Angewandte Chemie International Edition

Cover image for Vol. 55 Issue 23

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, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

  1. Reviews

    1. Thyroid Hormones

      Chemistry and Biology in the Biosynthesis and Action of Thyroid Hormones

      Santanu Mondal, Karuppusamy Raja, Prof. Dr. Ulrich Schweizer and Prof. Dr. Govindasamy Mugesh

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201601116

      Thumbnail image of graphical abstract

      A picture of health: Thyroid hormones are essential to control body metabolism, heart rate, neural development, as well as cardiovascular, renal, and brain functions. This Review discusses the chemistry and biology involved in the biosynthesis, plasma transport, metabolic pathways, and receptor-mediated action of thyroid hormones in relation to thyroid related disorders and their treatment.

  2. Communications

    1. α-Helical Peptides

      Helix Nucleation by the Smallest Known α-Helix in Water

      Dr. Huy N. Hoang, Dr. Russell W. Driver, Dr. Renée L. Beyer, Dr. Timothy A. Hill, Dr. Aline D. de Araujo, Dr. Fabien Plisson, Dr. Rosemary S. Harrison, Lena Goedecke, Dr. Nicholas E. Shepherd and Prof. David P. Fairlie

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201602079

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      Pep up your peptide: When an α-helical cyclic pentapeptide 1 was appended to one or both ends of a palindromic peptide ARAARAARA (≤5 % helicity), 67, 92, or 100 % α-helicity of the resulting peptide was observed (see picture). From the C-terminus of peptides, 1 nucleated at least six α-helical turns. Imperfect alignment of a backbone amide in 1 reduced helix nucleation when 1 was attached to the N-terminus, but was corrected by a second unit of 1.

    2. Siloxanes

      Janus-Cube Octasilsesquioxane: Facile Synthesis and Structure Elucidation

      Naoki Oguri, Dr. Yasunobu Egawa, Prof. Dr. Nobuhiro Takeda and Prof. Dr. Masafumi Unno

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201602413

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      Two-faced: A perfect “Janus cube” octasilsesquioxane, a nanoscale Janus particle with two different types of substituents, was synthesized through the cross-coupling of a “half-cube” sodium cyclosiloxanolate with another half-cube cyclic fluorosiloxane. The structure was confirmed by X-ray crystallography to be a Janus cube. Furthermore, this method represents a novel siloxane bond-forming reaction involving the coupling of a silanol salt and fluorosilane.

    3. Water Oxidation | Hot Paper

      Modification of Wide-Band-Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible-Light Water Oxidation

      Prof. Dr. Kazuhiko Maeda, Koki Ishimaki, Yuki Tokunaga, Dr. Daling Lu and Dr. Miharu Eguchi

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201602764

      Thumbnail image of graphical abstract

      When rutile TiO2, a wide-band-gap semiconductor, is modified with cobalt hydroxide nanoclusters, it can be used for photocatalytic water oxidation under visible-light irradiation at wavelengths of up to 850 nm. This material thus constitutes the first particulate photocatalyst that operates at such long wavelengths.

    4. Oxidation

      Direct Access to β-Fluorinated Aldehydes by Nitrite-Modified Wacker Oxidation

      Crystal K. Chu, Daniel T. Ziegler, Brian Carr, Zachary K. Wickens and Prof. Robert H. Grubbs

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201603424

      Thumbnail image of graphical abstract

      Out of Wack(er): The aldehyde-selective Wacker-type oxidation of allylic fluorides was accomplished using catalytic nitrite, thus providing a direct route to β-fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and regioselectivity. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation.

    5. Membrane Probes

      In Vivo Probe of Lipid II-Interacting Proteins

      Dr. Sourav Sarkar, Dr. Elizabeth A. Libby, Sean E. Pidgeon, Dr. Jonathan Dworkin and Dr. Marcos M. Pires

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201603441

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      Lipid II probes: Lipid II is a critical intermediate in the biosynthesis of bacterial cell walls and it is also the purported target of several antibiotic agents. Unnatural dipeptides were used to gain entry into the biosynthetic pathway to deliver a dual-functioning probe that can report on potential Lipid II-interacting proteins.

  3. Cover Pictures

    1. You have free access to this content
      Chromoselective Photocatalysis: Controlled Bond Activation through Light-Color Regulation of Redox Potentials

      Dr. Indrajit Ghosh and Burkhard König

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201604293

      Thumbnail image of graphical abstract

      Chromoselective activation of redox-active chemical bonds introduces a new selectivity parameter in visible-light photoredox catalysis. In their Communication (DOI: 10.1002/anie.201602349), I. Ghosh and B. König show that Rhodamine 6G, an inexpensive commercially available xanthene dye, shows different redox potentials under different colors (blue and green) of visible-light irradiation. This enables selective photocatalyst activation for sequential bond activations under different light sources.

    2. You have free access to this content
      Chemistry and Biology in the Biosynthesis and Action of Thyroid Hormones

      Santanu Mondal, Karuppusamy Raja, Prof. Dr. Ulrich Schweizer and Prof. Dr. Govindasamy Mugesh

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/anie.201604415

      Thumbnail image of graphical abstract

      Hormones secreted by the thyroid gland play an important role in lipid, carbohydrate, and protein metabolism, neural development, as well as cardiovascular, renal, and brain functions. The prohormone l-thyroxine (T4) undergoes monodeiodination by deiodinase enzymes to produce the biologically active hormone T3. G. Mugesh and co-workers describe in their Review (10.1002/anie.201601116) the biosynthesis, transport, metabolism, and mechanism of action of thyroid hormones as well as thyroid-related disorders.

  4. Communications

    1. Gas-Phase Reactions

      Gas-Phase Synthesis of 1-Silacyclopenta-2,4-diene

      Dr. Tao Yang, Dr. Beni B. Dangi, Aaron M. Thomas, Dr. Bing-Jian Sun, Tzu-Jung Chou, Prof. Dr. Agnes H. H. Chang and Prof. Dr. Ralf I. Kaiser

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602064

      Thumbnail image of graphical abstract

      Silole (1-silacyclopenta-2,4-diene) was obtained by the bimolecular reaction of the simplest silicon-bearing radical, silylidyne (SiH), with 1,3-butadiene (C4H6) in the gas phase under single-collision conditions. The picture shows the flux contour map of this crossed-beam reaction, which leads to silole by atomic hydrogen loss.

  5. Reviews

    1. Mismatch Repair

      The Intrinsic Fragility of DNA (Nobel Lecture)

      Prof. Tomas Lindahl

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602159

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      Our cells contain common molecules, such as water or oxygen, that can damage DNA. In his studies Tomas Lindahl has shown how specific repair enzymes remove and replace damaged parts of DNA in a process of vital importance.

  6. Communications

    1. Biological Electrocatalysts

      Bioreduction of Precious Metals by Microorganism: Efficient Gold@N-Doped Carbon Electrocatalysts for the Hydrogen Evolution Reaction

      Prof. Weijia Zhou, Tanli Xiong, Chaohong Shi, Prof. Jian Zhou, Kai Zhou, Prof. Nengwu Zhu, Prof. Ligui Li, Prof. Zhenghua Tang and Prof. Shaowei Chen

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602627

      Thumbnail image of graphical abstract

      Rags to riches: Gold nanoparticles supported on N-doped carbon (Au@NC) derived from the bioreduction of gold ions by Pycnoporus sanguineus cells are active HER electrocatalysts with a small onset potential of −54.1 mV and a Tafel slope of 76.8 mV dec−1. The catalyst is a stable and eco-friendly candidate for energy applications. Key: a) bioreduction by Au@microorganism, b) calcination, c) catalysis.

  7. Book Reviews

    1. Cleavage of Carbon–Carbon Single Bonds by Transition Metals. Edited by Masahiro Murakami and Naoto Chatani.

      Christophe Aïssa

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201604142

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2015. 296 pp., hardcover, € 135.00.—ISBN 978-3527336326

  8. Communications

    1. Histone Modifications

      Differentially Isotope-Labeled Nucleosomes to Study Asymmetric Histone Modification Crosstalk by Time-Resolved NMR Spectroscopy

      Dr. Stamatios Liokatis, Dr. Rebecca Klingberg, Prof. Dr. Song Tan and Prof. Dr. Dirk Schwarzer

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201601938

      Thumbnail image of graphical abstract

      Telling twins apart: Two copies of a single core histone were subjected to differential isotope-labeling and asymmetric post-translational modification (PTM) and then used to reconstitute nucleosomes. Reaction of these asymmetrically modified nucleosomes with histone-modifying enzymes enabled NMR monitoring of modification crosstalk in cis and in trans, in a time-resolved, qualitative, and quantitative manner.

