Angewandte Chemie International Edition

Cover image for Vol. 55 Issue 48

November 21, 2016

Volume 55, Issue 48

Pages 14875–15179

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. You have free access to this content
      Cover Picture: Uni-Directional Transportation on Peristome-Mimetic Surfaces for Completely Wetting Liquids (Angew. Chem. Int. Ed. 48/2016) (page 14875)

      Chuxin Li, Ning Li, Xinshi Zhang, Dr. Zhichao Dong, Prof. Huawei Chen and Prof. Lei Jiang

      Version of Record online: 3 NOV 2016 | DOI: 10.1002/anie.201610386

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      A lively topic for centuries has been the quest for the directional transportation of liquids without using external forces. In their Communication on page 14988 ff., Z. Dong, H. Chen, and co-workers mimic the surface morphologies of the peristome of Nepenthes alata through stereo-lithography to achieve uni-directional transportation without external energy input, even for completely wetting liquids. A postulated overflow-controlled liquid uni-directional spreading mechanism has been proven by X-ray microscopy.

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      Inside Cover: Solvent-Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products (Angew. Chem. Int. Ed. 48/2016) (page 14876)

      Michael C. Thompson, Dr. Jacob Ramsay and Prof. Dr. J. Mathias Weber

      Version of Record online: 7 NOV 2016 | DOI: 10.1002/anie.201610384

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      Bismuth is vaporized by a pulsed UV laser (background) to create a plasma containing Bi anions, which are entrained into a supersonic expansion of CO2, producing [Bi(CO2)n] clusters. In their Communication on page 15171 ff., J. M. Weber et al. show that small clusters have core ions based on BiCOO metalloformate complexes (center). Solvation by an increasing number of CO2 molecules leads to a change in the core ion structure from metalloformate to oxalate (foreground). Cover picture: the Weber group and Steve Burrows, JILA.

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      Inside Back Cover: Molecular Imaging of Growth, Metabolism, and Antibiotic Inhibition in Bacterial Colonies by Laser Ablation Electrospray Ionization Mass Spectrometry (Angew. Chem. Int. Ed. 48/2016) (page 15181)

      Dr. Hang Li, Pranav Balan and Prof. Akos Vertes

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/anie.201610558

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      Visualizing the interaction zoneRapidly emerging microbial resistance to antibiotics is a growing concern for the treatment of infectious diseases. In their Communication on page 15035 ff., A. Vertes et al. describe the application of laser ablation electrospray ionization (LAESI) in combination with mass spectrometry (MS) to gain deeper molecular insight into microbe–antibiotic interactions. LAESI-MS imaging enhances the quantitative nature of antibiotic susceptibility testing, while significantly reducing the required incubation time.

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      Back Cover: Non-Porous Iron(II)-Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest-Induced Topotactic Transformations (Angew. Chem. Int. Ed. 48/2016) (page 15182)

      Santiago Rodríguez-Jiménez, Dr. Humphrey L. C. Feltham and Prof. Sally Brooker

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/anie.201610433

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      Three guests, three colorsIn their Communication on page 15067 ff., S. Brooker et al. demonstrate reversible three-way guest sensing by a diiron(II) complex, which results in interconversion of a dark red low-spin form 1, an orange high-spin form 2, and a yellow form 3. Remarkably, these guest exchanges are reversible single-crystal to single-crystal (SCSC) transformations, and 1[RIGHTWARDS ARROW]3 involves a polymerization[RIGHTWARDS ARROW]depolymerization. Cover art: Michael Crawford (Dunedin).

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. You have free access to this content
      Frontispiece: Thiolate-Mediated Photoinduced Synthesis of Ultrafine Ag2S Quantum Dots from Silver Nanoparticles

      Yitao Cao, Dr. Wei Geng, Run Shi, Dr. Lu Shang, Prof. Geoffrey I. N. Waterhouse, Prof. Limin Liu, Prof. Li-Zhu Wu, Prof. Chen-Ho Tung, Prof. Yadong Yin and Prof. Tierui Zhang

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/anie.201684861

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      Quantum Dots. The viability of low-temperature photochemical approaches in metal sulfide synthesis is demonstrated by T. Zhang et al. in their Communication on page 14952 ff. through the synthesis of ultrafine Ag2S quantum dots from Ag nanoparticles.

  3. Editorials

    1. Top of page
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    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
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    12. Minireviews
    13. Reviews
    14. Communications
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      A Vibrant Science Lives from Within (pages 14878–14879)

      Prof. Dr. Ferdi Schüth

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201609519

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      “… For a discipline to remain lively and also attractive to young scientists, it needs to have its intrinsic key questions, grand intellectual challenges with the potential of stimulating the minds of generations of scientists, and of triggering discoveries in often unrelated fields. The origin of life is such a question for the field of chemistry. We should use this problem to illustrate the fascination of our science …” Read more in the Editorial by Ferdi Schüth.

  4. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
  5. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. You have free access to this content
      Corrigendum: Biosynthesis-Assisted Structural Elucidation of the Bartolosides, Chlorinated Aromatic Glycolipids from Cyanobacteria (page 14895)

      Dr. Pedro N. Leão, Hitomi Nakamura, Margarida Costa, Dr. Alban R. Pereira, Prof. Rosário Martins, Prof. Vitor Vasconcelos, Prof. William H. Gerwick and Prof. Emily P. Balskus

      Version of Record online: 18 NOV 2016 | DOI: 10.1002/anie.201609701

      This article corrects:
  6. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
  7. Author Profiles

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. Jincai Zhao (page 14902)

      Version of Record online: 13 JUN 2016 | DOI: 10.1002/anie.201605347

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      “My favorite food is roast lamb. If I were not a scientist, I would be a photographer ...” This and more about Jincai Zhao can be found on page 14902.

