Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 30

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, Zeitschrift für Chemie

  1. News

  2. Communications

    1. Aerogels | Very Important Paper

      An Easy Way To Prepare Monolithic Inorganic Oxide Aerogels

      Dr. Lili Ren, Sumin Cui, Fengchao Cao and Qinghui Guo

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201406387

      Thumbnail image of graphical abstract

      Not cracking up: A drying method based on the sublimation of organic solvent allows the rapid synthesis of the monolithic inorganic oxide aerogels without cracks from wet gels. The method proceeds by endothermic evaporation of organic solvent at the outer surface followed by sublimation of solidified solvent (see picture).

    2. Thermodynamics

      Aligning Electronic and Protonic Energy Levels of Proton-Coupled Electron Transfer in Water Oxidation on Aqueous TiO2

      Dr. Jun Cheng, Dr. Xiandong Liu, Dr. John A. Kattirtzi, Dr. Joost VandeVondele and Prof.Dr. Michiel Sprik

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405648

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      Scheming: A scheme for computing the thermochemistry of proton-coupled electron transfer (PCET) reactions at interfaces is described. In analogy with electronic energy levels, an appealing concept of protonic energy levels is proposed to visualize the thermodynamics of PCET in a level diagram. This diagram helps to elucidate the electronic and protonic components of thermodynamic overpotentials in photocatalysis.

    3. Synthetic Methods

      Synthesis of Isocoumarins through Three-Component Couplings of Arynes, Terminal Alkynes, and Carbon Dioxide Catalyzed by an NHC–Copper Complex

      Dr. Woo-Jin Yoo, Thanh V. Q. Nguyen and Prof. Dr. Shū Kobayashi

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404692

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      A facile synthetic protocol to isocoumarins consists of a three-component coupling reaction between 1-alkynes, 2-(trimethylsilyl)aryl triflates, and CO2 (see scheme). The key to this reaction was the use of a versatile N-heterocyclic carbene/copper complex that was able to catalyze multiple transformations within the three-component reaction.

    4. Gold–Carbenoids

      Chemoselective Carbophilic Addition of α-Diazoesters through Ligand-Controlled Gold Catalysis

      Yumeng Xi, Yijin Su, Zhaoyuan Yu, Boliang Dong, Edward J. McClain, Prof. Yu Lan and Prof. Xiaodong Shi

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404946

      Thumbnail image of graphical abstract

      Carbocation or carbene? The chemoselective addition of arenes and 1,3-diketones to α-aryldiazoesters was achieved through ligand-controlled gold catalysis. The gold catalyst with electron-deficient phosphite as the ancillary ligand exclusively gave the carbophilic addition products, thus representing a new and efficient approach to form “carbophilic carbocations”, which selectively react with carbon nucleophiles.

    5. Heterogeneous Catalysis

      Niobium(V) Saponite Clay for the Catalytic Oxidative Abatement of Chemical Warfare Agents

      Dr. Fabio Carniato, Dr. Chiara Bisio, Dr. Rinaldo Psaro, Prof. Leonardo Marchese and Dr. Matteo Guidotti

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405134

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      Heterogeneous catalysis against chemical weapons: A bifunctional NbV-containing saponite clay was prepared and found to be an optimal catalyst for the oxidative abatement of chemical warfare agents (CWA). In comparison to parent samples and a conventional commercial decontamination powder, a remarkable activity and high selectivity were obtained for the oxidation of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature.

    6. Metal Deposition

      Sorption-Determined Deposition of Platinum on Well-Defined Platelike WO3

      Kasper Wenderich, Aram Klaassen, Dr. Igor Siretanu, Prof. Frieder Mugele and Prof. Guido Mul

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405274

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      Positioned for action: Understanding of the mechanism behind the structure-directed photodeposition of metals is highly relevant for the optimization of photocatalysts. The preferential deposition of Pt on WO3 was found to be the result of intrinsic surface-charge differences of specific facets, rather than of the illumination-induced preferred spatial separation of electrons and holes (see picture).

    7. Cancer Immunotherapy

      Targeting Human C-Type Lectin-Like Molecule-1 (CLL1) with a Bispecific Antibody for Immunotherapy of Acute Myeloid Leukemia

      Dr. Hua Lu, Dr. Quan Zhou, Vishal Deshmukh, Dr. Hardeep Phull, Dr. Jennifer Ma, Dr. Virginie Tardif, Dr. Rahul R. Naik, Dr. Claire Bouvard, Dr. Yong Zhang, Dr. Seihyun Choi, Dr. Brian R. Lawson, Dr. Shoutian Zhu, Dr. Chan Hyuk Kim and Dr. Peter G. Schultz

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201405353

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      A bispecific antibody, αCLL1-αCD3, was synthesized using a genetically encoded unnatural amino acid, and shown to recruit cytotoxic T cells to CLL1-positive cells. The reported results validate the clinical potential of CLL1 as an AML-specific antigen for the generation of bispecific antibodies for the treatment of acute myeloid leukemia (AML).

    8. Block Copolymer Membrane

      Self-Assembled Isoporous Block Copolymer Membranes with Tuned Pore Sizes

      Dr. Haizhou Yu, Dr. Xiaoyan Qiu, Prof. Suzana P. Nunes and Prof. Klaus-Viktor Peinemann

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404491

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      Golden pores: Membranes with tunable cylindrical pore diameters between 3 and 20 nm were manufactured and tested for nanoparticle separation and controlled delivery of proteins. The pore size was regulated by electroless gold deposition. The precise size discrimination, facile and scalable fabrication processes, and biocompatible characteristics favor potential uses in the purification of nanoscale materials and drug delivery.

    9. Peptide Antivirals | Hot Paper

      Cell-Penetrating, Dimeric α-Helical Peptides: Nanomolar Inhibitors of HIV-1 Transcription

      Sangmok Jang, Dr. Soonsil Hyun, Seoyeon Kim, Seonju Lee, Prof. Dr. Im-Soon Lee, Prof. Dr. Masanori Baba, Prof. Dr. Yan Lee and Prof. Dr. Jaehoon Yu

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404684

      Thumbnail image of graphical abstract

      Going viral: Nearly quantitative penetration into eukaryotic cells and effective inhibition of the elongation of the short hairpin RNA transcript TAR at low nanomolar concentrations has been achieved by using dimeric α-helical peptide bundles based on leucine (L) and lysine (K). The effective inhibition of HIV-1 replication strongly suggests that these dimers have strong potential as anti-HIV-1 drugs.

    10. Mesoporous Polymeric Catalyst

      A Nanospherical Ordered Mesoporous Lewis Acid Polymer for the Direct Glycosylation of Unprotected and Unactivated Sugars in Water

      Dr. Fang Zhang, Chao Liang, Xiaotao Wu and Prof. Dr. Hexing Li

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404353

      Thumbnail image of graphical abstract

      Xanthone glycosides from sugars: A novel nanospherical ordered mesoporous Lewis acid polymer was synthesized by functionalizing the mesoporous phenol-formaldehyde polymer with scandium triflate groups. The functionalized polymer showed good catalytic activity, selectivity, and recyclability in the C-glycosylation reaction between simple sugars and cyclohexane-1,3-dimedone in water.

    11. Enzyme Models

      Hexacoordinate Nickel(II)/(III) Complexes that Mimic the Catalytic Cycle of Nickel Superoxide Dismutase

      Sudip K. Chatterjee, Ram Chandra Maji, Suman Kumar Barman, Prof. Dr. Marilyn M. Olmstead and Dr. Apurba K. Patra

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404133

      Thumbnail image of graphical abstract

      Copy cat: Hexacoordinate nickel(II)/(III) complexes are prepared which mimic the catalytic cycle of nickel superoxide dismutase (NiSOD) by an outer-sphere electron-transfer mechanism. The complexes employ a bis-tridentate N2S donor carboxamide ligand, N-2-phenylthiophenyl-2′-pyridinecarboxamide (HLPh), and have been structurally characterized and their SOD activities examined.

