Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 28

July 6, 2015

Volume 54, Issue 28

Pages 8001–8297

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. You have free access to this content
      Cover Picture: The Chemical Basis of Fungal Bioluminescence (Angew. Chem. Int. Ed. 28/2015) (page 8001)

      Dr. Konstantin V. Purtov, Dr. Valentin N. Petushkov, Dr. Mikhail S. Baranov, Dr. Konstantin S. Mineev, Dr. Natalja S. Rodionova, Zinaida M. Kaskova, Aleksandra S. Tsarkova, Dr. Alexei I. Petunin, Dr. Vladimir S. Bondar, Dr. Emma K. Rodicheva, Dr. Svetlana E. Medvedeva, Prof. Yuichi Oba, Yumiko Oba, Prof. Alexander S. Arseniev, Prof. Sergey Lukyanov, Prof. Josef I. Gitelson and Dr. Ilia V. Yampolsky

      Article first published online: 12 JUN 2015 | DOI: 10.1002/anie.201505051

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      Glowing fungi were described by Aristotle as early as the fourth century B.C. In their Communication on page 8124 ff., I. V. Yampolsky, J. I. Gitelson, and co-workers unveil the structure of fungal luciferin, a compound that is responsible for fungal biolumescence.

    2. You have free access to this content
      Inside Cover: Pim Kinase Inhibitors Evaluated with a Single-Molecule Engineered Nanopore Sensor (Angew. Chem. Int. Ed. 28/2015) (page 8002)

      Dr. Leon Harrington, Dr. Leila T. Alexander, Prof. Dr. Stefan Knapp and Prof. Dr. Hagan Bayley

      Article first published online: 25 JUN 2015 | DOI: 10.1002/anie.201505545

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      A nanopore-based label-free kinase inhibitor assay is described by H. Bayley et al. in their Communication on page 8154 ff. An α-hemolysin pore (white) in an artificial membrane binds kinase proteins (purple) through a modified subunit bearing a genetically fused peptide (orange). Binding of kinase molecules in the presence of nucleotides and inhibitors is observed in real-time by monitoring the flow of ionic current through the pore, and yields reliable inhibition constants for prospective drug molecules.

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      Inside Back Cover: Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles (Angew. Chem. Int. Ed. 28/2015) (page 8299)

      Dr. Andre Clayborne, Hee-Joon Chun, Prof. Rees B. Rankin and Prof. Jeff Greeley

      Article first published online: 10 JUN 2015 | DOI: 10.1002/anie.201504836

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      The crucial role of water in determining the mechanism of NO electroreduction on single-crystal Pt(111) surfaces is revealed by first principles density functional theory calculations, as described by J. Greeley et al. in their Communication on page 8255 ff. Water facilitates proton transfer to adsorbed surface intermediates with very low kinetic barriers, leading to ammonia production at modest overpotentials. It also promotes an unusual Eley–Rideal-type mechanism, wherein NO is converted into N2O through a specifically adsorbed trans-(NO)2 dimer at lower overpotentials.

    4. You have free access to this content
      Back Cover: The Corrole Radical (Angew. Chem. Int. Ed. 28/2015) (page 8400)

      Peter Schweyen, Dr. Kai Brandhorst, Richard Wicht, Benedikt Wolfram and Prof. Dr. Martin Bröring

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201505260

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      “What do you see?” “I see a corrole radical!” An attempt to prepare sterically protected tungsten corroles led unexpectedly to the first free-base corrole radical. In their Communication on page 8213 ff., M. Bröring and co-workers report an air-stable and easy-to-handle open-shell 17π (4n+1) porphyrinoid with a SOMO that resembles the symmetry of a Rorschach picture. The observed loss of one inner hydrogen atom results in an effectively planar molecular structure and the ability to bind divalent metal ions, such as Zn2+.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. You have free access to this content
      Frontispiece: Tracking Cancer Metastasis In Vivo by Using an Iridium-Based Hypoxia-Activated Optical Oxygen Nanosensor

      Xianchuang Zheng, Huang Tang, Chen Xie, Jialiang Zhang, Prof. Wei Wu and Prof. Xiqun Jiang

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201582861

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      Cancer Diagnostics A hypoxia-sensitive sensor for tracking cancer metastasis is reported by X. Q. Jiang et al. on page 8094 ff. After systemic administration of the sensor, cancer cells metastasizing to the lungs or to the lymph nodes are detected by whole-body optical imaging.

  3. Editorial

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. You have free access to this content
      Single-Molecule Chemistry is More than Superresolved Fluorescence Microscopy (pages 8004–8005)

      Prof. Dr. Michel Orrit

      Article first published online: 12 JUN 2015 | DOI: 10.1002/anie.201503674

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      „There is more than what meets the eye. After 25 years of optical experiments on single molecules, it is time to reflect on the insights and the present or potential applications that single-molecule optics, and more generally single-molecule chemistry, have brought to us. Subtle and detailed information can be gleaned from the wealth of signals single molecules relay to us from their nanometer-scale environment …“ Read more in the Editorial by Michel Orrit.

