Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 30

July 21, 2014

Volume 53, Issue 30

Pages 7677–7955

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Single-Particle Tracking and Modulation of Cell Entry Pathways of a Tetrahedral DNA Nanostructure in Live Cells (Angew. Chem. Int. Ed. 30/2014) (page 7677)

      Le Liang, Dr. Jiang Li, Dr. Qian Li, Prof. Qing Huang, Dr. Jiye Shi, Prof. Hao Yan and Prof. Chunhai Fan

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201405099

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      Tetrahedral DNA nanostructures can be readily taken up by cells. In their Communication on page 7745 ff., C. Fan, Q. Huang, and co-workers investigate the endocytotic internalization into mammalian cells and subsequent transport of these self-assembled DNA nanostructures by single-particle tracking. These results constitute the next step toward the development of novel drug-delivery systems based on nucleic acids.

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      Inside Cover: A General Copper-Mediated Nucleophilic 18F Fluorination of Arenes (Angew. Chem. Int. Ed. 30/2014) (page 7678)

      Dr. Matthew Tredwell, Dr. Sean M. Preshlock, Nicholas J. Taylor, Dr. Stefan Gruber, Dr. Mickael Huiban, Dr. Jan Passchier, Dr. Joël Mercier, Dr. Christophe Génicot and Prof. Véronique Gouverneur

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201405437

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      Radiolabeling of arenes with [18F]fluoride by a transformational method using readily available aryl boronic ester precursors is reported by V. Gouverneur and co-workers in their Communication on page 7751 ff. The picture illustrates, in the confinement of a PET (positron emission tomography) scanner, the annihilation event resulting from positron emission from [18F]fluoro-L-DOPA.

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      Inside Back Cover: Ultrathin WS2 Nanoflakes as a High-Performance Electrocatalyst for the Hydrogen Evolution Reaction (Angew. Chem. Int. Ed. 30/2014) (page 7957)

      Dr. Liang Cheng, Wenjing Huang, Qiufang Gong, Changhai Liu, Prof. Zhuang Liu, Prof. Yanguang Li and Prof. Hongjie Dai

      Article first published online: 26 MAY 2014 | DOI: 10.1002/anie.201405193

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      WS2 nanoflakes with monolayer thickness and abundant edges were synthesized through a high-temperature solution-phase method that is described by Z. Liu, Y. G. Li et al. in their Communication on page 7860 ff. These nanoflakes exhibited impressive activity and durability in electrocatalytic hydrogen-evolution reactions in acids and thus represent an attractive low-cost alternative to the precious platinum benchmark catalyst.

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      Back Cover: Elastic and Wearable Wire-Shaped Lithium-Ion Battery with High Electrochemical Performance (Angew. Chem. Int. Ed. 30/2014) (page 7958)

      Jing Ren, Ye Zhang, Wenyu Bai, Xuli Chen, Zhitao Zhang, Xin Fang, Wei Weng, Dr. Yonggang Wang and Prof. Huisheng Peng

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201405394

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      A safe wire-shaped lithium-ion battery consists of two composite yarns, which were prepared from aligned multi-walled carbon nanotubes and lithium oxides, as the anode and cathode. In their Communication on page 7864 ff., Y. Wang, H. Peng et al. describe that 97 % of the capacity of these lightweight and flexible batteries was retained after 1000 bending cycles. Furthermore, the wire-shaped batteries were woven into battery textiles.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
      Frontispiece: Hydrogen Abstraction/Acetylene Addition Revealed (page 7678)

      Dr. Dorian S. N. Parker, Prof. Ralf I. Kaiser, Dr. Tyler P. Troy and Dr. Musahid Ahmed

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201483071

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      Gas-Phase Chemistry In their Communication on page 7740 ff., R. I. Kaiser, M. Ahmed et al. use photo-ionization mass spectrometry to show the formation of naphthalene in the gas phase through the reaction of a phenyl radical with two acetylene molecules.

  3. Editorial

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
  4. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 30/2014 (pages 7683–7698)

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201490028

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Alexander Heckel (page 7704)

      Article first published online: 26 MAR 2014 | DOI: 10.1002/anie.201402186

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      “My favorite place on earth is under water. Guaranteed to make me laugh is a good pun. …” This and more about Alexander Heckel can be found on page 7704.

  7. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Liquid Phase Oxidation via Heterogeneous Catalysis. Organic Synthesis and Industrial Applications. Edited by Mario G. Clerici and Oxana A. Kholdeeva. (page 7707)

      Fabrizio Cavani

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201404813

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      John Wiley & Sons, Hoboken, 2013. 546 pp., hardcover, € 129.00.—ISBN 978-0470915523

  9. Highlight

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

      Direct Functionalization with Complete and Switchable Positional Control: Free Phenol as a Role Model (pages 7710–7712)

      Dr. Da-Gang Yu, Francisco de Azambuja and Prof. Dr. Frank Glorius

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403894

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      PhenAll: Recent breakthroughs in site-selective and direct functionalization of free phenols by transition-metal-catalyzed C[BOND]O or C[BOND]H bond activation are highlighted here as role models for the complete and switchable positional control of transformations of important core structures.

