cyclopentane and pyrrolidine derivatives. At the same time the co-generated reduced species TEMPO serves as a useful oxygenating functionality.

    2. Bioconjugation

      A Chemoenzymatic Approach to Protein Immobilization onto Crystalline Cellulose Nanoscaffolds

      Christina Uth, Stefan Zielonka, Sebastian Hörner, Dr. Nicolas Rasche, Andreas Plog, Dr. Hannes Orelma, Dr. Olga Avrutina, Dr. Kai Zhang and Prof. Dr. Harald Kolmar

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201404616

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      A modular approach was used for site-directed, bioorthogonal protein immobilization. The combination of enzyme-mediated ligation with highly efficient oxime ligation makes it possible to decorate sustainable nanocellulose platforms with fully functional proteins from different families.

    3. Biosensors | Hot Paper

      Chemical Vapor Detection Using a Reconstituted Insect Olfactory Receptor Complex

      Dr. Koji Sato and Prof. Shoji Takeuchi

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201404720

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      Gas sensing by ion channels: Insect olfactory receptors consist of ligand-gated ion channels. Using cell assembly and extracellular field potential recording techniques, olfactory receptor-expressing cell spheroids were formed (see picture). The spheroids electrically responded to chemical vapors at biologically relevant concentrations.

    4. Carbonylation

      Palladium-Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

      Dr. Kishore Natte, Dr. Andreas Dumrath, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201404833

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      Outsourcing CO: Novel protocols have been developed for conducting palladium-catalyzed reductive carbonylations and alkoxycarbonylations of aryl bromides using paraformaldehyde as an external CO source. The advantage of these methods: gaseous carbon monoxide is not needed.

  11. Minireviews

    1. Bioinorganic Chemistry

      Carbon-Monoxide-Releasing Molecules for the Delivery of Therapeutic CO In Vivo

      Dr. Sandra García-Gallego and Dr. Gonçalo J. L. Bernardes

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201311225

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      On target: Carbon-monoxide-releasing molecules (CORMs) are promising agents for the treatment of several diseases. CORMs are particularly good for enabling CO delivery in a controlled manner without affecting oxygen transport by hemoglobin. Significant progress in the methods for CO detection in live cells and the understanding of the reactivity of CORMs in vivo provides insights into CO biology and the design of safer, and more selective and efficient CORMs for clinical use.

  12. Reviews

    1. Hydrophobic Effect

      The Hydrophobic Effect Revisited—Studies with Supramolecular Complexes Imply High-Energy Water as a Noncovalent Driving Force

      Dr. Frank Biedermann, Prof. Dr. Werner M. Nau and Prof. Dr. Hans-Jörg Schneider

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201310958

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      Overcoming a phobia: Hydrophobic effects are traditionally described by the association of two lipophilic molecules, which then need less water molecules for solvation than two separate solutes, thus leading to either entropy or enthalpy gain. Investigations with supramolecular complexes have shown that another mechanism based on the replacement of hydrogen-bond-deficient high-energy water molecules in cavities can play a decisive role.

    2. Bioanalytical Methods

      In-Cell NMR and EPR Spectroscopy of Biomacromolecules

      Robert Hänsel, Laura M. Luh, Ivan Corbeski, Lukáš Trantirek and Prof. Volker Dötsch

      Article first published online: 28 JUL 2014 | DOI: 10.1002/anie.201311320

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      Magnets that attract cell biology: Magnetic resonance spectroscopy has been applied to cellular systems and tissues for a long time. The development of in-cell NMR and EPR spectroscopy now enables direct investigation of the conformation, dynamics, binding events, and posttranslational modifications of biological macromolecules in living cells. This Review summarizes the main techniques and applications to different cellular systems and macromolecules.

  13. Communications

    1. Hollow Nanostructures

      Hierarchical Zn/Ni-MOF-2 Nanosheet-Assembled Hollow Nanocubes for Multicomponent Catalytic Reactions

      Zhicheng Zhang, Yifeng Chen, Su He, Jingchao Zhang, Xiaobin Xu, Yong Yang, Farhat Nosheen, Faisal Saleem, Prof. Wei He and Prof. Xun Wang

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201406484

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      Cubed route: A facile surfactant-free solvothermal approach gives nanostructures that undergo a crystal-structure transformation from Zn/Ni-MOF-5 nanocubes to Zn/Ni-MOF-2 nanosheets. The nanosheets retain the cubic shape suggesting that the in situ synthesized nanocubes may act as a template. Immobilization of palladium in the nanosheet structure gives a catalyst for the alkoxycarbonylation of aryl iodides.

    2. Chalcogen Bonding

      The Dominant Role of Chalcogen Bonding in the Crystal Packing of 2D/3D Aromatics

      Dr. Jindřich Fanfrlík, Adam Přáda, Dr. Zdeňka Padělková, Adam Pecina, Dr. Jan Macháček, Dr. Martin Lepšík, Dr. Josef Holub, Prof. Aleš Růžička, Dr. Drahomír Hnyk and Prof. Pavel Hobza

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201405901

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      Chalcogen bonds of thiaboranes were found to be considerably stronger than σ-hole bonds in organic compounds. The reason is the highly positive belt of σ-holes on the positively charged sulfur atom. The charge distribution is the driving force for chalcogen bonding of thiaboranes.

    3. Radicals

      Persistent Antimony- and Bismuth-Centered Radicals in Solution

      Dr. Shintaro Ishida, Fumiya Hirakawa, Prof. Dr. Ko Furukawa, Dr. Kenji Yoza and Prof. Dr. Takeaki Iwamoto

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201405509

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      Persistent: The facile dissociation of distibines and dibismuthines with bulky bidentate alkyl groups leads to the corresponding persistent radicals in solution. The stibinyl and bismuthinyl radicals were spectroscopically characterized, and the thermodynamic parameters for their dissociation equilibria were estimated. The radicals reacted with a stable nitroxyl radical to give the cross-radical coupling products in good yields.