  4. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. You have free access to this content
      Corrigendum: Reconfiguration of Stereoisomers under Sonomechanical Activation (page 8021)

      Giancarlo Cravotto and Pedro Cintas

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201504650

      This article corrects:

      Reconfiguration of Stereoisomers under Sonomechanical Activation1

      Vol. 49, Issue 35, 6028–6030, Article first published online: 20 JUL 2010

    2. You have free access to this content
      Corrigendum: Controlling Radical Formation in the Photoactive Yellow Protein Chromophore (page 8021)

      Ciarán R. S. Mooney, Michael A. Parkes, Andreas Iskra and Helen H. Fielding

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201504564

      This article corrects:

      Controlling Radical Formation in the Photoactive Yellow Protein Chromophore1

      Vol. 54, Issue 19, 5646–5649, Article first published online: 17 MAR 2015

    3. You have free access to this content
      Corrigendum: Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides (page 8022)

      Ronglu Huang, Yangjie Huang, Xiaoxi Lin, Mingguang Rong and Prof. Dr. Zhiqiang Weng

      Article first published online: 30 JUN 2015 | DOI: 10.1002/anie.201504947

      This article corrects:

      Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides1

      Vol. 54, Issue 19, 5736–5739, Article first published online: 17 MAR 2015

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. Albrecht Berkessel (page 8028)

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201501562

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      “I admire dedication and true achievement—in all areas of life. My favorite way to spend a holiday is motorcycling (or skiing, depending on the season) in the Alps …” This and more about Albrecht Berkessel can be found on page 8028.

  8. News

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

    1. Top of page
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    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. Methods and Applications of Cycloaddition Reactions in Organic Synthesis. Edited by Nagatoshi Nishiwaki. (pages 8030–8031)

      Bernhard Witulski

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201504517

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      John Wiley & Sons, Hoboken, 2014. 672 pp., hardcover, € 167.50—ISBN 978-1118299883

  10. Reviews

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. Super-Resolution Microscopy

      Single Molecules, Cells, and Super-Resolution Optics (Nobel Lecture) (pages 8034–8053)

      Eric Betzig

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201501003

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      The resolution of a microscope is determined by the diffraction limit in classical microscopy, whereby objects that are separated by half a wavelength can no longer be visually separated. To go below the diffraction limit required several tricks and discoveries. In his Nobel Lecture, E. Betzig describes the developments that have led to modern super high-resolution microscopy.

    2. Nanoscopy with Focused Light (Nobel Lecture) (pages 8054–8066)

      Prof. Dr. Stefan W. Hell

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201504181

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      A picture is worth a thousand words—This doesn't only apply to everyday life but also to the natural sciences. It is, therefore, probably not by chance that the historical beginning of modern natural sciences very much coincides with the invention of light microscopy. S. W. Hell shows in his Nobel Lecture that the diffraction resolution barrier has been overcome by using molecular state transitions (e.g. on/off) to make nearby molecules transiently discernible.

    3. Single-Molecule Spectroscopy, Imaging, and Photocontrol: Foundations for Super-Resolution Microscopy (Nobel Lecture) (pages 8067–8093)

      Prof. Dr. W. E. (William E.) Moerner

      Article first published online: 18 JUN 2015 | DOI: 10.1002/anie.201501949

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      In the early 90s, many fascinating physical effects were observed when ensemble averaging was removed to allow study of individual molecules. The imaging of single molecules as well as observations of spectral diffusion, optical switching, and the ability to select different single molecules in the same focal volume by tuning the pumping laser frequency provided important forerunners of the later super-resolution microscopy with single molecules.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Reviews
    12. Communications
    1. Cancer Diagnostics

      Tracking Cancer Metastasis In Vivo by Using an Iridium-Based Hypoxia-Activated Optical Oxygen Nanosensor (pages 8094–8099)

      Xianchuang Zheng, Huang Tang, Chen Xie, Jialiang Zhang, Prof. Wei Wu and Prof. Xiqun Jiang

      Article first published online: 3 JUN 2015 | DOI: 10.1002/anie.201503067

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      Tracking down cancer: A hypoxia-sensitive optical oxygen nanosensor is reported for tracking cancer metastasis in vivo. After systemic administration of the nanosensor, cancer cells metastasizing to the lungs through the blood stream or to the lymph node through lymphatics can be effectively detected by whole-body optical imaging.

    2. Electrochemistry

      Extraordinary Supercapacitor Performance of a Multicomponent and Mixed-Valence Oxyhydroxide (pages 8100–8104)

      Dr. Jianli Kang, Akihiko Hirata, Luyang Chen, Shengli Zhu, Takeshi Fujita and Prof. Mingwei Chen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201500133

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      Electrochemical polarization of a de-alloyed nanoporous NiCuMn alloy was employed to synthesize a novel multicomponent mixed-valence oxyhydroxide based electrode. The oxyhydroxide/metal electrode possesses both high specific capacitance (627 F cm−3) at a current density of 0.25 A cm−3 and a wide working-potential window (1.8 V) in aqueous electrolyte, thereby resulting in a high energy and power densities with excellent cyclic stability.

