Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 36

September 1, 2014

Volume 53, Issue 36

Pages 9391–9673

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry (Angew. Chem. Int. Ed. 36/2014) (page 9391)

      Dr. Jiajia Dong, Dr. Larissa Krasnova, Prof. M. G. Finn and Prof. K. Barry Sharpless

      Version of Record online: 28 AUG 2014 | DOI: 10.1002/anie.201401157

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      A completely new click chemistry is described by K. B. Sharpless, M. G. Finn, and co-workers in their Review on page 9430 ff. The robust bond between SVI and F atoms (such as in the gas SO2F2 and Michael acceptor HC[DOUBLE BOND]CHSO2F) can be specifically activated by proton (often in the form of the bifluoride ion, HF2) or silicon centers (e.g. an aryl silyl ether) to create S–heteroatom linkages of surprising stability. Applications of this click 2.0 method to the synthesis of small molecules or polymers (see the Communication by K. B. Sharpless, V. V. Fokin et al. on page 9466 ff.), and the modification of biomolecules—each represented at the periphery of the image—are discussed.

    2. You have free access to this content
      Inside Cover: Syntheses, Structures, and Reactivities of Two Chalcogen-Stabilized Carbones (Angew. Chem. Int. Ed. 36/2014) (page 9392)

      Tomohito Morosaki, Tsubasa Suzuki, Dr. Wei-Wei Wang, Prof. Shigeru Nagase and Prof. Takayoshi Fujii

      Version of Record online: 30 JUN 2014 | DOI: 10.1002/anie.201406155

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      New carbones of the type Ph2E[RIGHTWARDS ARROW]C[LEFTWARDS ARROW]SPh2(NMe) (E=S or Se) were synthesized and characterized. T. Fujii et al. show in their Communication on page 9569 ff. that the double protonation of Ph2Se[RIGHTWARDS ARROW]C[LEFTWARDS ARROW]SPh2(NMe) gives a dication, whereas a C-metalated trication is obtained with silver(I). These reactions constitute the first experimental evidence for a carbodichalcogenurane behaving as a four-electron donor ligand.

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      Inside Back Cover: Development of a 18F-Labeled Tetrazine with Favorable Pharmacokinetics for Bioorthogonal PET Imaging (Angew. Chem. Int. Ed. 36/2014) (page 9675)

      Christoph Denk, Dennis Svatunek, Dr. Thomas Filip, Dr. Thomas Wanek, Dr. Daniel Lumpi, Prof. Johannes Fröhlich, Priv.-Doz. Dr. Claudia Kuntner and Dr. Hannes Mikula

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201406154

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      Bioorthogonal PET probes serve as highly valuable tools in the field of pretargeted molecular imaging. In their Communication on page 9655 ff., H. Mikula, C. Kuntner, and co-workers describe the development, synthesis, and characterization of a low-molecular-weight 18F-labeled tetrazine derivative that can be used for bioorthogonal PET imaging of dienophile-tagged (bio)molecules through the application of in vivo chemistry.

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      Back Cover: Simultaneous Assessment of Kinetic, Site-Specific, and Structural Aspects of Enzymatic Protein Phosphorylation (Angew. Chem. Int. Ed. 36/2014) (page 9676)

      Michiel van de Waterbeemd, Philip Lössl, Dr. Violette Gautier, Fabio Marino, Dr. Masami Yamashita, Prof. Dr. Elena Conti, Dr. Arjen Scholten and Prof. Dr. Albert J. R. Heck

      Version of Record online: 10 JUL 2014 | DOI: 10.1002/anie.201406162

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      Multiple aspects of protein phosphorylation can be addressed simultaneously by an analytical method described by A. J. R. Heck and co-workers in their Communication on page 9660 ff. Their approach integrates native and bottom-up mass spectrometry and provides insight into the site specificity, kinetics, and structural effects of this biochemical process.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. You have free access to this content
      Frontispiece: A Tandem In Situ Peptide Cyclization through Trifluoroacetic Acid Cleavage

      Dr. Koushik Chandra, Dr. Tapta Kanchan Roy, Dr. Deborah E. Shalev, Prof. Abraham Loyter, Prof. Chaim Gilon, Prof. R. Benny Gerber and Prof. Assaf Friedler

      Version of Record online: 28 AUG 2014 | DOI: 10.1002/anie.201483671

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      Tandem Peptide Cyclization A. Friedler et al. describe in their Communication on page 9450 ff. a tandem strategy involving in situ deprotection, cyclization, and trifluoroacetic acid cleavage for the solid-phase cyclization of peptides under highly acidic conditions.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Mohammad K. Nazeeruddin (page 9416)

      Version of Record online: 9 MAY 2014 | DOI: 10.1002/anie.201403995

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      “If I were not a scientist, I would be a businessman. I can never resist the taste of success. …” This and more about Mohammad K. Nazeeruddin can be found on page 9419.