    12. Batteries

      Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena

      M. Sc. Birte Jache and Dr. Philipp Adelhelm

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403734

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      In contrast to the general view, graphite can be used as an electrode material in sodium-ion batteries by taking advantage of the formation of ternary graphite intercalation compounds. The important features of this electrode reaction are the small irreversible capacity, the low overpotentials, and the superior cycle life. With a capacity close to 100 mAh g−1, the electrode is attractive for stationary applications.

    13. Bio-Nanomaterials

      Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

      Calum Kinnear, David Burnand, Dr. Martin J. D. Clift, Prof. Andreas F. M. Kilbinger, Prof. Barbara Rothen-Rutishauser and Prof. Alke Petri-Fink

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404100

      Thumbnail image of graphical abstract

      Polymer grafting: Gold nanorods can be functionalized with polyvinyl acetate, which hydrolyzes to polyvinyl alcohol. An aqueous dispersion of the resulting colloidally stable and nontoxic nanorods was tested by exposure to primary human blood monocyte derived macrophages.

  3. Minireviews

    1. Enantioselective Catalysis

      Catalytic Enantioselective C[BOND]H Functionalization of Alcohols by Redox-Triggered Carbonyl Addition: Borrowing Hydrogen, Returning Carbon

      John M. Ketcham, Inji Shin, T. Patrick Montgomery and Prof. Michael J. Krische

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403873

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      Borrowing with interest: The concept of exploiting alcohols and unsaturated reactants for the redox-triggered generation of nucleophile–electrophile pairs reinvents the chemistry of carbonyl addition, enabling a broad, new family of catalytic enantioselective C[BOND]C couplings.

  4. Communications

    1. Host–Guest Systems

      Activation Energies Control the Macroscopic Properties of Physically Cross-Linked Materials

      Dr. Eric A. Appel, Rebecca A. Forster, Dr. Alexandros Koutsioubas, Prof. Chris Toprakcioglu and Prof. Oren A. Scherman

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403192

      Thumbnail image of graphical abstract

      Supramolecular hydrogels were obtained by utilizing the host–guest interactions of the macrocycle cucurbit[8]uril (CB[8]) with various guest molecules. The mechanical strength of these materials is directly correlated to the energetic barrier of the dissociation of the CB[8] ternary complex cross-links, whereas the self-healing requires a low energetic barrier for complex association.

    2. Supported Nanoparticles | Very Important Paper

      Monitoring Morphology and Hydrogen Coverage of Nanometric Pt/γ-Al2O3 Particles by In Situ HERFD–XANES and Quantum Simulations

      Agnes Gorczyca, Dr. Virginie Moizan, Dr. Celine Chizallet, Dr. Olivier Proux, William Del Net, Eric Lahera, Dr. Jean-Louis Hazemann, Dr. Pascal Raybaud and Dr. Yves Joly

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201403585

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      Identifying the morphology of platinum nanoclusters supported on γ-alumina and the hydrogen coverage at a given temperature and hydrogen pressure is possible. The use of state-of-the-art methodologies combining high-resolution X-ray absorption near edge structure (XANES) in situ experiments, quantum molecular dynamics calculations, and XANES simulations gives unrivalled insights into catalyst characterization.

    3. Perovskite Solar Cells | Hot Paper

      A Fast Deposition-Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin-Film Solar Cells

      Manda Xiao, Dr. Fuzhi Huang, Wenchao Huang, Yasmina Dkhissi, Dr. Ye Zhu, Prof. Dr. Joanne Etheridge, Dr. Angus Gray-Weale, Prof. Dr. Udo Bach, Prof. Dr. Yi-Bing Cheng and Prof. Dr. Leone Spiccia

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405334

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      Fast and thin: Flat, uniform thin films of CH3NH3PbI3 perovskites have been produced by a fast, one-step procedure involving spin-coating of a DMF solution of CH3NH3PbI3 and immediate exposure to chlorobenzene to induce crystallization. Planar heterojunction solar cells made with these films gave a maximum power conversion efficiency of 16.2 %.

    4. Solar Cells | Very Important Paper

      Integrating Perovskite Solar Cells into a Flexible Fiber

      Longbin Qiu, Jue Deng, Xin Lu, Zhibin Yang and Prof. Huisheng Peng

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404973

      Thumbnail image of graphical abstract

      Wearable perovskite solar cells with a fiber structure are synthesized by continuously winding an aligned carbon nanotube (CNT) sheet onto a stainless-steel wire; photoactive materials are incorporated in between them through a solution process. The fiber-shaped perovskite solar cell exhibits an energy conversion efficiency of 3.3 % and may be woven into electronic textiles.

    5. Biocatalysis | Hot Paper

      Unprecedented Role of Hydronaphthoquinone Tautomers in Biosynthesis

      Dr. Syed Masood Husain, Dr. Michael A. Schätzle, Dr. Steffen Lüdeke and Prof. Dr. Michael Müller

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404560

      Thumbnail image of graphical abstract

      Breaking the cycle: In studies on the reduction of 2-hydroxynaphthoquinones to the stable 1,4-diketo tautomeric form of hydronaphthoquinones and their further reduction by fungal tetrahydroxynaphthalene reductase, diketo tautomers emerge as true intermediates in biosynthesis. Their formation breaks the (redox) cycle, thus protecting the cell from stress-related redox events.

    6. C[BOND]H Activation

      Easily Accessible Auxiliary for Palladium-Catalyzed Intramolecular Amination of C(sp2)[BOND]H and C(sp3)[BOND]H Bonds at δ- and ε-Positions

      Chao Wang, Changpeng Chen, Jingyu Zhang, Jian Han, Qian Wang, Kun Guo, Pei Liu, Mingyu Guan, Dr. Yingming Yao and Prof. Dr. Yingsheng Zhao

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404854

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      Remote access: The first application of an oxalyl amide to direct C[BOND]H functionalizations at remote positions was reported. The results showed both C(sp2)[BOND]H and C(sp3)[BOND]H bonds at δ- and ε-positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium-catalyzed intramolecular C[BOND]H amination.

    7. Metal–Metal Bonds

      Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction

      Dr. Andreas Stasch

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404284

      Thumbnail image of graphical abstract

      The new switcheroo: A dimeric magnesium(I) complex has been prepared by a simple redox reaction using a known magnesium(I) complex. The new complex is stabilized by a high oxidation state phosphorane-based ligand and undergoes a C[BOND]C coupling reaction with tert-butylisocyanate.

    8. Membrane Preparation | Hot Paper

      Coordination-Driven In Situ Self-Assembly Strategy for the Preparation of Metal–Organic-Framework Hybrid Membranes

      Rong Zhang, Prof. Shulan Ji, Dr. Naixin Wang, Lin Wang, Prof. Guojun Zhang and Jian-Rong Li

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403978

      Thumbnail image of graphical abstract

      Mopping up the mess: A hybrid membrane composed of the metal–organic framework (MOF) ZIF-8 and poly(sodium 4-styrenesulfonate) was prepared by coordination-driven in situ self-assembly method. The MOF particles were well-dispersed in the polymer in the resulting stable membrane (see picture), which showed excellent performance in the nanofiltration and separation of dyes from water.

    9. Self-Assembly

      Surface-Confined Self-Assembled Janus Tectons: A Versatile Platform towards the Noncovalent Functionalization of Graphene

      Dr. Ping Du, Maud Jaouen, Dr. Amandine Bocheux, Dr. Cyril Bourgogne, Zheng Han, Dr. Vincent Bouchiat, Dr. David Kreher, Dr. Fabrice Mathevet, Dr. Céline Fiorini-Debuisschert, Dr. Fabrice Charra and Prof. André-Jean Attias

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403572

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      Built to order: A library of Janus tectons equipped with small chemical groups or functional moieties has been synthesized. The self-assembly on sp2-hybridized carbon supports leads to the formation of well-organized adlayers with the same lattice parameters, as demonstrated by STM. The external exposed surface presents a wide range of functionalities positioned with a precise lateral order.

