Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 44

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, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

  1. Author Profiles

    1. Todd B. Marder

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409785

      Thumbnail image of graphical abstract

      I advise my students to see the world and keep an open mind. My favorite quote is “Never try to discourage thinking for you are sure to succeed” (Bertrand Russell).

  2. Cover Pictures

    1. Unravelling the Correlation between the Aspect Ratio of Nanotubular Structures and Their Electrochemical Performance To Achieve High-Rate and Long-Life Lithium-Ion Batteries

      Dr. Yuxin Tang, Dr. Yanyan Zhang, Jiyang Deng, Dr. Dianpeng Qi, Wan Ru Leow, Jiaqi Wei, Dr. Shengyan Yin, Prof. Zhili Dong, Prof. Rachid Yazami, Prof. Zhong Chen and Prof. Xiaodong Chen

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410022

      Thumbnail image of graphical abstract

      Understanding the relationship between the nanostructure of an electrode and its electrochemical performance is crucial for the development of high-perfomance lithium-ion batteries. In their Communication (DOI: 10.1002/anie.201406719), Z. Chen, X. Chen, and co-workers report that the aspect ratio of nanotubular materials determines battery performance at high charging/discharging rates. Their proof-of-concept batteries are very promising for energy-storage systems in electrical vehicles.

    2. Recognition of Nucleic Acid Junctions Using Triptycene-Based Molecules

      Stephanie A. Barros and Prof. David M. Chenoweth

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410021

      Thumbnail image of graphical abstract

      Rationally designed nucleic acid junction binders based on a triptycene scaffold were found to significantly stabilize DNA and RNA three-way junctions (3WJs). In their Communication (DOI: 10.1002/anie.201407061), D. M. Chenoweth and S. A. Barros report that the scaffold provides a new architecture for the development of junction binders with enhanced recognition properties. Initial cytotoxicity data in two human ovarian carcinoma cell lines are promising.

    3. A Reversible and Selective Inhibitor of Monoacylglycerol Lipase Ameliorates Multiple Sclerosis

      Dr. Gloria Hernández-Torres, Dr. Mariateresa Cipriano, Erika Hedén, Emmelie Björklund, Dr. Ángeles Canales, M. Sc. Debora Zian, M. Sc. Ana Feliú, Dr. Miriam Mecha, Dr. Carmen Guaza, Prof. Dr. Christopher J. Fowler, Prof. Dr. Silvia Ortega-Gutiérrez and Prof. Dr. María L. López-Rodríguez

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410020

      Thumbnail image of graphical abstract

      The inhibition of monoacylglycerol lipase (MAGL), the enzyme responsible for the inactivation of the endocannabinoid 2-arachidonoylglycerol, is a strategy for the treatment of multiple sclerosis. In their Communication (DOI: 10.1002/anie.201407807), M. L. López-Rodríguez and co-workers describe a potent, reversible, and selective inhibitor of MAGL that slows the clinical progression of MS without inducing undesirable CB1-mediated side effects.

    4. Biosynthesis of the Halogenated Mycotoxin Aspirochlorine in Koji Mold Involves a Cryptic Amino Acid Conversion

      Pranatchareeya Chankhamjon, Dr. Daniela Boettger-Schmidt, Dr. Kirstin Scherlach, Barbara Urbansky, Dr. Gerald Lackner, Daniel Kalb, Hans-Martin Dahse, Prof. Dr. Dirk Hoffmeister and Prof. Dr. Christian Hertweck

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409948

      Thumbnail image of graphical abstract

      The koji mold Aspergillus oryzae, which is widely used in food fermentations (e.g., sake production), produces the toxin aspirochlorine. C. Hertweck et al. elucidated in their Communication (DOI: 10.1002/anie.201407624) the biosynthetic pathway of this chlorinated epipolythiodioxopiperazine. An iterative non-ribosomal peptide synthetase assembles the diketopiperazine core from two phenylalanine units, one of which then undergoes an unprecedented conversion to glycine. Enzymatic halogenation of the second Phe unit significantly contributes to the biological activity of aspirochlorine.