  8. News

    1. Top of page
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    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
  9. Book Reviews

    1. Top of page
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    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. Sustainable Catalysis. With Non-endangered Metals, Part 1 and 2 Edited by Michael North. (page 14904)

      Valentine P. Ananikov

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/anie.201609778

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      RSC Publishing, 2016. 480+284 pp., hardcover, £ 300.00.—ISBN 978-1782620563

  10. Highlights

    1. Top of page
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    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. CO2 Conversion

      Promoting the Synthesis of Methanol: Understanding the Requirements for an Industrial Catalyst for the Conversion of CO2 (pages 14906–14908)

      Prof. Dr. Malte Behrens

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/anie.201607600

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      The hydrogenation of CO2 to methanol is a potential process for the sustainable production of synthetic liquid fuels. The Cu/ZnO catalyst employed for this reaction has been studied extensively for many years, and recent progress now has the potential to turn it into a prototype for complex promotional interactions in heterogeneous catalysis.

    2. Biocatalysis

      Directed Evolution of Iridium-Substituted Myoglobin Affords Versatile Artificial Metalloenzymes for Enantioselective C−C Bond-Forming Reactions (pages 14909–14911)

      Prof. Dr. Thomas R. Ward

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/anie.201607222

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      Upgrading myoglobin with iridium: A metal-substitution strategy has been used to afford a repurposed myoglobin for challenging cyclopropanation and intramolecular C−H activation reactions. The performance of the iridium-loaded myoglobin (orange sphere) was improved through directed evolution of eight active-site residues (yellow surface).

  11. Minireviews

    1. Top of page
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    4. Editorials
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    6. Corrigenda
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    8. Author Profiles
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    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. Cooperative Catalysis

      Cooperative Catalysis and Activation with N-Heterocyclic Carbenes (pages 14912–14922)

      Dr. Michael H. Wang and Prof. Karl A. Scheidt

      Version of Record online: 20 OCT 2016 | DOI: 10.1002/anie.201605319

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      N-Heterocyclic carbene (NHC) catalysis is a versatile and powerful strategy to construct complex molecules. To extend and enhance the reactivity of these nucleophiles, cooperative catalysis and related activation approaches have been developed by integrating complementary modes (Lewis/Brønsted acidity, transition-metal processes, photoredox). Recent contributions are summarized in this Minireview.

  12. Reviews

    1. Top of page
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    13. Reviews
    14. Communications
    1. Artificial Photosynthesis

      Heterogeneous Molecular Systems for Photocatalytic CO2 Reduction with Water Oxidation (pages 14924–14950)

      Dr. Xiao Liu, Dr. Shinji Inagaki and Prof.Dr. Jinlong Gong

      Version of Record online: 14 OCT 2016 | DOI: 10.1002/anie.201600395

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      When two become one: This Review describes recent developments in the heterogenization of metal-complex photocatalysts for the two half-reactions of artificial photosynthesis: water oxidation and CO2 photoreduction.

  13. Communications

    1. Top of page
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    3. Frontispiece
    4. Editorials
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profiles
    9. News
    10. Book Reviews
    11. Highlights
    12. Minireviews
    13. Reviews
    14. Communications
    1. Quantum Dots

      Thiolate-Mediated Photoinduced Synthesis of Ultrafine Ag2S Quantum Dots from Silver Nanoparticles (pages 14952–14957)

      Yitao Cao, Dr. Wei Geng, Run Shi, Dr. Lu Shang, Prof. Geoffrey I. N. Waterhouse, Prof. Limin Liu, Prof. Li-Zhu Wu, Prof. Chen-Ho Tung, Prof. Yadong Yin and Prof. Tierui Zhang

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201608019

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      Not only metals: Low temperature photoinduced syntheses allow improved control over reaction kinetics and the synthesis of metal nanoparticles with unusual morphologies. Here, the photoinduced synthesis of ultrafine Ag2S quantum dots from Ag nanoparticles was demonstrated for the first time. Further, a fundamental bridge was established between the intrinsic structures of silver thiolate intermediates and the Ag2S.

    2. Electrochemistry

      Magnesocene-Based Electrolytes: A New Class of Electrolytes for Magnesium Batteries (pages 14958–14962)

      Rainer Schwarz, Dr. Marijana Pejic, Philipp Fischer, Dr. Mario Marinaro, Dr. Ludwig Jörissen and Dr. Mario Wachtler

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201606448

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      Magnesium batteries: Reversible electrochemical magnesium plating and stripping is reported in a magnesocene-based electrolyte. The electrolyte shows minimal overpotentials, a high coulombic efficiency, and an excellent electrochemical cycling stability. The electrolyte is a first member of a new class of complex electrolytes.