    2. Hypervalent Compounds

      Rhodium-Catalyzed Geminal Oxyfluorination and Oxytrifluoro-Methylation of Diazocarbonyl Compounds

      Dr. Weiming Yuan, Dr. Lars Eriksson and Prof. Kálmán J. Szabó

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602137

      Thumbnail image of graphical abstract

      All functional: A new reaction for the rhodium-catalyzed geminal-difunctionalization-based fluorination is presented. The substrates are aromatic and aliphatic diazocarbonyl compounds, and the fluorine sources are either benziodoxole or benziodoxolon reagents. A variety of alcohol, phenol, and carboxylic acid reagents were employed to introduce the second functionality.

    3. Graphene Nanostructures | Hot Paper

      The Nanoparticle Size Effect in Graphene Cutting: A “Pac-Man” Mechanism

      Zongyang Qiu, Prof. Li Song, Prof. Jin Zhao, Prof. Zhenyu Li and Prof. Jinlong Yang

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602541

      Thumbnail image of graphical abstract

      Surface or interface? By employing a multiscale simulation approach, a “Pac-Man” mechanism is revealed for the nickel-nanoparticle-catalyzed cutting of graphene. Although the overall cutting rate is proportional to the surface area of the nanoparticle, it is found that the rate-limiting step is actually at the graphene–metal interface instead of on the nanoparticle surface.

    4. Photochemistry

      You have full text access to this OnlineOpen article
      Design and Synthesis of a Calcium-Sensitive Photocage

      Laurel M. Heckman, Jonathan B. Grimm, Dr. Eric R. Schreiter, Dr. Charles Kim, Dr. Mark A. Verdecia, Brenda C. Shields and Dr. Luke D. Lavis

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201602941

      Thumbnail image of graphical abstract

      A chemical coincidence detector: The first Ca2+-sensitive photocage, which releases a small molecule only in the presence of both light and elevated Ca2+ concentrations, has been synthesized. Caging a fluorophore with this ion-sensitive moiety yields a system that can permanently mark active neurons during an illumination-defined time period.

    5. Asymmetric Polymerization

      Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes

      Dr. Matthieu Jouffroy, Prof. Dr. Dominique Armspach, Prof. Dr. Dominique Matt, Prof. Dr. Kohtaro Osakada and Dr. Daisuke Takeuchi

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201603191

      Thumbnail image of graphical abstract

      Chain gang: Cationic PdII monophosphine complexes derived from α- and β-cyclodextrins (CDs) catalyze the homopolymerization of styrene under carbon monoxide pressure. Although CO coordination takes place under catalytic conditions, both complexes catalyze the formation of CO-free styrene polymers (magenta P). These macromolecules display optical activity as a result of the presence of stereoregular sequences within the overall atactic structure.

  9. Highlights

    1. Organocatalysis

      Chiral Catalyst Design: Cyclopentadiene-Based Brønsted Acids

      Dr. Ivana Fleischer

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/anie.201603672

      Thumbnail image of graphical abstract

      The combination of −I and −M effects and the aromaticity of the conjugate base renders the chiral pentacarboxy-substituted cyclopentadienes (PCCPs) acidic. Their convenient synthesis together with substrates derived from the chiral pool and their performance in the tested reactions renders them prodigious candidates to become a new and highly competitive class of chiral Brønsted acid catalysts.

  10. Communications

    1. Metalloenzymes

      [FeFe]-Hydrogenase with Chalcogenide Substitutions at the H-Cluster Maintains Full H2 Evolution Activity

      Dr. Jens Noth, Dr. Julian Esselborn, Dr. Jörn Güldenhaupt, Annika Brünje, Dr. Anne Sawyer, Dr. Ulf-Peter Apfel, Prof. Klaus Gerwert, Prof. Eckhard Hofmann, Dr. Martin Winkler and Prof. Thomas Happe

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201511896

      Thumbnail image of graphical abstract

      Cofactor swapping: The complex catalytic cofactor of [FeFe]-hydrogenases (H-cluster) exhibits an unexpected level of compositional plasticity. The complete chemical incorporation of an H-cluster analogue into HYDA1 from C. reinhardtii with chalcogenide replacement in the cubane subcluster yields an enzyme variant with full catalytic H2-production activity.

    2. Protein–Protein Interactions

      One-Pot N2C/C2C/N2N Ligation to Trap Weak Protein–Protein Interactions

      Dr. Lei Zhao, Christiane Ehrt, Dr. Oliver Koch and Dr. Yao-Wen Wu

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201601299

      Thumbnail image of graphical abstract

      Like-to-like: Weak transient protein–protein interactions play an important role in cellular dynamics. Novel C-terminus to C-terminus (C2C) and N-terminus to N-terminus (N2N) chemical protein ligation strategies give rise to a facile method for trapping weak protein–protein interactions in an unbiased manner using proximity-induced chemical ligations.

    3. Cross-Coupling

      Trifluoromethylation of Arylsilanes with [(phen)CuCF3]

      Johannes Morstein, Haiyun Hou, Chen Cheng and Prof. Dr. John F. Hartwig

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201601163

      Thumbnail image of graphical abstract

      All about the source: The first trifluoromethylation of arylsilanes occurs with [(phen)CuCF3] as the CF3 source and AgF as the activator under mild, oxidative conditions; the choice of both reagents was shown to be crucial for the reported transformation. The method shows high functional-group compatibility, and late-stage functionalization of active pharmaceutical ingredients is possible. DMF=N,N-dimethylformamide, phen=9,10-phenanthroline.

    4. Luminescent Nanoparticles

      Large-Scale Synthesis of Highly Luminescent Perovskite-Related CsPb2Br5 Nanoplatelets and Their Fast Anion Exchange

      Kun-Hua Wang, Liang Wu, Lei Li, Prof. Dr. Hong-Bin Yao, Prof. Dr. Hai-Sheng Qian and Prof. Dr. Shu-Hong Yu

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201602787

      Thumbnail image of graphical abstract

      The fast and the luminous: A new type of highly luminescent cesium lead halide nanoplatelets show fast anion exchange. Fast anion exchange in the as-synthesized CsPb2Br5 nanoplatelets has also been demonstrated to extend their photoluminescence spectra to the entire visible spectral region of 410 nm–670 nm.

    5. Templated Synthesis

      You have full text access to this OnlineOpen article
      Synthesis of Five-Porphyrin Nanorings by Using Ferrocene and Corannulene Templates

      Dr. Pengpeng Liu, Yutaka Hisamune, Martin D. Peeks, Dr. Barbara Odell, Juliane Q. Gong, Prof. Laura M. Herz and Prof. Harry L. Anderson

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201602909

      Thumbnail image of graphical abstract

      Strained to making point: Two templates were tested for their ability to direct the formation of a π-conjugated cyclic porphyrin pentamer. 1,3,5,7,9-penta(4-pyridyl)corannulene was found to be more effective than a ferrocene-based template, despite the fact that the radius of its N5 ligand set is almost 1 Å too small to fit the cavity of the nanoring.

  11. Cover Pictures

    1. You have free access to this content
      One-pot N-terminus to C-terminus/C-terminus to C-terminus/ N-terminus to N-terminus Ligation to Trap Weak Protein–Protein Interactions

      Dr. Lei Zhao, Christiane Ehrt, Dr. Oliver Koch and Dr. Yao-Wen Wu

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201603828

      Thumbnail image of graphical abstract

      Weak protein–protein interactions (PPIs) are readily trapped by one-pot chemical protein ligations. In their Communication (DOI: 10.1002/anie.201601299) Y.-W. Wu and co-workers describe a facile method for trapping weak PPIs in an unbiased manner using proximity-induced ligations. To expand the chemical ligation spectrum, novel C-terminus to C-terminus (C2C) and N-terminus to N-terminus (N2N) ligation strategies (head-to-head and tail-to-tail in the fish model in the picture) were developed.

  12. Highlights

    1. Heterogeneous Catalysis

      Single-Pass Catalytic Conversion of Syngas into Olefins via Methanol

      Prof. Unni Olsbye

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/anie.201603064

      Thumbnail image of graphical abstract

      All together now: Combination in a single reactor of the catalysts for converting syngas into methanol and methanol into olefins was recently reported by Cheng et al. This approach considerably simplifies the catalytic conversion of natural gas.