  6. News

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

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

      Chemistry in Stereo: The 49th Bürgenstock Conference (pages 9418–9420)

      Dr. Tanja Gulder and Prof. Dr. Tobias A. M. Gulder

      Version of Record online: 5 AUG 2014 | DOI: 10.1002/anie.201406309

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  8. Book Review

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Life at the Speed of Light. From the Double Helix to the Dawn of Digital Life. By J. Craig Venter. (pages 9421–9422)

      Nediljko Budisa

      Version of Record online: 11 AUG 2014 | DOI: 10.1002/anie.201405385

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      Viking, New York, 2013. 240 pp., hardcover, € 19.60.—ISBN 978-0670025404

  9. Highlight

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. C–H Activation

      Functionalization of Remote C[BOND]H Bonds: Expanding the Frontier (pages 9426–9428)

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

      Version of Record online: 27 JUL 2014 | DOI: 10.1002/anie.201405714

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

  10. Review

    1. Top of page
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    4. Graphical Abstract
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    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Click Chemistry

      Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry (pages 9430–9448)

      Dr. Jiajia Dong, Dr. Larissa Krasnova, Prof. M. G. Finn and Prof. K. Barry Sharpless

      Version of Record online: 11 AUG 2014 | DOI: 10.1002/anie.201309399

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      Old chemistry in new glory: Sulfonyl fluoride exchange (SuFEx) forges rugged inorganic links between carbon centers. Like most click reactions, it is an old process now improved to allow the underappreciated sulfate connection to be made for a variety of purposes. The various exchange events uniquely enabled by the use of fluoride are highlighted here in orange.

  11. Communications

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

      A Tandem In Situ Peptide Cyclization through Trifluoroacetic Acid Cleavage (pages 9450–9455)

      Dr. Koushik Chandra, Dr. Tapta Kanchan Roy, Dr. Deborah E. Shalev, Prof. Abraham Loyter, Prof. Chaim Gilon, Prof. R. Benny Gerber and Prof. Assaf Friedler

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201402789

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      A new approach for solid-phase peptide cyclization under highly acidic conditions involves tandem in situ deprotection, cyclization, and trifluoroacetic acid cleavage (see scheme). The cyclization occurs between a lysine side chain and a succinic acid derivative at the peptide N-terminus and proceeds via a highly active succinimide intermediate, which was isolated and characterized.

    2. Rotational Intergrowth

      On the Rotational Intergrowth of Hierarchical FAU/EMT Zeolites (pages 9456–9461)

      Maryam Khaleel, Andrew J. Wagner, Prof. K. Andre Mkhoyan and Prof. Michael Tsapatsis

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201402024

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      Atypical morphology: Hierarchical faujasite is identified as an intergrowth of FAU and EMT. It is proposed that, under the appropriate growth conditions of faceting and branching, this intergrowth with a very small fraction of EMT, not detectable by XRD, leads to the repetitively branched morphology of faujasite.

    3. Synthetic Methods

      Catalytic Enantioselective Carboannulation with Allylsilanes (pages 9462–9465)

      Nicolas R. Ball-Jones, Dr. Joseph J. Badillo, Ngon T. Tran and Prof. Annaliese K. Franz

      Version of Record online: 13 JUL 2014 | DOI: 10.1002/anie.201403607

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      It's a trap: The catalytic asymmetric carboannulation of alkylidene oxindole, coumarin, and malonate substrates with allylsilanes in the presence of a ScIII/BArF/indapybox catalyst affords functionalized cyclopentanes containing a quaternary carbon center with high stereoselectivity. Enantioselective allylation and asymmetric lactone formation by trapping of the β-silyl carbocation are also presented.

    4. Sulfuryl-Based Click Chemistry | Hot Paper

      SuFEx-Based Synthesis of Polysulfates (pages 9466–9470)

      Jiajia Dong, K. Barry Sharpless, Luke Kwisnek, James S. Oakdale and Valery V. Fokin

      Version of Record online: 5 AUG 2014 | DOI: 10.1002/anie.201403758

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      High-molecular-weight polysulfates are readily formed from aromatic bis(silyl ethers) and bis(fluorosulfates) in the presence of a base catalyst. The polymers were obtained in nearly quantitative yield under neat conditions, they are more resistant to chemical degradation than their polycarbonate analogues and exhibit excellent mechanical, optical, and oxygen-barrier properties. BPA=bisphenol A.

    5. Cooperative Biosensors

      Using the Population-Shift Mechanism to Rationally Introduce “Hill-type” Cooperativity into a Normally Non-Cooperative Receptor (pages 9471–9475)

      Anna J. Simon, Prof. Dr. Alexis Vallée-Bélisle, Prof. Dr. Francesco Ricci, Dr. Herschel M. Watkins and Prof. Dr. Kevin W. Plaxco

      Version of Record online: 11 JUL 2014 | DOI: 10.1002/anie.201403777

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      Natural bioreceptors use cooperativity to improve their sensitivity to subtle changes in ligand concentration. This useful property was rationally engineered into a normally non-cooperative biosensor, significantly enhancing its responsiveness (see picture). The ability to rationally engineer cooperativity should prove useful in applications such as biosensors, molecular logics, and responsive materials.