    3. Nanotechnology

      Hypoxia Induced by Upconversion-Based Photodynamic Therapy: Towards Highly Effective Synergistic Bioreductive Therapy in Tumors (pages 8105–8109)

      Dr. Yanyan Liu, Prof. Yong Liu, Prof. Wenbo Bu, Dr. Chao Cheng, Dr. Changjing Zuo, Dr. Qingfeng Xiao, Yong Sun, Dr. Dalong Ni, Dr. Chen Zhang, Dr. Jianan Liu and Prof. Jianlin Shi

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500478

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      Synergetic therapy: Strong hypoxia created by upconversion photodynamic therapy (UC-PDT) activates bioreductive pro-drugs co-delivered to form cytotoxic species, thereby potentiating the synergetic anticancer efficacy of UC-PDT. This process was accomplished by using upconversion-based nanoparticles designed to simultaneously deliver photosensitizer molecules and bioreductive pro-drugs in silica layers.

    4. Electrochemistry

      Thin-Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection (pages 8110–8113)

      Dr. Majid Ghahraman Afshar, Dr. Gastón A. Crespo and Prof. Eric Bakker

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500797

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      A chemically selective electrochemical proton pump creates a concentration perturbation in a thin-layer sample that is detected by a pH probe placed opposite. The proposed methodology is applicable for a range of ions and is demonstrated here for direct alkalinity measurements. L=ionophore; R=cation exchanger; Jinline image=proton flux; IFS=inner filling solution.

    5. Gold Nanoparticles

      DNA-Encoded Tuning of Geometric and Plasmonic Properties of Nanoparticles Growing from Gold Nanorod Seeds (pages 8114–8118)

      Tingjie Song, Dr. Longhua Tang, Li Huey Tan, Dr. Xiaojing Wang, Nitya Sai Reddy Satyavolu, Dr. Hang Xing, Dr. Zidong Wang, Prof. Jinghong Li, Prof. Haojun Liang and Prof. Yi Lu

      Article first published online: 10 JUN 2015 | DOI: 10.1002/anie.201500838

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      Controlling nanoparticle morphology was achieved by tuning the overgrowth of gold nanorods using DNA as a capping ligand. Kinetic studies show two representative pathways for the shape control. Furthermore, the geometric and plasmonic properties of the gold nanoparticles could be precisely controlled by adjusting the base composition of the DNA sequences or by introducing phosphorothioate modifications in the DNA.

    6. Biocatalytic Self-Assembly

      Biocatalytic Pathway Selection in Transient Tripeptide Nanostructures (pages 8119–8123)

      Charalampos G. Pappas, Ivan R. Sasselli and Prof. Rein V. Ulijn

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201500867

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      Off the beaten track: Sequence-dependent kinetic pathway selection in chemically fueled catalytic self-assembly of tripeptides is demonstrated, in which the control of the lifetime of the nanostructures is dictated by chemical design. Mimicking the unique features of these systems may open up opportunities to create supramolecular systems for non-equilibrium motility and shape control.

    7. Bioluminescence

      The Chemical Basis of Fungal Bioluminescence (pages 8124–8128)

      Dr. Konstantin V. Purtov, Dr. Valentin N. Petushkov, Dr. Mikhail S. Baranov, Dr. Konstantin S. Mineev, Dr. Natalja S. Rodionova, Zinaida M. Kaskova, Aleksandra S. Tsarkova, Dr. Alexei I. Petunin, Dr. Vladimir S. Bondar, Dr. Emma K. Rodicheva, Dr. Svetlana E. Medvedeva, Prof. Yuichi Oba, Yumiko Oba, Prof. Alexander S. Arseniev, Prof. Sergey Lukyanov, Prof. Josef I. Gitelson and Dr. Ilia V. Yampolsky

      Article first published online: 11 JUN 2015 | DOI: 10.1002/anie.201501779

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      Getting the green light: Hispidin is shown to be a luciferin precursor in at least four evolutionary distant genera of luminous fungi. However, its biosynthesis alone does not result in fungal bioluminescence. Two enzymes are required: first a hydroxylase converts the hispidin into 3-hydroxyhispidin, which acts as the luciferin, which undergoes a subsequent oxidation in the presence of a luciferase.

    8. Protein Dynamics

      Kinetic Cooperativity in Human Pancreatic Glucokinase Originates from Millisecond Dynamics of the Small Domain (pages 8129–8132)

      Dr. Mioara Larion, Dr. Alexandar L. Hansen, Dr. Fengli Zhang, Dr. Lei Bruschweiler-Li, Dr. Vitali Tugarinov, Prof. Dr. Brian G. Miller and Prof. Dr. Rafael Brüschweiler

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501204

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      Distant but decisive: Kinetic cooperativity is an intrinsic property of glucokinase that enables it to maintain whole-body glucose homeostasis. The small-domain dynamics of glucokinase on the millisecond timescale have now been quantified by NMR spectroscopic experiments and found to be responsible for this effect by interfering with the turnover rate constant and generating non-Michaelis–Menten kinetics (see picture).