    3. Protein–Protein Interactions

      You have full text access to this OnlineOpen article
      Probing Functional Heteromeric Chemokine Protein–Protein Interactions through Conformation-Assisted Oxime Ligation (pages 14963–14966)

      Stijn M. Agten, Dr. Rory R. Koenen, Dr. Hans Ippel, Veit Eckardt, Dr. Philipp von Hundelshausen, Prof. Dr. Kevin H. Mayo, Prof. Dr. Christian Weber and Prof. Dr. Tilman M. Hackeng

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201607036

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      Kissing chemokines: Heteromeric chemokine interactions are implicated in various inflammatory diseases. Because it is unclear whether pathological effects are caused by heterodimerization or by additive effects of separate chemokines, a covalent oxime-linked chemokine heterodimer was synthesized. Oxime ligation was accelerated by interactions between the chemokines, and the heterodimer showed enhanced function compared to mixed chemokines.

    4. Borrowing Hydrogen

      Manganese-Catalyzed Hydrogen-Autotransfer C−C Bond Formation: α-Alkylation of Ketones with Primary Alcohols (pages 14967–14971)

      Dr. Miguel Peña-López, Patrick Piehl, Saravanakumar Elangovan, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201607072

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      Something borrowed, something new: A hydrogen-autotransfer reaction catalyzed by manganese(I) PNP pincer complexes was developed for the α-alkylation of ketones with alcohols (see scheme). Structurally diverse primary alcohols were used to functionalize a wide range of ketones, including 2-oxindole, estrone 3-methyl ether, and testosterone, by this straightforward method.

    5. Perovskites

      Benign-by-Design Solventless Mechanochemical Synthesis of Three-, Two-, and One-Dimensional Hybrid Perovskites (pages 14972–14977)

      Alexander D. Jodlowski, Dr. Alfonso Yépez, Prof. Rafael Luque, Prof. Luis Camacho and Prof. Gustavo de Miguel

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201607397

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      Mill it! A straightforward solventless mechanochemical method enabled the preparation of four types of hybrid perovskites in large amounts as polycrystalline powders with high purity and excellent optoelectronic properties. Two archetypal 3D perovskites (MAPbI3 and FAPbI3), a 2D perovskite (Gua2PbI4), and a “double-chain” 1D perovskite (GuaPbI3) were synthesized (see picture; MA=methylammonium, FA=formamidinium, Gua=guanidinium).

    6. Inhibitors | Very Important Paper

      You have full text access to this OnlineOpen article
      Structural Snapshots for Mechanism-Based Inactivation of a Glycoside Hydrolase by Cyclopropyl Carbasugars (pages 14978–14982)

      Christopher Adamson, Robert J. Pengelly, Saeideh Shamsi Kazem Abadi, Dr. Saswati Chakladar, Jason Draper, Prof. Robert Britton, Dr. Tracey M. Gloster and Prof. Andrew J. Bennet

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.201607431

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      Cyclopropyl carbocycle inhibitors of a glycoside hydrolase act by covalently modifying the nucleophilic carboxylate while still retaining the strained cyclopropyl ring. A combined synthetic, kinetic, and structural study reveals the conformational itinerary for this family of carbocyclic inactivators through the incorporation of a fluorine atom into the inhibitor structure.

    7. Gas-Phase Chemistry

      Hydrogen-Abstraction/Acetylene-Addition Exposed (pages 14983–14987)

      Dr. Tao Yang, Dr. Tyler P. Troy, Dr. Bo Xu, Dr. Oleg Kostko, Dr. Musahid Ahmed, Prof. Dr. Alexander M. Mebel and Prof. Dr. Ralf I. Kaiser

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.201607509

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      Born of fire: The reaction routes leading to the formation of polycyclic aromatic hydrocarbons present in the interstellar medium remain ambiguous. By revealing the reactivity of the styrenyl and the ortho-vinylphenyl radicals with acetylene, the first solid experimental evidence on the formation of naphthalene in a simulated combustion environment is provided, validating the postulated hydrogen-abstraction/acetylene-addition mechanism.

    8. Liquid Spreading

      Uni-Directional Transportation on Peristome-Mimetic Surfaces for Completely Wetting Liquids (pages 14988–14992)

      Chuxin Li, Ning Li, Xinshi Zhang, Dr. Zhichao Dong, Prof. Huawei Chen and Prof. Lei Jiang

      Version of Record online: 21 SEP 2016 | DOI: 10.1002/anie.201607514

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      Running uphill: Peristome-mimetic surfaces with uni-directional transportation are fabricated to direct liquid motion even for complete wetting liquids. The directional spreading methodology was shown to be spontaneously driven without energy input. This uni-directional transportation system could facilitate the construction of a wide variety of fluidic machines out of traditional materials.

    9. Photochemistry

      Rich Athermal Ground-State Chemistry Triggered by Dynamics through a Conical Intersection (pages 14993–14996)

      Dr. Benoit Mignolet, Dr. Basile F. E. Curchod and Prof. Dr. Todd J. Martínez

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.201607633

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      An outlaw molecule: Theoretical studies show that sulfine exhibits an incredibly rich chemistry upon light-irradiation, challenging the traditional view of photochemical and photodecomposition reactions due to highly nonstatistical behavior.

    10. Medical Chemistry | Hot Paper

      A Synthetic Loop Replacement Peptide That Blocks Canonical NF-κB Signaling (pages 14997–15001)

      Dr. Paul A. Bruno, Dr. Alex Morriss-Andrews, Andrew R. Henderson, Prof. Dr. Charles L. Brooks III and Prof. Dr. Anna K. Mapp

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201607990

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      A peptide-based inhibitor of canonical NF-κB signaling, in which a hydrogen bond in the NBD peptide is synthetically replaced by a non-labile bond, shows an about 10-fold increased potency relative to the original inhibitor. The success of the synthetic replacement of a peptide loop suggests that the general strategy could be broadly useful for discovering modulators of many protein–protein interactions mediated by such structures.