    6. Cyclophanes

      Electron Delocalization in a Rigid Cofacial Naphthalene-1,8:4,5-bis(dicarboximide) Dimer (pages 9476–9481)

      Yilei Wu, Dr. Marco Frasconi, Daniel M. Gardner, Dr. Paul R. McGonigal, Dr. Severin T. Schneebeli, Prof. Michael R. Wasielewski and Prof. J. Fraser Stoddart

      Version of Record online: 10 JUL 2014 | DOI: 10.1002/anie.201403816

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      Two are better than one: A doubly-bridged naphthalene diimide (NDI) cyclophane has been synthesized. It shows efficient π-orbital overlap between two rigid cofacial NDI units. The resulting through-space electronic delocalization in the neutral as well as reduced states induces emergent photophysical, electrochemical, and magnetic properties both in solution and in the solid phase.

    7. Methane Conversion

      Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl2O4 Cluster Anions (pages 9482–9486)

      Dr. Yan-Xia Zhao, Zi-Yu Li, Zhen Yuan, Dr. Xiao-Na Li and Prof. Dr. Sheng-Gui He

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201403953

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      One atom is enough: The negatively charged oxide cluster PtAl2O4 is an active species in thermal methane conversion. The single platinum atom activates methane and delivers two hydrogen atoms to the “oxide support” Al2O4. Methane is then transformed to formaldehyde with a high selectivity.

    8. Electroactive Cell Surfaces

      Cell-Surface Engineering by a Conjugation-and-Release Approach Based on the Formation and Cleavage of Oxime Linkages upon Mild Electrochemical Oxidation and Reduction (pages 9487–9492)

      Abigail Pulsipher, Debjit Dutta, Wei Luo and Prof. Muhammad N. Yousaf

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201404099

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      Rewired for assembly on demand: Cell surfaces were tailored with bioorthogonal switchable hydroquinone groups by liposome–cell fusion for chemoselective conjugation with aminooxy-tethered cells by mild electrochemical oxidation and release by electrochemical reduction (see scheme). The modulation of cell–cell interactions in this way enabled the generation of 3D tissue structures.

    9. Catalyst Stability

      Nanoparticle Growth in Supported Nickel Catalysts during Methanation Reaction—Larger is Better (pages 9493–9497)

      Peter Munnik, Marjolein E. Z. Velthoen, Petra E. de Jongh, Krijn P. de Jong and Cedric J. Gommes

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201404103

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      Mind the breakage: The conversion of CO and H2 to CH4 over Ni catalysts suffers from particle growth through [Ni(CO)4]-mediated Ostwald ripening. By varying the size and distance of the Ni particles, the size was found to be key: Small 3–4 nm particles grow to large inactive particles, breaking the pore structure of the silica support, while medium 8–9 nm particles remain confined by the pores resulting in stable catalysts.

    10. Lithium-Ion Batteries | Very Important Paper

      In Situ Quantification and Visualization of Lithium Transport with Neutrons (pages 9498–9502)

      Danny X. Liu, Jinghui Wang, Ke Pan, Dr. Jie Qiu, Prof. Marcello Canova, Prof. Lei R. Cao and Prof. Anne C. Co

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201404197

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      An in-depth study: In situ neutron depth profiling has been demonstrated to provide temporal and spatial measurement of Li concentration and visualization of its transposition upon charging and discharging of a Li-ion cell (see picture). The delithiation process shows the removal of Li near the surface, which leads to a decreased coulombic efficiency.

    11. Metal-Free Catalysis

      High-Rate Oxygen Electroreduction over Graphitic-N Species Exposed on 3D Hierarchically Porous Nitrogen-Doped Carbons (pages 9503–9507)

      Wenhui He, Chunhuan Jiang, Jiabo Wang and Prof. Lehui Lu

      Version of Record online: 10 JUL 2014 | DOI: 10.1002/anie.201404333

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      Spotlighting nitrogen: Preferential exposure of graphitic-N species (GNs) on the surface of bi-continuous N-doped carbon (NC) films that feature hierarchically porous frameworks has been achieved. This unique design was used to identify the catalytic nature of GNs which paves the way to developing highly active metal-free NC electrocatalysts for oxygen reduction.

    12. Second Messenger

      Synthesis of Densely Phosphorylated Bis-1,5-Diphospho-myo-Inositol Tetrakisphosphate and its Enantiomer by Bidirectional P-Anhydride Formation (pages 9508–9511)

      Samanta Capolicchio, Dr. Huanchen Wang, Divyeshsinh T. Thakor, Dr. Stephen B. Shears and Dr. Henning J. Jessen

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201404398

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      Fully charged: Highly charged bis-diphosphoinositol tetrakisphosphates can be prepared in enantiomerically pure form. These synthetically challenging molecules have the most congested 3D array of phosphates known. The absolute configuration of the two enantiomers is shown by X-ray analysis of the two compounds individually soaked into crystals of the kinase domain of human diphosphoinositol pentakisphosphate kinase 2 (PPIP5K2KD).