    9. Semiconducting Nanostructures

      Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly (pages 8133–8138)

      Dr. Jean-Hubert Olivier, Dr. Jaehong Park, Dr. Pravas Deria, Dr. Jeff Rawson, Yusong Bai, Dr. Amar S. Kumbhar and Prof. Michael J. Therien

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501364

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      Nanohybrid compositions based on (6,5) chirality-enriched SWNTs and a chiral n-type polymer (S-PBN(b)-Ph4PDI) that exploits a perylenediimide-containing repeat unit undergo light-driven electron–hole pair generation. Rigorously controlled SWNT:electron acceptor stoichiometry and organization enable spectroscopic characterization of the photoinduced charge carrier signatures and evaluation of the associated charge separation and charge migration dynamics by pump-probe transient absorption spectroscopy.

    10. Multivalent Polymer Nanocomplex

      Multivalent Polymer Nanocomplex Targeting Endosomal Receptor of Immune Cells for Enhanced Antitumor and Systemic Memory Response (pages 8139–8143)

      Sun-Young Kim, Min Beom Heo, Dr. Geum-Sook Hwang, Youngae Jung, Dr. Do Yeol Choi, Prof. Dr. Yeong-Min Park and Prof. Dr. Yong Taik Lim

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501380

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      Enhanced immunostimulation: A multivalent polymer nanocomplex for the effective intracellular delivery and subsequent multivalent display of immunostimulatory cytosine-phosphate-guanine oligodeoxynucleotides (CpG ODNs) in antigen-presenting cells is described. Mice vaccinated with dendritic cells treated with the nanocomplex exhibited tumor growth inhibition as well as a strong antitumor memory response. HA=hyaluronic acid, PLL=poly(L-lysine).

    11. DNA Self-Assembly

      Hyperbranched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits (pages 8144–8148)

      Dr. Sai Bi, Min Chen, Xiaoqiang Jia, Ying Dong and Prof. Dr. Zonghua Wang

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501457

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      DNA branches out: A hyperbranched hybridization chain reaction is reported for the self-assembly of dendritic DNA structures triggered by an initiator DNA strand. By using this method, ultrasensitive detection of target DNA was achieved and three-input concatenated logic circuits have been constructed which can operate as keypad locks for biocomputing security systems at the molecular level.

    12. Photocatalysis

      Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S (pages 8149–8153)

      Summayya Kouser, S. R. Lingampalli, Dr.  P. Chithaiah, Anand Roy, Sujoy Saha, Prof. Umesh V. Waghmare and Prof. C. N. R. Rao

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201501532

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      Anionic doping: Cosubstitution of CdS and ZnS by P, Cl and N, F brings about remarkable changes in the electronic structure of these materials as the electronic band gaps are significantly decreased (Eg=band-gap energy). The effect of both P, Cl and N, F in CdS and ZnS were studied by DFT calculations, and the changes were measured by high-resolution X-ray photoelectron spectroscopy.

    13. Drug Screening | Hot Paper

      Pim Kinase Inhibitors Evaluated with a Single-Molecule Engineered Nanopore Sensor (pages 8154–8159)

      Dr. Leon Harrington, Dr. Leila T. Alexander, Prof. Dr. Stefan Knapp and Prof. Dr. Hagan Bayley

      Article first published online: 8 JUN 2015 | DOI: 10.1002/anie.201503141

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      Unbiased selection: A kinase inhibitor screening approach was developed that uses a radically different basis of detection than existing methods. Engineered protein nanopores allow the label-free determination of inhibition constants, are scalable to high-throughput, and circumvent biases inherent in prevailing technologies.

    14. Chiral Borospherenes

      Cage-Like B41+ and B422+: New Chiral Members of the Borospherene Family (pages 8160–8164)

      Qiang Chen, Su-Yan Zhang, Hui Bai, Wen-Juan Tian, Ting Gao, Hai-Ru Li, Chang-Qing Miao, Dr. Yue-Wen Mu, Hai-Gang Lu, Prof. Dr. Hua-Jin Zhai and Prof. Dr. Si-Dian Li

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501588

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      Chiral cations: Following the recently observed C3/C2 B39 and D2d B40, two new chiral members C1 B41+ and C2 B422+ are introduced to the borospherene family. These chiral borospherene cations are composed of twelve interwoven boron double chains with six hexagonal and heptagonal faces and exhibit σ plus π double delocalization, which can be viewed as cuborenes analogous to cubane (C8H8).

    15. Lithium–Air Battery

      Direct Detection of the Superoxide Anion as a Stable Intermediate in the Electroreduction of Oxygen in a Non-Aqueous Electrolyte Containing Phenol as a Proton Source (pages 8165–8168)

      Prof. Zhangquan Peng, Dr. Yuhui Chen, Prof. Peter G. Bruce and Prof. Ye Xu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502039

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      Stable superoxide found in gold ORR: An in situ spectroscopic study of the oxygen reduction reaction (ORR) on gold in a DMSO electrolyte containing phenol as a proton source shows that the ORR can begin with 1e transfer to O2. Thus O2, not HO2, is the first stable intermediate during the ORR to hydrogen peroxide. The unusual stability of O2 is explained using DFT calculations.