  14. Highlights

    1. C–H Activation

      Functionalization of Remote C[BOND]H Bonds: Expanding the Frontier

      Johannes Schranck, Dr. Anis Tlili and Prof. Dr. Matthias Beller

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201405714

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      Novel tool set: New methodologies for the functionalization of remote C[BOND]H bonds have been developed recently. In diverse approaches high selectivities are achieved for the functionalization of less reactive C(sp2)[BOND]H as well as C(sp3)[BOND]H bonds distal to any substituents.

  15. Communications

    1. Synthetic Methods

      You have full text access to this OnlineOpen article
      Palladium-Catalyzed Synthesis of Ammonium Sulfinates from Aryl Halides and a Sulfur Dioxide Surrogate: A Gas- and Reductant-Free Process

      Edward J. Emmett, Dr. Barry R. Hayter and Prof. Michael C. Willis

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201404527

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      ’SO’2 versatile: The combination of an aryl halide, the SO2 surrogate DABSO, a Pd0 catalyst, isopropyl alcohol, and triethylamine delivers the corresponding ammonium sulfinate salts. Isopropyl alcohol serves as both the solvent and formal reductant, thus allowing the efficient formation of sulfinate intermediates in a process free of gaseous reagents and inorganic reductants. The salts can be converted into sulfones, sulfonamides, and sulfonyl chlorides.

  16. Editorials

    1. You have free access to this content
      Catalytic Processes that Changed the World: 100 Years Max-Planck-Institut für Kohlenforschung

      Prof. Dr. Benjamin List

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201406956

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      … In this special issue of Angewandte Chemie, which is indeed very special for us, you as a reader should get an impression of what, in our opinion, constitutes the research in and around the Max-Planck-Institut für Kohlenforschung. You will notice the diversity of the research topics that are covered by researchers at the Institute …” Read more in the Editorial by Benjamin List.

  17. Communications

    1. Chemical Genomics | Hot Paper

      Mapping Polyamide–DNA Interactions in Human Cells Reveals a New Design Strategy for Effective Targeting of Genomic Sites

      Graham S. Erwin, Devesh Bhimsaria, Asuka Eguchi and Prof. Aseem Z. Ansari

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201405497

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      Siteseeing: The first mapping of pyrrole/imidazole polyamides across several genomic sites with distinct chromatin characteristics in live cells is reported. Bioinformatic analysis of the data shows that clustered binding sites best predict binding in cells. The results point to a new design principle to deploy polyamides and perhaps other synthetic molecules to effectively target desired genomic sites in vivo.

  18. Book Reviews

    1. Photochemistry and Photophysics. Concepts, Research, Applications. By Vincenzo Balzani, Paola Ceroni and Alberto Juris.

      Xiang Ma and He Tian

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201405219

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      Wiley-VCH, Weinheim, 2014. 504 pp., hardcover, € 72.00.—ISBN 978-3527334797

  19. Reviews

    1. Molecular Modeling

      Development of Multiscale Models for Complex Chemical Systems: From H+H2 to Biomolecules (Nobel Lecture)

      Prof. Martin Karplus

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201403924

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      Although the laws governing the motions of atoms are quantum mechanical, the key realization that made possible the simulation of the dynamics of complex systems, including biomolecules, was that a classical mechanical description of the atomic motions is adequate in most cases. From M. Karplus’ own perspective, this realization was derived from calculations on the symmetric exchange reaction, H+H2[RIGHTWARDS ARROW]H2+H.

  20. Communications

    1. Trifluoroethylation

      Palladium-Catalyzed Cascade C[BOND]H Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho-Trifluoroethylstyrenes

      Hao Zhang, Dr. Pinhong Chen and Prof. Dr. Guosheng Liu

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201403793

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      The palladium-catalyzed selective C[BOND]H bond trifluoroethylation of aryl iodides allows for an efficient synthesis of a variety of ortho-trifluoroethyl-substituted styrenes. Preliminary mechanistic studies indicate that the reaction might proceed through rate-determining oxidative addition of CF3CH2I to a palladacycle.

    2. Synthetic Methods

      Stereoselective Construction of 1,3-Disilylcyclopentane Derivatives by Scandium-Catalyzed [3+2] Cycloaddition of Allylsilanes to β-Silylenones

      Dr. Kazuhiro Okamoto, Eisuke Tamura and Prof. Dr. Kouichi Ohe

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201404218

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      Two silicon atoms collaborate: The Sc(OTf)3-catalyzed stereoselective [3+2] cycloaddition of allylsilanes to β-silylenones with migration of one silyl group has been developed. The electronic effect of two silyl groups plays a key role for selective cycloaddition. Two silyl groups of the obtained cycloadduct can be regioselectively oxidized into hydroxy groups. X-ray crystal structure: C gray, H white, Si yellow, O red.

    3. Photosynthesis

      Photocatalytic Water Oxidation by a Mixed-Valent MnIII3MnIVO3 Manganese Oxo Core that Mimics the Natural Oxygen-Evolving Center

      Dr. Rami Al-Oweini, Dr. Andrea Sartorel, Dr. Bassem S. Bassil, Dr. Mirco Natali, Dr. Serena Berardi, Prof. Franco Scandola, Prof. Ulrich Kortz and Prof. Marcella Bonchio

      Article first published online: 27 JUL 2014 | DOI: 10.1002/anie.201404664

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      Artificial photosynthesis: A mixed-valent tetramanganese oxo core that is anchored on an inorganic polyoxotungstate ligand acts as a functional analogue of the oxygen-evolving complex of photosystem II. In the presence of [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) and S2O82−, the complex enables the evolution of O2 within a light-driven catalytic cycle.