    13. Heterogeneous Catalysis

      Highly Efficient “On Water” Catalyst-Free Nucleophilic Addition Reactions Using Difluoroenoxysilanes: Dramatic Fluorine Effects (pages 9512–9516)

      Jin-Sheng Yu, Yun-Lin Liu, Jing Tang, Prof. Dr. Xin Wang and Prof. Dr. Jian Zhou

      Version of Record online: 17 JUL 2014 | DOI: 10.1002/anie.201404432

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      It's on! The C[BOND]F⋅⋅⋅H[BOND]O interactions between suitably fluorinated nucleophiles and a hydrogen-bond network at the phase boundary of an oil droplet facilitate “on water” catalyst-free reactions. Accordingly, the title reaction of difluoroenoxysilanes with aldehydes, activated ketones, and isatylidene malononitriles was developed, thus leading to α,α-difluoro-β-hydroxy ketones and quaternary oxindoles.

    14. Doped Ceria | Hot Paper

      Defect Chemistry of Singly and Doubly Doped Ceria: Correlation between Ion Transport and Energetics (pages 9517–9521)

      Dr. Salih Buyukkilic, Prof. Sangtae Kim and Prof. Alexandra Navrotsky

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201404618

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      A unique correlation: The correlation between the energetics and the ionic conductivity, σi, of ceria that was singly or doubly doped with neodymia and samaria has now also been confirmed for high temperatures. The maximum formation enthalpy of the oxide solid solution, ΔHf,ox, coincides with the maximum σi at/near dopant fractions of 0.10, 0.15, and 0.20 in Ce1−xNdxO2−0.5x, Ce1−xSmxO2−0.5x, and Ce1−xSm0.5xNd0.5xO2−0.5x, respectively.

    15. DNA Analogues

      Synthesis of Triazole-linked Homonucleoside Polymers through Topochemical Azide–Alkyne Cycloaddition (pages 9522–9525)

      Atchutarao Pathigoolla and Prof. Dr. Kana M. Sureshan

      Version of Record online: 13 JUL 2014 | DOI: 10.1002/anie.201404797

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      Crystals go click: Modified DNA analogues are attractive materials for applications in many fields, however, the synthesis of DNA analogues by conventional methods is difficult owing to poor yield and efficiency and tedious purification. A highly homogeneous, enzyme-stable, crystalline ssDNA analogue was synthesized regiospecifically in quantitative yield through single-crystal-to-single-crystal azide–alkyne cycloaddition polymerization of a modified nucleoside.

    16. Functional Materials

      Self-Healable Electrically Conducting Wires for Wearable Microelectronics (pages 9526–9531)

      Hao Sun, Xiao You, Yishu Jiang, Guozhen Guan, Xin Fang, Jue Deng, Peining Chen, Dr. Yongfeng Luo and Prof. Huisheng Peng

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201405145

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      Wires with a will to survive: Self-healable conducting wires were developed by coating electrically conducting carbon nanotubes on the surface of polymer fibers. The wires were used to fabricate wire-shaped supercapacitors, whose high specific capacitance of 140.0 F g−1 or 1.34 mF cm−1 was restored after breakage to 92 % by self-healing.

    17. Nanoparticle Adsorption

      Langmuir Analysis of Nanoparticle Polyvalency in DNA-Mediated Adsorption (pages 9532–9538)

      Matthew N. O'Brien, Dr. Boya Radha, Dr. Keith A. Brown, Matthew R. Jones and Prof. Chad A. Mirkin

      Version of Record online: 13 JUL 2014 | DOI: 10.1002/anie.201405317

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      Stuck on Au: A model system is defined that allows the quantification of nanoparticle adsorption energy under conditions that satisfy the assumptions of the Langmuir adsorption model. This advance could enable fundamental studies of nanoparticles relating to adsorption chemistry, biological processes, and materials by design.

    18. Natural Products

      Total Synthesis of Gracilamine (pages 9539–9543)

      Yingbo Shi, Baochao Yang, Shujun Cai and Prof. Dr. Shuanhu Gao

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201405418

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      Simple building blocks were employed in the total synthesis of gracilamine, a pentacyclic Amaryllidaceae alkaloid. The synthesis features a mild photo-Nazarov reaction, intramolecular 1,4-addition, and an intramolecular Mannich reaction. This strategy provides a novel approach to prepare gracilamine derivatives and structurally related natural products.

    19. Cancer Therapeutics

      A Multifunctional Nanomicelle for Real-Time Targeted Imaging and Precise Near-Infrared Cancer Therapy (pages 9544–9549)

      Jiangwei Tian, Dr. Lin Ding, Prof. Huangxian Ju, Dr. Yongchao Yang, Xilan Li, Prof. Zhen Shen, Dr. Zhi Zhu, Prof. Jun-Sheng Yu and Prof. Chaoyong James Yang

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405490

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      All in one: A lysosome-aimed multifunctional nanomicelle (Apt-TNP) was developed by integrating a target-cell-specific aptamer, a pH-activatable fluorescent probe, and a near-infrared photosensitizer. Apt-TNP enables simultaneous cancer imaging, photodynamic therapy, and real-time self-feedback of therapeutic efficacy.