    11. Biocatalysis

      Immobilization of a Bacterial Cytochrome P450 Monooxygenase System on a Solid Support (pages 15002–15006)

      Cheau Yuaan Tan, Dr. Hidehiko Hirakawa, Risa Suzuki, Tomoaki Haga, Fumiya Iwata and Prof. Teruyuki Nagamune

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.201608033

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      Multiple enzymes immobilized: Bacterial cytochrome P450 enzymes catalytically require electrons that are carried by electron-transfer proteins from NAD(P)H-dependent reductases. A heterotrimeric, protein-mediated assembly of a P450, electron-transfer protein, and reductase on solid supports enabled co-immobilization of the three proteins close to each other and allowed electron transfer between the P450 and reductase.

    12. Block Copolymers

      Exploiting Host–Guest Interactions for the Synthesis of a Rod–Rod Block Copolymer with Crystalline and Liquid-Crystalline Blocks (pages 15007–15011)

      Dr. Feng Zhou, Ke-Hua Gu, Zhen-Yu Zhang, Meng-Yao Zhang, Sheng Zhou, Prof. Dr. Zhihao Shen and Prof. Dr. Xing-He Fan

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.201608043

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      One or the other: By making use of host–guest interactions, the supramolecular rod–rod block copolymer P(EO@TPP)-b-PVBP was constructed. As the PVBP segments arrange themselves as nematic phases, the crystalline structure of the inclusion complex P(EO@TPP) is destroyed. The nanostructure is thus clearly affected by the interplay between the two blocks.

    13. Perovskites

      Lead-Free, Blue Emitting Bismuth Halide Perovskite Quantum Dots (pages 15012–15016)

      Meiying Leng, Zhengwu Chen, Ying Yang, Dr. Zha Li, Kai Zeng, Kanghua Li, Dr. Guangda Niu, Yisu He, Qingchao Zhou and Prof. Jiang Tang

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608160

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      Better than Sn or Pb: The synthesis and optical characterization of bismuth-based MA3Bi2Br9 perovskite quantum dots with a photoluminescence quantum yield of up to 12 % is described. Further, the photoluminescence peaks of MA3Bi2X9 QDs (X=Cl, Br, I) could be easily tuned from 360 to 540 nm through anion exchange.

    14. Surface Chemistry

      Long-Range Hydrophilic Attraction between Water and Polyelectrolyte Surfaces in Oil (pages 15017–15021)

      Chen Shi, Bin Yan, Lei Xie, Ling Zhang, Jingyi Wang, Prof. Atsushi Takahara and Prof. Hongbo Zeng

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201608219

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      Wetting phenomena: A long-range hydrophilic attraction in an oil medium was discovered between water and zwitterionic, cationic, and anionic polyelectrolyte molecules using an atomic force microscopy technique. The unexpected strong attraction could possibly be attributed to a strong dipolar interaction due to the large dipole moment of the polyelectrolyte molecules.

    15. Host–Guest Systems

      Maximizing Coordination Capsule–Guest Polar Interactions in Apolar Solvents Reveals Significant Binding (pages 15022–15026)

      David P. August, Dr. Gary S. Nichol and Dr. Paul J. Lusby

      Version of Record online: 3 NOV 2016 | DOI: 10.1002/anie.201608229

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      Molecular encapsulation: A combination of apolar solvents and weakly interacting anions has been used to maximize the non-covalent interactions between a simple Pd2L4 host and various charge-neutral guest molecules, leading to some of the highest association constants ever reported for a coordination capsule system.

    16. Metal–Organic Frameworks | Hot Paper

      A Rigid Nested Metal–Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions (pages 15027–15030)

      Dr. Qiang Gao, Dr. Jian Xu, Prof. Dapeng Cao, Dr. Ze Chang and Prof. Xian-He Bu

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608250

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      A thermal cork screw: Counterions act as removable corks blocking the pore openings of a rigid nested metal–organic framework (MOF). The thermoresponsive gating adsorption behavior of the MOF is dominated by the counterion corks, rather than the flexibility modes of other stimuli-responsive MOFs. On heating, the corks are removed from the openings, on cooling they return.

    17. Molecular Capsules

      An M2L4 Molecular Capsule with a Redox Switchable Polyradical Shell (pages 15031–15034)

      Dr. Kohei Yazaki, Shogo Noda, Dr. Yuya Tanaka, Dr. Yoshihisa Sei, Prof. Dr. Munetaka Akita and Dr. Michito Yoshizawa

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608350

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      Polyradical capsule: A new M2L4 molecular capsule is quantitatively formed by mixing metal ions and dihydrophenazine-based ligands. The capsule has a spherical nanocavity enclosed by eight redox-active, dihydrophenazine panels. Electrochemical and chemical oxidation of the capsule leads to the reversible generation of a stable tetra(radical cation) capsule.

    18. Molecular Imaging | Hot Paper

      Molecular Imaging of Growth, Metabolism, and Antibiotic Inhibition in Bacterial Colonies by Laser Ablation Electrospray Ionization Mass Spectrometry (pages 15035–15039)

      Dr. Hang Li, Pranav Balan and Prof. Akos Vertes

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/anie.201607751

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      Visualizing the interaction zone: Laser ablation electrospray ionization (LAESI) in combination with mass spectrometry (MS) was applied to gain deeper molecular insight into microbe–antibiotic interactions. LAESI-MS imaging enhances the quantitative nature of antibiotic susceptibility testing while significantly reducing the required incubation time.