    10. Asymmetric Synthesis

      Asymmetric Hydroxylative Phenol Dearomatization Promoted by Chiral Binaphthylic and Biphenylic Iodanes

      Cyril Bosset, Romain Coffinier, Dr. Philippe A. Peixoto, Mourad El Assal, Dr. Karinne Miqueu, Dr. Jean-Marc Sotiropoulos, Dr. Laurent Pouységu and Prof. Stéphane Quideau

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201403571

      Thumbnail image of graphical abstract

      The selective oxygenation of iodobinaphthyls and iodobiphenyls afforded either λ3- or λ5-iodanes, which were evaluated for their capacity to promote asymmetric intermolecular hydroxylative phenol dearomatizations (HPDs). Most remarkably, a C2-symmetrical biphenylic λ5-iodane induced the HPD reaction/[4+2] cyclodimerization cascade of thymol into bis(thymol) with enantiomeric excesses of up to 94 %.

    11. Hybrid Nanomaterials

      Preparation of MoS2–MoO3 Hybrid Nanomaterials for Light-Emitting Diodes

      Dr. Zongyou Yin, Xiao Zhang, Dr. Yongqing Cai, Junze Chen, Dr. Jen It Wong, Dr. Yee-Yan Tay, Dr. Jianwei Chai, Jumiati Wu, Dr. Zhiyuan Zeng, Dr. Bing Zheng, Prof. Hui Ying Yang and Prof. Hua Zhang

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201402935

      Thumbnail image of graphical abstract

      LED’s glow: MoS2–MoO3 hybrid nanomaterials are prepared by the heat-assisted partial oxidation of MoS2 nanosheets in air (1) followed by a thermal-annealing-driven crystallization (2). The obtained hybrid nanomaterial exhibits p-type conductivity and is employed in a heterojunction of n-type SiC/p-type MoS2–MoO3 for light-emitting diodes (3), from which multi-wavelength electroluminescent emission is detected.

    12. Noncovalent Interactions

      Understanding a Host–Guest Model System through 129Xe NMR Spectroscopic Experiments and Theoretical Studies

      Emmanuelle Dubost, Jean-Pierre Dognon, Bernard Rousseau, Gaëlle Milanole, Christophe Dugave, Yves Boulard, Estelle Léonce, Céline Boutin and Patrick Berthault

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405349

      Thumbnail image of graphical abstract

      How hosts handle a noble guest: A combination of NMR spectroscopy and quantum chemistry enabled thorough analysis of the noncovalent interactions inside a xenon–host complex. The validation of this approach with a family of cryptophane hosts derived by treatment with H2O2 from the structure shown paves the way for the design of potent smart hyperpolarized 129Xe NMR sensors.

    13. Sustainable Chemistry

      An “All-Green” Catalytic Cycle of Aqueous Photoionization

      Prof. Dr. Martin Goez, Christoph Kerzig and Robert Naumann

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405693

      Thumbnail image of graphical abstract

      Green light and a cheap, even bioavailable, sacrificial donor produce hydrated electrons in the displayed catalytic cycle. The catalyst is a popular metal complex functioning as a “container” for a radical anion. The cycle could open a pathway toward the solar-driven reductive detoxification of halogenated organic waste. equation image=MeOPhO; equation image=MeOPhO.; MLCT=*[RuIII(bpy)2(bpy.)]2+; OER=[RuII(bpy)2(bpy.)]+; GS=[RuII(bpy)3]2+; bpy=2,2′-bipyridine.

  5. Cover Pictures

    1. A High-Pressure NMR Probe for Aqueous Geochemistry

      Dr. Brent G. Pautler, Christopher A. Colla, Dr. Rene L. Johnson, Peter Klavins, Dr. Stephen J. Harley, Dr. C. André Ohlin, Prof. Dimitri A. Sverjensky, Dr. Jeffrey H. Walton and Prof. William H. Casey

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406751

      Thumbnail image of graphical abstract

      Geochemical models for aqueous solution equilibria extend to pressures and temperatures well beyond experimental spectroscopies that could test the predictions. W. H. Casey and co-workers describe in their Communication (10.1002/anie.201404994) a simple NMR probe that can allow spectroscopy on solutions at pressures near those of Earth′s continental crust. (Greg Pautler Graphic Design, Ontario, Canada, is thanked for designing and donating the artwork.)

    2. Bonding Nature of Local Structural Motifs in Amorphous GeTe

      Dipl.-Chem. Volker L. Deringer, Dr. Wei Zhang, Dr. Marck Lumeij, Dipl.-Chem. Stefan Maintz, Prof. Dr. Matthias Wuttig, Prof. Dr. Riccardo Mazzarello and Prof. Dr. Richard Dronskowski

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406993

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      A glimpse into amorphous materials. In their Communication (10.1002/anie.201404223) R. Mazzarello, R. Dronskowski et al. investigate the bonding nature of amorphous GeTe, a prototypical phase-change data-storage material. Starting from a molecular-dynamics snapshot, the role of different structural motifs is elucidated by use of new tools; this way, the chemical “language” of bonding and coordination polyhedra may be transferred to the amorphous state.

    3. Integrating Perovskite Solar Cells into a Flexible Fiber

      Longbin Qiu, Jue Deng, Xin Lu, Zhibin Yang and Prof. Huisheng Peng

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406844

      Thumbnail image of graphical abstract

      Wearable perovskite solar cells with a fiber structure are synthesized according to a procedure that is described by H. Peng et al. in their Communication (DOI: 10.1002/anie.201404973) and entails continuously winding an aligned carbon nanotube sheet onto a stainless steel wire; photoactive materials are incorporated in between them through a solution process. The fiber-shaped perovskite solar cells exhibit an energy conversion efficiency of 3.3 % that is not affected by bending.

    4. Selective Targeting of Tumor and Stromal Cells By a Nanocarrier System Displaying Lipidated Cathepsin B Inhibitor

      G. Mikhaylov, Dr. D. Klimpel, Dr. N. Schaschke, Dr. U. Mikac, M. Vizovisek, Dr. M. Fonovic, Prof. V. Turk, Prof. Boris Turk and Dr. Olga Vasiljeva

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406845

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      A new drug delivery system targeting cancer-associated extracellular cathepsin B is described by B. Turk, O. Vasiljeva, et al. in their Communication (DOI: 10.1002/anie.201402305). The developed system is based on a lipidated cathepsin B-specific inhibitor incorporated into the envelope of the liposomal nanocarrier that could be used for selective targeting of tumor and stroma cells in the tumor micronvironment, while sparing the healthy normal cells.

    5. Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks

      Nhung T. T. Nguyen, Dr. Hiroyasu Furukawa, Dr. Felipe Gándara, Dr. Hoang T. Nguyen, Kyle E. Cordova and Prof. Omar M. Yaghi

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406995

      Thumbnail image of graphical abstract

      Selective capture of CO2 in the presence of N2 and H2O is possible with hydrophobic zeolitic imidazolate frameworks (ZIFs) with the important chabazite topology. These materials, prepared by O. M. Yaghi and co-workers (in their Communication 10.1002/anie.201403980), are shown to perform three consecutive cycles without loss in performance. Remarkably, between each cycle, the ZIFs were fully regenerated at ambient temperature using a N2 flow.

  6. Highlights

    1. Membranes

      Graphene Oxide: A New Platform for High-Performance Gas- and Liquid-Separation Membranes

      Dr. Zachary P. Smith and Prof. Benny D. Freeman

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201404407

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      Depending on size: Graphene oxide can be deposited into thin layers having defects and inter-layer structures with dimensions that are appropriate for separating molecules based on size differences and enable rapid transport through these structures. The picture illustrates the pathway of two differently sized molecules through the graphene oxide layers.