    16. Conformational Analysis

      Noncovalent Lone Pair⋅⋅⋅(No-π!)-Heteroarene Interactions: The Janus-Faced Hydroxy Group (pages 8169–8174)

      Dr. Ilias Pavlakos, Dr. Tanzeel Arif, Dr. Abil E. Aliev, Prof. William B. Motherwell, Dr. Graham J. Tizzard and Dr. Simon J. Coles

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502103

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      Fatal attraction: The noncovalent interaction of a hydroxy group with pyrazines and quinoxalines involves a lone pair (lp)–heteroarene attraction which is stronger and solvent independent when measured relative to the π-facial hydrogen bond to a benzene ring. Organic fluorides also prefer the heteroarene ring over benzene. The attraction between a quinoxaline and a terminal alkyne is stronger than an OH–arene interaction.

    17. Polycycles | Hot Paper

      Tetrabenzoperipentacene: Stable Five-Electron Donating Ability and a Discrete Triple-Layered β-Graphite Form in the Solid State (pages 8175–8178)

      Akinobu Matsumoto, Dr. Mitsuharu Suzuki, Dr. Daiki Kuzuhara, Dr. Hironobu Hayashi, Prof. Dr. Naoki Aratani and Prof. Dr. Hiroko Yamada

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502466

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      Triple the fun: Synthesis of an all-carbon conjugated tetrabenzoperipentacene was achieved. The single-crystal X-ray structure revealed that the molecules form a triple-layered cluster-like β-graphite. The remarkably rigid carbon framework results in a small Stokes shift and fully reversible five-electron oxidation potentials.

    18. Electrocatalysis

      Iron Carbide Nanoparticles Encapsulated in Mesoporous Fe-N-Doped Carbon Nanofibers for Efficient Electrocatalysis (pages 8179–8183)

      Zhen-Yu Wu, Xing-Xing Xu, Bi-Cheng Hu, Dr. Hai-Wei Liang, Dr. Yue Lin, Dr. Li-Feng Chen and Prof. Dr. Shu-Hong Yu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502173

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      Nanocomposite electrocatalyst: A high-performance electrocatalyst for the oxygen reduction reaction (ORR) is based on Fe3C nanoparticles encapsulated in mesoporous Fe-N-doped carbon nanofibers. It can be synthesized from low-cost and abundant precursors and exhibits excellent electrocatalytic performance for the ORR in both alkaline and acidic media.

    19. Inorganic Membranes | Hot Paper

      From Chemical Gardens to Fuel Cells: Generation of Electrical Potential and Current Across Self-Assembling Iron Mineral Membranes (pages 8184–8187)

      Dr. Laura M. Barge, Yeghegis Abedian, Dr. Michael J. Russell, Ivria J. Doloboff, Dr. Julyan H. E. Cartwright, Dr. Richard D. Kidd and Dr. Isik Kanik

      Article first published online: 12 MAY 2015 | DOI: 10.1002/anie.201501663

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      Chemical gardens: Self-assembling membranes in iron sulfide and iron hydroxide reaction systems were studied. The electrical potential and current generated by precipitation of the inorganic membranes were measured. The battery-like properties of the chemical gardens were demonstrated by linking multiple experiments in series, which produced sufficient electrical power to light an external light-emitting diode.

    20. Electrocatalysis

      One-Step Synthesis of Self-Supported Nickel Phosphide Nanosheet Array Cathodes for Efficient Electrocatalytic Hydrogen Generation (pages 8188–8192)

      Dr. Xiaoguang Wang, Dr. Yury V. Kolen'ko, Dr. Xiao-Qing Bao, Prof. Dr. Kirill Kovnir and Dr. Lifeng Liu

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502577

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      Hydrogen generation on self-supported three-dimensional nickel phosphide nanosheet array cathodes is reported. The nanosheets have been fabricated by direct phosphorization of commercial nickel foams using phosphorus vapor and show superior electrocatalytic activity and stability in acidic medium toward H2 generation.

    21. Asymmetric Synthesis | Hot Paper

      Stereoselective Organocatalytic Synthesis of Oxindoles with Adjacent Tetrasubstituted Stereocenters (pages 8193–8197)

      Oliver D. Engl, Dr. Sven P. Fritz and Prof. Dr. Helma Wennemers

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502976

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      Crowd around: Oxindoles with adjacent fully substituted stereogenic centers were formed by mild organocatalytic addition reactions with high diastereo- and enantioselectivities. The synthetic versatility of the products with orthogonally addressable functional moieties was showcased in the synthesis of derivatives of the bioactive oxindole AG-041R.

    22. Asymmetric Synthesis

      Catalytic Enantioselective Reaction of α-Aminoacetonitriles Using Chiral Bis(imidazoline) Palladium Catalysts (pages 8198–8202)

      Masaru Kondo, Tomoki Nishi, Prof. Dr. Tsubasa Hatanaka, Prof. Dr. Yasuhiro Funahashi and Prof. Dr. Shuichi Nakamura

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503098

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      Good yields and diastereo- and enantioselectivities were observed for the title reaction with various imines using chiral bis(imidazoline)/Pd catalysts. The reaction of α-aminonitriles with di-tert-butyl azodicarboxylate afforded chiral α,α-diaminonitrile in high yield with high enantioselectivity. acac=acetylacetonate, Boc=tert-butoxycarbonyl.