  21. Essays

    1. Zeolites in Biorefineries

      Will Zeolite-Based Catalysis be as Relevant in Future Biorefineries as in Crude Oil Refineries?

      Prof. Pierre A. Jacobs, Dr. Michiel Dusselier and Prof. Bert F. Sels

      Article first published online: 25 JUL 2014 | DOI: 10.1002/anie.201400922

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      Approved catalysts for fuels of the future: Transition from petroleum- to biomass-based fuel economy will require new conversion strategies. This Essay describes how recent developments in zeolite synthesis and modification allow adapting zeolite properties to achieve selective conversion of biomass compounds.

  22. Communications

    1. Modified Peptides

      Peptide Modifications Differentially Alter G Protein-Coupled Receptor Internalization and Signaling Bias

      Veronika Mäde, Stefanie Babilon, Dr. Navjeet Jolly, Lizzy Wanka, Dr. Kathrin Bellmann-Sickert, Dr. Luis E. Diaz Gimenez, Dr. Karin Mörl, Prof. Dr. Helen M. Cox, Prof. Dr. Vsevolod V. Gurevich and Prof. Dr. Annette G. Beck-Sickinger

      Article first published online: 25 JUL 2014 | DOI: 10.1002/anie.201403750

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      PEGylation and lipidation have been found to enhance ligand preference for anorexigenic G protein-coupled human Y receptors. Lipidation biased the agonist towards arrestin recruitment and internalization, whereas PEGylation precluded receptor internalization and prolonged signaling independently of the cell system and modified residue, thus indicating novel modes of action.

    2. Reversible Dimerization

      A Bioorthogonal Small-Molecule-Switch System for Controlling Protein Function in Live Cells

      Dr. Peng Liu, Abram Calderon, Dr. Georgios Konstantinidis, Dr. Jian Hou, Dipl. Stephanie Voss, Dr. Xi Chen, Fu Li, Soumya Banerjee, Dr. Jan-Erik Hoffmann, Christiane Theiss, Dr. Leif Dehmelt and Dr. Yao-Wen Wu

      Article first published online: 25 JUL 2014 | DOI: 10.1002/anie.201403463

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      Hitching a ride: A novel bioorthogonal and reversible chemically induced dimerization system has been developed. Translocation of constitutively active Rac1 to the plasma membrane resulted in rapid and reversible lamellipodia formation in live cells.

    3. DNA Repair

      Ribose-Protonated DNA Base Excision Repair: A Combined Theoretical and Experimental Study

      Dr. Keyarash Sadeghian, Dr. Denis Flaig, Iris D. Blank, Dr. Sabine Schneider, Dr. Ralf Strasser, Dr. Dimitrios Stathis, Dr. Malte Winnacker, Prof. Dr. Thomas Carell and Prof. Dr. Christian Ochsenfeld

      Article first published online: 25 JUL 2014 | DOI: 10.1002/anie.201403334

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      Sugar is the target: QM/MM (quantum mechanics/molecular mechanics) calculations with more than 1000 QM atoms for describing the catalytic pocket unravel the base excision repair mechanism of bacterial glycosylase, MutM. In contrast to conventional assumptions, MutM first attacks the ribose ring. Activity assays and a new crystal structure of the MutM lesion complex strongly support such a repair process with a higher involvement of the sugar ring.

    4. Metal–Organic Frameworks

      Perturbation of Spin Crossover Behavior by Covalent Post-Synthetic Modification of a Porous Metal–Organic Framework

      John E. Clements, Dr. Jason R. Price, Dr. Suzanne M. Neville and Prof. Cameron J. Kepert

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201402951

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      Changing the switch: Covalent post-synthetic modification (PSM; see picture) of a pillaring ligand in a new porous FeII spin crossover framework occurs with retention of single crystallinity to generate a closely related framework phase that exhibits markedly different switching behaviors (see picture). This conversion establishes covalent modification as a new method for controlling spin crossover in this emerging class of porous multifunctional materials.

    5. C[BOND]H Activation

      Cobalt-Catalyzed, Aminoquinoline-Directed C(sp2)[BOND]H Bond Alkenylation by Alkynes

      Dr. Liene Grigorjeva and Prof. Olafs Daugulis

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201404579

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      In the air: Excellent functional-group tolerance is observed in the title reaction, and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2⋅4 H2O as the catalyst, Mn(OAc)2 as the co-catalyst, and oxygen (from air) as the terminal oxidant. Piv=pivalate.

    6. Nanobioanalysis

      Nanoelectrode for Amperometric Monitoring of Individual Vesicular Exocytosis Inside Single Synapses

      Yu-Tao Li, Shu-Hui Zhang, Dr. Li Wang, Rong-Rong Xiao, Wei Liu, Xin-Wei Zhang, Prof. Zhuan Zhou, Prof. Christian Amatore and Prof. Wei-Hua Huang

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201404744

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      Chemical neurotransmission occurs at chemical synapse, but up to now there was no means for direct monitoring of neurotransmitter exocytosis and its precise kinetics from inside individual infinitesimal synapse. A novel finite conical nanoelectrode is fabricated and used in a newly developed amperometric method (see picture) for probing inside what appears to be single synapses.

    7. Li-S Batteries

      Towards a Safe Lithium–Sulfur Battery with a Flame-Inhibiting Electrolyte and a Sulfur-Based Composite Cathode

      Prof. Jiulin Wang, Fengjiao Lin, Hao Jia, Prof. Jun Yang, Prof. Charles W. Monroe and Prof. Yanna NuLi

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201405157

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      Fire away: A nonflammable sulfur composite cathode has been shown to maintain extremely stable electrochemical activity over 750 cycles and exhibit a discharge capacity greater than 800 mA h−1 g−1(sulfur) at a high rate of 10 C in a flame-inhibiting electrolyte. The safe electrolyte was generated from a phosphite additive that participates in interfacial reactions on the cathode and accelerates Li-ion diffusion more than tenfold.