  7. News

  8. Communications

    1. C[BOND]H Functionalization

      Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in C[BOND]H Functionalizations

      Dr. David J. Burns and Prof. Hon Wai Lam

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201406072

      Thumbnail image of graphical abstract

      When two become one: 1,3-Enynes containing allylic hydrogens cis to the alkyne are shown to act as one-carbon partners, rather than two-carbon partners, in various rhodium-catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double C[BOND]H activation, involving a hitherto rare example of the 1,4-migration of a RhIII species.

    2. Protein Dynamics | Hot Paper

      Local Transient Unfolding of Native State PAI-1 Associated with Serpin Metastability

      Dr. Morten B. Trelle, Dr. Jeppe B. Madsen, Prof. Peter A. Andreasen and Prof. Dr. Thomas J. D. Jørgensen

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201402796

      Thumbnail image of graphical abstract

      Serpin proteins are prone to pathological conformational change, for instance by conversion to an inactive, so-called latent form. Using advanced hydrogen/deuterium-exchange mass spectrometry transient unfolding of a serpin is shown under native condition. Based on these observations, a new mechanism (see picture) is proposed.

    3. Organocatalysis

      Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All-Carbon Stereogenic Center: Total Syntheses of (−)-Rhazinilam and (−)-Leucomidine B

      Jean-Baptiste Gualtierotti, Delphine Pasche, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Article first published online: 22 JUL 2014 | DOI: 10.1002/anie.201405842

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      Breaking symmetry: Achiral bislactones (1) undergo desymmetrization by reaction with alcohol in the presence of chiral imidodiphosphoric acids. The monoacids 2, having an all-carbon stereogenic center, were obtained in good to excellent yields and enantioselectivities. Concise total syntheses of (−)-rhazinilam and (−)-leucomidine B were subsequently developed using 2 as a common starting material.

  9. Highlights

    1. Cycloadditions

      Münchnones—New Facets after 50 Years

      Prof. Dr. Hans-Ulrich Reissig and Dr. Reinhold Zimmer

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201405092

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      Developed and named 50 years ago in Munich, the mesoionic münchnones have had an astonishing career. New multicomponent reactions and enantioselective cycloadditions are discussed. They demonstrate the versatility of the münchnone approach to nitrogen heterocycles.

  10. Communications

    1. Asymmetric Catalysis

      High Performance of a Palladium Phosphinooxazoline Catalyst in the Asymmetric Arylation of Cyclic N-Sulfonyl Ketimines

      Chunhui Jiang, Prof. Dr. Yixin Lu and Prof. Dr. Tamio Hayashi

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201406147

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      Chiral cyclic sulfamidates are obtained by the asymmetric addition of arylboronic acids to six-membered cyclic N-sulfonyl ketimines. A cationic palladium complex with a chiral phosphine-oxazoline ligand (iPr-phox) shows high catalytic activity and enantioselectivity to give the products in high yields with 96–99.9 % ee. The cyclic sulfamidates exhibit a tetrasubstituted stereogenic center with an amino group and a triaryl or alkyldiaryl group as substituents.

    2. Electrocatalysis

      You have full text access to this OnlineOpen article
      Metal-Free Dihydrogen Oxidation by a Borenium Cation: A Combined Electrochemical/Frustrated Lewis Pair Approach

      Elliot J. Lawrence, Thomas J. Herrington, Dr. Andrew E. Ashley and Dr. Gregory G. Wildgoose

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201405721

      Thumbnail image of graphical abstract

      The potential that is required for non-aqueous H2 oxidation at a carbon electrode can be significantly reduced by using a borenium cation in a combined electrochemical/frustrated Lewis pair approach. This system exhibits faster electrode kinetics, increased stability to electrogenerated protons, and improved catalyst recycling over a previously reported system that is based on the borane Lewis acid B(C6F5)3.

    3. Synthetic Methods

      Rapid Access to β-Trifluoromethyl-Substituted Ketones: Harnessing Inductive Effects in Wacker-Type Oxidations of Internal Alkenes

      Michael M. Lerch, Dr. Bill Morandi, Zachary K. Wickens and Prof. Dr. Robert H. Grubbs

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201404712

      Thumbnail image of graphical abstract

      Synthetically highly desirable β-trifluoromethyl-substituted ketones can be rapidly accessed by a trifluoromethyl-directed Wacker oxidation starting from alkenes bearing an allylic trifluoromethyl group (see scheme). This effect seems to be dominantly inductive and can override coordinative effects. The reaction has a broad substrate scope and affords products in high yields and very high regioselectivity.

    4. Polymer Sensors

      Fluorescence Sensing of Amine Vapors Using a Cationic Conjugated Polymer Combined with Various Anions

      Dr. Sébastien Rochat and Prof. Dr. Timothy M. Swager

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201404439

      Thumbnail image of graphical abstract

      A sensor array comprising a conjugated cationic polymer combined with various counter-anions was developed. This simple approach allows the creation of polymer formulations able to detect vapors of industrially relevant amines in low ppm concentrations by fluorescence quenching measurements. Further, the array’s response is useful to identify the nature of the analyte using pattern-based recognition algorithms.

    5. Cycloaddition

      [HCo(CO)4]-Catalyzed Three-component Cycloaddition of Epoxides, Imines, and Carbon Monoxide: Facile Construction of 1,3-Oxazinan-4-ones

      Lixia Liu and Prof. Huailin Sun

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201403998

      Thumbnail image of graphical abstract

      Cobalt and CO: The title reaction is described to proceed in the presence of [HCo(CO)4] as the catalyst. The reaction occurs for a wide variety of imines and various substituted epoxides, thus providing an efficient and atom-economic route to 1,3-oxazinan-4-ones, with various substitution patterns, from simple and readily available starting materials.

    6. Smart Therapeutic Nanoparticles

      Angiopep-Conjugated Electro-Responsive Hydrogel Nanoparticles: Therapeutic Potential for Epilepsy

      Dr. Xiaoying Ying, Dr. Yi Wang, Dr. Jiao Liang, Dr. Jiaxing Yue, Dr. Cenglin Xu, Dr. Lina Lu, Dr. Zhenghao Xu, Prof. Dr. Jianqing Gao, Prof. Dr. Yongzhong Du and Prof. Dr. Zhong Chen

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201403846

      Thumbnail image of graphical abstract

      Smart vesicles: Electro-responsive hydrogel nanoparticles (ERHNPs) modified with angiopep-2 (ANG) were loaded with the antiepileptic drug phenytoin sodium (PHT). The complex ANG-PHT-ERHNPs can easily transport the drug into the brain and a fast release could be achieved by the application of an electric field, leading to a reduction of the severity of the seizure onset.

    7. Biomass Conversion

      Pd/NbOPO4 Multifunctional Catalyst for the Direct Production of Liquid Alkanes from Aldol Adducts of Furans

      Qi-Neng Xia, Qian Cuan, Xiao-Hui Liu, Prof. Xue-Qing Gong, Prof. Guan-Zhong Lu and Prof. Yan-Qin Wang

      Article first published online: 18 JUL 2014 | DOI: 10.1002/anie.201403440

      Thumbnail image of graphical abstract

      Fueling fuel production: Biomass conversion into liquid fuel depends on the design of multifunctional catalysts. In the direct conversion of furan-based aldol adducts into liquid alkanes over a Pd/NbOPO4 catalyst under mild conditions (see scheme), NbOx species played an important role in C[BOND]O bond cleavage.

  11. Cover Pictures

    1. A Metal-Free Three-Component Reaction for the Regioselective Synthesis of 1,4,5-Trisubstituted 1,2,3-Triazoles

      Dr. Joice Thomas, Dr. Jubi John, Nikita Parekh and Prof. Dr. Wim Dehaen

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201406875

      Thumbnail image of graphical abstract

      An efficient multicomponent reaction for the synthesis of highly functionalized 1,4,5-trisubstituted 1,2,3-triazoles from easily accessible starting materials, such as aldehydes, nitroalkanes, and organic azides, is described by W. Dehaen et al. in their Communication (DOI: 10.1002/anie.201403453). The statue “Fonske” or “Fons Sapientiae” (Latin for “fountain of wisdom”) is located on the campus of the KU Leuven, Belgium and depicts a university student who lets wisdom flow into his head while reading a book.