    19. Organometallic Polymers | Hot Paper

      Arsole-Containing π-Conjugated Polymer by the Post-Element-Transformation Technique (pages 15040–15043)

      Dr. Yoshimasa Matsumura, Makoto Ishidoshiro, Dr. Yasuyuki Irie, Dr. Hiroaki Imoto, Prof. Dr. Kensuke Naka, Prof. Dr. Kazuyoshi Tanaka, Prof. Dr. Shinsuke Inagi and Prof. Dr. Ikuyoshi Tomita

      Version of Record online: 7 NOV 2016 | DOI: 10.1002/anie.201608404

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      Colorful polymer: An arsole-containing π-conjugated polymer was prepared by reacting the titanacyclopentadiene unit of an organometallic polymer with an arsenic-containing building block. The resulting polymer exhibits a low LUMO energy level, quasi-reversible redox behavior, and an excellent ability to coordinate gold(I) chloride.

    20. Photochromism

      Temperature-Controlled Switchable Photochromism in Solid Materials (pages 15044–15048)

      Alex Julià-López, Dr. Jordi Hernando, Dr. Daniel Ruiz-Molina, Pablo González-Monje, Dr. Josep Sedó and Dr. Claudio Roscini

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608408

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      Positive or negative: Solid composites with switchable positive/negative photochromism were obtained by embedding core–shell microcapsules containing photochromic solutions of spiropyran dyes in acidic phase-change media in polymeric matrices. The photochromism of these materials could be switched by inducing the melting/solidification of the encapsulated medium through a change in temperature.

    21. Zeolite Engineering

      The Mosaic Structure of Zeolite Crystals (pages 15049–15052)

      Dr. Zhengxing Qin, Dr. Georgian Melinte, Prof. Jean-Pierre Gilson, Prof. Maguy Jaber, Prof. Krassimir Bozhilov, Dr. Philippe Boullay, Dr. Svetlana Mintova, Prof. Ovidiu Ersen and Dr. Valentin Valtchev

      Version of Record online: 31 OCT 2016 | DOI: 10.1002/anie.201608417

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      Etch it out: A controlled fluoride medium treatment is used to expose the local structure of zeolite crystals. Unexpectedly high concentrations of nanometer-sized crystalline domains, separated by low-angle boundaries, were discovered.

    22. Phase Transitions | Hot Paper

      High-Pressure Phase Transformations in TiPO4: A Route to Pentacoordinated Phosphorus (pages 15053–15057)

      Dr. Maxim Bykov, Dr. Elena Bykova, Dr. Michael Hanfland, Dr. Hanns-Peter Liermann, Dr. Reinhard K. Kremer, Prof. Dr. Robert Glaum, Prof. Dr. Leonid Dubrovinsky and Prof. dr. Sander van Smaalen

      Version of Record online: 31 OCT 2016 | DOI: 10.1002/anie.201608530

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      Under pressure: The first example of a phosphorus atom coordinated by five oxygen atoms in an inorganic network structure was found in titanium(III) orthophosphate, TiPO4, at 48 GPa. This phase was characterized by synchrotron single-crystal X-ray diffraction in diamond anvil cells.

    23. Heme Proteins

      HNO-Binding in Heme Proteins: Effects of Iron Oxidation State, Axial Ligand, and Protein Environment (pages 15058–15061)

      Dr. Rahul L. Khade, Yuwei Yang, Yelu Shi and Prof. Dr. Yong Zhang

      Version of Record online: 31 OCT 2016 | DOI: 10.1002/anie.201608539

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      Nitroxyl coordination is an important step for its biological function. It is shown that 1) HNO preferably coordinates to iron(II) porphyrins as compared to iron(III) owing to better metal-to-ligand back-donation, 2) the axial ligand strongly influences HNO coordination through trans and charge donation effects, and 3) the heme protein environment has a significant effect on HNO hydrogen bonding.

    24. Chiral Nanostructures

      Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer (pages 15062–15066)

      Ming Deng, Dr. Li Zhang, Dr. Yuqian Jiang and Prof. Dr. Minghua Liu

      Version of Record online: 3 NOV 2016 | DOI: 10.1002/anie.201608638

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      To get new chirality: Achiral purine nucleobases (A and G) triggered Fmoc-glutamic acid (Fmoc-Glu) to assemble into helical nanostructures and mediated chirality transfer from glutamic acid to another achiral component, thioflavin T (ThT).

    25. Chemical Sensors

      Non-Porous Iron(II)-Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest-Induced Topotactic Transformations (pages 15067–15071)

      Santiago Rodríguez-Jiménez, Dr. Humphrey L. C. Feltham and Prof. Sally Brooker

      Version of Record online: 12 OCT 2016 | DOI: 10.1002/anie.201608813

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      Three guests, three colours: Reversible three way-guest sensing by a diiron(II) complex (blue sphere Fe) results in interconversion of dark red low spin 1 (red box MeCN) with high spin orange 2 (orange triangle EtOH) and yellow 3 (yellow circle H2O). Remarkably these guest exchanges are reversible single-crystal-to-single-crystal (SCSC) transformations. Crystallography also reveals that SCSC transformation 13 involves a polymerization⇌depolymerization.