    5. Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries

      Dr. Santanab Giri, Swayamprabha Behera and Prof. Puru Jena

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409947

      Thumbnail image of graphical abstract

      Currently used electrolytes in Li-ion batteries mostly contain toxic halogens. In their Communication (DOI: 10.1002/anie.201408648), P. Jena et al. use first-principles calculations to show that all these electrolytes are based on superhalogens, i.e., that the vertical electron detachment energies of the moieties that constitute the anions are larger than those of any halogen atom. Several superhalogens do not contain a single halogen atom and their potential as effective electrolytes was studied. Among the identified halogen-free electrolytes, Li(CB11H12) is shown to have the greatest potential.

    6. Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality

      Sandra Arias, Dr. Félix Freire, Prof. Dr. Emilio Quiñoá and Prof. Dr. Ricardo Riguera

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409945

      Thumbnail image of graphical abstract

      The supramolecular assembly of helical polymers, namely poly(aryl acetylenes), with monovalent metal cations (Li+, Na+, and Ag+) leads to a number of different macroscopically chiral nanostructures, such as nanospheres, nanotubes, toroids, and gels, with the capacity to encapsulate a variety of organic and inorganic substances. The cover picture illustrates this fruitful “chemical tornado”, which is presented by F. Freire, R. Riguera, et al. in their Communication (DOI: 10.1002/anie.201406884).

  3. Communications

    1. Azaporphyrin Ligands

      A 3-Pyridyl-5,15-Diazaporphyrin Nickel(II) Complex as a Bidentate Metalloligand for Transition Metals

      Ayaka Yamaji, Prof. Dr. Ji-Young Shin, Prof. Dr. Yoshihiro Miyake and Prof. Dr. Hiroshi Shinokubo

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408852

      Thumbnail image of graphical abstract

      Porphyrin coordination: A 3-pyridyl-5,15-diazaporphyrin NiII complex acts as a bidentate metalloligand forming stable metal complexes with PtII, RuII, and RhI centers (see picture). Single-crystal X-ray analysis confirms the formation of dative bonds between the meso-nitrogen atoms and the metal ions.

    2. Fuel Cells

      Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques

      Dr. Shinobu Takao, Dr. Oki Sekizawa, Dr. Shin-ichi Nagamatsu, Dr. Takuma Kaneko, Dr. Takashi Yamamoto, Dr. Gabor Samjeské, Dr. Kotaro Higashi, Dr. Kensaku Nagasawa, Dr. Takuya Tsuji, Dr. Motohiro Suzuki, Dr. Naomi Kawamura, Dr. Masaichiro Mizumaki, Prof. Dr. Tomoya Uruga and Prof. Dr. Yasuhiro Iwasawa

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408845

      Thumbnail image of graphical abstract

      Catalyst characterization: Platinum species in a Pt/C cathode catalyst layer were mapped by spatially resolved X-ray absorption fine structure (XAFS) methods. Information on the oxidation and leaching of Pt cathode nanoparticles in degraded polymer electrolyte fuel cells (PEFCs) is obtained, which is relevant for the mechanism of PEFC degradation.

    3. RNA Arrays

      Enzymatic Fabrication of High-Density RNA Arrays

      Dr. Cheng-Hsien Wu, Matthew T. Holden and Prof. Lloyd M. Smith

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408747

      Thumbnail image of graphical abstract

      Molecular duplicating: A new technique converts DNA arrays to high-density arrays of RNA. The process functions by synthesizing a DNA array containing short RNA primers, followed by steps of transcription and DNase digestion to produce only the desired RNA sequences bound to the surface.

    4. Azepines

      A Catalytic Diastereoselective Formal [5+2] Cycloaddition Approach to Azepino[1,2-a]indoles: Putative Donor–Acceptor Cyclobutanes as Reactive Intermediates

      Raynold Shenje, M. Cynthia Martin and Prof. Dr. Stefan France

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408429

      Thumbnail image of graphical abstract

      The diastereoselective synthesis of azepino[1,2-a]indoles is enabled by a formal [5+2] cycloaddition approach. The reaction presumably proceeds through a Lewis acid catalyzed formal [2+2] cycloaddition of an alkene with an N-indolyl alkylidene β-amide ester to form a donor–acceptor cyclobutane intermediate, which subsequently undergoes an intramolecular ring-opening cyclization.