    2. Motion Capture and Manipulation of a Single Synthetic Molecular Rotor by Optical Microscopy

      Dr. Tomohiro Ikeda, Takahiro Tsukahara, Prof. Ryota Iino, Prof. Masayuki Takeuchi and Prof. Hiroyuki Noji

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201406750

      Thumbnail image of graphical abstract

      Single-molecule motion capture and the manipulation of a synthetic molecular rotor are described by H. Noji et al. in their Communication (DOI: 10.1002/anie.201403091). The stepwise intramolecular rotation of a double-decker porphyrin, a known 1 nm molecular rotor, was directly visualized with a relatively large bead probe (ca. 200 nm) by optical microscopy. With this technique, elemental properties of synthetic molecular machines that cannot be resolved by ensemble measurements can be elucidated.

  12. Communications

    1. Metal–Metal Interactions

      First Stabilization of 14-Electron Rhodium(I) Complexes by Hemichelation

      Christophe Werlé, Corinne Bailly, Dr. Lydia Karmazin-Brelot, Xavier-Frédéric Le Goff, Dr. Michel Pfeffer and Dr. Jean-Pierre Djukic

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201405240

      Thumbnail image of graphical abstract

      Touching from a distance: The syntheses of unprecedented T-shaped 14-electron RhI hemichelates is made possible by choosing the anti-[(η66-fluorenyl){Cr(CO)3}2]-based benzylic anion as an ambiphilic hemichelating ligand, and treating it with [{Rh(nbd)Cl}2] (nbd=norbornadiene) or [{Rh(CO)2Cl}2].

  13. Cover Pictures

    1. Maximum Noble-Metal Efficiency in Catalytic Materials: Atomically Dispersed Surface Platinum

      Dr. Albert Bruix, Dr. Yaroslava Lykhach, Dr. Iva Matolínová, M. Sc. Armin Neitzel, Dr. Tomáš Skála, Dr. Nataliya Tsud, Dr. Mykhailo Vorokhta, M. Sc. Vitalii Stetsovych, M. Sc. Klára Ševčíková, Dr. Josef Mysliveček, M. Sc. Roman Fiala, M. Sc. Michal Václavů, Dr. Kevin C. Prince, Dr. Stéphanie Bruyère, Dr. Valérie Potin, Prof. Dr. Francesc Illas, Prof. Dr. Vladimír Matolín, Prof. Dr. Jörg Libuda and Prof. Dr. Konstantin M. Neyman

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201406634

      Thumbnail image of graphical abstract

      Low-cost platinum-based catalysts. Cooperation of researchers from five European countries allowed Pt-CeO2 materials with the highest possible noble-metal dispersion to be prepared and characterized. As V. Matolín, J. Libuda, K. M. Neyman, and co-workers show in their Communication (10.1002/anie.201402342) surface atomic Pt2+ species are stabilized in {100} “nanopockets” of CeO2, decreasing the amount of platinum required for catalysis, thus lowering the cost of their implementation for applications, such as in fuel-cell devices.

    2. Selection of DNA-Encoded Small Molecule Libraries Against Unmodified and Non-Immobilized Protein Targets

      Peng Zhao, Zitian Chen, Yizhou Li, Dawei Sun, Yuan Gao, Prof. Yanyi Huang and Prof. Xiaoyu Li

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201406636

      Thumbnail image of graphical abstract

      Selection of DNA-encoded libraries (DELs) has become an important method to discover potent and specific binders against protein targets. In their Communication (DOI: 10.1002/anie.201404830), Y. Huang, X. Li, and co-workers describe a new DEL selection method, in which ligand binding induces the formation of a stable complex that is resistant to nuclease digestion (Pac-Man) in order to achieve enrichment. Such iterated selections can be realized with completely unmodified and non-immobilized targets.

    3. Aerogels with 3D Ordered Nanofiber Skeletons of Liquid-Crystalline Nanocellulose Derivatives as Tough and Transparent Insulators

      Yuri Kobayashi, Assoc. Prof. Tsuguyuki Saito and Prof. Akira Isogai

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201406635

      Thumbnail image of graphical abstract

      Aerogels with 3D-ordered nanofiber skeletons of liquid-crystalline nanocellulose are described by T. Saito et al. in their Communication (DOI: 10.1002/anie.201405123). The nanocellulose is composed of mechanically strong, surface-carboxylated cellulose nanofibers dispersed in a nematic order, which were prepared from abundant wood biomass through a water-based process. These aerogels display good insulation properties, optical transparency, and mechanical toughness.

  14. Communications

    1. Synthetic Methods

      Nickel-Catalyzed Cross-Coupling of Functionalized Difluoromethyl Bromides and Chlorides with Aryl Boronic Acids: A General Method for Difluoroalkylated Arenes

      Yu-Lan Xiao, Wen-Hao Guo, Guo-Zhen He, Qiang Pan and Prof. Dr. Xingang Zhang

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201405653

      Thumbnail image of graphical abstract

      Simple and easy: The first example of nickel-catalyzed difluoroalkylation of aryl boronic acids with functionalized difluoromethyl bromides and chlorides has been developed. This cross-coupling process features a broad substrate scope, a cheap catalyst, and excellent functional-group compatibility.

    2. Supramolecular Chemistry

      Water Encapsulation by Nanomicelles

      Dr. Iker León, Dr. Judith Millán, Dr. Emilio J. Cocinero, Prof. Alberto Lesarri and Dr. José A. Fernández

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201405652

      Thumbnail image of graphical abstract

      Caught! The hydration of nanomicelles in the gas-phase is observed by spectroscopic methods and quantum chemical calculations. The trimer of propofol with a water molecule forms cyclic hydrogen-bond networks but, the tetramer encapsulates the water molecule within the hydrophilic core.

    3. Self-Assembly

      A Supramolecular Sorting Hat: Stereocontrol in Metal–Ligand Self-Assembly by Complementary Hydrogen Bonding

      Michael C. Young, Lauren R. Holloway, Amber M. Johnson and Prof. Richard J. Hooley

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201405242

      Thumbnail image of graphical abstract

      Abracadabra: The stereoselective self-assembly of an unsymmetrical metal–ligand cage can be controlled by self-complementary hydrogen bonding between alcohol-containing ligands as well as between ligands and suitable anion guests.

    4. Microfluidic Chips

      Integration of Platinum Nanoparticles with a Volumetric Bar-Chart Chip for Biomarker Assays

      Dr. Yujun Song, Prof. Xuefeng Xia, Prof. Xifeng Wu, Prof. Ping Wang and Prof. Lidong Qin

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404349

      Thumbnail image of graphical abstract

      No more (or less) than meets the eye: Platinum nanoparticles (PtNPs) efficiently catalyze the reaction of H2O2 to form oxygen gas, the generation of which can be measured by microfluidics technology. Thus, when integrated with ELISA, a volumetric bar-chart chip (see picture) enabled the quantitative visual detection of cancer biomarkers in serum and on the cell surface on the basis of the catalase-like activity of PtNPs.

    5. Luminescence Imaging

      Image-Contrast Technology Based on the Electrochemiluminescence of Porous Silicon and Its Application in Fingerprint Visualization

      Jie Tan, Linru Xu, Tong Li, Prof. Bin Su and Prof. Jianmin Wu

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404948

      Thumbnail image of graphical abstract

      Fit for a modern Sherlock: Electrochemiluminescence by porous silicon (pSi) has a regular dynamic process involving activation, strong emission, and fading. This process can be perturbed by chemicals adsorbed on the pSi surface. The contrast in luminescence intensity between adjacent areas with different surface chemistry enabled the visualization of latent fingerprints and a trinitrotoluene (TNT) residue in a fingerprint with high resolution (see picture).