    8. Group 14 Chemistry

      N-Heterocyclic Carbene Coordinated Neutral and Cationic Heavier Cyclopropylidenes

      Dr. Anukul Jana, Dipl.-Chem. Isabell Omlor, Dr. Volker Huch, Prof. Dr. Henry S. Rzepa and Prof. Dr. David Scheschkewitz

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201405238

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      He is heavy and he′s my brother: NHC-coordinated cyclopropenylidene analogues with molecular scaffolds exclusively formed by heavier Group 14 elements are accessible from the corresponding vinylidene isomers by exchange of the NHC ligand for a smaller NHC. The residual chloride in one of these heavier cyclic carbenes can be expelled by a second equivalent of NHC to generate cationic derivatives of the imidazolium type.

  23. Reviews

    1. Molecular Modeling

      Multiscale Modeling of Biological Functions: From Enzymes to Molecular Machines (Nobel Lecture)

      Prof. Arieh Warshel

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201403689

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      A detailed understanding of the action of biological molecules is a pre-requisite for advances in health sciences, however, using a full quantum mechanical representation of large molecular systems is practically impossible. The solution to this has emerged from the realization that large systems can be spatially divided into a region where the quantum mechanical description is essential, with the remainder of the system being represented by empirical force fields.

  24. Communications

    1. C[BOND]O Bond Cleavage

      Catalytic Cleavage of Ether C[BOND]O Bonds by Pincer Iridium Complexes

      Michael C. Haibach, Nicholas Lease and Prof. Alan S. Goldman

      Article first published online: 24 JUL 2014 | DOI: 10.1002/anie.201402576

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      A catalyst for ether direction: Cleavage of the alkyl C[BOND]O bond of aryl ethers is catalyzed by pincer Ir catalysts, without the need for additional reagents, including H2. The corresponding phenols are generated in up to 99 % conversion, with reaction times as short as 1 hour.

  25. News

  26. Communications

    1. Aerogels | Very Important Paper

      An Easy Way To Prepare Monolithic Inorganic Oxide Aerogels

      Dr. Lili Ren, Sumin Cui, Fengchao Cao and Qinghui Guo

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201406387

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      Not cracking up: A drying method based on the sublimation of organic solvent allows the rapid synthesis of the monolithic inorganic oxide aerogels without cracks from wet gels. The method proceeds by endothermic evaporation of organic solvent at the outer surface followed by sublimation of solidified solvent (see picture).

    2. Thermodynamics

      Aligning Electronic and Protonic Energy Levels of Proton-Coupled Electron Transfer in Water Oxidation on Aqueous TiO2

      Dr. Jun Cheng, Dr. Xiandong Liu, Dr. John A. Kattirtzi, Dr. Joost VandeVondele and Prof.Dr. Michiel Sprik

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405648

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      Scheming: A scheme for computing the thermochemistry of proton-coupled electron transfer (PCET) reactions at interfaces is described. In analogy with electronic energy levels, an appealing concept of protonic energy levels is proposed to visualize the thermodynamics of PCET in a level diagram. This diagram helps to elucidate the electronic and protonic components of thermodynamic overpotentials in photocatalysis.

    3. Synthetic Methods

      Synthesis of Isocoumarins through Three-Component Couplings of Arynes, Terminal Alkynes, and Carbon Dioxide Catalyzed by an NHC–Copper Complex

      Dr. Woo-Jin Yoo, Thanh V. Q. Nguyen and Prof. Dr. Shū Kobayashi

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404692

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      A facile synthetic protocol to isocoumarins consists of a three-component coupling reaction between 1-alkynes, 2-(trimethylsilyl)aryl triflates, and CO2 (see scheme). The key to this reaction was the use of a versatile N-heterocyclic carbene/copper complex that was able to catalyze multiple transformations within the three-component reaction.

    4. Gold–Carbenoids

      Chemoselective Carbophilic Addition of α-Diazoesters through Ligand-Controlled Gold Catalysis

      Yumeng Xi, Yijin Su, Zhaoyuan Yu, Boliang Dong, Edward J. McClain, Prof. Yu Lan and Prof. Xiaodong Shi

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404946

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      Carbocation or carbene? The chemoselective addition of arenes and 1,3-diketones to α-aryldiazoesters was achieved through ligand-controlled gold catalysis. The gold catalyst with electron-deficient phosphite as the ancillary ligand exclusively gave the carbophilic addition products, thus representing a new and efficient approach to form “carbophilic carbocations”, which selectively react with carbon nucleophiles.

    5. Heterogeneous Catalysis

      Niobium(V) Saponite Clay for the Catalytic Oxidative Abatement of Chemical Warfare Agents

      Dr. Fabio Carniato, Dr. Chiara Bisio, Dr. Rinaldo Psaro, Prof. Leonardo Marchese and Dr. Matteo Guidotti

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405134

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      Heterogeneous catalysis against chemical weapons: A bifunctional NbV-containing saponite clay was prepared and found to be an optimal catalyst for the oxidative abatement of chemical warfare agents (CWA). In comparison to parent samples and a conventional commercial decontamination powder, a remarkable activity and high selectivity were obtained for the oxidation of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature.