  13. Communications

    1. Atomic-Scale Engineering | Hot Paper

      Low-Temperature Cationic Rearrangement in a Bulk Metal Oxide

      Dr. Man-Rong Li, Maria Retuerto, Prof. Peter W. Stephens, Prof. Mark Croft, Dr. Denis Sheptyakov, Vladimir Pomjakushin, Zheng Deng, Dr. Hirofumi Akamatsu, Venkatraman Gopalan, Dr. Javier Sánchez-Benítez, Felix O. Saouma, Prof. Joon I. Jang, Prof. David Walker and Prof. Martha Greenblatt

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201511360

      Thumbnail image of graphical abstract

      The unprecedented low-temperature (150–300 °C) cationic rearrangement in bulk Mn2FeMoO6 leads to a transition from a Ni3TeO6-type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties, which demonstrates remarkable physical property tunneling through atomic-scale manipulation in bulk oxide under mild conditions.

  14. Reviews

    1. Nitrogenases

      Nitrogenases—A Tale of Carbon Atom(s)

      Prof. Dr. Yilin Hu and Prof. Dr. Markus W. Ribbe

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201600010

      Thumbnail image of graphical abstract

      A close rapport exists between nitrogenase and carbon through the interstitial carbide of the cofactor of nitrogenase and through the ability of nitrogenase to reduce small carbon compounds to hydrocarbons. Recent advances reveal a radical-SAM-dependent mechanism of carbide insertion into the nitrogenase cofactor and suggest a role of the interstitial carbide in maintaining the stability while permitting certain flexibility of the cofactor structure during catalysis.

  15. Communications

    1. Total Synthesis

      Rapid Construction of a Benzo-Fused Indoxamycin Core Enabled by Site-Selective C−H Functionalizations

      T. Aaron Bedell, Graham A. B. Hone, Dr. Damien Valette, Prof. Jin-Quan Yu, Prof. Huw M. L. Davies and Prof.Prof. Erik J. Sorensen

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201602024

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      Methods for functionalizing carbon–hydrogen bonds are featured in a new synthesis of the tricyclic core architecture that characterizes the indoxamycin family of secondary metabolites. A diastereoselective dirhodium carbene insertion followed by an ester-directed oxidative Heck cyclization are key steps of this synthesis.

  16. Cover Pictures

    1. You have free access to this content
      Peripheral Templation Generates an MII6L4 Guest-Binding Capsule

      Felix J. Rizzuto, Dr. Wen-Yuan Wu, Dr. Tanya K. Ronson and Prof. Jonathan R. Nitschke

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604252

      Thumbnail image of graphical abstract

      Supramolecular templation usually employs tightly bound molecules that occupy a central cavity. In their Communication (DOI: 10.1002/anie.201602135), J. R. Nitschke et al. report that a template bound in fast exchange at the periphery of an assembly can also be used, as demonstrated by the generation of a pseudo-octahedral coordination cage that cannot be formed in the presence of centrally binding agents. This design principle allows a templated cage to participate in host–guest chemistry without removing the peripherally bound template.

    2. You have free access to this content
      Iridium-Catalyzed Enantioselective Hydroalkynylation of Enamides for the Synthesis of Homopropargyl Amides

      Xiao-Yan Bai, Zi-Xuan Wang and Prof. Dr. Bi-Jie Li

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604414

      Thumbnail image of graphical abstract

      An iridium-catalyzed asymmetric hydroalkynylation of enamides occurs regioselectively at the enamide β position. In their Communication (DOI: 10.1002/anie.201601792), B.-J. Li and co-workers report a method for the straightforward synthesis of chiral homopropargyl amides with a stereocenter β to the amide. As illustrated in the cover image, enamide and alkyne undergo rapid union to form a chiral product.

    3. You have free access to this content
      Synthesis of Highly Uniform Molybdenum–Glycerate Spheres and Their Conversion into Hierarchical MoS2 Hollow Nanospheres for Lithium-Ion Batteries

      Dr. Yawen Wang, Dr. Le Yu and Prof. Xiong Wen (David) Lou

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604636

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      A self-templating method has been developed to synthesize hierarchical MoS2 hollow nanospheres from highly uniform Mo–glycerate solid spheres. In their Communication (DOI: 10.1002/anie.201601673) X. W. Lou and co-workers first synthesize Mo–glycerate spheres with readily tunable sizes by a solvothermal process. The subsequent, as-obtained hierarchical MoS2 structures are formed from ultrathin subunits, have a hollow interior, and give a promising performance as the anode material for lithium-ion batteries.

    4. You have free access to this content
      Kinetically Controlled Sequential Growth of Surface-Grafted Chiral Supramolecular Copolymers

      Hendrik Frisch, Eva-Corinna Fritz, Friedrich Stricker, Lars Schmüser, Daniel Spitzer, Dr. Tobias Weidner, Prof. Dr. Bart Jan Ravoo and Prof. Dr. Pol Besenius

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604416

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      A modular strategy for the synthesis of surface-confined supramolecular copolymers is reported by P. Besenius, B. J. Ravoo, and co-workers in their Communication (10.1002/anie.201601048). The sequential addition of aqueous solutions containing the anionic or cationic comonomer enables the stepwise growth of alternating copolymers from gold surfaces. Charge regulation passivates the growing chain end and yields kinetically trapped chiral copolymers with a tunable height of 5–19 nm.

    5. You have free access to this content
      Size-Controlled Formation of Noble-Metal Nanoparticles in Aqueous Solution with a Thiol-Free Tripeptide

      Stefano Corra, Dr. Urszula Lewandowska, Dr. Edmondo M. Benetti and Prof. Dr. Helma Wennemers

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604536

      Thumbnail image of graphical abstract

      Monodisperse noble-metal nanoparticles (in the example PdNPs) can be formed in aqueous solution in the presence of a thiol-free tripeptide as shown by H. Wennemers and co-workers in their Communication (DOI: 10.1002/anie.201510337). The cover depicts how the peptide upon complexation to Pd2+ ions and their reduction to Pd0 controls the nanoparticle generation by forming a compact peptidic coat around the metal core.

  17. Reviews

    1. Mismatch Repair

      Mechanisms in E. coli and Human Mismatch Repair (Nobel Lecture)

      Prof. Paul Modrich

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201601412

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      DNA molecules are not completely stable, they are subject to chemical or photochemical damage and errors that occur during DNA replication resulting in mismatched base pairs. Through mechanistic studies Paul Modrich showed how replication errors are corrected by strand-directed mismatch repair in Escherichia coli and human cells.

  18. Communications

    1. Drug Delivery

      The Methylene Alkoxy Carbamate Self-Immolative Unit: Utilization for the Targeted Delivery of Alcohol-Containing Payloads with Antibody–Drug Conjugates

      Dr. Robert V. Kolakowski, Karl T. Haelsig, Kim K. Emmerton, Chris I. Leiske, Jamie B. Miyamoto, Julia H. Cochran, Dr. Robert P. Lyon, Dr. Peter D. Senter and Dr. Scott C. Jeffrey

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201601506

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      MAC out: A strategy for the conjugation of alcohol-containing payloads to antibodies has been developed using the methylene alkoxy carbamate (MAC) self-immolative unit. A series of MAC β-glucuronide model constructs were prepared and demonstrated high stability at physiological pH, and efficiently released alcohol drug surrogates under the action of β-glucuronidase.

    2. Photocatalysis | Hot Paper

      Chromoselective Photocatalysis: Controlled Bond Activation through Light-Color Regulation of Redox Potentials

      Dr. Indrajit Ghosh and Burkhard König

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201602349

      Thumbnail image of graphical abstract

      I see your two colors, shining through: The xanthene dye rhodamine 6G is a moderately reducing photoredox catalyst if irradiated with green light, but provides an high reduction power of −2.4 V vs. SCE upon blue-light irradiation. This allows control of the selectivity of photocatalytic C−H arylation reactions through changing the color of the light.

    3. CO2 Capture

      Hierarchically Mesoporous o-Hydroxyazobenzene Polymers: Synthesis and Their Applications in CO2 Capture and Conversion

      Guipeng Ji, Dr. Zhenzhen Yang, Dr. Hongye Zhang, Dr. Yanfei Zhao, Dr. Bo Yu, Zhishuang Ma and Prof. Dr. Zhimin Liu

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201602667

      Thumbnail image of graphical abstract

      CO2 just POPs in: In water and without any templates, hierarchically mesoporous o-hydroxyazobenzene polymers with high surface areas are synthesized. The porous organic polymers (POPs) showed excellent solubility in polar and apolar solvents, good adsorption capacity for metal ions, ultrahigh selectivity for CO2/N2 separation, and excellent performance for catalyzing CO2 conversion.

    4. Photocatalysis | Very Important Paper

      Stable Aqueous Photoelectrochemical CO2 Reduction by a Cu2O Dark Cathode with Improved Selectivity for Carbonaceous Products

      Xiaoxia Chang, Dr. Tuo Wang, Dr. Peng Zhang, Yijia Wei, Jiubing Zhao and Prof. Dr. Jinlong Gong

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201602973

      Thumbnail image of graphical abstract

      Copper on the dark side: Cu2O preferentially reduced CO2 to fuels while suppressing hydrogen evolution. It was found that the photogenerated holes primarily account for the instability of Cu2O. The Cu2O was used as a dark cathode to minimize the adverse effects of holes, achieving excellent stability and a selectivity of 92.6 % for carbonaceous products in CO2 photoreduction.