    23. Organocatalytic Asymmetric 1,6-Addition/1,4-Addition Sequence to 2,4-Dienals for the Synthesis of Chiral Chromans (pages 8203–8207)

      Pernille H. Poulsen, Karla Santos Feu, Bruno Matos Paz, Prof. Dr. Frank Jensen and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503370

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      One six one four: Based on a 1,6-Friedel–Crafts/1,4-oxa-Michael sequence, an organocatalyst directs the reaction of hydroxyarenes with a vinylogous iminium-ion intermediate to give only one out of four possible regioisomers. The reaction provides optically active chromans in high yields with up to 99 % ee.

    24. Perovskites

      The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers (pages 8208–8212)

      Nicholas Aristidou, Dr. Irene Sanchez-Molina, Thana Chotchuangchutchaval, Dr. Michael Brown, Dr. Luis Martinez, Dr. Thomas Rath and Prof. Saif A. Haque

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503153

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      The influence of light and oxygen on the stability of CH3NH3PbI3 perovskite-based photoactive layers is investigated. Upon exposure to both light and dry air, the mesoporous (mp) Al2O3/CH3NH3PbI3 layers decompose to methylamine, PbI2, and I2. This degradation is initiated by the reaction of superoxide (O2) with the methylammonium moiety of the perovskite absorber. MA=methyl ammonium, CB=conduction band, VB=valence band.

    25. Porphyrinoids

      The Corrole Radical (pages 8213–8216)

      Peter Schweyen, Dr. Kai Brandhorst, Richard Wicht, Benedikt Wolfram and Prof. Dr. Martin Bröring

      Article first published online: 12 JUN 2015 | DOI: 10.1002/anie.201503624

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      Surprisingly radical was the outcome of an attempt to prepare sterically protected tungsten corroles. Instead of a heavy-metal chelate, a chlorinated corrole radical (see picture) was formed as an air-stable and easy-to-handle open-shell 17π (4n+1) porphyrinoid. The loss of one inner H atom results in a planar molecular structure with the ability to bind divalent metal ions, such as zinc(II).

    26. Plant Polyphenols

      Gallotannins and Tannic Acid: First Chemical Syntheses and In Vitro Inhibitory Activity on Alzheimer’s Amyloid β-Peptide Aggregation (pages 8217–8221)

      Dr. Tahiri Sylla, Prof. Laurent Pouységu, Dr. Grégory Da Costa, Dr. Denis Deffieux, Prof. Jean-Pierre Monti and Prof. Stéphane Quideau

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201411606

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      Hexa- and decagalloylglucoses, which belong to the gallotannin plant polyphenols, were chemically synthesized for the first time, and a method for the selective synthesis of the monogalloylglucoses α- and β-glucogallin was developed. An in vitro evaluation showed that the non-natural α-glucogallin and a natural β-hexagalloylglucose are potent inhibitors of amyloid β-peptide aggregation.

    27. Rare-Earth Elements

      An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium (pages 8222–8225)

      Justin A. Bogart, Connor A. Lippincott, Dr. Patrick J. Carroll and Prof. Eric J. Schelter

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501659

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      Reuse and recycle: A tripodal nitroxide ligand is used in the separation of Nd and Dy and gives good recoveries from Nd/Dy(OTf)3 mixtures. The separation factor SNd/Dy=359 achieved is an improvement over conventional separation methods involving liquid–liquid extractions. This method will contribute to incentivizing recycling of Nd/Dy permanent magnetic materials.

    28. Glycoproteins

      Chemical Synthesis of O-Glycosylated Human Interleukin-2 by the Reverse Polarity Protection Strategy (pages 8226–8230)

      Dr. Yuya Asahina, Shinobu Komiya, Ami Ohagi, Rina Fujimoto, Dr. Hiroko Tamagaki, Katsuhiro Nakagawa, Dr. Takashi Sato, Prof. Dr. Shizuo Akira, Prof. Dr. Toshifumi Takao, Dr. Akira Ishii, Prof. Dr. Yoshiaki Nakahara and Prof. Dr. Hironobu Hojo

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201501847

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      Take your Pic: Total synthesis of the glycosylated human interleukin-2 (IL-2) has been achieved. The poor solubility of the C-terminal half during purification and ligation was overcome by using the reverse polarity protection of the carboxylic acid by a picolyl (Pic) ester. Together with a new prolyl thioester synthesis for the (28–65) segment, the desired IL-2, having full biological activity, was successfully prepared.

    29. Synthetic Methods

      Pd-Catalyzed Regioselective Activation of gem-Difluorinated Cyclopropanes: A Highly Efficient Approach to 2-Fluorinated Allylic Scaffolds (pages 8231–8235)

      Jun Xu, Ebrahim-Alkhalil Ahmed, Bin Xiao, Qian-Qian Lu, Yun-Long Wang, Chu-Guo Yu and Prof. Yao Fu

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502308

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      C[BOND]C bond cleavage under Pd catalysis induces a regioselective activation of gem-difluorinated cyclopropanes. The reaction provides access to a variety of 2-fluoroallylic scaffolds with high Z-selectivity and represents the first general application of gem-difluorinated cyclopropanes as reaction partners in transition-metal-catalyzed cross-coupling reactions.