  10. Essay

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

      Classification Framework for Graphene-Based Materials (pages 7714–7718)

      Dr. Peter Wick, Dr. Anna E. Louw-Gaume, Dr. Melanie Kucki, Prof. Harald F. Krug, Prof. Kostas Kostarelos, Prof. Bengt Fadeel, Prof. Kenneth A. Dawson, Dr. Anna Salvati, Prof. Ester Vázquez, Dr. Laura Ballerini, Dr. Mauro Tretiach, Dr. Fabio Benfenati, Dr. Emmanuel Flahaut, Dr. Laury Gauthier, Prof. Maurizio Prato and Dr. Alberto Bianco

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403335

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      Graphing graphene: Because the naming of graphene-based materials (GBMs) has led to confusion and inconsistency, a classification approach is necessary. Three physical-chemical properties of GBMs have been defined by the GRAPHENE Flagship Project of the European Union for the unequivocal classification of these materials (see grid).

  11. Review

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

      Chemistry with Graphene and Graphene Oxide—Challenges for Synthetic Chemists (pages 7720–7738)

      Dr. Siegfried Eigler and Prof. Dr. Andreas Hirsch

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201402780

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      The well-controlled synthesis of new graphene and graphene oxide derivatives as well as determination of the atomic structure are key challenges for synthetic chemists. Structure–property relationships must be exploited to use the full potential of graphene derivatives in upcoming applications. This Review focuses on concepts in the chemistry of graphene and graphene oxide with the aim of encouraging chemists to enhance the field of research.

  12. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Gas-Phase Chemistry

      Hydrogen Abstraction/Acetylene Addition Revealed (pages 7740–7744)

      Dr. Dorian S. N. Parker, Prof. Ralf I. Kaiser, Dr. Tyler P. Troy and Dr. Musahid Ahmed

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201404537

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      Formation of naphthalene: The prototype polycyclic aromatic hydrocarbon naphthalene is shown by photo-ionization mass spectrometry to be formed in the gas phase through the reaction of a phenyl radical with two acetylene molecules (see picture). The first direct experimental evidence of the existence of the hydrogen abstraction–acetylene addition mechanism is given which so far had only been speculated theoretically.

    2. DNA Nanostructures

      Single-Particle Tracking and Modulation of Cell Entry Pathways of a Tetrahedral DNA Nanostructure in Live Cells (pages 7745–7750)

      Le Liang, Dr. Jiang Li, Dr. Qian Li, Prof. Qing Huang, Dr. Jiye Shi, Prof. Hao Yan and Prof. Chunhai Fan

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201403236

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      Transported to a better place: The endocytotic internalization of tetrahedral DNA nanostructures (TDNs) into cells by a caveolin-dependent pathway was investigated through single-particle tracking. The subsequent microtubule-dependent transport of the TDNs to the lysosomes for digestion (see figure) could be redirected to the nucleus by functionalization of the TDNs.

    3. Radiochemistry | Hot Paper

      A General Copper-Mediated Nucleophilic 18F Fluorination of Arenes (pages 7751–7755)

      Dr. Matthew Tredwell, Dr. Sean M. Preshlock, Nicholas J. Taylor, Dr. Stefan Gruber, Dr. Mickael Huiban, Dr. Jan Passchier, Dr. Joël Mercier, Dr. Christophe Génicot and Prof. Véronique Gouverneur

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201404436

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      18F-labeling for PET: The nucleophilic 18F fluorination of pinacol-derived aryl boronic esters is achieved with [18F]KF/K222 in the presence of [Cu(OTf)2(py)4] (OTf=trifluoromethanesulfonate, py=pyridine); this unprecedented method can produce a clinical dose of 6-[18F]fluoro-L-DOPA in two steps (fluorination followed by deprotection) from a readily available shelf-stable arylBPin precursor (see scheme). RCY=decay-corrected radiochemical yield

    4. Red Phosphors

      Tailoring of Deep-Red Luminescence in Ca2SiO4:Eu2+ (pages 7756–7759)

      Dr. Yasushi Sato, Prof. Dr. Hideki Kato, Dr. Makoto Kobayashi, Prof. Dr. Takaki Masaki, Prof. Dr. Dae-Ho Yoon and Prof. Dr. Masato Kakihana

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201402520

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      A dicalcium silicate phosphor, Ca2−xEuxSiO4, emits red light in response to blue-light excitation. When excited at 450 nm, deep-red emission at 650 nm was clearly observed in Ca1.2Eu0.8SiO4. The picture shows a photograph of the corresponding Ca1.20Eu0.80SiO4 phosphor upon excitation with blue LEDs. The external and internal quantum efficiencies were 44 % and 50 %, respectively.

    5. Gold Catalysis

      Mechanistic Study of Gold(I)-Catalyzed Hydroamination of Alkynes: Outer or Inner Sphere Mechanism? (pages 7760–7764)

      Dipl.-Chem. Alexander Zhdanko and Prof. Dr. Martin E. Maier

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201402557

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      Which way is right? Experimental mechanistic study of hydroamination reveals the formation of conformationally flexible auro-iminium salts Au-Im, which originate from protonation of the vinyl gold species B. Rotation around the C[BOND]CAu bond is the reason for the loss of stereospecificity of protodeauration, which explains earlier stereochemical results. This shows that the reaction proceeds through the outer sphere mechanism.