    5. Trace Elements

      Binding of Chromium(III) to Transferrin Could be Involved in Detoxification of Dietary Chromium(III) Rather Than Transport of an Essential Trace Element

      Dr. Aviva Levina, Dr. T. H. Nguyen Pham and Prof. Peter A. Lay

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201602996

      Thumbnail image of graphical abstract

      You shall not pass: CrIII has been proposed to be an essential trace element and has been postulated to be taken up through binding to the Fe transport protein transferrin. However, binding of CrIII to vacant FeIII binding sites on transferrin was found to block rather than promote cellular accumulation of CrIII. It thus appears that this process could in fact be a protective mechanism against CrIII toxicity rather than a mechanism of CrIII uptake.

    6. Venom Peptides | Hot Paper

      Autocrine-Based Selection of Drugs that Target Ion Channels from Combinatorial Venom Peptide Libraries

      Dr. Hongkai Zhang, Dr. Mingjuan Du, Dr. Jia Xie, Xiao Liu, Jingying Sun, Dr. Wei Wang, Xiu Xin, Prof. Lourival D. Possani, Dr. Kyungmoo Yea and Prof. Richard A. Lerner

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201603052

      Thumbnail image of graphical abstract

      Pick your poison: Cysteine-knot peptides were extracted from the venom database by using bioinformatics and used to create a lentiviral vector library for the autocrine-based selection of peptides targeting ion channels. Interaction of the membrane-tethered venom peptide with the ion channel results in the protease-mediated release of a transcription factor (orange), which triggers expression of a reporter gene (red).

  19. Book Reviews

    1. Cyclopropanes in Organic Synthesis. By Oleg G. Kulinkovich.

      Daniel B. Werz

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201603984

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      John Wiley and Sons, Hoboken 2015. 432 pp., hardcover, € 135.00.—ISBN 978-1118057438

  20. Cover Pictures

    1. You have free access to this content
      Janus-Cube Octasilsesquioxane: Facile Synthesis and Structure Elucidation

      Naoki Oguri, Dr. Yasunobu Egawa, Prof. Dr. Nobuhiro Takeda and Prof. Dr. Masafumi Unno

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604248

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      The Janus cube has landed, which could be a giant leap for materials science. In their Communication (DOI: 10.1002/anie.201602413), M. Unno and co-workers, report the synthesis and X-ray crystal structure of a perfect “Janus cube” octasilsesquioxane, a nanoscale Janus particle with two different types of substituents. This structure was synthesized through the novel cross-coupling of sodium cyclosiloxanolate and cyclic fluorosiloxane “half-cubes”.

    2. You have free access to this content
      Isorecticular Synthesis of Dissectible Molecular Bamboo Tubes of Hexarhenium(I) Benzene-1,2,3,4,5,6-hexaolate Complexes

      Prof. Dr. Tien-Wen Tseng, Dr. Tzuoo-Tsair Luo, Shi-Hao Liao, Kai-Hsiang Lu and Prof. Dr. Kuang-Lieh Lu

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604287

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      The Star of David is the structural motif of the important macromolecular blocks, which have a doubly tri-legged structure and can be stacked together by applying lock-and-key strategies. In their Communication (10.1002/anie.201602327) T. W. Tseng, K. L. Lu, and co-workers show how this approach can lead to the systematic construction of dissectible bamboo-like metal organic tubes (resembling the form of the tower Taipei 101).

    3. You have free access to this content
      Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface Enhanced Raman Spectroscopy

      Qiran Cai, Srikanth Mateti, Prof. Wenrong Yang, Dr. Rob Jones, Dr. Kenji Watanabe, Prof. Takashi Taniguchi, Prof. Shaoming Huang, Prof. Ying Chen and Dr. Lu Hua Li

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/anie.201604295

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      Atomically thin boron nitride nanosheets have many desirable properties for surface enhanced Raman spectroscopy. In their Communication (10.1002/anie.201600517) Y. Chen, L. H. Li, and co-workers show that when used to cover plasmonic silver nanoparticles (Ag NPs), atomically thin boron nitride nanosheets can enhance the sensitivity by up to two orders of magnitude. The impermeability and thermal stability of boron nitride nanosheets protects the Ag NPs from oxidation so that the substrates can be regenerated by heating in air and reused.

  21. Communications

    1. NMR Spectroscopy

      CLIP-COSY: A Clean In-Phase Experiment for the Rapid Acquisition of COSY-type Correlations

      Martin R. M. Koos, Dr. Grit Kummerlöwe, Lukas Kaltschnee, Prof. Dr. Christina M. Thiele and Prof. Dr. Burkhard Luy

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201510938

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      A cozy COSY: The COSY experiment is one of the fundamental two-dimensional NMR experiments. A severe drawback of state-of-the-art implementations is the complex line shape, demanding long data acquisitions. Clean in-phase COSY (CLIP-COSY) combines the unique information from COSY experiments with a simple line shape (as in NOESY-type spectra), and enables rapid acquisition and the combination with homonuclear decoupling.

    2. DNA Nanoimprinting

      Transfer of Two-Dimensional Oligonucleotide Patterns onto Stereocontrolled Plasmonic Nanostructures through DNA-Origami-Based Nanoimprinting Lithography

      Yinan Zhang, Prof. Jie Chao, Prof. Huajie Liu, Fei Wang, Prof. Shao Su, Bing Liu, Prof. Lan Zhang, Dr. Jiye Shi, Prof. Lihua Wang, Prof. Wei Huang, Prof. Lianhui Wang and Prof. Chunhai Fan

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201512022

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      The transfer of knowledge: DNA origami acts as a copy-machine-like platform to precisely decorate the surface of gold nanoparticles (AuNPs) with DNA anchor strands. These strands are subsequently employed to construct discrete AuNP clusters with designed chirality.

    3. Biocatalysis

      Application to Photocatalytic H2 Production of a Whole-Cell Reaction by Recombinant Escherichia coli Cells Expressing [FeFe]-Hydrogenase and Maturases Genes

      Dr. Yuki Honda, Prof. Hidehisa Hagiwara, Prof. Shintaro Ida and Prof. Tatsumi Ishihara

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201600177

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      An inorganic–bio hybrid photocatalyst for photocatalytic H2 production was developed. A biocatalyst involving whole-cell recombinant E. coli cells expressing genes encoding [FeFe]-hydrogenase and relevant maturases (rectangle) was combined with TiO2 (circle) via the methylviologen MV2+/MV+. couple.

    4. Molecular Motion | Hot Paper

      Dissipative and Autonomous Square-Wave Self-Oscillation of a Macroscopic Hybrid Self-Assembly under Continuous Light Irradiation

      Tomonori Ikegami, Dr. Yoshiyuki Kageyama, Kazuma Obara and Prof. Sadamu Takeda

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201600218

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      Oscillate wildly: In a limit-cycle self-oscillatory motion of a macroscopic assembly, the assembly permanently flips under continuous blue-light irradiation. Mechanical self-oscillation showing a spatio-temporal pattern is established by successively alternating photoisomerization processes and multi-stable phase transitions.

    5. Host–Guest Chemistry

      Manifesting Subtle Differences of Neutral Hydrophilic Guest Isomers in a Molecular Container by Phase Transfer

      Hyun Hee L. Lee, Jong Wha Lee, Yoonjung Jang, Dr. Young Ho Ko, Prof. Dr. Kimoon Kim and Prof. Dr. Hugh I. Kim

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201601320

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      Mass spectrometry (MS) and phase transfer was used to distinguish between complexes of curcurbit[7]uril and four isomeric monosaccharides in the gas phase. The sensitivity of MS enabled a quantitative analysis of monosaccharide concentrations, and this method could be applied to a variety of other host–guest systems.

    6. Asymmetric Catalysis

      Chiral Nanoparticles/Lewis Acids as Cooperative Catalysts for Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Amides

      Dr. Tomohiro Yasukawa, Yuuki Saito, Dr. Hiroyuki Miyamura and Prof. Dr. Shū Kobayashi

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201601559

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      It can abide amides: Cooperative catalysts consisting of heterogeneous chiral Rh/Ag nanoparticles and a metal Lewis acid, Sc(OTf)3 show high catalytic activities and outstanding enantioselectivities for asymmetric 1,4-addition reactions of arylboronic acids with α,β-unsaturated amides. The reaction is regarded as challenging owing to low reactivity of the amide substrates.