    6. Multiple C[BOND]H Activation | Hot Paper

      One-Pot Synthesis of Highly Substituted Polyheteroaromatic Compounds by Rhodium(III)-Catalyzed Multiple C[BOND]H Activation and Annulation

      Jayachandran Jayakumar, Dr. Kanniyappan Parthasarathy, Yi-Hsiang Chen, Tai-Hua Lee, Prof. Dr. Shih-Ching Chuang and Prof. Dr. Chien-Hong Cheng

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201405183

      Thumbnail image of graphical abstract

      Activated and annulated: A rhodium-catalyzed one-pot synthesis of highly substituted polyheteroaromatic compounds from N-hydroxybenzamidines and alkynes is described. This reaction likely proceeds through multiple C[BOND]H bond activation and annulation.

    7. Amorphous Materials | Very Important Paper

      Bonding Nature of Local Structural Motifs in Amorphous GeTe

      Dipl.-Chem. Volker L. Deringer, Dr. Wei Zhang, Dr. Marck Lumeij, Dipl.-Chem. Stefan Maintz, Prof. Dr. Matthias Wuttig, Prof. Dr. Riccardo Mazzarello and Prof. Dr. Richard Dronskowski

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404223

      Thumbnail image of graphical abstract

      Amorphous—no problem! Analyzing a crystalline structure by breaking it down into local fragments and covalent bonds is a technique that chemists have long perfected. With new tools at hand, this chemical language can be extended to amorphous solid-state materials—in this case, to the phase-change memory alloy germanium telluride.

    8. Selective CO2 Capture in ZIFs | Hot Paper

      Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks

      Nhung T. T. Nguyen, Dr. Hiroyasu Furukawa, Dr. Felipe Gándara, Dr. Hoang T. Nguyen, Kyle E. Cordova and Prof. Omar M. Yaghi

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201403980

      Thumbnail image of graphical abstract

      Wetting their appetite for CO2: Hydrophobic zeolitic imidazolate frameworks (ZIFs) with the chabazite (CHA) topology selectively capture CO2 from N2 in the presence of water. They thus overcome crucial challenges faced by many other porous materials for which even the smallest amount of water causes decomposition or decreases the materials’ ability to capture CO2.

    9. Lewis Acids

      Highly Electron-Deficient and Air-Stable Conjugated Thienylboranes

      Dr. Xiaodong Yin, Jiawei Chen, Prof. Roger A. Lalancette, Prof. Dr. Todd B. Marder and Prof. Dr. Frieder Jäkle

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201403700

      Thumbnail image of graphical abstract

      The bigger the better: Sterically demanding 2,4,6-tri-tert-butylphenyl (Mes*) or 2,4,6-tris(trifluoromethyl)phenyl (FMes) groups do not prevent but rather promote coplanarity and enhance electronic communication within conjugated thienylboranes. FMes exerts a strong electron-withdrawing effect which results in significant lowering of the LUMO energy level and high Lewis acidity toward fluoride anions, while ensuring stability in air and towards acid or base.

    10. Ionic Liquids

      On the Formation of a Protic Ionic Liquid in Nature

      Prof. Li Chen, Genevieve E. Mullen, Myriam Le Roch, Cody G. Cassity, Prof. Nicolas Gouault, Prof. Henry Y. Fadamiro, Prof. Robert E. Barletta, Prof. Richard A. O'Brien, Prof. Richard E. Sykora, Prof. Alexandra C. Stenson, Prof. Kevin N. West, Howard E. Horne, Jeffrey M. Hendrich, Kang Rui Xiang and Prof. James H. Davis Jr.

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404402

      Thumbnail image of graphical abstract

      Crazy about Ionic Liquids: Throughout the southern United States, the invasive ant species S. invicta (fire ants) and N. fulva (tawny crazy ants) vie for resources. During confrontations, N. fulva is sprayed by S. invicta with a lipophilic, piperidine-based venom. The former defeats this chemical attack by grooming with its own venom, formic acid. The combination forms a protic ionic liquid, which is the first naturally occurring ionic liquid to be reported.

    11. Heterogeneous Catalysis

      Highly Efficient “On Water” Catalyst-Free Nucleophilic Addition Reactions Using Difluoroenoxysilanes: Dramatic Fluorine Effects

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

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404432

      Thumbnail image of graphical abstract

      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.

    12. Solar Fuel Production

      Photothermal Conversion of CO2 into CH4 with H2 over Group VIII Nanocatalysts: An Alternative Approach for Solar Fuel Production

      Xianguang Meng, Dr. Tao Wang, Dr. Lequan Liu, Dr. Shuxin Ouyang, Dr. Peng Li, Huilin Hu, Dr. Tetsuya Kako, Dr. Hideo Iwai, Dr. Akihiro Tanaka and Prof. Jinhua Ye

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404953

      Thumbnail image of graphical abstract

      Heated by light: The photothermal conversion of CO2 into CH4 over Group VIII nanocatalysts provides a method for the production of solar fuels with high solar-light utilization efficiency. The overall water-based CO2 conversion process is proposed to combine light-driven H2 production by water splitting and photothermal CO2 conversion with H2.

    13. Strained Polycycles

      Synthesis of Bridged Oxafenestranes from Pleuromutilin

      Robert W. Hicklin, Tania L. López Silva and Prof. Paul J. Hergenrother

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404765

      Thumbnail image of graphical abstract

      Fenestranes are highly strained molecules possessing a quaternary carbon with bonds that deviate from the canonical tetrahedral geometry. The natural product pleuromutilin can be used as a starting material for the synthesis of bridged [4.5.5.5]- and [4.5.7.5]oxafenestranes through a carbocation rearrangement cascade. X-ray crystallography shows that these compounds exhibit significant planarization of the central tetracoordinate carbon.

    14. Nitrogen Photofixation | Hot Paper

      Plasmon-Induced Ammonia Synthesis through Nitrogen Photofixation with Visible Light Irradiation

      Dr. Tomoya Oshikiri, Prof. Kosei Ueno and Prof. Hiroaki Misawa

      Article first published online: 17 JUL 2014 | DOI: 10.1002/anie.201404748

      Thumbnail image of graphical abstract

      See the light of day: A plasmon-induced ammonia synthesis technique that responds to visible light and is based on a strontium titanate (SrTiO3) photoelectrode loaded with gold nanoparticles has been developed. It is deduced that plasmon-induced charge separation at the Au/SrTiO3 interface promotes oxidation in the anodic chamber and subsequent nitrogen reduction on the cathodic side.

  15. Author Profiles

    1. Xi Zhang

      Article first published online: 16 JUL 2014 | DOI: 10.1002/anie.201405908

      Thumbnail image of graphical abstract

      I can never resist good food. My biggest motivation is to understand the principles behind interesting phenomena.

  16. Cover Pictures

    1. Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation

      Andreas W. Hauser, Narbe Mardirossian, Julien A. Panetier, Martin Head-Gordon, Alexis T. Bell and Peter Schwerdtfeger

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201406608

      Thumbnail image of graphical abstract

      The attachment of a suitable “bouncer” molecule to the rim of a graphene pore prevents the passage of the undesired enantiomer while letting its mirror image through. In their Communication (DOI: 10.1002/anie.201403145) A. W. Hauser, P. Schwerdtfeger et al. report that a small difference in the geometry of the temporary dimer complex, which is formed by the “bouncer” and the penetrating molecule, is transformed into a significant difference for the transmission barrier.

    2. Protein Interactions with Polymer Coatings and Biomaterials

      M. Sc. Qiang Wei, M. Sc. Tobias Becherer, Dr. Stefano Angioletti-Uberti, Prof. Dr. Joachim Dzubiella, Dr. Christian Wischke, Dr. Axel T. Neffe, Prof. Dr. Andreas Lendlein, Prof. Dr. Matthias Ballauff and Prof. Rainer Haag

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201406350

      Thumbnail image of graphical abstract

      Polymeric material coatings, such as Teflon and hydrophilic polymer surfaces can prevent protein adhesion to generate protein-resistant surfaces. The Review by R. Haag et al. (DOI: 10.1002/anie.201400546) describes the methods and recent advances in the field of protein interactions on polymeric materials. The cover picture illustrates the adsorption of proteins (egg white) to material surfaces as exemplified by the egg in the pan. (Graphic designed by Achim Wiedekind with a background picture by Ruben Haag.)