    26. Fluorination | Hot Paper

      Photoredox Activation of SF6 for Fluorination (pages 15072–15075)

      T. Andrew McTeague and Prof. Dr. Timothy F. Jamison

      Version of Record online: 4 NOV 2016 | DOI: 10.1002/anie.201608792

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      Unlocking SF6’s potential: Photoredox catalysis enables the conversion of SF6, an inert gas, into an active fluorinating species using visible light. Under both batch and continuous-flow conditions, deoxyfluorination of allylic alcohols is effected with high chemoselectivity and is tolerant of a wide range of functional groups.

    27. Molecular Electronics

      Determining the Attenuation Factor in Molecular Wires Featuring Covalent and Noncovalent Tectons (pages 15076–15080)

      Sonia Vela, Stefan Bauroth, Dr. Carmen Atienza, Dr. Agustín Molina-Ontoria, Prof. Dr. Dirk M. Guldi and Prof. Dr. Nazario Martín

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608973

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      Whizzing along the wire: A series of electron-donor–acceptor hybrids of a zinc porphyrin and C60 connected through molecular wires based on a combination of covalent and noncovalent interactions (see picture) exhibited efficient charge transport. Hydrogen-bonding interactions and p-phenylene oligomers of different lengths were responsible for electron transfer in these molecular wires.

    28. Analytical Methods

      Excited Fluorophores Enhance the Opening of Vesicles at Electrode Surfaces in Vesicle Electrochemical Cytometry (pages 15081–15085)

      Neda Najafinobar, Jelena Lovrić, Dr. Soodabeh Majdi, Johan Dunevall, Prof. Ann-Sofie Cans and Prof. Andrew Ewing

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201609178

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      Vesicle electrochemical cytometry has been developed as a novel technique to measure the content of individual vesicles. It is proposed that bringing an excited fluorophore into close contact with the membrane enhances vesicle opening through the oxidation of membrane lipids (and perhaps proteins), which leads to a more disrupted membrane and both better adsorption of vesicles to the electrode surface and an electroporation-formed fusion pore.

    29. Methane Dehydroaromatization

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      Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM-5-Catalyzed Methane Dehydroaromatization (pages 15086–15090)

      Dr. Nikolay Kosinov, Ferdy J. A. G. Coumans, Evgeny Uslamin, Prof. Freek Kapteijn and Prof. Emiel J. M. Hensen

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201609442

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      Quicken the pulse: Supplying short oxygen pulses to a catalytic bed of molybdenum/ZSM-5 during methane dehydroaromatization leads to selective coke combustion. Catalyst deactivation is mitigated without degradation of molybdenum content and zeolite crystallinity, resulting in higher benzene productivity.

    30. Cycloaddition

      Nickel-Catalyzed Chemo- and Enantioselective Coupling between Cyclobutanones and Allenes: Rapid Synthesis of [3.2.2] Bicycles (pages 15091–15095)

      Dr. Xuan Zhou and Prof. Dr. Guangbin Dong

      Version of Record online: 4 NOV 2016 | DOI: 10.1002/anie.201609489

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      Bicycle, bicycle: An intramolecular nickel-catalyzed (4+2) coupling between cyclobutanones and allenes by C−C cleavage is reported that provides a unique approach for accessing [3.2.2] bicyclic scaffolds. The reaction is efficient, chemoselective, and pH/redox neutral. Excellent enantioselectivity is also achieved.

    31. Metallylenes | Hot Paper

      A Bis(silylenyl)pyridine Zero-Valent Germanium Complex and Its Remarkable Reactivity (pages 15096–15099)

      Yu-Peng Zhou, Dr. Miriam Karni, Dr. Shenglai Yao, Prof. Yitzhak Apeloig and Prof. Dr. Matthias Driess

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201609520

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      Germanium-enriched: The synthesis and unusual chemical and electronic properties of the first zero-valent germanium (“germylone”) iron complex [SiNSi]GeFe(CO)4 are reported. This complex was further transformed into an unprecedented mixed-valent push–pull Ge0[RIGHTWARDS ARROW]GeCl2 complex.

    32. Heterocycle Synthesis

      Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of Alkenes and Application to the Construction of Medium-Sized Rings (pages 15100–15104)

      Dr. Zhong-Liang Li, Dr. Xiao-Hua Li, Na Wang, Ning-Yuan Yang and Prof. Dr. Xin-Yuan Liu

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608198

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      The old 1,2: A novel 1,2-formyl functionalization of unactivated alkenes involving formyl migration and addition of radicals to alkenes has been developed for access to synthetically important β-functionalized aldehydes. The analogous keto-carbonyl migration has been performed to synthesize challenging medium-sized diketones, which were additionally transformed into complex fused rings.

    33. Spin Crossover | Very Important Paper

      Hysteretic Four-Step Spin Crossover within a Three-Dimensional Porous Hofmann-like Material (pages 15105–15109)

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

      Version of Record online: 21 OCT 2016 | DOI: 10.1002/anie.201605418

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      Four-step SCO: A porous 3D spin crossover (SCO) framework material that displays a four-step transition with long-range ordering of FeII sites is reported. From only one unique site in the high-spin state, three intermediate phases with individual high-spin/low-spin patterns are produced upon cooling to the fully low-spin state.