    20. Tumor Imaging

      You have full text access to this OnlineOpen article
      CXCR4-Targeted and MMP-Responsive Iron Oxide Nanoparticles for Enhanced Magnetic Resonance Imaging (pages 9550–9554)

      Juan Gallo, Nazila Kamaly, Ioannis Lavdas, Elizabeth Stevens, Quang-De Nguyen, Marzena Wylezinska-Arridge, Eric O. Aboagye and Nicholas J. Long

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405442

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      Cleave and cluster: Iron oxide nanoparticles were produced that display azide (red) or alkyne (blue) groups masked by PEG-linked tumor-targeting peptides (green) that bind to the CXCR4 receptor. Matrix metalloproteinases (MMPs) in the tumor microenvironment specifically cleave the peptide linker at the base of the PEG moiety to expose the cross-reactive azide and alkyne groups. This leads to the assembly of clusters and thus to an enhancement of the MRI signal.

    21. Asymmetric Catalysis

      Enantioselective Formation of Cyano-Bearing All-Carbon Quaternary Stereocenters: Desymmetrization by Copper-Catalyzed N-Arylation (pages 9555–9559)

      Dr. Fengtao Zhou, Gui-Juan Cheng, Wenqiang Yang, Yan Long, Shasha Zhang, Prof. Dr. Yun-Dong Wu, Dr. Xinhao Zhang and Prof. Dr. Qian Cai

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405575

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      Playing center: An enantioselective formation of cyano-bearing all-carbon quaternary stereocenters in 1,2,3,4-tetrahydroquinolines and 2,3,4,5-tetrahydro-1H-benzo[b]azepines by the title reaction was developed. A cyano group at the prochiral center played a key role for the high enantioselectivity and worked as an important functional group for further transformations.

    22. Water Structuring | Hot Paper

      Charge Asymmetry at Aqueous Hydrophobic Interfaces and Hydration Shells (pages 9560–9563)

      Dr. Rüdiger Scheu, Blake M. Rankin, Yixing Chen, Dr. Kailash C. Jena, Prof. Dr. Dor Ben-Amotz and Prof. Dr. Sylvie Roke

      Version of Record online: 13 JUL 2014 | DOI: 10.1002/anie.201310266

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      Guilty as charged: Water is often modeled as a dielectric continuum, but the molecular structure of water is asymmetric. Two ions that have a virtually identical size, shape, and structure, but an opposite charge sign have been investigated to see whether charge makes a fundamental difference to water structuring. The spectroscopic data for the hydration and interface structures are found to be remarkably different for opposite charges.

    23. Single-Layer Materials

      Surface-Confined Single-Layer Covalent Organic Framework on Single-Layer Graphene Grown on Copper Foil (pages 9564–9568)

      Lirong Xu, Xin Zhou, Prof. Wei Quan Tian, Teng Gao, Yan Feng Zhang, Prof. Shengbin Lei and Prof. Zhong Fan Liu

      Version of Record online: 21 AUG 2014 | DOI: 10.1002/anie.201400273

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      Co-condensation between benzene-1,3,5-tricarbaldehyde and p-phenylenediamine on a graphene surface leads to a surface covalent organic framework (COF) with single-layer thickness. Strong coupling between the surface COF and graphene was confirmed by the significant mixing of states and the relatively large interaction energy revealed by STM and DFT simulation.

    24. Carbones

      Syntheses, Structures, and Reactivities of Two Chalcogen-Stabilized Carbones (pages 9569–9571)

      Tomohito Morosaki, Tsubasa Suzuki, Dr. Wei-Wei Wang, Prof. Shigeru Nagase and Prof. Takayoshi Fujii

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201404795

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      Carbodichalcogenuranes: New carbones of the type Ph2E[RIGHTWARDS ARROW]C[LEFTWARDS ARROW]SPh2(NMe) [E=S (1) or Se (2)] were synthesized and characterized. The carbone 2 can be used to generate a doubly protonated dication and a C-metalated trication with silver(I) and thus provide the first experimental proof of carbodichalcogenurane behaving as a four-electron donor ligand.

    25. Ruthenium Catalysis

      Ruthenium-Catalyzed Oxidative Transformations of Terminal Alkynes to Ketenes By Using Tethered Sulfoxides: Access to β-Lactams and Cyclobutanones (pages 9572–9576)

      Youliang Wang, Zhitong Zheng and Prof. Dr. Liming Zhang

      Version of Record online: 11 JUL 2014 | DOI: 10.1002/anie.201403796

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      Oxidant included: The oxidation of in situ generated Ru vinylidenes with the help of tethered sulfoxides results in the net transformation of terminal alkynes to valuable ketenes. They undergo characteristic ketene [2+2] cycloaddition reactions with tethered alkenes and external imines, yielding synthetically versatile bicyclic cyclobutanones and β-lactams.