  4. Highlights

    1. Synthetic Methods

      Thiyl Radicals: From Simple Radical Additions to Asymmetric Catalysis

      Hariharaputhiran Subramanian, Ramkumar Moorthy and Prof. Dr. Mukund P. Sibi

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408781

      Thumbnail image of graphical abstract

      Thiyl radicals at play: Thiyls are significant free-radical intermediates both in biology and chemistry. The recent search for new enantioselective methods in radical chemistry has led to the inclusion of these radicals in the toolbox of chiral organocatalysts.

  5. Reviews

    1. Vesicle Transport

      The Molecular Machinery of Neurotransmitter Release (Nobel Lecture)

      Prof. Thomas C. Südhof

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201406359

      Thumbnail image of graphical abstract

      The most important property of synaptic transmission is its speed, which is crucial for the overall workings of the brain. In his Nobel Lecture, T. C. Südhof explains how the synaptic vesicle and the plasma membrane undergo rapid fusion during neurotransmitter release and how this process is spatially organized, such that opening of Ca2+-channels allows rapid translation of the entering Ca2+ signal into a fusion event.

  6. Communications

    1. Protein Folding | Hot Paper

      Capturing the Mechanical Unfolding Pathway of a Large Protein with Coiled-Coil Probes

      Qing Li, Zackary N. Scholl and Prof. Piotr E. Marszalek

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201407211

      Thumbnail image of graphical abstract

      An antiparallel coiled coil (CC) mechanical probe that can be used to assess the unfolding mechanism of a protein is developed. When a protein is studied by single-molecule force spectroscopy, the probe enables the assignment of force peaks to structural elements when the unfolding process passes through the location of the CC probe without significant disturbance of the host protein structure.

    2. Zintl Cluster Compounds

      On the Formation of Intermetalloid Clusters: Titanocene(III)diammin as a Versatile Reactant Toward Nonastannide Zintl Clusters

      Dr. Christian B. Benda, Dr. Markus Waibel and Prof. Dr. Thomas F. Fässler

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407855

      Thumbnail image of graphical abstract

      MSn8—Like the seeds of a blowball: In the presence of Zintl anions, titanocene(IV) dichloride is reduced in liquid ammonia, and a titanocene(III) diammin complex is formed. Stepwise ligand exchange reactions lead to a variety of intermediate TinSnm clusters that give insight into the formation of larger intermetalloid clusters.

    3. Nitrous Oxide

      Synthesis of Triazenes with Nitrous Oxide

      Gregor Kiefer, Dr. Tina Riedel, Prof. Paul J. Dyson, Dr. Rosario Scopelliti and Prof. Kay Severin

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408597

      Thumbnail image of graphical abstract

      Synthesis with laughing gas: Triazenes can be obtained by the reaction of N2O with secondary lithium amides and Grignard reagents. The new synthetic method allows access to triazenes with alkenyl and alkynyl substituents at the 1-position. Some of the alkynyl triazenes show selective anticancer activity in cell cultures.

    4. Heterogeneous Catalysis

      Thermal Non-Oxidative Aromatization of Light Alkanes Catalyzed by Gallium Nitride

      Dr. Lu Li, Xiaoyue Mu, Wenbo Liu, Xianghua Kong, Shizhao Fan, Prof. Dr. Zetian Mi and Prof. Dr. Chao-Jun Li

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408754

      Thumbnail image of graphical abstract

      Light weights: The readily available nondoped GaN material possesses superior thermal stability and catalytic activity towards the non-oxidative aromatization of light alkanes (from C1 to C6) at elevated temperature. Theoretical calculations propose an energetically favorable adsorption interaction between methane and the m-plane of GaN.

    5. Hypervalent Compounds

      Mild Silver-Mediated Geminal Difluorination of Styrenes using an Air- and Moisture-Stable Fluoroiodane Reagent

      Nadia O. Ilchenko, Dr. Boris O. A. Tasch and Prof. Kálmán J. Szabó

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408812

      Thumbnail image of graphical abstract

      Phenomenal phenonium: A formal F2 addition to styrenes was carried out by using stable and safe fluorinating reagents under mild reaction conditions. The reaction proceeds via a phenonium intermediate.