    7. Oxygen Reduction | Hot Paper

      Nitrogen-Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction

      Dr. Akira Miura, Dr. Carolina Rosero-Navarro, Dr. Yuji Masubuchi, Dr. Mikio Higuchi, Prof. Dr. Shinichi Kikkawa and Prof. Dr. Kiyoharu Tadanaga

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201601568

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      The catalytic activities of manganese oxynitrides with different nitrogen contents in the oxygen reduction reaction (ORR) in alkaline solution were investigated. An increase in the nitrogen content of rock-salt-type manganese oxynitrides increases the valence of manganese and leads to enhanced catalytic activity.

    8. Organometallic Helicenes

      Iron Alkynyl Helicenes: Redox-Triggered Chiroptical Tuning in the IR and Near-IR Spectral Regions and Suitable for Telecommunications Applications

      Dr. Chengshuo Shen, Dr. Goulc'hen Loas, Dr. Monika Srebro-Hooper, Dr. Nicolas Vanthuyne, Dr. Loïc Toupet, Dr. Olivier Cador, Dr. Frédéric Paul, Prof. Juan T. López Navarrete, Prof. Francisco J. Ramírez, Dr. Belén Nieto-Ortega, Prof. Juan Casado, Prof. Jochen Autschbach, Prof. Marc Vallet and Dr. Jeanne Crassous

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201601633

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      Chiroptical switch: Iron alkynyl[6]helicene complexes have been synthesized. Vibrational circular dichroism and Raman optical activity spectra are used to investigate how the oxidation of the complexes to form radical cations influences their vibrational modes. The optical rotation of these chiral species (inline image ; measured in ° cm2 dmol−1) changes sign at wavelengths typically used for telecommunications (1.54 µm).

    9. Flexible Batteries

      An All-Solid-State Fiber-Shaped Aluminum–Air Battery with Flexibility, Stretchability, and High Electrochemical Performance

      Yifan Xu, Yang Zhao, Jing Ren, Ye Zhang and Prof. Dr. Huisheng Peng

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201601804

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      Wear it! A family of fiber-shaped aluminum–air batteries with high electrochemical performance was created by designing cross-stacked carbon-nanotube/Ag sheets as the air cathode to enhance gas diffusion, catalyze oxygen reduction, and promote charge transport. The batteries are flexible and stretchable, and can be woven into various textiles (see photographs of an LED watch powered by two fiber-shaped Al–air batteries connected in series).

    10. [3+2] Cycloaddition

      Enantiodivergent Combination of Natural Product Scaffolds Enabled by Catalytic Enantioselective Cycloaddition

      Dr. Hao Xu, Christopher Golz, Prof. Dr. Carsten Strohmann, Dr. Andrey P. Antonchick and Prof. Dr. Herbert Waldmann

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201602084

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      Two for one offer: An efficient method based on copper(I)-catalyzed [3+2] cycloadditions has been developed for the enantiodivergent combination of natural product derived tropane and pyrrolidine scaffolds. The strategy enables the synthesis of two enantiopure products in a one-pot reaction with one chiral catalyst in high diastereo- and enantioselectivity.

    11. Spin-Crossover Materials | Hot Paper

      First Step Towards a Devil's Staircase in Spin-Crossover Materials

      Dr. Elzbieta Trzop, Dr. Daopeng Zhang, Dr. Lucia Piñeiro-Lopez, Dr. Francisco J. Valverde-Muñoz, Prof. M. Carmen Muñoz, Dr. Lukas Palatinus, Dr. Laurent Guerin, Prof. Hervé Cailleau, Prof. Jose Antonio Real and Prof. Eric Collet

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201602441

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      The devil is in the detail: Periodic and aperiodic spin-state concentration waves form during “Devil's staircase”-type spin-crossover in a new bimetallic 2D coordination polymer {Fe[(Hg(SCN)3)2](4,4′-bipy)2}n.

    12. Expanded Porphyrins

      Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)

      Masataka Umetani, Dr. Takayuki Tanaka, Taeyeon Kim, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/anie.201602874

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      Building bridges: A reaction sequence involving oxidation with PbO2, a Corey–Fuchs reaction, and Fritsch–Buttenberg–Wiechell rearrangement allowed double ring expansion from a porphyrin to a tetradehydro[20]porphyrin(2.1.2.1) (see scheme), which was reduced to a didehydro[20]porphyrin(2.1.2.1) and a [20]porphyrin(2.1.2.1). These planar porphyrins exhibited 20 π antiaromatic character.

    13. Bioinorganic Chemistry

      Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)–Oxo Complex by Changing Only the Reaction Temperature

      Dr. Jieun Jung, Surin Kim, Dr. Yong-Min Lee, Prof. Dr. Wonwoo Nam and Prof. Dr. Shunichi Fukuzumi

      Version of Record online: 18 MAY 2016 | DOI: 10.1002/anie.201602460

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      The switchover of the reaction mechanism from electron transfer (ET) to hydrogen-atom transfer (HAT) for a protonated nonheme manganese(IV)–oxo complex was investigated. The switchover occurs in the presence of triflic acid by changing only the reaction temperature in the boundary region between ET and HAT pathways. KIE=kinetic isotope effect; black=mesitylene, red=[D12]mesitylene.

  22. Minireviews

    1. Scaffold Diversity

      Scaffold Diversity Synthesis and Its Application in Probe and Drug Discovery

      Dr. Miguel Garcia-Castro, Stefan Zimmermann, Dr. Muthukumar G. Sankar and Dr. Kamal Kumar

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201508818

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      Complexity and diversity: The synthesis of compound libraries with a high degree of scaffold diversity has been addressed by transforming suitable common intermediates into various molecular frameworks or by using natural products as a source of scaffold diversity. In this Minireview, recent developments towards the construction of such libraries and their application in drug and probe discovery are summarized.

  23. Communications

    1. Ionic Liquids

      Tuning the Hydrophilicity and Hydrophobicity of the Respective Cation and Anion: Reversible Phase Transfer of Ionic Liquids

      Wenhui Yao, Dr. Huiyong Wang, Dr. Guokai Cui, Zhiyong Li, Dr. Anlian Zhu, Prof. Suojiang Zhang and Prof. Jianji Wang

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201600419

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      “Smart” liquids: Functionalized ionic liquids (ILs) were developed and show reversible phase transfer between water and organics upon heating and cooling owing to the conformation change of the PEG chain of the IL upon change of temperature. A highly efficient, recyclable, and controllable CuI-catalyzed cycloaddition reaction was achieved by using ILs as the entrainer and catalyst activator, as well as the controller of the reaction.

    2. Photochemistry

      Protein-Framed Multi-Porphyrin Micelles for a Hybrid Natural–Artificial Light-Harvesting Nanosystem

      Yannan Liu, Jiyang Jin, Hongping Deng, Ke Li, Dr. Yongli Zheng, Dr. Chunyang Yu and Prof. Yongfeng Zhou

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201601516

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      Nanopomegranate: A micellar light-harvesting nanosystem was prepared consisting of one phycocyanin protein acceptor in the core and many porphyrin donors packed in a pomegranate-like manner in the shell. The system inhibited donor self-quenching effectively and displayed efficient transfer of excitation energy in water.

    3. Nanocomposites | Very Important Paper

      Chemical-Bonding-Directed Hierarchical Assembly of Nanoribbon-Shaped Nanocomposites of Gold Nanorods and Poly(3-hexylthiophene)

      Shuang Pan, Luze He, Prof. Juan Peng, Prof. Feng Qiu and Prof. Zhiqun Lin

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201603189

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      Turning fibers into ribbons: Nanoribbon-shaped nanocomposites composed of a conjugated polymer, poly(3-hexylthiophene) (P3HT), and plasmonic gold nanorods (AuNRs) are produced by a co-assembly of thiol-terminated P3HT nanofibers with dodecanethiol-coated AuNRs. Owing to plasmon coupling between adjacent aligned AuNRs these nanocomposites show broadened and red-shifted absorption bands.

    4. Asymmetric Hydrogenation

      Highly Enantioselective Iridium-Catalyzed Hydrogenation of Cyclic Enamides

      Ernest Salomó, Dr. Sílvia Orgué, Prof. Antoni Riera and Prof. Xavier Verdaguer

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201602219

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      Diversity matters: Three chiral components (an amino acid, an amino alcohol, and a P-stereogenic phosphine) form the novel MaxPHOX ligand template and thus enable the synthesis of catalysts with broad structural diversity. From a small library of MaxPHOX–Ir complexes, two catalysts were identified for the highly enantioselective hydrogenation of enamides derived from α- and β-tetralones (see scheme).