    26. Nanostructures

      Self-Supported Cu3P Nanowire Arrays as an Integrated High-Performance Three-Dimensional Cathode for Generating Hydrogen from Water (pages 9577–9581)

      Dr. Jingqi Tian, Qian Liu, Ningyan Cheng, Prof. Abdullah M. Asiri and Prof. Xuping Sun

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201403842

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      Down to the wire: Self-supported Cu3P nanowire arrays on porous copper foam (Cu3P NW/CF) were derived from topotactic low-temperature phosphidation of its Cu(OH)2 NW/CF precursor. As an integrated hydrogen-evolving cathode, Cu3P NW/CF exhibits excellent catalytic activity and durability with nearly 100 % Faradaic efficiency in acidic aqueous electrolytes.

    27. Palladium Catalysis

      Palladium-Catalyzed Carbonylative α-Arylation of 2-Oxindoles with (Hetero)aryl Bromides: Efficient and Complementary Approach to 3-Acyl-2-oxindoles (pages 9582–9586)

      Zhong Lian, Stig D. Friis and Prof. Dr. Troels Skrydstrup

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201404217

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      Carbonylate it! 3-Acyl-2-oxindoles are directly obtained through an efficient Pd-catalyzed carbonylative α-arylation of 2-oxindoles with aryl and heteroaryl bromides. Only a mild base is required for the deprotonation and good to excellent yields are obtained even with heteroaromatic substrates.

    28. Kinetics

      Tunneling Assists the 1,2-Hydrogen Shift in N-Heterocyclic Carbenes (pages 9587–9591)

      Sharmistha Karmakar and Dr. Ayan Datta

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201404368

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      Tunnel vision: Reactions such as 1,2-hydrogen shifts in N-heterocyclic carbenes with small barriers are shown to exhibit exotic quantum mechanical phenomena such as nonclassical reflections at ambient experimental conditions. A small barrier also leads to smaller kinetic isotope effects because of efficient quantum mechanical tunneling of both H and D.

    29. Zeolites

      An Extra-Large-Pore Zeolite with Intersecting 18-, 12-, and 10-Membered Ring Channels (pages 9592–9596)

      Fei-Jian Chen, Prof. Yan Xu and Prof. Hong-Bin Du

      Version of Record online: 11 JUL 2014 | DOI: 10.1002/anie.201404608

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      Extra-large-pore molecular sieves: An extra-large-pore zeolite (NUD-1) was synthesized by using an approach based on supramolecular self-assemblies of small aromatic organic structure-directing cations (see picture). The zeolite possesses interconnecting 18-, 12-, and 10-membered ring channels, built from the same building units as those of the zeolites ITQ-33 and ITQ-44.

    30. Glycosides

      gem-Difluorocarbadisaccharides: Restoring the exo-Anomeric Effect (pages 9597–9602)

      Bixue Xu, Luca Unione, Dr. Joao Sardinha, Shaoping Wu, Prof. Mélanie Ethève-Quelquejeu, Prof. Amelia Pilar Rauter, Prof. Yves Blériot, Dr. Yongmin Zhang, Dr. Sonsoles Martín-Santamaría, Dr. Dolores Díaz, Prof. Jesus Jiménez-Barbero and Prof. Matthieu Sollogoub

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405008

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      Taking effect: The combination of chemical synthesis, NMR methods, and calculations show that it is possible to restore the anomeric effect for an acetal when replacing one of the oxygen atoms by a CF2 group. This result provides key findings as it strongly suggests the importance of the stereoelectronic component for the anomeric effect, and may open new avenues for sugar-based drug design.

    31. NHC Catalysis

      N-Heterocyclic-Carbene-Catalyzed Synthesis of 2-Aryl Indoles (pages 9603–9607)

      M. Todd Hovey, Dr. Christopher T. Check, Alexandra F. Sipher and Prof. Karl A. Scheidt

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201405035

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      Umpolung: N-heterocyclic carbene catalysis is used for the convergent and efficient transition-metal-free synthesis of 2-aryl-indoles. The interception of a highly reactive and transient aza-ortho-quinone methide by an acyl anion equivalent is central to this successful strategy. The reaction exhibits high yields and a wide scope, and it has been applied to a streamlined synthesis of a kinase inhibitor.

    32. O2 Activation

      Selective Ortho-Hydroxylation–Defluorination of 2-Fluorophenolates with a Bis(μ-oxo)dicopper(III) Species (pages 9608–9612)

      Joan Serrano-Plana, Dr. Isaac Garcia-Bosch, Dr. Ryosuke Miyake, Dr. Miquel Costas and Dr. Anna Company

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201405060

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      O in, F out: [CuIII2(μ-O)2(m-XYLMeAN)]2+ is a bis(μ-oxo)dicopper(III) species and promotes the electrophilic ortho-hydroxylation–defluorination of 2-fluorophenolates to give the corresponding catechols. Isotopic labeling shows that the incoming oxygen atom originates from the bis(μ-oxo) unit. Ortho-hydroxylation–defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine.