    6. Conformation Analysis

      Dynamics of Intact Immunoglobulin G Explored by Drift-Tube Ion-Mobility Mass Spectrometry and Molecular Modeling (pages 7765–7769)

      Kamila J. Pacholarz, Dr. Massimiliano Porrini, Dr. Rachel A. Garlish, Dr. Rebecca J. Burnley, Dr. Richard J. Taylor, Dr. Alistair J. Henry and Prof. Perdita E. Barran

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201402863

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      Dancing antibodies: Collision cross-sections of immunoglobulins G1 and G4 have been determined using linear drift-tube ion-mobility mass spectrometry. Intact antibodies and Fc hinge fragments possess far higher intrinsic flexibility than proteins of comparable size. This is rationalized with MD simulations, which reveal dynamics between linked folded domains. The IgG1 subclass is less dynamic than the IgG4 subclass in the absence of solvent.

    7. Template-Directed Synthesis

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      Cyclodextrin-Templated Porphyrin Nanorings (pages 7770–7773)

      Pengpeng Liu, Dr. Patrik Neuhaus, Dr. Dmitry V. Kondratuk, Prof.  T. Silviu Balaban and Prof. Harry L. Anderson

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201402917

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      Floppy yet effective: Cyclodextrins have been decorated with pyridine legs to create chiral templates for directing the synthesis of nanorings consisting of six or seven zinc porphyrin macrocycles. The flexibility of these cyclodextrin derivatives does not make them less effective as templates, and it only slightly reduces the cooperativity of their interactions with the nanorings.

    8. Metal–Organic Frameworks

      Separating Xylene Isomers by Commensurate Stacking of p-Xylene within Channels of MAF-X8 (pages 7774–7778)

      Ariana Torres-Knoop, Prof. Dr. Rajamani Krishna and Dr. David Dubbeldam

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201402894

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      Think inside the box: By viewing the channels of metal–organic frameworks as “bookshelves”, we can exploit the concept of commensurate stacking to design highly para-xylene selective structures. A screening study reveals the metal–organic framework MAF-X8 possesses this property and is found to be superior to currently used technology such as BaX zeolite.

    9. NO-Responsive Polymers

      Biomimetic Polymers Responsive to a Biological Signaling Molecule: Nitric Oxide Triggered Reversible Self-assembly of Single Macromolecular Chains into Nanoparticles (pages 7779–7784)

      Dr. Jinming Hu, Dr. Michael R. Whittaker, Dr. Hien Duong, Yang Li, Prof. Dr. Cyrille Boyer and Prof. Dr. Thomas P. Davis

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403147

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      NO problem: Polymerization of NO-responsive monomers containing o-phenylenediamine functional groups has led to the formation of NO-responsive macromolecular chains that act as truly biomimetic polymers. Exposure to NO results in the thermoresponsive copolymers undergoing self-assembly into micellar structures (see example). The NO-triggered self-assembly process with turn on fluorescence was further used to image endogenous NO.

    10. Biotransformations

      A Biocompatible Alkene Hydrogenation Merges Organic Synthesis with Microbial Metabolism (pages 7785–7788)

      Dr. Gopal Sirasani, Liuchuan Tong and Prof. Emily P. Balskus

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403148

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      Reduction to practice: A hydrogenation reaction has been developed that employs hydrogen generated in situ by a microorganism and a biocompatible palladium catalyst to reduce alkenes on a synthetically useful scale. This type of transformation, which directly combines tools from organic chemistry with the metabolism of a living organism for small-molecule production, represents a new strategy for chemical synthesis.

    11. Chiral Hydrogels

      Control of Three-Dimensional Cell Adhesion by the Chirality of Nanofibers in Hydrogels (pages 7789–7793)

      Guo-Feng Liu, Prof. Di Zhang and Prof. Chuan-Liang Feng

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403249

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      A blockbuster in 3D: Cell behavior in a 3D environment was greatly influenced by the chirality of nanofibers created by supramolecular hydrogelators. Only one enantiomer of a 1,4-benzenedicarboxamide phenylalanine derivative 1 formed nanofibers that led to high cell-adhesion and cell-proliferation densities (bottom right). Models of the extracellular matrix designed by this strategy could provide the desirable cell density for tissue engineering.

    12. Biosynthesis

      The Molecular Basis of Conjugated Polyyne Biosynthesis in Phytopathogenic Bacteria (pages 7794–7798)

      Claudia Ross, Dr. Kirstin Scherlach, Florian Kloss and Prof. Dr. Christian Hertweck

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201403344

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      Triple trouble: The genes for a bacterial polyyne biosynthesis pathway were discovered in the plant pathogen Burkholderia caryophylli. Caryoynencin biosynthesis involves bacteria-specific desaturases/acetylenases and a cytochrome P450 monooxygenase. Highly fragile polyynes were successfully trapped and isolated from a crude metabolite mixture by an in situ click reaction. Homologous polyyne gene clusters were found in various bacterial genomes.