    5. Bioinorganic Chemistry

      An Organometallic Compound which Exhibits a DNA Topology-Dependent One-Stranded Intercalation Mode

      Dr. Zhujun Ma, Dr. Giulia Palermo, Dr. Zenita Adhireksan, Dr. Benjamin S. Murray, Thibaud von Erlach, Prof. Paul J. Dyson, Prof. Ursula Rothlisberger and Prof. Curt A. Davey

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201602145

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      Binding preferences: Using crystallographic methods and molecular dynamics simulations it was shown that adducts formed by the anticancer agent [(η6-5,8,9,10-tetrahydroanthracene)Ru(ethylenediamine)Cl][PF6] on a nucleosome comprise a novel one-stranded intercalation and DNA distortion mode. The adduct dimorphism and DNA topology dependence might contribute to the unusually high cytotoxicity of this anticancer agent.

    6. Molecular Dynamics

      A Three-Site Mechanism for Agonist/Antagonist Selective Binding to Vasopressin Receptors

      Noureldin Saleh, Dr. Giorgio Saladino, Prof. Dr. Francesco L. Gervasio, Elke Haensele, Dr. Lee Banting, Dr. David C. Whitley, Prof. Dr. Jana Sopkova-de Oliveira Santos, Prof. Ronan Bureau and Prof. Dr. Timothy Clark

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201602729

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      Three distinct binding sites are revealed by molecular-dynamics simulations with metadynamics enhanced sampling for arginine vasopressin (AVP) within its V2-receptor (V2R). Two of these, the vestibule (magenta) and intermediate (green) sites, block (antagonize) the receptor, and the third is the orthosteric activation (agonist) site (blue). The resulting three-site mechanism separates agonists from antagonists and explains subtype selectivity.

    7. Analytical Methods | Hot Paper

      A Disposable Planar Paper-Based Potentiometric Ion-Sensing Platform

      Jinbo Hu, Prof. Andreas Stein and Prof. Philippe Bühlmann

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/anie.201603017

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      Paper-based sensors: Embedding a potentiometric cell into paper brings selective ion sensors into the reach of users with limited resources and training. The paper-based device is simple to use, does not need any pretreatment, and requires only a low sample volume of 20 μL. It can be used to detect clinically relevant ions in biological samples with high sensitivity and reproducibility. ISE=ion-selective electrode.

    8. Microporous Materials

      EU-12: A Small-Pore, High-Silica Zeolite Containing Sinusoidal Eight-Ring Channels

      Juna Bae, Jung Cho, Jeong Hwan Lee, Dr. Sung Man Seo and Prof. Suk Bong Hong

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/anie.201600146

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      Structure elucidation: The structure of the small-pore zeolite EU-12, which has remained unknown during the past 30 years, was determined by synchrotron powder X-ray diffraction and Rietveld analyses (see picture). EU-12 shows a superior catalytic performance for the dehydration of ethanol.

    9. Redox Homeostasis

      Monitoring the Glutathione Redox Reaction in Living Human Cells by Combining Metabolic Labeling with Heteronuclear NMR

      Xing Jin, Soeun Kang, Prof. Shinya Tanaka and Prof. Sunghyouk Park

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/anie.201601026

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      Oxidation counter measures: The glutathione (GSH) redox reaction is critical for defense against cellular reactive oxygen species. Endogenous synthesis of GSH from isotope-labeled cysteine was exploited to enable measurement of the intracellular GSH redox reaction in live cells by NMR. This enabled real-time monitoring of GSH redox reactions in cells resistant to the glioblastoma drug temozolomide (TMZ), and the results suggest a possible new mechanism of resistance.

    10. Natural Products

      Total Synthesis of (+)-Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

      Ze-Xin Zhang, Si-Cong Chen and Prof. Dr. Lei Jiao

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/anie.201602771

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      All at once: A palladium-catalyzed asymmetric cascade cyclization enabled one-step construction of the tetracyclic core framework of the indole alkaloid (+)-minfiensine. A palladium-catalyzed Heck-type cyclization completed its total synthesis efficiently.

    11. Host–Guest Systems

      Uptake of Hydrocarbons in Aqueous Solution by Encapsulation in Acyclic Cucurbit[n]uril-Type Molecular Containers

      Dr. Xiaoyong Lu and Prof. Dr. Lyle Isaacs

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201602671

      Thumbnail image of graphical abstract

      Be my guest: Acyclic cucurbit[n]uril (CB[n]) type containers are more efficient than macrocyclic CB[7] and CB[8] at promoting the efficient uptake of poorly water soluble hydrocarbons into aqueous solution through formation of complexes. The hydrophobic driving force for complexation of aliphatic, alicyclic, and polycyclic hydrocarbons inside acyclic CB[n] rivals that of CB[7] and CB[8].

    12. Radical Reactions

      A Bulky Thiyl-Radical Catalyst for the [3+2] Cyclization of N-Tosyl Vinylaziridines and Alkenes

      Dr. Takuya Hashimoto, Kohei Takino, Kazuki Hato and Prof. Dr. Keiji Maruoka

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201602723

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      Bulk it up: A thiyl-radical-catalyzed cyclization reaction of N-tosyl vinylaziridines and alkenes was developed as a new synthetic method for the generation of substituted pyrrolidines (see scheme). The key to making this process accessible to a broad range of substrates is the use of a sterically demanding thiyl radical to prevent the undesired degradation of the catalyst.

  24. News

  25. Cover Pictures

    1. You have free access to this content
      Radiation Damage and Racemic Protein Crystallography Reveal the Unique Structure of the GASA/Snakin Protein Superfamily

      Ho Yeung, Dr. Christopher J. Squire, Yuliana Yosaatmadja, Dr. Santosh Panjikar, Gemma López, Prof. Dr. Antonio Molina, Prof. Dr. Edward N. Baker, Dr. Paul W. R. Harris and Prof. Dr. Margaret A. Brimble

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201604250

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      The antimicrobial protein snakin-1, isolated from potatoes, displays a uniquely folded three-dimensional structure held together by six disulfide bonds. In their Communication (DOI: 10.1002/anie.201602719), M. A. Brimble, C. J. Squire, and co-workers describe how they used a radiation damage induced phasing (RIP) method to solve the racemic crystal structure of the protein, exploiting specific X-ray radiation induced breakage of an endogenous C−I bond.

    2. You have free access to this content
      Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins

      Dr. Yusuke Kita, Shoji Hida, Kenya Higashihara, Dr. Himanshu Sekhar Jena, Kosuke Higashida and Prof. Dr. Kazushi Mashima

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201604253

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      He shoots, he scores! Efficient rhodium(III) catalysts for asymmetric hydrogenation of simple olefins without any directing groups are described by K. Mashima and co-workers in their Communication (DOI: 10.1002/anie.201601748). Compared with the corresponding rhodium(I) catalysts, chloride-bridged dinuclear rhodium(III) complexes bearing chiral diphosphine ligands are superior catalysts for asymmetric hydrogenation of (E)-propene-1,2-diyldibenzene and its derivatives, as well as allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones.

    3. You have free access to this content
      Chemical-Bonding-Directed Hierarchical Assembly of Nanoribbon-Shaped Nanocomposites of Gold Nanorods and Poly(3-hexylthiophene)

      Shuang Pan, Luze He, Prof. Juan Peng, Prof. Feng Qiu and Prof. Zhiqun Lin

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201604251

      Thumbnail image of graphical abstract

      Ants, mimicking gold nanorods (AuNRs) are attracted by sugar, or in this case, thiol-terminated poly(3-hexylthiophene) (P3HT) nanofibers. In their Communication (10.1002/anie.201603189), J. Peng, Z. Lin, and co-workers describe a facile bottom-up co-assembly strategy for crafting hierarchical nanoribbon-shaped P3HT/AuNR nanocomposites composed of P3HT-SH nanoribbons with AuNRs aligned on the surface of the nanoribbon.

    4. You have free access to this content
      First Step Towards a Devil's Staircase in Spin-Crossover Materials

      Dr. Elzbieta Trzop, Dr. Daopeng Zhang, Dr. Lucia Piñeiro-Lopez, Dr. Francisco J. Valverde-Muñoz, Prof. M. Carmen Muñoz, Dr. Lukas Palatinus, Dr. Laurent Guerin, Prof. Hervé Cailleau, Prof. Jose Antonio Real and Prof. Eric Collet

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201604286

      Thumbnail image of graphical abstract

      The devil is in the detail: Periodic and aperiodic spin-state concentration waves form during “Devil's staircase”-type spin-crossover in a new bimetallic 2D coordination polymer {Fe[(Hg(SCN)3)2](4,4′-bipy)2}n. In their Communication (DOI: 10.1002/anie.201602441), J. A. Real, E. Collet et al. describe the appearance of spin-state concentration waves between long-range spatially ordered structures of low- and high-spin states during multi-step spin-crossover.