    33. Organo-Photocatalysis | Hot Paper

      Light-Driven Organocatalysis Using Inexpensive, Nontoxic Bi2O3 as the Photocatalyst (pages 9613–9616)

      Dr. Paola Riente, Alba Matas Adams, Dr. Josep Albero, Prof. Emilio Palomares and Prof. Miquel A. Pericàs

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201405118

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      Now it's bismuth time! The asymmetric intermolecular α-alkylation of aldehydes with α-bromocarbonyl compounds can be achieved under visible-light irradiation by combining the second-generation MacMillan catalyst and an inexpensive, nontoxic, and commercially available Bi2O3 powder. This reaction also proceeded with high efficiency when the reaction vial was exposed to the morning sunlight in Tarragona, Spain.

    34. Hypervalent Compounds

      The I[DOUBLE BOND]X (X=O,N,C) Double Bond in Hypervalent Iodine Compounds: Is it Real? (pages 9617–9621)

      Alexander S. Ivanov, Ivan A. Popov, Prof. Dr. Alexander I. Boldyrev and Prof. Dr. Viktor V. Zhdankin

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201405142

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      Singled out: The nature of the I[BOND]X (X=O, N, C) chemical bonding was examined and compared amongst different hypervalent iodine molecules. The common I[DOUBLE BOND]X representation is questioned by results of chemical bonding analyses which confirm the presence of I[RIGHTWARDS ARROW]O, I[RIGHTWARDS ARROW]N, and I[RIGHTWARDS ARROW]C single dative bonds in such compounds.

    35. Organo Cascade Reactions | Hot Paper

      Asymmetric Synthesis of Highly Substituted β-Lactones through Oxidative Carbene Catalysis with LiCl as Cooperative Lewis Acid (pages 9622–9626)

      Srikrishna Bera, Dr. Ramesh C. Samanta, Dr. Constantin G. Daniliuc and Prof. Dr. Armido Studer

      Version of Record online: 11 JUL 2014 | DOI: 10.1002/anie.201405200

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      Highly substituted β-lactones are generated by NHC catalysis of enals with β-diketones, β-ketoesters, and malonates bearing a β-oxyalkyl substituent at the α-position. LiCl acts as cooperative Lewis acid. The organocascade comprises two C[BOND]C bond formations and one C[BOND]O bond formation. Up to four contiguous stereogenic centers including two fully substituted stereocenters are formed with high diastereo- and enantioselectivity.

    36. C[BOND]N Coupling

      C[BOND]NH2 Bond Formation Mediated by Iridium Complexes (pages 9627–9631)

      Dipl.-Chem. Inmaculada Mena, Dr. Miguel A. Casado, Dr. Víctor Polo, Dr. Pilar García-Orduña, Prof. Fernando J. Lahoz and Prof. Luis A. Oro

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405237

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      Making C[BOND]NH2 bonds: [Ir[BOND]NH2] fragments can effect a nucleophilic attack to a coordinated olefin, thereby forming a C[BOND]NH2 bond under mild conditions. This reaction follows a bimolecular mechanism induced by the high nucleophilicity of the amido moiety. Alternatively, a discrete chloro complex is able to activate ammonia by forming a C[BOND]NH2 bond with a coordinated olefin.

    37. Asymmetric Synthesis | Hot Paper

      Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions (pages 9632–9636)

      Zhiyong Yu, Robert J. Ely and Prof. James P. Morken

      Version of Record online: 15 JUL 2014 | DOI: 10.1002/anie.201405455

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      Borylation-based synthesis: The development of a strategy for stereocontrol in catalytic diene hydroboration enables the synthesis of a critical building block for the assembly of (+)-discodermolide. Combined with asymmetric catalytic diboration, hydroformylation, and borylative aldehyde–diene coupling reactions, (+)-discodermolide could then be prepared from simple hydrocarbon-based building blocks.

    38. Metathesis

      Iodonium Metathesis Reactions (pages 9637–9639)

      Takahito Kasahara, Young Jin Jang, Léanne Racicot, Dimitrios Panagopoulos, Dr. Steven H. Liang and Prof. Dr. Marco A. Ciufolini

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201405594

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      Mixed diaryliodoniumtriflates are obtained through treatment of aryl iodides with diaryliodonium triflates. A possible mechanism for the metathesis reaction is proposed.

    39. Synthetic Methods

      Highly Enantioselective Rhodium(I)-Catalyzed Carbonyl Carboacylations Initiated by C[BOND]C Bond Activation (pages 9640–9644)

      Laetitia Souillart and Prof. Dr. Nicolai Cramer

      Version of Record online: 14 JUL 2014 | DOI: 10.1002/anie.201405834

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      Delivering the goods: Asymmetric carbonyl carboacylations of aldehydes and ketones provide access to functionalized bicyclic lactones. The rhodium(I)-catalyzed transformation is induced by an enantiotopic C[BOND]C bond activation of a cyclobutanone and the transient rhodacyclic adds across an appended carbonyl group to deliver the lactones in excellent enantioselectivities.