    13. Amyloid Fibrils

      Cold Denaturation of α-Synuclein Amyloid Fibrils (pages 7799–7804)

      Tatsuya Ikenoue, Prof. Dr. Young-Ho Lee, Prof. Dr. József Kardos, Miyu Saiki, Prof. Dr. Hisashi Yagi, Prof. Dr. Yasushi Kawata and Prof. Dr. Yuji Goto

      Article first published online: 11 JUN 2014 | DOI: 10.1002/anie.201403815

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      Chilling stress causes stable α-synuclein fibrils to dissociate into monomers. Monomers detach directly from the fibril ends. Amyloid-specific charge repulsion caused by the burial of charged residues in fibril cores induces cold denaturation of α-synuclein fibrils. At elevated temperatures, the dissociation of monomers from fibril ends also takes place, which is further amplified by fibril breakage.

    14. Laser Spectroscopy

      Conformation-Specific Circular Dichroism Spectroscopy of Cold, Isolated Chiral Molecules (pages 7805–7808)

      Aram Hong, Chang Min Choi, Han Jun Eun, Changseop Jeong, Prof. Jiyoung Heo and Prof. Nam Joon Kim

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201403916

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      Taking the pulse: Conformation-specific circular dichroism spectra of cold chiral molecules in a supersonic jet were obtained using circularly polarized laser pulses generated by synchronizing the firing of nanosecond laser pulses to the oscillation of a photoelastic modulator (PEM). Reported herein is the first resonant two-photon ionization (R2PI) CD spectra of ephedrine using the method.

    15. Fluorescence Probes

      Water-Soluble Triarylboron Compound for ATP Imaging In Vivo Using Analyte-Induced Finite Aggregation (pages 7809–7813)

      Xiaoyan Li, Xudong Guo, Lixia Cao, Zhiqing Xun, Dr. Shuangqing Wang, Dr. Shayu Li, Prof. Dr. Yi Li and Prof. Dr. Guoqiang Yang

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201403918

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      Tracking device: The triarylboron compound in the scheme displays an apparent ATP-dependent fluorescence enhancement. The analyte, ATP, induces finite aggregation and endows the indicator with appreciable photostability and superior tolerance to environmental electrolytes, thus leading to its successful application to the monitoring of ATP levels in vitro and in vivo. ATP=adenosine 5′-triphosphate.

    16. Phthalocyanine Analogues

      18π-Electron Tautomeric Benziphthalocyanine: A Functional Near-Infrared Dye with Tunable Aromaticity (pages 7814–7818)

      Naoyuki Toriumi, Dr. Atsuya Muranaka, Dr. Keiichi Hirano, Kengo Yoshida, Dr. Daisuke Hashizume and Prof. Dr. Masanobu Uchiyama

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201404020

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      Controlling tautomerism: An 18π- electron aromatic benziphthalocyanine consists of two 18π-electron tautomers, a weakly aromatic phenol form, and a strongly aromatic quinoidal form. This equilibrium can be controlled by chemical modification and by solvent effects, enabling tuning of the aromaticity and near-infrared absorption.

    17. Metal–Organic Frameworks | Hot Paper

      Hydrogen Storage in a Potassium-Ion-Bound Metal–Organic Framework Incorporating Crown Ether Struts as Specific Cation Binding Sites (pages 7819–7822)

      Dr. Dae-Woon Lim, Seung An Chyun and Prof. Myunghyun Paik Suh

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201404265

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      Crown ethers strut their stuff: The metal–organic framework SNU-200 incorporates 18-crown-6 moieties as a cation binding site. SNU-200 binds K+, NH4+, and methyl viologen2+ (MV2+) and their counteranions. Its gas sorption properties depend on the bound cation. The K+/SCN bound SNU-200 shows the highest isosteric heat (9.92 kJ mol−1) of H2 adsorption, a result of the open metal sites on the K+ ions.

    18. Supramolecular Chemistry

      The Self-Sorting Behavior of Circular Helicates and Molecular Knots and Links (pages 7823–7827)

      Jean-François Ayme, Dr. Jonathon E. Beves, Dr. Christopher J. Campbell and Prof. David A. Leigh

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201404270

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      It takes all sorts: Tris(bidentate) ligand strands that differ in length by just two atoms self-sort into circular helicates of different sizes with a monoamine and into different molecular topologies—a molecular Solomon link and a pentafoil knot—with a diamine (see picture).

    19. β-Strand Templates

      Macrocyclic Protease Inhibitors with Reduced Peptide Character (pages 7828–7831)

      Dr. Krystle C. H. Chua, Dr. Markus Pietsch, Xiaozhou Zhang, Stephanie Hautmann, Hon Y. Chan, Dr. John B. Bruning, Prof. Dr. Michael Gütschow and Prof. Dr. Andrew D. Abell

      Article first published online: 5 JUN 2014 | DOI: 10.1002/anie.201404301

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      The incorporation of a pyrrole into a peptide backbone generates simple macrocycles that adopt a β-strand geometry. The attachment of a P1 amino aldehyde to these templates then gives rise to potent protease inhibitors (see example, top, which has Ki values of 440 pM and 920 pM against the cysteine cathepsins L and S, respectively). A crystal structure of a related derivative bound to chymotrypsin (see picture, bottom) confirms the design.