    6. Metal Deposition

      Sorption-Determined Deposition of Platinum on Well-Defined Platelike WO3

      Kasper Wenderich, Aram Klaassen, Dr. Igor Siretanu, Prof. Frieder Mugele and Prof. Guido Mul

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405274

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      Positioned for action: Understanding of the mechanism behind the structure-directed photodeposition of metals is highly relevant for the optimization of photocatalysts. The preferential deposition of Pt on WO3 was found to be the result of intrinsic surface-charge differences of specific facets, rather than of the illumination-induced preferred spatial separation of electrons and holes (see picture).

    7. Cancer Immunotherapy

      Targeting Human C-Type Lectin-Like Molecule-1 (CLL1) with a Bispecific Antibody for Immunotherapy of Acute Myeloid Leukemia

      Dr. Hua Lu, Dr. Quan Zhou, Vishal Deshmukh, Dr. Hardeep Phull, Dr. Jennifer Ma, Dr. Virginie Tardif, Dr. Rahul R. Naik, Dr. Claire Bouvard, Dr. Yong Zhang, Dr. Seihyun Choi, Dr. Brian R. Lawson, Dr. Shoutian Zhu, Dr. Chan Hyuk Kim and Dr. Peter G. Schultz

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405353

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      A bispecific antibody, αCLL1-αCD3, was synthesized using a genetically encoded unnatural amino acid, and shown to recruit cytotoxic T cells to CLL1-positive cells. The reported results validate the clinical potential of CLL1 as an AML-specific antigen for the generation of bispecific antibodies for the treatment of acute myeloid leukemia (AML).

    8. Block Copolymer Membrane

      Self-Assembled Isoporous Block Copolymer Membranes with Tuned Pore Sizes

      Dr. Haizhou Yu, Dr. Xiaoyan Qiu, Prof. Suzana P. Nunes and Prof. Klaus-Viktor Peinemann

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404491

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      Golden pores: Membranes with tunable cylindrical pore diameters between 3 and 20 nm were manufactured and tested for nanoparticle separation and controlled delivery of proteins. The pore size was regulated by electroless gold deposition. The precise size discrimination, facile and scalable fabrication processes, and biocompatible characteristics favor potential uses in the purification of nanoscale materials and drug delivery.

    9. Peptide Antivirals | Hot Paper

      Cell-Penetrating, Dimeric α-Helical Peptides: Nanomolar Inhibitors of HIV-1 Transcription

      Sangmok Jang, Dr. Soonsil Hyun, Seoyeon Kim, Seonju Lee, Prof. Dr. Im-Soon Lee, Prof. Dr. Masanori Baba, Prof. Dr. Yan Lee and Prof. Dr. Jaehoon Yu

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404684

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      Going viral: Nearly quantitative penetration into eukaryotic cells and effective inhibition of the elongation of the short hairpin RNA transcript TAR at low nanomolar concentrations has been achieved by using dimeric α-helical peptide bundles based on leucine (L) and lysine (K). The effective inhibition of HIV-1 replication strongly suggests that these dimers have strong potential as anti-HIV-1 drugs.

    10. Mesoporous Polymeric Catalyst

      A Nanospherical Ordered Mesoporous Lewis Acid Polymer for the Direct Glycosylation of Unprotected and Unactivated Sugars in Water

      Dr. Fang Zhang, Chao Liang, Xiaotao Wu and Prof. Dr. Hexing Li

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404353

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      Xanthone glycosides from sugars: A novel nanospherical ordered mesoporous Lewis acid polymer was synthesized by functionalizing the mesoporous phenol-formaldehyde polymer with scandium triflate groups. The functionalized polymer showed good catalytic activity, selectivity, and recyclability in the C-glycosylation reaction between simple sugars and cyclohexane-1,3-dimedone in water.

    11. Enzyme Models

      Hexacoordinate Nickel(II)/(III) Complexes that Mimic the Catalytic Cycle of Nickel Superoxide Dismutase

      Sudip K. Chatterjee, Ram Chandra Maji, Suman Kumar Barman, Prof. Dr. Marilyn M. Olmstead and Dr. Apurba K. Patra

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404133

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      Copy cat: Hexacoordinate nickel(II)/(III) complexes are prepared which mimic the catalytic cycle of nickel superoxide dismutase (NiSOD) by an outer-sphere electron-transfer mechanism. The complexes employ a bis-tridentate N2S donor carboxamide ligand, N-2-phenylthiophenyl-2′-pyridinecarboxamide (HLPh), and have been structurally characterized and their SOD activities examined.

    12. Batteries

      Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena

      M. Sc. Birte Jache and Dr. Philipp Adelhelm

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403734

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      In contrast to the general view, graphite can be used as an electrode material in sodium-ion batteries by taking advantage of the formation of ternary graphite intercalation compounds. The important features of this electrode reaction are the small irreversible capacity, the low overpotentials, and the superior cycle life. With a capacity close to 100 mAh g−1, the electrode is attractive for stationary applications.

    13. Bio-Nanomaterials

      Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

      Calum Kinnear, David Burnand, Dr. Martin J. D. Clift, Prof. Andreas F. M. Kilbinger, Prof. Barbara Rothen-Rutishauser and Prof. Alke Petri-Fink

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404100

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      Polymer grafting: Gold nanorods can be functionalized with polyvinyl acetate, which hydrolyzes to polyvinyl alcohol. An aqueous dispersion of the resulting colloidally stable and nontoxic nanorods was tested by exposure to primary human blood monocyte derived macrophages.

  27. Minireviews

    1. Enantioselective Catalysis

      Catalytic Enantioselective C[BOND]H Functionalization of Alcohols by Redox-Triggered Carbonyl Addition: Borrowing Hydrogen, Returning Carbon

      John M. Ketcham, Inji Shin, T. Patrick Montgomery and Prof. Michael J. Krische

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403873

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      Borrowing with interest: The concept of exploiting alcohols and unsaturated reactants for the redox-triggered generation of nucleophile–electrophile pairs reinvents the chemistry of carbonyl addition, enabling a broad, new family of catalytic enantioselective C[BOND]C couplings.