    40. Polymerization Catalysis

      Zirconium Allyl Complexes as Participants in Zirconocene-Catalyzed α-Olefin Polymerizations (pages 9645–9649)

      Dr. Dmitrii E. Babushkin, Dr. Valentina N. Panchenko and Prof. Dr. Hans-Herbert Brintzinger

      Version of Record online: 7 JUL 2014 | DOI: 10.1002/anie.201403673

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      A combination of UV/Vis and NMR spectrometric methods reveals that polymer-carrying cationic Zr allyl complexes derived by β-hydride and subsequent proton abstraction from a Zr polymeryl cation make up about 90 % of the catalyst content when 1-hexene is polymerized with a cationic ansa-zirconocene catalyst at 25 °C.

    41. C[BOND]H Activation

      The C[BOND]H Activation/1,3-Diyne Strategy: Highly Selective Direct Synthesis of Diverse Bisheterocycles by RhIII Catalysis (pages 9650–9654)

      Dr. Da-Gang Yu, Francisco de Azambuja, Tobias Gensch, Dr. Constantin G. Daniliuc and Prof. Dr. Frank Glorius

      Version of Record online: 1 JUL 2014 | DOI: 10.1002/anie.201403782

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      Di-verse: The use of the C[BOND]H activation/1,3-diyne general strategy allowed the challenges of selectivity (chemo-, regio-, and mono-/diannulation) to be overcome. This allowed direct construction of diverse polysubstituted bisheterocycles, which are highly important but difficult to access, through the formation of four strategic bonds with high efficiency and high selectivity.

    42. Bioorthogonal Imaging

      Development of a 18F-Labeled Tetrazine with Favorable Pharmacokinetics for Bioorthogonal PET Imaging (pages 9655–9659)

      Christoph Denk, Dennis Svatunek, Dr. Thomas Filip, Dr. Thomas Wanek, Dr. Daniel Lumpi, Prof. Johannes Fröhlich, Priv.-Doz. Dr. Claudia Kuntner and Dr. Hannes Mikula

      Version of Record online: 2 JUL 2014 | DOI: 10.1002/anie.201404277

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      In vivo click and PET it! A low-molecular-weight radiolabeled tetrazine derivative was prepared by direct [18F]-fluorination (see structure on the left in the figure). PET/MR imaging revealed fast and homogenous biodistribution including in the brain (right). PET/MR=positron emission tomography/magnetic resonance.

    43. Protein Mass Spectrometry

      Simultaneous Assessment of Kinetic, Site-Specific, and Structural Aspects of Enzymatic Protein Phosphorylation (pages 9660–9664)

      Michiel van de Waterbeemd, Philip Lössl, Dr. Violette Gautier, Fabio Marino, Dr. Masami Yamashita, Prof. Dr. Elena Conti, Dr. Arjen Scholten and Prof. Dr. Albert J. R. Heck

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201404637

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      Comprehensive monitoring of protein phosphorylation: Phosphate incorporation is a universal modification of cellular proteins with multiple functional implications. The combination of native and “bottom-up” mass spectrometry makes it possible to simultaneously visualize dynamic noncovalent protein interactions, identify phosphorylated amino acids, and quantify all occurring phospho-isoforms to generate kinetic data.

    44. Energetic Materials | Hot Paper

      Chlorine-Free Pyrotechnics: Copper(I) Iodide as a “Green” Blue-Light Emitter (pages 9665–9668)

      Prof. Dr. Thomas M. Klapötke, Dr. Magdalena Rusan and Dr. Jesse J. Sabatini

      Version of Record online: 9 JUL 2014 | DOI: 10.1002/anie.201405195

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      Out of the blue: A suitable blue-light-emitting pyrotechnic with low sensitivities to various ignition stimuli has been developed without the need to employ chlorine-containing materials. With copper(I) iodide proven as a suitable blue-light emitter in pyrotechnics, the risk of generating highly carcinogenic polychlorinated aromatic compounds during the combustion process is eliminated.

    45. Supramolecular Switches

      Photoresponsive Switches at Surfaces Based on Supramolecular Functionalization with Azobenzene–Oligoglycerol Conjugates (pages 9669–9673)

      Olaf Nachtigall, Dr. Christian Kördel, Leonhard H. Urner and Prof. Dr. Rainer Haag

      Version of Record online: 8 JUL 2014 | DOI: 10.1002/anie.201403331

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      The thermal and light-induced photoisomerization of bifunctional azobenzene–oligoglycerol conjugates was examined in solution and on supramolecularly functionalized gold nanoparticles and planar gold surfaces. The wettability of the functionalized gold surfaces could be reversibly switched with light. Thermal half-lives of Z-isomers were determined for different environments to provide information about the stability of the functional switches for further applications.

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