  7. Highlights

    1. Homogeneous Catalysis

      Iron-Catalyzed Hydrogenation of Esters to Alcohols

      Dr. Philippe Dupau, Minh-Loan Tran Do, Dr. Sylvain Gaillard and Prof. Dr. Jean-Luc Renaud

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407613

      Thumbnail image of graphical abstract

      Iron made it”: Recent breakthroughs in the hydrogenation of esters to alcohols by well-defined iron pincer complexes are highlighted. These complexes demonstrate promising efficiency and selectivities.

  8. Communications

    1. Crystal Structures

      The Polymorphs of L-Phenylalanine

      Franziska Stefanie Ihlefeldt, Fredrik Bjarte Pettersen, Aidan von Bonin, Malgorzata Zawadzka and Prof. Carl Henrik Görbitz

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201406886

      Thumbnail image of graphical abstract

      It was long considered impossible to prepare crystals of L-phenylalanine, the prototypical aromatic amino acid. High-quality crystals have now been obtained that provide solid-state data for two polymorphs. For one of these polymorphs the C2 space group previously assigned was revised to P21 (with Z′=4). Nice crystals can also be grown from solutions of dl-phenylalanine, but these are not proper racemic crystals.

    2. Core–Shell Structures

      One-Nanometer-Precision Control of Al2O3 Nanoshell through Solution-Based Synthesis Route

      Wei Zhang, Zi-Xiang Chi, Wen-Xin Mao, Prof. Rong-Wen Lv, Prof. An-Min Cao and Prof. Li-Jun Wan

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201406856

      Thumbnail image of graphical abstract

      Uniform surface coatings of Al2O3 with a thickness controllable at the one nanometer level were achieved by a solution-based synthesis route. Application of this coating methodology to LiCoO2 showed that its battery performance as a cathode material can be optimized by means of systematic surface control.

  9. Obituaries

    1. Franz Hillenkamp (19362014)

      Peter Roepstorff

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409504

      Thumbnail image of graphical abstract

      Franz Hillenkamp was one of the pioneers in contemporary mass spectrometry, and in 1985, he discovered, together with his postdoc Michael Karas, the principle of matrix assisted laser desorption ionization mass spectrometry (MALDI-MS).

  10. News

  11. Cover Pictures

    1. Translating Bacterial Detection by DNAzymes into a Litmus Test

      Kha Tram, Pushpinder Kanda, Prof. Dr. Bruno J. Salena, Prof. Dr. Shuangyan Huan and Prof. Dr. Yingfu Li

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409655

      Thumbnail image of graphical abstract

      Color change is common in nature and often signifies a seasonal transition, such as from summer to autumn. In their Communication (DOI: 10.1002/anie.201407021), S. Huan, Y. Li and co-workers report a new colorimetric detection method that takes advantage of an old technology. The design makes use of a DNAzyme, urease, and magnetic beads to translate the presence of E. coli bacteria into an increase in the pH value, thereby enabling colorimetric detection using the litmus test.

  12. Communications

    1. Heterocycle Synthesis

      Rhodium-Catalyzed NH Insertion of Pyridyl Carbenes Derived from Pyridotriazoles: A General and Efficient Approach to 2-Picolylamines and Imidazo[1,5-a]pyridines

      Yi Shi, Dr. Anton V. Gulevich and Prof. Dr. Vladimir Gevorgyan

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408335

      Thumbnail image of graphical abstract

      Insert here: A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. esp=α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid, Ts=4-toluenesulfonyl.

    2. Anti-Corrosion Coatings | Hot Paper

      Polyoxometalate Ionic Liquids as Self-Repairing Acid-Resistant Corrosion Protection

      M. Sc. Sven Herrmann, M. Sc. Monika Kostrzewa, Prof. Dr. Andreas Wierschem and Prof. Dr. Carsten Streb

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408171

      Thumbnail image of graphical abstract

      This corrosion: Hydrophobic polyoxometalate-based ionic liquids (POM-ILs) are used as temporary acid-resistant coatings for copper metal. Complete protection against acid vapors and liquid acids is observed and the POM-IL coating can withstand mechanical damage by a self-repairing mechanism. The compounds are easily removed and recovered for subsequent usage.