    20. Natural Product Synthesis

      Asymmetric, Stereodivergent Synthesis of (−)-Clusianone Utilizing a Biomimetic Cationic Cyclization (pages 7832–7837)

      Jonathan H. Boyce and Prof. Dr. John A. Porco Jr.

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201404437

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      Aim for selectivity: (−)-Clusianone was produced by a stereodivergent asymmetric total synthesis in six steps from commercial materials. The synthesis utilizes a challenging formic acid-mediated cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms.

    21. Heterojunction-Mediated Catalysis

      Nanojunction-Mediated Photocatalytic Enhancement in Heterostructured CdS/ZnO, CdSe/ZnO, and CdTe/ZnO Nanocrystals (pages 7838–7842)

      Clive Eley, Dr. Tong Li, Fenglin Liao, Dr. Simon Michael Fairclough, Dr. Jason M. Smith, Prof. George Smith and Prof. Shik Chi Edman Tsang

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404481

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      That's a (quantum dot) wrap! A series of highly active semiconductor photocatalysts have been synthesized by growing wurtzite-ZnO tetrahedrons around pre-formed CdS, CdSe, and CdTe quantum dots. The resulting heterostructured CdX/ZnO nanocrystals with extensive type-II nanojunctions exhibit rapid photocatalytic decomposition of organic molecules in aqueous media.

    22. Enzyme Models

      Demonstration of the Heterolytic O[BOND]O Bond Cleavage of Putative Nonheme Iron(II)[BOND]OOH(R) Complexes for Fenton and Enzymatic Reactions (pages 7843–7847)

      Suhee Bang, Sora Park, Dr. Yong-Min Lee, Dr. Seungwoo Hong, Dr. Kyung-Bin Cho and Prof. Dr. Wonwoo Nam

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201404556

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      Ironed out: One-electron reduction of mononuclear nonheme FeIII[BOND]OOH and FeIII[BOND]OOR complexes by ferrocene derivatives resulted in the formation of the corresponding FeIVO complexes. Reduction of the FeIII to FeII species is the rate-determining step (r.d.s.), followed by the heterolytic O[BOND]O bond cleavage to give the FeIVO complexes. The results provide the first example of this pathway to form FeIVO intermediates which occur in nonheme iron enzymatic and Fenton reactions.

    23. Protein Design

      Engineering Specificity Changes on a RanBP2 Zinc Finger that Binds Single-Stranded RNA (pages 7848–7852)

      Dr. Marylène Vandevenne, Dr. Mitchell R. O'Connell, Stephanie Helder, Dr. Nicholas E. Shepherd, Prof. Jacqueline M. Matthews, Dr. Ann H. Kwan, Prof. David J. Segal and Prof. Joel P. Mackay

      Article first published online: 9 JUL 2014 | DOI: 10.1002/anie.201402980

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      Variation on a theme: A combinatorial library of RanBP2-type zinc finger (ZF) domains has been engineered in an effort to select variants with distinct RNA-binding preferences. One variant was shown to successfully discriminate the sequence GCC over GGU and AAA, but only in the context of a three-ZF polypeptide. This study provides proof of principle that the specificity of RNA-binding modules based on ZF domains can be successfully altered.

    24. Fullerenes

      Synthesis of Long-Sought C66 with Exohedral Stabilization (pages 7853–7855)

      Cong-Li Gao, Xiang Li, Dr. Yuan-Zhi Tan, Xin-Zhou Wu, Dr. Qianyan Zhang, Prof.Dr. Su-Yuan Xie and Prof. Rong-Bin Huang

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201402625

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      Captured at last! Elusive #4348C66 was stabilized exohedrally to give a fullerene derivative identified as #4348C66Cl10 by X-ray single-crystal diffraction (see picture). The isolation of this chlorofullerene supports the existence of #4348C66 in the carbon arc.

    25. Natural Products | Hot Paper

      Discovery of Clostrubin, an Exceptional Polyphenolic Polyketide Antibiotic from a Strictly Anaerobic Bacterium (pages 7856–7859)

      Dr. Sacha Pidot, Dr. Keishi Ishida, Michael Cyrulies and Prof. Dr. Christian Hertweck

      Article first published online: 14 MAY 2014 | DOI: 10.1002/anie.201402632

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      Hold your breath: Genomics-based metabolic profiling of Clostridium beijerinckii led to the discovery of clostrubin, the first polyketide isolated from an obligate anaerobe. The unusual polyphenolic compound demonstrates pronounced antibiotic activity against a variety of bacterial pathogens. Isotope labeling revealed that the novel ring topology results from noncanonical chain folding that deviates from the pathways used by aerobic microorganisms.

    26. Electrocatalysis | Hot Paper

      Ultrathin WS2 Nanoflakes as a High-Performance Electrocatalyst for the Hydrogen Evolution Reaction (pages 7860–7863)

      Dr. Liang Cheng, Wenjing Huang, Qiufang Gong, Changhai Liu, Prof. Zhuang Liu, Prof. Yanguang Li and Prof. Hongjie Dai

      Article first published online: 18 MAY 2014 | DOI: 10.1002/anie.201402315

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      Ultrathin WS2 nanoflakes were synthesized according to a new high-temperature solution-phase method. These nanoflakes may be used as efficient catalysts for the electrocatalytic hydrogen evolution reaction and represent an attractive alternative to the expensive platinum benchmark catalysts.