  28. Communications

    1. Host–Guest Systems

      Activation Energies Control the Macroscopic Properties of Physically Cross-Linked Materials

      Dr. Eric A. Appel, Rebecca A. Forster, Dr. Alexandros Koutsioubas, Prof. Chris Toprakcioglu and Prof. Oren A. Scherman

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403192

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      Supramolecular hydrogels were obtained by utilizing the host–guest interactions of the macrocycle cucurbit[8]uril (CB[8]) with various guest molecules. The mechanical strength of these materials is directly correlated to the energetic barrier of the dissociation of the CB[8] ternary complex cross-links, whereas the self-healing requires a low energetic barrier for complex association.

    2. Supported Nanoparticles | Very Important Paper

      Monitoring Morphology and Hydrogen Coverage of Nanometric Pt/γ-Al2O3 Particles by In Situ HERFD–XANES and Quantum Simulations

      Agnes Gorczyca, Dr. Virginie Moizan, Dr. Celine Chizallet, Dr. Olivier Proux, William Del Net, Eric Lahera, Dr. Jean-Louis Hazemann, Dr. Pascal Raybaud and Dr. Yves Joly

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403585

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      Identifying the morphology of platinum nanoclusters supported on γ-alumina and the hydrogen coverage at a given temperature and hydrogen pressure is possible. The use of state-of-the-art methodologies combining high-resolution X-ray absorption near edge structure (XANES) in situ experiments, quantum molecular dynamics calculations, and XANES simulations gives unrivalled insights into catalyst characterization.

    3. Perovskite Solar Cells | Hot Paper

      A Fast Deposition-Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin-Film Solar Cells

      Manda Xiao, Dr. Fuzhi Huang, Wenchao Huang, Yasmina Dkhissi, Dr. Ye Zhu, Prof. Dr. Joanne Etheridge, Dr. Angus Gray-Weale, Prof. Dr. Udo Bach, Prof. Dr. Yi-Bing Cheng and Prof. Dr. Leone Spiccia

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405334

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      Fast and thin: Flat, uniform thin films of CH3NH3PbI3 perovskites have been produced by a fast, one-step procedure involving spin-coating of a DMF solution of CH3NH3PbI3 and immediate exposure to chlorobenzene to induce crystallization. Planar heterojunction solar cells made with these films gave a maximum power conversion efficiency of 16.2 %.

    4. Solar Cells | Very Important Paper

      Integrating Perovskite Solar Cells into a Flexible Fiber

      Longbin Qiu, Jue Deng, Xin Lu, Zhibin Yang and Prof. Huisheng Peng

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404973

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      Wearable perovskite solar cells with a fiber structure are synthesized by continuously winding an aligned carbon nanotube (CNT) sheet onto a stainless-steel wire; photoactive materials are incorporated in between them through a solution process. The fiber-shaped perovskite solar cell exhibits an energy conversion efficiency of 3.3 % and may be woven into electronic textiles.

    5. Biocatalysis | Hot Paper

      Unprecedented Role of Hydronaphthoquinone Tautomers in Biosynthesis

      Dr. Syed Masood Husain, Dr. Michael A. Schätzle, Dr. Steffen Lüdeke and Prof. Dr. Michael Müller

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404560

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      Breaking the cycle: In studies on the reduction of 2-hydroxynaphthoquinones to the stable 1,4-diketo tautomeric form of hydronaphthoquinones and their further reduction by fungal tetrahydroxynaphthalene reductase, diketo tautomers emerge as true intermediates in biosynthesis. Their formation breaks the (redox) cycle, thus protecting the cell from stress-related redox events.

    6. C[BOND]H Activation

      Easily Accessible Auxiliary for Palladium-Catalyzed Intramolecular Amination of C(sp2)[BOND]H and C(sp3)[BOND]H Bonds at δ- and ε-Positions

      Chao Wang, Changpeng Chen, Jingyu Zhang, Jian Han, Qian Wang, Kun Guo, Pei Liu, Mingyu Guan, Dr. Yingming Yao and Prof. Dr. Yingsheng Zhao

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404854

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      Remote access: The first application of an oxalyl amide to direct C[BOND]H functionalizations at remote positions was reported. The results showed both C(sp2)[BOND]H and C(sp3)[BOND]H bonds at δ- and ε-positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium-catalyzed intramolecular C[BOND]H amination.

    7. Metal–Metal Bonds

      Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction

      Dr. Andreas Stasch

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404284

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      The new switcheroo: A dimeric magnesium(I) complex has been prepared by a simple redox reaction using a known magnesium(I) complex. The new complex is stabilized by a high oxidation state phosphorane-based ligand and undergoes a C[BOND]C coupling reaction with tert-butylisocyanate.

    8. Membrane Preparation | Hot Paper

      Coordination-Driven In Situ Self-Assembly Strategy for the Preparation of Metal–Organic-Framework Hybrid Membranes

      Rong Zhang, Prof. Shulan Ji, Dr. Naixin Wang, Lin Wang, Prof. Guojun Zhang and Jian-Rong Li

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403978

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      Mopping up the mess: A hybrid membrane composed of the metal–organic framework (MOF) ZIF-8 and poly(sodium 4-styrenesulfonate) was prepared by coordination-driven in situ self-assembly method. The MOF particles were well-dispersed in the polymer in the resulting stable membrane (see picture), which showed excellent performance in the nanofiltration and separation of dyes from water.