    30. Cross-Coupling

      Ligand-Free Copper-Catalyzed Negishi Coupling of Alkyl-, Aryl-, and Alkynylzinc Reagents with Heteroaryl Iodides (pages 8236–8240)

      Surendra Thapa, Arjun Kafle, Dr. Santosh K. Gurung, Adam Montoya, Patrick Riedel and Prof. Ramesh Giri

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201502379

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      Simply copper: Primary, secondary, and tertiary alkylzinc reagents couple with heteroaryl iodides in the presence of ligand-free CuI without complications arising from β-hydride elimination and rearrangement. The reactions can also be extended to the coupling of aryl- and alkynylzinc reagents. DMF=N,N-dimethylformamide.

    31. Asymmetric Catalysis

      Rhodium-Catalyzed [3+2+2] and [2+2+2] Cycloadditions of Two Alkynes with Cyclopropylideneacetamides (pages 8241–8244)

      Tomoka Yoshida, Yuki Tajima, Masayuki Kobayashi, Koji Masutomi, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502505

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      ‘Cat nap’: The cationic RhI/H8-binap complex catalyzes the [3+2+2] cycloaddition of 1,6-diynes with cyclopropylideneacetamides to produce cycloheptadienes. In contrast, the cationic RhI/(S)-binap complex catalyzes the enantioselective [2+2+2] cycloaddition of terminal alkynes, acetylenedicarboxylates, and cyclopropylideneacetamides to produce spiro-cyclohexadienes.

    32. Heterocycles

      Zinc-Catalyzed Alkyne Oxidation/C[BOND]H Functionalization: Highly Site-Selective Synthesis of Versatile Isoquinolones and β-Carbolines (pages 8245–8249)

      Long Li, Bo Zhou, Yong-Heng Wang, Chao Shu, Yi-Fei Pan, Prof. Dr. Xin Lu and Prof. Dr. Long-Wu Ye

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502553

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      Swap gold for zinc: The title reaction was achieved by a zinc(II)-catalyzed alkyne oxidation/C[BOND]H functionalization sequence. In contrast to the well-established gold-catalyzed intermolecular alkyne oxidation, the over-oxidation can be suppressed in this system and the reaction most likely proceeds by a Friedel–Crafts-type pathway. Tf=trifluoromethanesulfonyl, PG=protecting group.

    33. Synthetic Methods

      Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations (pages 8250–8254)

      Meera Mehta, Dr. Michael H. Holthausen, Ian Mallov, Dr. Manuel Pérez, Dr. Zheng-Wang Qu, Prof. Dr. Stefan Grimme and Prof. Dr. Douglas W. Stephan

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502579

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      Taking out the O: The salts of the title cations were used in the catalytic stepwise hydrosilylation and deoxygenation of ketones. The dependency of the reaction outcome on Lewis acidity was investigated. In addition, the mechanism of the reduction was probed experimentally as well as with DFT calculations.

    34. NO Electroreduction

      Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles (pages 8255–8258)

      Dr. Andre Clayborne, Hee-Joon Chun, Prof. Rees B. Rankin and Prof. Jeff Greeley

      Article first published online: 5 JUN 2015 | DOI: 10.1002/anie.201502104

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      Path finder: The mechanism of nitric oxide electroreduction to ammonia on Pt(111) is investigated using a combination of first principles calculations and electrokinetic rate theories. The results demonstrate that ammonia is produced through a series of water-assisted protonation and bond dissociation steps at modest voltages.

    35. Cross-Coupling

      Design of New Ligands for the Palladium-Catalyzed Arylation of α-Branched Secondary Amines (pages 8259–8262)

      Nathaniel H. Park, Ekaterina V. Vinogradova, Dr. David S. Surry and Prof. Dr. Stephen L. Buchwald

      Article first published online: 1 JUN 2015 | DOI: 10.1002/anie.201502626

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      Coupled by design: The arylation of sterically demanding α-branched secondary amines was enabled through the design of new palladium catalyst systems. These catalysts help suppress the undesired β-hydride elimination pathways and are effective for the cross-coupling of a wide array of hindered amine nucleophiles with aryl and heteroaryl electrophiles.

    36. Organocatalysis

      Organocatalytic Activation of the Leaving Group in the Intramolecular Asymmetric SN2′ Reaction (pages 8263–8266)

      Yusuke Kuroda, Dr. Shingo Harada, Akinori Oonishi, Dr. Yousuke Yamaoka, Prof. Dr. Ken-ichi Yamada and Prof. Dr. Kiyosei Takasu

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201502831

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      Leaving-group activation: A Brønsted acid catalyzed intramolecular enantioselective SN2′ reaction was developed utilizing trichloroacetimidate as a leaving group. The findings indicated that dual activation of the substrates is operative. This metal-free allylic alkylation allows highly enantioselective access to 2-vinylpyrrolidines bearing various substituents.