  17. Communications

    1. Self-Assembly | Hot Paper

      Reversible Supramolecular Assembly at Specific DNA Sites: Nickel-Promoted Bivalent DNA Binding with Designed Peptide and Bipyridyl–Bis(benzamidine) Components

      Mateo I. Sánchez, Jesús Mosquera, Prof. M. Eugenio Vázquez and Prof. José L. Mascareñas

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405726

      Thumbnail image of graphical abstract

      Nickel(II) salts promote the assembly of a bis(histidine)-modified peptide that is derived from a bZIP transcription factor and a bipyridine-substituted bis(benzamidine) unit at specific DNA sites. This supramolecular system features some key properties of naturally occurring DNA-binding proteins, such as bivalence, selectivity, responsiveness to external agents, and reversibility.

    2. Homologation | Very Important Paper

      Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters

      Phillip J. Unsworth, Dr. Daniele Leonori and Prof. Varinder K. Aggarwal

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405700

      Thumbnail image of graphical abstract

      Three more: The 3C homologation of chiral pinacol boronic esters gives di- or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5-stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)-jasplakinolide.

    3. Solid Electrolytes

      Poly(dimethylsiloxane)-Supported Ionogels with a High Ionic Liquid Loading

      Ariel I. Horowitz and Prof. Matthew J. Panzer

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405691

      Thumbnail image of graphical abstract

      Supportive, despite their differences: The immiscibility of poly(dimethylsiloxane) (PDMS) and ionic liquids (ILs) was overcome by a simple sol–gel reaction (see picture) to create PDMS-supported ILs (ionogels) with IL loadings of up to 80 % by mass. The ionogels exhibited high ionic conductivity and excellent mechanical behavior, with an elastic modulus of approximately 60 kPa without fatigue over 5000 cycles, even at elevated temperatures.

    4. Asymmetric Catalysis

      Enantioselective Formation of Cyano-Bearing All-Carbon Quaternary Stereocenters: Desymmetrization by Copper-Catalyzed N-Arylation

      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

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405575

      Thumbnail image of graphical abstract

      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.

    5. Perovskite Solar Cells | Hot Paper

      High-Performance Hole-Extraction Layer of Sol–Gel-Processed NiO Nanocrystals for Inverted Planar Perovskite Solar Cells

      Zonglong Zhu, Yang Bai, Teng Zhang, Dr. Zhike Liu, Dr. Xia Long, Zhanhua Wei, Zilong Wang, Lixia Zhang, Prof. Jiannong Wang, Prof. Feng Yan and Prof. Shihe Yang

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405176

      Thumbnail image of graphical abstract

      The advantages are crystal clear: A transparent layer of NiO nanocrystals fabricated by a simple sol–gel processing method acted as an efficient hole-transport layer in an inverted perovskite solar cell. With the NiO film (see picture), a cell efficiency of 9.11 % was observed: by far the highest for a planar perovskite solar cell based on an inorganic hole-extraction layer.

    6. Biocatalysis

      A Tailor-Made Chimeric Thiamine Diphosphate Dependent Enzyme for the Direct Asymmetric Synthesis of (S)-Benzoins

      Dr. Robert Westphal, Dipl.-Biol. Constantin Vogel, Carlo Schmitz, Prof. Dr. Jürgen Pleiss, Prof. Dr. Michael Müller, Prof. Dr. Martina Pohl and Dr. Dörte Rother

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405069

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      Hybrid vigor: Combining the active-site characteristics of two thiamine diphosphate (ThDP) dependent enzymes solved the long-standing problem of enzymatic asymmetric (S)-benzoin synthesis starting from commercially available benzaldehydes. The resulting rationally designed hybrid enzyme provides access to various (S)-benzoins with excellent enantiomeric excess and good conversion.

    7. Polymeric Catalysts | Hot Paper

      A Polyphenylene Support for Pd Catalysts with Exceptional Catalytic Activity

      Dr. Feng Wang, Jerrik Mielby, Dr. Felix Herrmann Richter, Dr. Guanghui Wang, Dr. Gonzalo Prieto, Dr. Takeshi Kasama, Dr. Claudia Weidenthaler, Hans-Josef Bongard, Prof. Dr. Søren Kegnæs, Prof. Dr. Alois Fürstner and Prof. Dr. Ferdi Schüth

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201404912

      Thumbnail image of graphical abstract

      Support with benefits: A composite catalyst is synthesized by palladium-catalyzed Suzuki coupling which directly results in formation of palladium nanoparticles confined to a porous polyphenylene network. A polyphenylene support serves as an excellent platform for metal-catalyzed reactions, which are typically carried out under homogeneous conditions.

    8. Glycopeptides

      Synthesis of the Highly Glycosylated Hydrophilic Motif of Extensins

      Dr. Akihiro Ishiwata, Dr. Sophon Kaeothip, Dr. Yoichi Takeda and Dr. Yukishige Ito

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201404904

      Thumbnail image of graphical abstract

      Just a phase: Stereoselective synthesis of one of the highly glycosylated hydrophilic motifs of extensins has been completed. Key steps were a 2-(naphthyl)methylether-mediated intramolecular aglycon delivery to the stereoselective construction of the Ser(Galp1) and Hyp(Arafn) (n=1, 3, 4) fragments and Fmoc solid-phase peptide synthesis (SPPS) for the highly glycosylated pentapeptide motif.

    9. Photophysics

      UV Excited-State Photoresponse of Biochromophore Negative Ions

      Dr. Anastasia V. Bochenkova, Dr. Benedikte Klærke, Dr. Dennis B. Rahbek, Dr. Jyoti Rajput, Dr. Yoni Toker and Prof. Lars H. Andersen

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201404609

      Thumbnail image of graphical abstract

      Higher electronically excited states of the green fluorescent protein chromophore anion have been probed directly by action absorption spectroscopy. The high density of these UV molecular resonances in the UV makes electron detachment in the gas phase efficient. Quantum calculations show this electronic band inside the protein to be resonant with the quasicontinuum of a solvated electron, thus suggesting its major role in the photophysics in the UV region.

    10. Carbohydrates

      Synthesis of the Heparin-Based Anticoagulant Drug Fondaparinux

      Dr. Cheng-Hsiu Chang, Larry S. Lico, Dr. Teng-Yi Huang, Dr. Shu-Yi Lin, Dr. Chi-Liang Chang, Prof. Dr. Susan D. Arco and Prof. Dr. Shang-Cheng Hung

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201404154

      Thumbnail image of graphical abstract

      Working against the clot: The synthetic anticoagulant fondaparinux, a pentasaccharide based on the antithrombin-binding domain of heparin, was prepared in a concise and efficient manner in the shortest route reported to date. The application of one-pot strategies, the use of common intermediates, and the efficient preparation of monosaccharide building blocks from commercial sources are key features of this approach.

    11. Nanostructures

      Self-Supported Cu3P Nanowire Arrays as an Integrated High-Performance Three-Dimensional Cathode for Generating Hydrogen from Water

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

      Article first published 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.

    12. Dihydrogen Bonding

      Evidence of Dihydrogen Bonding of a Chiral Amine–Borane Complex in Solution by VCD Spectroscopy

      Dr. Christian Merten, Christopher J. Berger, Dr. Robert McDonald and Prof. Dr. Yunjie Xu

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201403690

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      A chiral amine–borane is investigated by vibrational circular dichroism (VCD) spectroscopy. By comparison of experimental and calculated spectra, a unique VCD pattern associated with the formation of dihydrogen-bonded dimers in solution is identified. Different dihydrogen binding arrangements in solution and in solid state are characterized.