    9. Self-Assembly

      Surface-Confined Self-Assembled Janus Tectons: A Versatile Platform towards the Noncovalent Functionalization of Graphene

      Dr. Ping Du, Maud Jaouen, Dr. Amandine Bocheux, Dr. Cyril Bourgogne, Zheng Han, Dr. Vincent Bouchiat, Dr. David Kreher, Dr. Fabrice Mathevet, Dr. Céline Fiorini-Debuisschert, Dr. Fabrice Charra and Prof. André-Jean Attias

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403572

      Thumbnail image of graphical abstract

      Built to order: A library of Janus tectons equipped with small chemical groups or functional moieties has been synthesized. The self-assembly on sp2-hybridized carbon supports leads to the formation of well-organized adlayers with the same lattice parameters, as demonstrated by STM. The external exposed surface presents a wide range of functionalities positioned with a precise lateral order.

    10. Asymmetric Synthesis

      Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes

      Cyril Bosset, Romain Coffinier, Dr. Philippe A. Peixoto, Mourad El Assal, Dr. Karinne Miqueu, Dr. Jean-Marc Sotiropoulos, Dr. Laurent Pouységu and Prof. Stéphane Quideau

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403571

      Thumbnail image of graphical abstract

      The selective oxygenation of iodobinaphthyls and iodobiphenyls afforded either λ3- or λ5-iodanes, which were evaluated for their capacity to promote asymmetric intermolecular hydroxylative phenol dearomatizations (HPDs). Most remarkably, a C2-symmetrical biphenylic λ5-iodane induced the HPD reaction/[4+2] cyclodimerization cascade of thymol into bis(thymol) with enantiomeric excesses of up to 94 %.

    11. Hybrid Nanomaterials

      Preparation of MoS2–MoO3 Hybrid Nanomaterials for Light-Emitting Diodes

      Dr. Zongyou Yin, Xiao Zhang, Dr. Yongqing Cai, Junze Chen, Dr. Jen It Wong, Dr. Yee-Yan Tay, Dr. Jianwei Chai, Jumiati Wu, Dr. Zhiyuan Zeng, Dr. Bing Zheng, Prof. Hui Ying Yang and Prof. Hua Zhang

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201402935

      Thumbnail image of graphical abstract

      LED’s glow: MoS2–MoO3 hybrid nanomaterials are prepared by the heat-assisted partial oxidation of MoS2 nanosheets in air (1) followed by a thermal-annealing-driven crystallization (2). The obtained hybrid nanomaterial exhibits p-type conductivity and is employed in a heterojunction of n-type SiC/p-type MoS2–MoO3 for light-emitting diodes (3), from which multi-wavelength electroluminescent emission is detected.

    12. Noncovalent Interactions

      Understanding a Host–Guest Model System through 129Xe NMR Spectroscopic Experiments and Theoretical Studies

      Emmanuelle Dubost, Jean-Pierre Dognon, Bernard Rousseau, Gaëlle Milanole, Christophe Dugave, Yves Boulard, Estelle Léonce, Céline Boutin and Patrick Berthault

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405349

      Thumbnail image of graphical abstract

      How hosts handle a noble guest: A combination of NMR spectroscopy and quantum chemistry enabled thorough analysis of the noncovalent interactions inside a xenon–host complex. The validation of this approach with a family of cryptophane hosts derived by treatment with H2O2 from the structure shown paves the way for the design of potent smart hyperpolarized 129Xe NMR sensors.

    13. Sustainable Chemistry

      An “All-Green” Catalytic Cycle of Aqueous Photoionization

      Prof. Dr. Martin Goez, Christoph Kerzig and Robert Naumann

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405693

      Thumbnail image of graphical abstract

      Green light and a cheap, even bioavailable, sacrificial donor produce hydrated electrons in the displayed catalytic cycle. The catalyst is a popular metal complex functioning as a “container” for a radical anion. The cycle could open a pathway toward the solar-driven reductive detoxification of halogenated organic waste. equation image=MeOPhO; equation image=MeOPhO.; MLCT=*[RuIII(bpy)2(bpy.)]2+; OER=[RuII(bpy)2(bpy.)]+; GS=[RuII(bpy)3]2+; bpy=2,2′-bipyridine.

  29. Cover Pictures

    1. A High-Pressure NMR Probe for Aqueous Geochemistry

      Dr. Brent G. Pautler, Christopher A. Colla, Dr. Rene L. Johnson, Peter Klavins, Dr. Stephen J. Harley, Dr. C. André Ohlin, Prof. Dimitri A. Sverjensky, Dr. Jeffrey H. Walton and Prof. William H. Casey

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406751

      Thumbnail image of graphical abstract

      Geochemical models for aqueous solution equilibria extend to pressures and temperatures well beyond experimental spectroscopies that could test the predictions. W. H. Casey and co-workers describe in their Communication (10.1002/anie.201404994) a simple NMR probe that can allow spectroscopy on solutions at pressures near those of Earth′s continental crust. (Greg Pautler Graphic Design, Ontario, Canada, is thanked for designing and donating the artwork.)

    2. Bonding Nature of Local Structural Motifs in Amorphous GeTe

      Dipl.-Chem. Volker L. Deringer, Dr. Wei Zhang, Dr. Marck Lumeij, Dipl.-Chem. Stefan Maintz, Prof. Dr. Matthias Wuttig, Prof. Dr. Riccardo Mazzarello and Prof. Dr. Richard Dronskowski

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406993

      Thumbnail image of graphical abstract

      A glimpse into amorphous materials. In their Communication (10.1002/anie.201404223) R. Mazzarello, R. Dronskowski et al. investigate the bonding nature of amorphous GeTe, a prototypical phase-change data-storage material. Starting from a molecular-dynamics snapshot, the role of different structural motifs is elucidated by use of new tools; this way, the chemical “language” of bonding and coordination polyhedra may be transferred to the amorphous state.