    5. You have free access to this content
      In Situ Functionalized Polymers for siRNA Delivery

      Juan M. Priegue, Daniel N. Crisan, Dr. José Martínez-Costas, Prof. Dr. Juan R. Granja, Dr. Francisco Fernandez-Trillo and Dr. Javier Montenegro

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201604083

      Thumbnail image of graphical abstract

      Hydrazone-activated polymers with a consistent degree of polymerization but with different post-polymerization functionalization were employed as scaffolds for siRNA delivery. In their Communication (DOI: 10.1002/anie.201601441), J. Montenegro, F. Fernandez-Trillo et al. report the preparation of amphiphilic polymers and their evaluation as oligonucleotide transporters in artificial vesicles and human cells. Cover design by Bea Perez and Javier Montenegro, drawn by Bea Perez.

  26. Communications

    1. Epigenetics

      Development of a DNA-Templated Peptide Probe for Photoaffinity Labeling and Enrichment of the Histone Modification Reader Proteins

      Xue Bai, Dr. Congcong Lu, Dr. Jin Jin, Shanshan Tian, Zhenchang Guo, Pu Chen, Dr. Guijin Zhai, Shuzhen Zheng, Prof. Xiwen He, Dr. Enguo Fan, Prof. Yukui Zhang and Prof. Kai Zhang

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/anie.201602558

      Thumbnail image of graphical abstract

      Do you read me? A DNA-templated peptide probe was developed to identify the reader proteins of histone post-translational modifications. The method, based on DNA-templated chemistry and photo-crosslinking technologies, can label and enrich the reader of H3K4me3 (histone H3 lysine 4 trimethylation) in a whole cell lysate.

    2. Heterometallic Complexes

      Polynuclear Gold [AuI]4, [AuI]8, and Bimetallic [AuI4AgI] Complexes: C−H Functionalization of Carbonyl Compounds and Homogeneous Carbonylation of Amines

      Ekaterina S. Smirnova, Dr. José M. Muñoz Molina, Alice Johnson, Dr. Nuno A. G. Bandeira, Prof. Carles Bo and Prof. Antonio M. Echavarren

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201603200

      Thumbnail image of graphical abstract

      Gold aplenty: The synthesis of tetranuclear gold complexes, a structurally unprecedented octanuclear complex with a planar [AuI8] core, and pentanuclear [AuI4MI] (M=Cu, Ag) complexes is presented. The linear [AuI4] complex undergoes C−H functionalization of carbonyl compounds under mild reaction conditions. In addition, [AuI4AgI] catalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles.

    3. Carbonylation | Very Important Paper

      Copper-Catalyzed Carbonylative Coupling of Cycloalkanes and Amides

      Yahui Li, Dr. Kaiwu Dong, Fengxiang Zhu, Zechao Wang and Prof. Dr. Xiao-Feng Wu

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201603235

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      A copper-catalyzed carbonylative synthesis of imides starting from cycloalkanes and amides has been developed. The imides were prepared in good yields by carbonylation of a C(sp3)−H bond of the cycloalkane with the amides acting as weak nucleophiles (DTBP=di-tert-butylperoxide, 1,10-phen=1,2-phenanthroline hydrate).

    4. Nanostructures

      Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers

      Mohamed B. Zakaria, Dr. Cuiling Li, Dr. Qingmin Ji, Bo Jiang, Dr. Satoshi Tominaka, Dr. Yusuke Ide, Dr. Jonathan P. Hill, Prof. Katsuhiko Ariga and Prof. Yusuke Yamauchi

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201603223

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      Layer Cake: Deposition of nickel-based cyano-bridged coordination polymer (NiCNNi) flakes on the surface of graphene oxide (GO) sheets allows the formation of lamellar nanoarchitectures. Regulated thermal treatment under nitrogen produces an Ni3C–GO composite with a similar morphology to the starting material. This approach may be applicable to other inorganic–organic hybrids for the formation of ordered layer-by-layer (LbL) architectures.

  27. Cover Pictures

    1. You have free access to this content
      Measuring the Elasticity of Poly-l-Proline Helices with Terahertz Spectroscopy

      Michael T. Ruggiero, Dr. Juraj Sibik, Prof. Roberto Orlando, Dr. J. Axel Zeitler and Prof. Timothy M. Korter

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201603825

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      An approach combining terahertz spectroscopy, X-ray diffraction, and solid-state density functional theory was utilized to accurately measure the elasticities of poly-l-proline helices by probing their spring-like vibrational motions. In their communication (DOI: 10.1002/anie.201602268), T. M. Korter and co-workers reveal that poly-l-proline is less rigid than commonly expected, and that the all-cis and all-trans helical forms exhibit significantly different Young's moduli.

  28. Communications

    1. Electrocatalysis

      Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2(110) Model Electrode

      Dr. Kai S. Exner, Dr. Josef Anton, Prof. Dr. Timo Jacob and Prof. Dr. Herbert Over

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201511804

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      Beyond thermodynamics: An intimate interplay of thermodynamics and kinetics from first principles together with microkinetic modeling allows the microscopic processes of the chlorine evolution reaction over a RuO2(110) model electrode to be unraveled. This combined approach may provide a general roadmap on how electrocatalytic reactions can be studied to gain unprecedented molecular insight.

    2. Biosynthesis

      Unveiling the Biosynthetic Pathway of the Ribosomally Synthesized and Post-translationally Modified Peptide Ustiloxin B in Filamentous Fungi

      Ying Ye, Dr. Atsushi Minami, Yuya Igarashi, Dr. Miho Izumikawa, Dr. Myco Umemura, Dr. Nozomi Nagano, Prof. Dr. Masayuki Machida, Dr. Teppei Kawahara, Prof. Dr. Kazuo Shin-ya, Prof. Dr. Katsuya Gomi and Prof. Dr. Hideaki Oikawa

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602611

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      The biosynthetic machinery for the fungal ribosomally synthesized and post-translationally modified peptide (RiPP) ustiloxin was elucidated by gene inactivation, heterologous expression, and in vitro studies. The details include formation of a cyclic peptide by novel oxidases harboring a DUF3328 motif and unique modification reactions for construction of the side chain on the aromatic ring. These findings set the stage for elucidating the biosynthesis of fungal RiPPs.

    3. Aldol Reactions

      Stereoselective Arene-Forming Aldol Condensation: Synthesis of Axially Chiral Aromatic Amides

      Vincent C. Fäseke and Prof. Dr. Christof Sparr

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602689

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      Amine amid amides: A chiral amine-catalyzed arene-forming aldol condensation providing axially chiral aromatic amides is described. The reaction proceeds with excellent atroposelectivity at ambient temperature within minutes. The substrate scope was expanded by employing an in situ reduction, thus furnishing atropisomers characterized by their distinct spatial arrangement and remarkable configurational stability.

    4. Total Synthesis

      Isolation and Asymmetric Total Synthesis of Perforanoid A

      Chao Lv, Dr. Xiaohui Yan, Qian Tu, Dr. Yingtong Di, Dr. Chunmao Yuan, Dr. Xin Fang, Prof. Dr. Yaacove Ben-David, Lei Xia, Prof. Dr. Jianxian Gong, Prof. Dr. Yuemao Shen, Prof. Dr. Zhen Yang and Prof. Dr. Xiaojiang Hao

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602783

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      When life gives you limonoids: A novel limonoid, perforanoid A, was isolated, and an asymmetric total synthesis was achieved in 10 steps. The key steps are chiral tertiary aminonaphthol mediated enantioselective alkenylation of an aldehyde to an allylic alcohol, Pd-catalyzed coupling of the allylic alcohol with vinyl ether to form the γ-lactone ring, and cyclopentenone ring formation through a Rh-catalyzed Pauson–Khand reaction.

    5. Organocatalysis

      Catalytic Asymmetric Inverse-Electron-Demand 1,3-Dipolar Cycloaddition of C,N-Cyclic Azomethine Imines with Azlactones: Access to Chiral Tricyclic Tetrahydroisoquinolines

      Xihong Liu, Yijie Wang, Dongxu Yang, Jinlong Zhang, Prof. Dongsheng Liu and Prof. Wu Su

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602880

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      A bifunctional organocatalyst is employed to mediate the title reaction. The process affords a series of C1-substituted tetrahydroisoquinolines, featuring a pyrazolidinone scaffold, with excellent yields and stereoselectivities. Ts=4-toluenesulfonyl.