    27. Lithium-Ion Batteries | Very Important Paper

      Elastic and Wearable Wire-Shaped Lithium-Ion Battery with High Electrochemical Performance (pages 7864–7869)

      Jing Ren, Ye Zhang, Wenyu Bai, Xuli Chen, Zhitao Zhang, Xin Fang, Wei Weng, Dr. Yonggang Wang and Prof. Huisheng Peng

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201402388

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      Super-stretchy: A novel and safe wire-shaped lithium-ion battery consists of two composite yarns, which were made from aligned multi-walled carbon nanotubes (MWCNT) and lithium titanium oxide (LTO) or lithium manganese oxide (LMO), as the anode and cathode. These wire-shaped batteries were woven into light, flexible, and stretchable battery textiles.

    28. Homogeneous Catalysis

      Gold-Catalyzed C(sp3)[BOND]H/C(sp)[BOND]H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3-Alkynyl Polysubstituted Furans (pages 7870–7874)

      Yuanhong Ma, Shuai Zhang, Shiping Yang, Dr. Feijie Song and Prof. Dr. Jingsong You

      Article first published online: 6 JUN 2014 | DOI: 10.1002/anie.201402475

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      Pure and simple: The first gold-catalyzed C(sp3)[BOND]H/C(sp)[BOND]H cross-coupling/cyclization/oxidative alkynylation sequence of 1,3-dicarbonyl compounds reacting with terminal alkynes has been achieved under mild reaction conditions by taking advantage of the unique redox property and carbophilic π acidity of gold. Ultimately, 3-alkynyl polysubstituted furans are synthesized concisely and regiospecifically from simple starting materials.

    29. Bond Theory

      Covalent Hypercoordination: Can Carbon Bind Five Methyl Ligands? (pages 7875–7878)

      Dr. William C. McKee, Dr. Jay Agarwal, Prof. Dr. Henry F. Schaefer III and Prof. Dr. Paul von R. Schleyer

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403314

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      C(CH3)5+ is the first example of a five-coordinate carbon atom bound only to separate (monodentate) carbon ligands. This species illustrates the limits of carbon bonding, exhibiting Lewis-violating “electron-deficient bonds” between the hypercoordinate carbon and its methyl groups. Though not kinetically persistent under standard laboratory conditions, its dissociation activation barriers may permit C(CH3)5+ fleeting existence near 0 K.

    30. Solubility Determination

      Predicting the Relative Solubilities of Racemic and Enantiopure Crystals by Density-Functional Theory (pages 7879–7882)

      Dr. Alberto Otero-de-la-Roza, Blessing Huynh Cao, Ivy K. Price, Prof. Dr. Jason E. Hein and Prof. Dr. Erin R. Johnson

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403541

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      Solubility forecasting: Using a simple thermodynamic model and first-principles density-functional calculations, it is possible to predict the difference in solubility between the enantiopure and racemic solid phases. This approach uses dispersion-corrected density functionals and on average it is capable of accurately predicting the solution-phase enantiomeric excess to within about 10 % of experimental measurements (see picture).

    31. Enantioselectivity

      Chemical Kinetic Resolution of Unprotected β-Substituted β-Amino Acids Using Recyclable Chiral Ligands (pages 7883–7886)

      Shengbin Zhou, Dr. Jiang Wang, Xia Chen, Dr. José Luis Aceña, Prof. Dr. Vadim A. Soloshonok and Prof. Dr. Hong Liu

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201403556

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      The nick of time: A chemical method for resolution of unprotected β-amino acids rac-1 was developed through enantioselective formation and disassembly of nickel(II) complexes to deliver the target β-substituted β-amino acids in good yields and excellent enantioselectivity. The chiral ligands are inexpensive and can be quantitatively recycled. The procedure was used for the preparation of anti-diabetic drug sitagliptin.

    32. Plasmonic Photoelectrochemistry

      Prolonged Hot Electron Dynamics in Plasmonic-Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis (pages 7887–7891)

      Joseph S. DuChene, Brendan C. Sweeny, Dr. Aaron C. Johnston-Peck, Dr. Dong Su, Dr. Eric A. Stach and Prof. Dr. Wei David Wei

      Article first published online: 11 JUN 2014 | DOI: 10.1002/anie.201404259

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      Harvesting hot electrons: Plasmon-mediated electron transfer (PMET) in plasmonic (Au/TiO2) photoanodes provides a unique pathway for procuring excited-state electrons that exhibit lifetimes commensurate with the prolonged timescales required for solar photochemistry. These long-lived electrons were harnessed for visible-light-driven hydrogen evolution from water (see picture).

    33. Homogeneous Catalysis | Hot Paper

      Broad-Spectrum Catalysts for the Ambient Temperature Anti-Markovnikov Hydration of Alkynes (pages 7892–7895)

      Dr. Le Li, Mingshuo Zeng and Dr. Seth B. Herzon

      Article first published online: 25 JUN 2014 | DOI: 10.1002/anie.201404320

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      Alkyne hydration: Half-sandwich ruthenium complexes derived from 5,5′-bis(trifluoromethyl)-2,2′-bipyridine show a high activity for the anti-Markovnikov hydration of terminal alkynes (see picture). A wide array of alkynes are efficiently hydrated to aldehydes using 2 mol % metal loadings at 25 °C within 8–24 h.