    34. Molecular Sleds | Hot Paper

      Sliding on DNA: From Peptides to Small Molecules (pages 15110–15114)

      Kan Xiong, Graham S. Erwin, Prof. Aseem Z. Ansari and Prof. Paul C. Blainey

      Version of Record online: 4 NOV 2016 | DOI: 10.1002/anie.201606768

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      Synthetic small molecules with a wide range of chemical functionality can slide on DNA, and specific modifications can be used to tune crucial properties like DNA affinity and sliding speed. The picture shows a polyamide bound to DNA and its trajectory when sliding on DNA.

    35. Enantioselective Synthesis

      Organocatalytic, Enantioselective Synthesis of Cyclohexadienone Containing Hindered Spirocyclic Ethers through an Oxidative Dearomatization/Oxa-Michael Addition Sequence (pages 15115–15119)

      Reddy Rajasekhar Reddy, Dr. Satish Sonbarao Gudup and Prof. Prasanta Ghorai

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201607039

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      An asymmetric oxa-Michael reaction of α-tertiary alcohols using chiral squaramide catalysts is reported. The reaction provided a broad array of sterically hindered tetrahydrofurans and tetrahydropyrans attached to a cyclohexadienone moiety in spiro fashion. Good yields and enantioselectivities were observed. The oxo-cycles obtained were transformed into chromans without disturbing the enantioselectivity.

    36. Lithium Ion Separation | Hot Paper

      Polystyrene Sulfonate Threaded through a Metal–Organic Framework Membrane for Fast and Selective Lithium-Ion Separation (pages 15120–15124)

      Dr. Yi Guo, Dr. Yulong Ying, Dr. Yiyin Mao, Prof. Xinsheng Peng and Prof. Banglin Chen

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201607329

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      Going separate-Li: Intergrown and continuous HKUST-1 membranes through which polystyrene sulfonate (PSS) has been threaded are constructed, giving rise to a three-dimensional network of sulfonate groups. As a result of different binding affinities to sulfonate and size sieving effects, the membrane allows very fast and selective lithium-ion transportation, and thus separation from other metal ions.

    37. Organocatalysis

      Catalytic Enantioselective Aza-Piancatelli Rearrangement (pages 15125–15128)

      Dr. Huilin Li, Prof. Rongbiao Tong and Prof. Jianwei Sun

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201607714

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      Piancatelli rapido: An efficient organocatalytic enantioselective aza-Piancatelli rearrangement is disclosed. The powerful process provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available 2-furfurylcarbinols with excellent chemo-, enantio-, and diastereoselectivities under mild reaction conditions.

    38. Synthetic Methods

      Nickel-Catalyzed Esterification of Aliphatic Amides (pages 15129–15132)

      Liana Hie, Emma L. Baker, Sarah M. Anthony, Dr. Jean-Nicolas Desrosiers, Dr. Chris Senanayake and Prof. Dr. Neil K. Garg

      Version of Record online: 4 NOV 2016 | DOI: 10.1002/anie.201607856

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      Going aliphatic: In prior studies the nickel-catalyzed activation of aromatic amides to forge C−C or C−heteroatom bonds through cleavage on the amide C−N bond has been developed. The first nickel-catalyzed activation of amides derived from aliphatic carboxylic acids is now described, thus overcoming the key limitation associated with this class of reactions.

    39. Macrocycles

      carbo-Naphthalene: A Polycyclic carbo-Benzenoid Fragment of α-Graphyne (pages 15133–15136)

      Kévin Cocq, Nathalie Saffon-Merceron, Yannick Coppel, Corentin Poidevin, Valérie Maraval and Remi Chauvin

      Version of Record online: 2 NOV 2016 | DOI: 10.1002/anie.201608300

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      Towards α-graphyne: A ring carbo-mer of naphthalene, C32Ar8 (Ar=p-n-pentylphenyl), was obtained as a stable blue chromophore in 19 steps. The two carbo-benzenes o-C18Ar4(C≡C−SiiPr3)2 and C18Ar6 are also described. The carbo-naphthalene bicycle is locally aromatic according to structural and magnetic criteria. The stability and aromaticity of this smallest fused molecular fragment of α-graphyne allows prediction of the same properties for the carbon allotrope itself.

    40. Cross-Coupling Reactions

      Palladium(0)-Catalyzed Intermolecular Arylative Dearomatization of β-Naphthols (pages 15137–15141)

      Ren-Qi Xu, Ping Yang, Hang-Fei Tu, Shou-Guo Wang and Prof. Dr. Shu-Li You

      Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.201608724

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      2-Naphthalenones made easy: Pd0-catalyzed intermolecular arylative dearomatization of β-naphthols with aryl halides is described. It was found that Q-Phos could facilitate the palladium-catalyzed cross-coupling dearomatization of β-naphthols while avoiding O-arylation, to construct 2-naphthalenones in excellent yields and with high chemoselectivity.

    41. Arylation

      An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel–Crafts-type Arylation Reactions of C-Alkynyl Imines (pages 15142–15146)

      Yingcheng Wang, Liang Jiang, Long Li, Jun Dai, Dan Xiong and Prof. Dr. Zhihui Shao

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201608918

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      Enantioenriched propargylamines were synthesized in asymmetric Friedel–Crafts-type arylation reactions of in situ generated N-Boc-protected C-alkynyl imines with phenols, indoles, pyrrole, and 2-methoxyfuran. This process constitutes the first asymmetric Friedel–Crafts reaction with electron-deficient phenols.