    37. Structure Elucidation

      A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed-Shell Electronic State (pages 8267–8270)

      Dr. Daisuke Sakamaki, Soichiro Yano, Toshiyuki Kobashi, Prof. Dr. Shu Seki, Dr. Takuya Kurahashi, Prof. Dr. Seijiro Matsubara, Dr. Akihiro Ito and Prof. Dr. Kazuyoshi Tanaka

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502949

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      In a (closed) nut shell: A novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom has been prepared. This molecule has an unexpected closed-shell electronic state, even at room temperature, in spite of its structural similarity to the galvinoxyl radical. The molecule features two C[BOND]N bonds with multiple-bond character and a remarkably low HOMO–LUMO gap.

    38. Hydrogenation Reactions

      Pd–Pb Alloy Nanocrystals with Tailored Composition for Semihydrogenation: Taking Advantage of Catalyst Poisoning (pages 8271–8274)

      Dr. Wenxin Niu, Dr. Yongjun Gao, Dr. Weiqing Zhang, Prof. Ning Yan and Prof. Xianmao Lu

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201503148

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      Taking advantage of poisons: The poisoning effect of lead(II) ions can alter the shapes of Pd–Pb alloy nanocrystals. It endows the alloy nanocrystals with superior selectivity for the semihydrogenation of alkynes.

    39. Cesium Fluorides

      Molecular CsF5 and CsF2+ (pages 8275–8278)

      Dr. Andrey Yu. Rogachev, Dr. Mao-sheng Miao, Dr. Gabriel Merino and Dr. Roald Hoffmann

      Article first published online: 3 JUN 2015 | DOI: 10.1002/anie.201500402

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      Breaking into cores: Formal core orbitals sometimes may take part in bonding. An instance is provided in theoretical studies of the bonding of CsF5 (see picture) and CsF2+. The results also suggest that these metastable high fluorides of cesium may be experimentally accessible.

    40. Polyfluoride Anions | Very Important Paper

      Fluorine-Rich Fluorides: New Insights into the Chemistry of Polyfluoride Anions (pages 8279–8283)

      M. Sc. Thomas Vent-Schmidt, Dipl.-Chem. Felix Brosi, B. Sc. Jens Metzger, Dr. Tobias Schlöder, Prof. Xuefeng Wang, Prof. Lester Andrews, Dr. Carsten Müller, Dr. Helmut Beckers and Prof. Sebastian Riedel

      Article first published online: 3 JUN 2015 | DOI: 10.1002/anie.201502624

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      Give me F,F,F,F,F, five: The polyfluoride anions [F5] and Cs+[F3] have been identified by matrix-isolation spectroscopy and quantum-chemical methods. The V-shaped [F5] ion gives rise to a band found in many IR laser ablation experiments that, up to now, could not be assigned.

    41. Heterocycles

      Construction of an Internally B3N3-Doped Nanographene Molecule (pages 8284–8286)

      Dr. Matthias Krieg, Florian Reicherter, Dr. Peter Haiss, Dr. Markus Ströbele, Dr. Klaus Eichele, Michael-John Treanor, Prof. Dr. Renald Schaub and Prof. Dr. Holger F. Bettinger

      Article first published online: 26 MAY 2015 | DOI: 10.1002/anie.201412165

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      A change of heart: The borazine derivative of hexa-peri-hexabenzocoronene was produced in a high-temperature reaction through multiple dehydrogenation of a borazine. The solid-state structure of this BN-doped HBC (BN-HBC) is isotypic with that of the parent HBC. Scanning tunneling microscopy shows that BN-HBC lies flat on Au(111) in a two-dimensional pattern.

    42. Synthetic Methods

      An Iodine-Catalyzed Hofmann–Löffler Reaction (pages 8287–8291)

      Dr. Claudio Martínez and Prof. Dr. Kilian Muñiz

      Article first published online: 28 MAY 2015 | DOI: 10.1002/anie.201501122

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      Iodine does it! The first catalytic Hofmann–Löffler reaction proceeds with a combination of catalytic amounts of molecular iodine and a modified hypervalent iodine(III) reagent. The reaction proceeds under mild catalytic conditions and the intramolecular C[BOND]H amination addresses primary, secondary, and tertiary C[BOND]H groups.

    43. Charge Transfer | Hot Paper

      Carbon Nanodots: Supramolecular Electron Donor–Acceptor Hybrids Featuring Perylenediimides (pages 8292–8297)

      Volker Strauss, Johannes T. Margraf, Konstantin Dirian, Dr. Zois Syrgiannis, Prof. Dr. Maurizio Prato, Dr. Cordula Wessendorf, Prof. Dr. Andreas Hirsch, Prof. Dr. Timothy Clark and Prof. Dr. Dirk M. Guldi

      Article first published online: 27 MAY 2015 | DOI: 10.1002/anie.201502482

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      Long-term separation: Charge-transfer complexes formed by electron-donating carbon nanodots and electron-accepting perylenediimides are prepared. In ultrafast pump-probe experiments (see picture) the charge-separated state with a lifetime of 210 ps was found.

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