    34. C[BOND]H Activation

      Asymmetric Synthesis of Isoindolones by Chiral Cyclopentadienyl-Rhodium(III)-Catalyzed C[BOND]H Functionalizations (pages 7896–7899)

      Baihua Ye and Prof. Dr. Nicolai Cramer

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201404895

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      Heterocycle synthesis: Chiral isoindolones are obtained by rhodium(III)-catalyzed enantioselective reactions of aryl hydroxamates with alkyl-substituted diazo esters through C[BOND]H functionalization under mild conditions. Chiral cyclopentadienyl ligands with a biaryl backbone lead to excellent enantioselectivities.

    35. Metalloenzyme Design | Hot Paper

      A De Novo Designed Metalloenzyme for the Hydration of CO2 (pages 7900–7903)

      Dr. Virginia M. Cangelosi, Dr. Aniruddha Deb, Prof. James E. Penner-Hahn and Prof. Vincent L. Pecoraro

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201404925

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      Chasing down the cheetah: A synthetic metalloenzyme was created that is capable of catalyzing the hydration of carbon dioxide with an efficiency within 1400-fold of carbonic anhydrase II, one of the most efficient enzymes known. This designed zinc enzyme performs better than small-molecule models of carbonic anhydrase. Picture: Zn purple, N dark blue, O red, C cyan.

    36. Gold Catalysis

      Gold-Catalyzed Diastereoselective Cycloisomerization of Alkylidene-Cyclopropane-Bearing 1,6-Diynes (pages 7904–7907)

      Dr. Hongchao Zheng, Laura L. Adduci, Dr. Ryan J. Felix and Prof. Dr. Michel R. Gagné

      Article first published online: 11 JUN 2014 | DOI: 10.1002/anie.201405147

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      When gold met alkylidenecyclopropane: Cationic gold catalysts can mediate the highly exothermic (≈60 kcal mol−1) cycloisomerization of 1,6-diynes bearing an alkylidene cyclopropane moiety. This diastereoselective methodology efficiently generates 1,2-trimethylenenorbornanes, an important building block for abiotic targets and sesquiterpene natural products. DCE=1,2-dichloroethane, Tf=trifluoromethanesulfonyl, Tol=Tolyl.

    37. Carboiodination

      Additive Effects in the Palladium-Catalyzed Carboiodination of Chiral N-Allyl Carboxamides (pages 7908–7912)

      David A. Petrone, Hyung Yoon, Dr. Harald Weinstabl and Prof. Dr. Mark Lautens

      Article first published online: 10 JUN 2014 | DOI: 10.1002/anie.201404007

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      A-mean combination: A general and efficient synthesis of chiral dihydroisoquinolinones by a highly diastereoselective Pd0-catalyzed carboiodination is reported. As an additive, the bulky tertiary amine base PMP (1,2,2,6,6-pentamethylpiperidine) is presumed to act as a weakly coordinating ligand, leading to a significant and general increase in diastereoselectivity. The utility of the method was applied to the asymmetric formal synthesis of (+)-corynoline.

    38. Organic Azides

      The Synthesis of α-Azidoesters and Geminal Triazides (pages 7913–7917)

      Dr. Philipp Klahn, Hellmuth Erhardt, Dr. Andreas Kotthaus and Prof. Dr. Stefan F. Kirsch

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201402433

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      Either/or: Geminal triazides are rapidly constructed with broad scope by the use of oxocarboxylic acids, iodomethyl ketones, or terminal olefins as starting substrates in oxidative azidations with a mild derivative of 2-iodoxybenzoic acid and sodium azide. Along with this little-studied class of organic azides, α-azidoesters were also synthesized.

    39. C[BOND]H Activation

      A 2,6-Bis(phenylamino)pyridinato Titanium Catalyst for the Highly Regioselective Hydroaminoalkylation of Styrenes and 1,3-Butadienes (pages 7918–7922)

      Jaika Dörfler, Till Preuß, Alexandra Schischko, Dr. Marc Schmidtmann and Prof. Dr. Sven Doye

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201403203

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      Linear progress: A new Ti complex with 2,6-bis(phenylamino)pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.

    40. Asymmetric Catalysis

      Brønsted Acid Catalyzed, Conjugate Addition of β-Dicarbonyls to In Situ Generated ortho-Quinone Methides—Enantioselective Synthesis of 4-Aryl-4H-Chromenes (pages 7923–7927)

      M. Sc. Osama El-Sepelgy, M. Sc. Stefan Haseloff, Dr. Santosh Kumar Alamsetti and Prof. Dr. Christoph Schneider

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201403573

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      Chiral phosphoric acids permit the in situ generation of hydrogen-bonded ortho-quinone methides which react with β-diketones and β-keto esters with excellent enantioselectivity and furnish valuable 4-aryl-4H-chromenes and related heterocycles upon subsequent cyclodehydration. These observations extend the substrate scope of enantioselective phosphoric acid catalysis towards an important additional class of compounds.