    3. Integrating Perovskite Solar Cells into a Flexible Fiber

      Longbin Qiu, Jue Deng, Xin Lu, Zhibin Yang and Prof. Huisheng Peng

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406844

      Thumbnail image of graphical abstract

      Wearable perovskite solar cells with a fiber structure are synthesized according to a procedure that is described by H. Peng et al. in their Communication (DOI: 10.1002/anie.201404973) and entails continuously winding an aligned carbon nanotube sheet onto a stainless steel wire; photoactive materials are incorporated in between them through a solution process. The fiber-shaped perovskite solar cells exhibit an energy conversion efficiency of 3.3 % that is not affected by bending.

    4. Selective Targeting of Tumor and Stromal Cells By a Nanocarrier System Displaying Lipidated Cathepsin B Inhibitor

      G. Mikhaylov, Dr. D. Klimpel, Dr. N. Schaschke, Dr. U. Mikac, M. Vizovisek, Dr. M. Fonovic, Prof. V. Turk, Prof. Boris Turk and Dr. Olga Vasiljeva

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406845

      Thumbnail image of graphical abstract

      A new drug delivery system targeting cancer-associated extracellular cathepsin B is described by B. Turk, O. Vasiljeva, et al. in their Communication (DOI: 10.1002/anie.201402305). The developed system is based on a lipidated cathepsin B-specific inhibitor incorporated into the envelope of the liposomal nanocarrier that could be used for selective targeting of tumor and stroma cells in the tumor micronvironment, while sparing the healthy normal cells.

    5. Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks

      Nhung T. T. Nguyen, Dr. Hiroyasu Furukawa, Dr. Felipe Gándara, Dr. Hoang T. Nguyen, Kyle E. Cordova and Prof. Omar M. Yaghi

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406995

      Thumbnail image of graphical abstract

      Selective capture of CO2 in the presence of N2 and H2O is possible with hydrophobic zeolitic imidazolate frameworks (ZIFs) with the important chabazite topology. These materials, prepared by O. M. Yaghi and co-workers (in their Communication 10.1002/anie.201403980), are shown to perform three consecutive cycles without loss in performance. Remarkably, between each cycle, the ZIFs were fully regenerated at ambient temperature using a N2 flow.

  30. Highlights

    1. Membranes

      Graphene Oxide: A New Platform for High-Performance Gas- and Liquid-Separation Membranes

      Dr. Zachary P. Smith and Prof. Benny D. Freeman

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404407

      Thumbnail image of graphical abstract

      Depending on size: Graphene oxide can be deposited into thin layers having defects and inter-layer structures with dimensions that are appropriate for separating molecules based on size differences and enable rapid transport through these structures. The picture illustrates the pathway of two differently sized molecules through the graphene oxide layers.

  31. News

  32. Communications

    1. C[BOND]H Functionalization

      Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in C[BOND]H Functionalizations

      Dr. David J. Burns and Prof. Hon Wai Lam

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406072

      Thumbnail image of graphical abstract

      When two become one: 1,3-Enynes containing allylic hydrogens cis to the alkyne are shown to act as one-carbon partners, rather than two-carbon partners, in various rhodium-catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double C[BOND]H activation, involving a hitherto rare example of the 1,4-migration of a RhIII species.

    2. Protein Dynamics | Hot Paper

      Local Transient Unfolding of Native State PAI-1 Associated with Serpin Metastability

      Dr. Morten B. Trelle, Dr. Jeppe B. Madsen, Prof. Peter A. Andreasen and Prof. Dr. Thomas J. D. Jørgensen

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201402796

      Thumbnail image of graphical abstract

      Serpin proteins are prone to pathological conformational change, for instance by conversion to an inactive, so-called latent form. Using advanced hydrogen/deuterium-exchange mass spectrometry transient unfolding of a serpin is shown under native condition. Based on these observations, a new mechanism (see picture) is proposed.

    3. Organocatalysis

      Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All-Carbon Stereogenic Center: Total Syntheses of (−)-Rhazinilam and (−)-Leucomidine B

      Jean-Baptiste Gualtierotti, Delphine Pasche, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405842

      Thumbnail image of graphical abstract

      Breaking symmetry: Achiral bislactones (1) undergo desymmetrization by reaction with alcohol in the presence of chiral imidodiphosphoric acids. The monoacids 2, having an all-carbon stereogenic center, were obtained in good to excellent yields and enantioselectivities. Concise total syntheses of (−)-rhazinilam and (−)-leucomidine B were subsequently developed using 2 as a common starting material.

  33. Highlights

    1. Cycloadditions

      Münchnones—New Facets after 50 Years

      Prof. Dr. Hans-Ulrich Reissig and Dr. Reinhold Zimmer

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201405092

      Thumbnail image of graphical abstract

      Developed and named 50 years ago in Munich, the mesoionic münchnones have had an astonishing career. New multicomponent reactions and enantioselective cycloadditions are discussed. They demonstrate the versatility of the münchnone approach to nitrogen heterocycles.

  34. Communications

    1. Asymmetric Catalysis

      High Performance of a Palladium Phosphinooxazoline Catalyst in the Asymmetric Arylation of Cyclic N-Sulfonyl Ketimines

      Chunhui Jiang, Prof. Dr. Yixin Lu and Prof. Dr. Tamio Hayashi

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201406147

      Thumbnail image of graphical abstract

      Chiral cyclic sulfamidates are obtained by the asymmetric addition of arylboronic acids to six-membered cyclic N-sulfonyl ketimines. A cationic palladium complex with a chiral phosphine-oxazoline ligand (iPr-phox) shows high catalytic activity and enantioselectivity to give the products in high yields with 96–99.9 % ee. The cyclic sulfamidates exhibit a tetrasubstituted stereogenic center with an amino group and a triaryl or alkyldiaryl group as substituents.

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