    13. BN-Arynes

      BN-Phenanthryne: Cyclotetramerization of an 1,2-Azaborine Derivative

      Dipl.-Chem. Matthias Müller, Dr. Cäcilia Maichle-Mössmer and Prof. Dr. Holger F. Bettinger

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201403213

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      Making a first appearance: A BN-aryne analogous to 9,10-phenanthryne can be formed by thermolysis of the 9-azido-9-borafluorene and can undergo cyclotetramerization.

    14. Supramolecular Chemistry

      Harnessing the Liquid-Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

      Dr. Artur Ciesielski, Sébastien Haar, Dr. Mirella El Gemayel, Huafeng Yang, Joseph Clough, Georgian Melinte, Dr. Marco Gobbi, Dr. Emanuele Orgiu, Dr. Marco V. Nardi, Giovanni Ligorio, Dr. Vincenzo Palermo, Prof. Norbert Koch, Prof. Ovidiu Ersen, Dr. Cinzia Casiraghi and Prof. Paolo Samorì

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201402696

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      Graphene dispersions: A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in 1-methyl-2-pyrrolidinone (see picture). Simple molecular modules are used, which act as dispersion-stabilizing compounds during a liquid-phase exfoliation process, leading to an increase in the concentration of graphene dispersions.

    15. Water Oxidation

      Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst

      Dr. Wei-Tsung Lee, Salvador B. Muñoz III, Dr. Diane A. Dickie and Prof. Jeremy M. Smith

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201402407

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      Ligand-controlled switch: Simple modification of the substituent on a pyridinophane macrocycle ligand converts the corresponding MnII complex from a hydrogen peroxide disproportionation catalyst to a water oxidation catalyst. Preliminary results indicate that the catalyst is mononuclear.

    16. Molecular Electronics

      Orientation-Controlled Single-Molecule Junctions

      Sepideh Afsari, Dr. Zhihai Li and Prof. Dr. Eric Borguet

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201402343

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      The conductivity of a single aromatic ring, perpendicular to its plane, is determined (see picture; I=current). The formation of highly ordered structures of mesitylene oriented parallel to an Au (111) plane enables direct contacts between a scanning tunneling microscopy tip and the π-system of mesitylene for creating highly conductive Au/aromatic/Au junctions under ambient conditions.

    17. Glycosides

      gem-Difluorocarbadisaccharides: Restoring the exo-Anomeric Effect

      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

      Article first published 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.

    18. C[BOND]N Coupling

      C[BOND]NH2 Bond Formation Mediated by Iridium Complexes

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

      Article first published 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.

    19. Modified Nucleosides

      Synthesis and Duplex-Stabilizing Properties of Fluorinated N-Methanocarbothymidine Analogues Locked in the C3′-endo Conformation

      Michael E. Jung, Timothy A. Dwight, Frederic Vigant, Michael E. Østergaard, Eric E. Swayze and Punit P. Seth

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405283

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      The power of conviction: The efficient synthesis, antiviral activity, and duplex-stabilizing properties of both isomers, 2 and 3, of the 2′-fluoro analogue of N-methanocarbathymidine (N-MCT) are reported. Incorporation of the fluorine substituent at the 2′-position of the N-MCT scaffold was found to have a strong positive effect on duplex thermal stability.

    20. Heterocycles

      Expedient Synthesis of Fused Azepine Derivatives using a Sequential Rhodium(II)-Catalyzed Cyclopropanation/1-Aza-Cope Rearrangement of Dienyltriazoles

      Erica E. Schultz, Vincent N. G. Lindsay and Prof. Richmond Sarpong

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405356

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      A general method for the formation of fused dihydroazepines from 1-sulfonyl-1,2,3-triazoles bearing a tethered diene is reported. The process involves an intramolecular cyclopropanation of an α-imino rhodium(II) carbenoid, leading to a transient 1-imino-2-vinylcyclopropane intermediate which rapidly undergoes a 1-aza-Cope rearrangement to generate the products in moderate to excellent yields. Ts=4-toluenesulfonyl.

    21. Asymmetric Synthesis | Hot Paper

      Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions

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

      Article first published 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.

  18. Reviews

    1. Protein-Resistant Surfaces

      Protein Interactions with Polymer Coatings and Biomaterials

      M. Sc. Qiang Wei, M. Sc. Tobias Becherer, Dr. Stefano Angioletti-Uberti, Prof. Dr. Joachim Dzubiella, Dr. Christian Wischke, Dr. Axel T. Neffe, Prof. Dr. Andreas Lendlein, Prof. Dr. Matthias Ballauff and Prof. Rainer Haag

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201400546

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      The prevention of protein interactions plays a major role in every day’s life, e.g. on common Teflon surfaces. This review focuses on recent developments in analytical, biochemical, and theoretical techniques that lead to a better understanding of polymeric biomaterials for applications as bioinert and biospecific surface coating materials in biomedical systems.

  19. Highlights

    1. Renewable Resources

      Plant Biomass Fractionation Meets Catalysis

      Dr. Roberto Rinaldi

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201404464

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      Catalytic biorefining: Beyond the deconstruction of plant biomass, emerging processes for catalytic biomass fractionation are directed towards rationally designing the properties of the isolated biomass components through and for catalysis. The full potential of catalysis in the conversion of the isolated fractions into chemicals and fuels can thus be exploited.

  20. Communications

    1. Cancer Therapeutics

      A Multifunctional Nanomicelle for Real-Time Targeted Imaging and Precise Near-Infrared Cancer Therapy

      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

      Article first published 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.

    2. Tumor Imaging

      CXCR4-Targeted and MMP-Responsive Iron Oxide Nanoparticles for Enhanced Magnetic Resonance Imaging

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

      Article first published 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.

    3. Platinum DNA Intercalators

      Luminescent Cyclometalated Platinum(II) Complex Forms Emissive Intercalating Adducts with Double-Stranded DNA and RNA: Differential Emissions and Anticancer Activities

      Taotao Zou, Dr. Jia Liu, Dr. Ching Tung Lum, Dr. Chensheng Ma, Ruth Chau-Ting Chan, Dr. Chun-Nam Lok, Dr. Wai-Ming Kwok and Prof. Dr. Chi-Ming Che

      Article first published online: 15 JUL 2014 | DOI: 10.1002/anie.201405384

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      Making light of DNA: The luminescent PtII pincer complex [Pt(C^N^N)(C≡NtBu)]ClO4 intercalates into DNA and forms an unconventional emissive exciplex. The emission profile and excited-state lifetime are sensitive to nucleic acid structure, which is used to differentiate between dsRNA and dsDNA. The complex shows strong in vitro cytotoxicity and suppresses tumor growth in an animal model.

  21. Author Profiles

    1. Lai-Sheng Wang

      Article first published online: 14 JUL 2014 | DOI: 10.1002/anie.201406121

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      My favorite molecule is C60. My favorite saying is “Results not published equals experiments not done”.

  22. Communications

    1. Purely Organic Phosphors

      Tailoring Intermolecular Interactions for Efficient Room-Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices

      Dr. Min Sang Kwon, Dongwook Lee, Sungbaek Seo, Jaehun Jung and Prof. Dr. Jinsang Kim

      Article first published online: 14 JUL 2014 | DOI: 10.1002/anie.201404490

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      A bright idea: Rationally designed strong intermolecular hydrogen and halogen bonds between a novel phosphor and a poly(vinyl alcohol) (PVA) matrix led to bright room-temperature phosphorescence (RTP) with a quantum yield of 24 %. Modulation of the strength of halogen and hydrogen bonding in the purely organic phosphor–PVA system by water enabled reversible switching between phosphorescence (green) and fluorescence (blue).

    2. NHC Catalysis

      N-Heterocyclic-Carbene-Catalyzed Synthesis of 2-Aryl Indoles

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

      Article first published 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 are reported, and has been applied to a streamlined synthesis of a kinase inhibitor.

    3. Functional Materials

      Self-Healable Electrically Conducting Wires for Wearable Microelectronics

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

      Article first published 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.

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