    41. Regioselective Metalations

      New In Situ Trapping Metalations of Functionalized Arenes and Heteroarenes with TMPLi in the Presence of ZnCl2 and Other Metal Salts (pages 7928–7932)

      M. Sc. Annette Frischmuth, Dr. Maitane Fernández, M. Sc. Nadja M. Barl, M. Sc. Florian Achrainer, Prof. Dr. Hendrik Zipse, Dr. Guillaume Berionni, Prof. Dr. Herbert Mayr, Prof. Dr. Konstantin Karaghiosoff and Prof. Dr. Paul Knochel

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201403688

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      Fast, faster, the fastest: Aromatic and heterocyclic substrates, when treated with TMPLi (TMP=2,2,6,6-tetramethylpiperidyl), undergo a kinetic lithiation and then a transmetalation with a metal salt such as MgCl2, ZnCl2, or CuCN. This allows an expedited metalation of sensitive pyridines bearing a nitro, ester, or cyano group and allows the preparation of kinetic regioisomers of functionalized aromatic compounds or heterocycles.

    42. Flow Metalation

      Continuous Flow Magnesiation of Functionalized Heterocycles and Acrylates with TMPMgCl⋅LiCl (pages 7933–7937)

      Dr. Trine P. Petersen, Matthias R. Becker and Prof. Dr. Paul Knochel

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404221

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      Go with the flow: Flow conditions allow a practical metalation of functionalized heterocycles and various acrylates in the presence of the base TMPMgCl⋅LiCl (TMP=2,2,6,6-tetramethylpiperidyl). More convenient temperatures and very fast reaction times can usually be achieved by applying the flow conditions. Sensitive acrylic derivatives can be magnesiated under flow conditions. Furthermore, the flow reactions are readily scalable without further optimization.

    43. Host–Guest Chemistry

      Mechanism of Host–Guest Complex Formation and Identification of Intermediates through NMR Titration and Diffusion NMR Spectroscopy (pages 7938–7942)

      M. Sc. Jan-Hendrik Lamm, B. Sc. Philipp Niermeier, Dr. Andreas Mix, Dr. Jasmin Chmiel, Beate Neumann, Dr. Hans-Georg Stammler and Prof. Dr. Norbert W. Mitzel

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201402145

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      Dynamic host–guest complexation was studied using a new combination of NMR titration and diffusion NMR experiments. The host is the bidentate 1,8-bis[(diethylgallanyl)ethynyl]anthracene, the guests are pyrimidine and pyridine. The analysis of the diffusion NMR experiments requires tailor-made reference compounds of the same shape for comparison.

    44. Metalloid Clusters

      The Intermetalloid Cluster [(Cp*AlCu)6H4], Embedding a Cu6 Core Inside an Octahedral Al6 Shell: Molecular Models of Hume–Rothery Nanophases (pages 7943–7947)

      Dr. Chelladurai Ganesamoorthy, M. Sc. Jana Weßing, M. Sc. Clarissa Kroll, Dr. Rüdiger W. Seidel, Dr. Christian Gemel and Prof. Dr. Roland A. Fischer

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201402149

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      Aluminum–copper cluster: The novel intermetallic cluster [(Cp*AlCu)6H4] was selectively obtained from the reaction of [Cp*Al]4 and [Ph3PCuH]6. The stronger affinity of Cp*Al towards Cu sweeps the phosphine ligands from the hydride derivative and furnishes an octahedral Al6 cage to encapsulate the Cu6 core. The hydrido cluster M12H4 reacts with benzonitrile to give the stoichiometric insertion product [(Cp*AlCu)6H3(N=CHPh)].

    45. Biomolecule Interaction Analysis

      Thermophoresis in Nanoliter Droplets to Quantify Aptamer Binding (pages 7948–7951)

      Susanne A. I. Seidel, Niklas A. Markwardt, Simon A. Lanzmich and Prof. Dieter Braun

      Article first published online: 4 JUN 2014 | DOI: 10.1002/anie.201402514

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      In 10 nL droplets, AMP-aptamer affinity, cooperativity, and buffer dependence were quantified by thermophoresis. Compared to established capillary measurements, sample consumption was cut down by a factor of 50. In locally heated nL samples, temperature, Marangoni flow, and concentration were analyzed by fluorescence microscopy and numerical simulation. Miniaturization and the 1536-well plate format make the method high-throughput and automation friendly.

    46. Guided Covalent Networks

      Substrate Templating Guides the Photoinduced Reaction of C60 on Calcite (pages 7952–7955)

      Robert Lindner, Dr. Philipp Rahe, Dr. Markus Kittelmann, Prof. Dr. André Gourdon, Dr. Ralf Bechstein and Prof. Dr. Angelika Kühnle

      Article first published online: 1 APR 2014 | DOI: 10.1002/anie.201309128

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      Reactions on insulators: C60 fullerenes undergo a photochemical reaction on calcite, a bulk insulator. The irradiated structures are investigated by non-contact atomic force microscopy. Domains of covalently linked molecules form along specific substrate directions. The observed directional reaction is readily explained by a model based on lattice mismatch minimization.

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