    42. CO2 Reduction

      Metal-Free Reduction of CO2 to Methoxyborane under Ambient Conditions through Borondiformate Formation (pages 15147–15151)

      Dr. Samaresh Chandra Sau, Rameswar Bhattacharjee, Pavan K. Vardhanapu, Gonela Vijaykumar, Prof. Dr. Ayan Datta and Prof. Dr. Swadhin K. Mandal

      Version of Record online: 7 NOV 2016 | DOI: 10.1002/anie.201609040

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      It's metal free! An abnormal N-heterocyclic carbene acts as an efficient metal-free catalyst for the reduction of CO2 to methoxyborane under ambient conditions in the presence of a range of hydroboranes. The catalytically active reaction intermediate was structurally characterized by single-crystal X-ray diffraction and the mechanistic details were unraveled.

    43. Nanoclusters

      Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl-Protected Body-Centered Cubic Cluster [Au7Ag8(C≡CtBu)12]+ (pages 15152–15156)

      Yu Wang, Dr. Haifeng Su, Liting Ren, Dr. Sami Malola, Dr. Shuichao Lin, Prof. Boon K. Teo, Prof. Hannu Häkkinen and Prof. Nanfeng Zheng

      Version of Record online: 3 NOV 2016 | DOI: 10.1002/anie.201609144

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      Alkali metals meet coinage metals: Alkali metal ions and copper atoms were incorporated into the hexacapped body-centered cubic cluster [AuAg8Au6(C≡C-tBu)12]+. Whereas the copper atoms prefer capping sites, the alkali metal ions tend to replace Ag atoms at the vertices. The substitution of one Ag atom with a Na+ ion quenched the photoluminescence of the parent compound.

    44. Natural Product Synthesis

      Bioinspired Total Synthesis of the Dimeric Indole Alkaloid (+)-Haplophytine by Direct Coupling and Late-Stage Oxidative Rearrangement (pages 15157–15161)

      Dr. Hitoshi Satoh, Ken-ichi Ojima, Dr. Hirofumi Ueda and Prof. Dr. Hidetoshi Tokuyama

      Version of Record online: 7 NOV 2016 | DOI: 10.1002/anie.201609285

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      Direct and to the point: In a bioinspired convergent total synthesis of the dimeric indole alkaloid (+)-haplophytine, the two segments were coupled directly in a Friedel–Crafts reaction mediated by AgNTf2. Another key step was the construction of the diazabicyclo[3.3.1]nonane skeleton by a highly chemoselective late-stage aerobic oxidation/skeletal rearrangement cascade (see scheme).

    45. G-Quadruplexes

      Sugar–Edge Interactions in a DNA–RNA G-Quadruplex: Evidence of Sequential C−H⋅⋅⋅O Hydrogen Bonds Contributing to RNA Quadruplex Folding (pages 15162–15165)

      Jonathan Dickerhoff, Dr. Bettina Appel, Prof. Dr. Sabine Müller and Prof. Dr. Klaus Weisz

      Version of Record online: 7 NOV 2016 | DOI: 10.1002/anie.201608275

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      Replacing a single 2′-deoxyriboguanosine with riboguanosine in a suitable position of a DNA quadruplex leaves its overall fold unaffected. NMR spectral data strongly suggest the presence of CHO hydrogen-bonding interactions between the O2′ of the rG sugar and C8−H of the 3′-neighboring guanine in these hybrids. Based on a survey of available quadruplex structures, corresponding CHO interactions may be critical for RNA quadruplex folding.

    46. Alkene Difunctionalization

      Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes (pages 15166–15170)

      Andreas Lerchen, Tobias Knecht, Dr. Constantin G. Daniliuc and Prof. Dr. Frank Glorius

      Version of Record online: 27 OCT 2016 | DOI: 10.1002/anie.201608729

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      It′s cobaltastic: An unprecedented regioselective and entirely atom-economic cobalt(III)-catalyzed method for the non-annulative, intermolecular carboamination of alkenes enables the direct synthesis of acyclic unnatural amino acid derivatives in a redox-neutral fashion. Moreover Cp*CoIII and Cp*RhIII catalysts gave different products under otherwise identical conditions.

    47. CO2 Reduction Catalysis

      Solvent-Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products (pages 15171–15174)

      Michael C. Thompson, Dr. Jacob Ramsay and Prof. Dr. J. Mathias Weber

      Version of Record online: 12 OCT 2016 | DOI: 10.1002/anie.201607445

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      Solvation matters: Increasing the cluster size of [Bi(CO2)n] cluster anions leads to a structural change of the core ion (see scheme; Bi blue, C black, O red). This behavior provides important insight into the molecular mechanism of heterogeneous CO2 reduction catalysis under aprotic conditions.

    48. Catalytic Hydrogenation

      A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes (pages 15175–15179)

      Tobias Schwob and Prof. Dr. Rhett Kempe

      Version of Record online: 31 OCT 2016 | DOI: 10.1002/anie.201608321

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      Reduce, reuse, recycle: A reusable nanocomposite cobalt catalyst was developed that is easy to synthesize and can be handled in air. It efficiently mediates the selective hydrogenation of nitroarenes, as well as the direct synthesis of imines or benzimidazoles from nitroarenes and aldehydes. Functional groups that are highly sensitive to hydrogenation are well tolerated, and the hydrogenation activity can be regenerated through temperature-programmed reduction.

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