    6. Gold Catalysis

      Gold(I)-Catalyzed Generation of the Two Components of a Formal [4+2] Cycloaddition Reaction for the Synthesis of Tetracyclic Pyrano[2,3,4-de]chromenes

      Dr. Tamara Arto, Prof. Dr. Francisco J. Fañanás and Prof. Félix Rodríguez

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602948

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      Good as gold: A gold-catalyst was used to transform an alkynylsalicylaldehyde and an alkynamine into a heterodiene and dienophile that further react through a formal cycloaddition reaction. This reaction produces complex tetracyclic pyrano[2,3,4-de]chromenes from two very simple starting materials with complete atom economy and with selective formation of bonds, cycles, and stereocenters.

    7. Mechanochromic Materials

      Bismuth-Based Coordination Polymers with Efficient Aggregation-Induced Phosphorescence and Reversible Mechanochromic Luminescence

      Dr. Oksana Toma, Magali Allain, Dr. Francesco Meinardi, Dr. Alessandra Forni, Dr. Chiara Botta and Prof. Nicolas Mercier

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602602

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      Coordination polymers based on bismuth(III) and N-oxide-4,4′-bipyridine strongly phosphoresce in the solid state with quantum yields of up to 85 %, which is likely to due aggregation-induced emission. These materials also show reversible mechanochromic luminescence (MCL).

    8. Heterogeneous Catalysis | Hot Paper

      Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica

      Dr. Xiao Liu, Yoshifumi Maegawa, Dr. Yasutomo Goto, Prof. Kenji Hara and Dr. Shinji Inagaki

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201601453

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      Uncharted waters: Using bipyridine-periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand, efficient heterogeneous iridium catalysts (Ir-Bpy-PMO) for water oxidation were obtained. This catalyst had an activity comparable to the analogous homogeneous iridium catalyst and showed one order of magnitude higher activity than that of the previously reported heterogeneous iridium catalysts.

    9. Water Oxidation

      Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

      Yan Xie, Dr. David W. Shaffer, Dr. Anna Lewandowska-Andralojc, Dr. David J. Szalda and Dr. Javier J. Concepcion

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201601943

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      Breaking down barriers: Multifunctional bipyridyl diphosphonate ligands provide redox-potential leveling through charge compensation and σ donation to allow easy access to high oxidation states of ruthenium-based water oxidation catalysts (see structure; L=picoline or isoquinoline). They also shuttle protons in and out of the catalytic site, reducing activation barriers for proton-coupled processes.

    10. Peptide Modulators

      An In-tether Chiral Center Modulates the Helicity, Cell Permeability, and Target Binding Affinity of a Peptide

      Kuan Hu, Hao Geng, Qingzhou Zhang, Qisong Liu, Mingsheng Xie, Chengjie Sun, Wenjun Li, Huacan Lin, Dr. Fan Jiang, Prof. Tao Wang, Prof. Yun-Dong Wu and Prof. Zigang Li

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201602806

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      Chirality induced helicity: A precisely positioned in-tether carbon chiral center was able to modulate the helicity, cell permeability, and target binding affinity of a peptide. This study provides an excellent method for studying the relationship between the conformation and biochemical/biophysical properties of peptides.

    11. Nanostructures

      Controlled Growth of a Hierarchical Nickel Carbide “Dandelion” Nanostructure

      Liang Qiao, Dr. Wenxia Zhao, Dr. Yueling Qin and Prof. Mark T. Swihart

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/anie.201603456

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      Dandelion clocks: Highly hierarchical but nonporous nanostructures of nickel carbide (Ni3C) with a unique “dandelion” morphology are prepared. The time evolution of these nanostructures suggests a mechanism for their formation. This type of hierarchical nanocrystal, which provides large accessible specific surface area, can be valuable in numerous catalytic and electrocatalytic applications.

    12. Asymmetric Catalysis

      An Iridium(I) N-Heterocyclic Carbene Complex Catalyzes Asymmetric Intramolecular Allylic Amination Reactions

      Dr. Ke-Yin Ye, Qiang Cheng, Dr. Chun-Xiang Zhuo, Prof. Li-Xin Dai and Prof. Dr. Shu-Li You

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/anie.201603266

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      A chiral iridium(I) N-heterocyclic carbene complex catalyzes highly enantioselective intramolecular allylic amination reactions. This method provides facile access to biologically important enantioenriched indolopiperazinones and piperazinones in good yields. Mechanistic investigations reveal that the C−H activation occurs at the position ortho to the N-aryl group of the ligand.

    13. Isocyanoterpenes

      A Formal Enantiospecific Synthesis of 7,20-Diisocyanoadociane

      Philipp C. Roosen and Prof. Christopher D. Vanderwal

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/anie.201603581

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      A highly stereocontrolled synthesis of the “Corey dione”, a late-stage intermediate from which 7,20-diisocyanoadociane (DICA) has been made previously, was developed. The adoption of chiral-pool starting material (−)-perillaldehyde permits an enantiospecific synthesis, and the overall approach should be broadly applicable to other isocyanoterpenes.

    14. Polymerization

      Crystalline Isotactic Polar Polypropylene from the Palladium-Catalyzed Copolymerization of Propylene and Polar Monomers

      Yusuke Ota, Dr. Shingo Ito, Dr. Minoru Kobayashi, Dr. Shinichi Kitade, Kazuya Sakata, Takao Tayano and Prof. Kyoko Nozaki

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/anie.201600819

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      Control center: High-molecular-weight polypropylenes can be obtained by using palladium catalysts bearing menthyl-substituted phosphine-sulfonate ligands for the isospecific homopolymerization of propylene or the copolymerization of propylene with polar monomers. The introduction of substituents at the ortho-position relative to the sulfonate group favors enantiomorphic site control over chain end control in the chain propagation step.

    15. Protein Synthesis | Hot Paper

      Parallel Chemical Protein Synthesis on a Surface Enables the Rapid Analysis of the Phosphoregulation of SH3 Domains

      Robert Zitterbart and Prof. Dr. Oliver Seitz

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/anie.201601843

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      A fast track to analyze the phosphoregulation of proteins has been realized by immobilization of peptide hydrazides through hydrazone ligation with self-purified peptide thioesters, a radical-induced desulfurization, and a surface-based binding assay. The method shows that tyrosine phosphorylation can induce both a loss and a gain in the ligand affinity of the SH3 domains of Abl kinases.

    16. Protein Dynamics

      The Role of Dynamics and Allostery in the Inhibition of the eIF4E/eIF4G Translation Initiation Factor Complex

      Dr. Nicola Salvi, Dr. Evangelos Papadopoulos, Dr. Martin Blackledge and Prof. Gerhard Wagner

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/anie.201603254

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      Lost in translation: The interaction between the eIF4E/eIF4G subunits of the translation initiation factor complex eIF4F is a promising target for cancer treatment. A powerful inhibitor of this interaction, 4EGI-1, was shown to act by altering the conformational equilibrium in eIF4E to favor conformations characterized by increased flexibility in the eIF4G binding site.

    17. Electrochemistry

      Induced Potential in Porous Carbon Films through Water Vapor Absorption

      Dr. Kang Liu, Peihua Yang, Dr. Song Li, Jia Li, Tianpeng Ding, Guobin Xue, Qian Chen, Prof. Guang Feng and Prof. Jun Zhou

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/anie.201602708

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      Sustainable electrical potential can be induced by water vapor adsorption on a piece of porous carbon film with two sides bearing different functional-group contents (LFGR and HFGR; see figure). Experimental results and theoretical calculations show that the induced potential arises from free proton transfer that is driven by the difference in proton concentration caused by an imbalance in the proportion of oxygen-containing functional groups.

    18. Supramolecular Chemistry

      Regio-, Stereo-, and Atropselective Synthesis of C60 Fullerene Bisadducts by Supramolecular-Directed Functionalization

      Dr. Giovanni Bottari, Dr. Olga Trukhina, Dr. Axel Kahnt, Dr. Michael Frunzi, Prof. Dr. Yasujiro Murata, Dr. Antonio Rodríguez-Fortea, Prof. Dr. Josep M. Poblet, Prof. Dr. Dirk M. Guldi and Prof. Dr. Tomás Torres

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/anie.201602713

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      E pluribus unum: A conceptually novel, supramolecular-directed functionalization approach is presented in which noncovalent interactions between untethered residues have been used to amplify (>2800-fold) the regio-, stereo-, and atropselective formation of a C60 fullerene bisadduct racemate. Remarkably, both enantiomers represent the first examples of fullerene derivatives with combined central, axial, and helical chirality.

    19. Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups

      Jungwun Hwang, Ping Li, Mark D. Smith and Prof. Ken D. Shimizu

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/anie.201602752

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      Bulk up: Bulky alkyl groups can form either stabilizing or destabilizing interactions depending on their relative distance from the molecular surface of interaction. The presented data point to the refinement of the classical paradigm for steric effects simply based on the molecular size.

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