    3. Lithium Batteries | Hot Paper

      Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions

      Dr. Cheng Ma, Dr. Ezhiylmurugan Rangasamy, Dr. Chengdu Liang, Prof. Jeffrey Sakamoto, Dr. Karren L. More and Dr. Miaofang Chi

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408124

      Thumbnail image of graphical abstract

      In sharp contrast to other garnets, the cubic Li7La3Zr2O12 preserved its structure upon Li+/H+ exchange in aqueous solutions. Subsequent immersion in a 2 M LiOH solution gave reverse Li+/H+ exchange, and the structure remained unchanged. Thus cubic Li7La3Zr2O12 has the desired properties to be the solid electrolyte in aqueous lithium batteries.

    4. Enzymatic Route to Cyclic Peptides | Hot Paper

      An Efficient Method for the In Vitro Production of Azol(in)e-Based Cyclic Peptides

      Dr. Wael E. Houssen, Andrew F. Bent, Dr. Andrew R. McEwan, Nathalie Pieiller, Dr. Jioji Tabudravu, Dr. Jesko Koehnke, Greg Mann, Rosemary I. Adaba, Dr. Louise Thomas, Dr. Usama W. Hawas, Dr. Huanting Liu, Dr. Ulrich Schwarz-Linek, Prof. Margaret C. M. Smith, Prof. James H. Naismith and Prof. Marcel Jaspars

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408082

      Thumbnail image of graphical abstract

      Heterocycle-containing cyclic peptides are promising scaffolds for the pharmaceutical industry, but their chemical synthesis is very challenging. A new universal method has been devised to prepare these compounds using a set of engineered marine-derived enzymes and substrates.

    5. Nanostructures

      A Twisting Electronic Nanoswitch Made of DNA

      Dr. Yu Chuan Huang and Prof. Dipankar Sen

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407729

      Thumbnail image of graphical abstract

      A mechatronic DNA nanoswitch is composed of a tight, topologically constrained composite of four DNA strands, in which a core of four guanine-rich single strands structurally and electronically links together four DNA double helices. The addition and removal of K+ or Sr2+ cations promote the formation of alternative conformers, which show strikingly distinct electronic properties.

    6. Noncovalent Interactions

      Sequence and Chiral Selectivity of Drug–DNA Interactions Revealed by Force Spectroscopy

      Qiongzheng Hu and Prof. Shoujun Xu

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407093

      Thumbnail image of graphical abstract

      A force to be reckoned with: Intercalation of a drug molecule in a DNA duplex causes a variation in the binding force of the duplex. The differential binding force (ΔF) can be probed precisely using the force-induced remnant magnetization spectroscopy technique. The technique allows the sequence specificity of DNA and chiral selectivity of drug molecules to be revealed.

  13. Book Reviews

    1. Bridging Heterogeneous and Homogeneous Catalysis. Concepts, Strategies, and Applications. Edited by Can Li and Yan Liu.

      John Meurig Thomas

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408712

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2014. 656 pp., hardcover, € 159.00.—ISBN 978-3527335831

  14. Communications

    1. Water Splitting

      Enhanced Water Splitting at Thin Film Tungsten Trioxide Photoanodes Bearing Plasmonic Gold–Polyoxometalate Particles

      Dr. Renata Solarska, Krzysztof Bienkowski, Dr. Sylwia Zoladek, Aldona Majcher, Dr. Tomasz Stefaniuk, Prof. Pawel J. Kulesza and Prof. Jan Augustynski

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408374

      Thumbnail image of graphical abstract

      A mesoporous photoanode consisting of WO3 decorated with polyoxometalate-capped Au nanoparticles (NPs) showed a significant enhancement of the visible-light-assisted photoelectrolysis of water. Shielding of the NPs avoids the formation of recombination centers at the photoanode surface. The large increase of water splitting photocurrents is assigned to a combined plasmonic and catalytic effect of the Au NPs on the WO3 surface.

    2. Electrocatalysis | Very Important Paper

      Scanning Electrochemical Microscopy of Individual Catalytic Nanoparticles

      Tong Sun, Yun Yu, Brian J. Zacher and Prof. Michael V. Mirkin

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408408

      Thumbnail image of graphical abstract

      Tip size matters: Extremely small polished platnium electrodes were used as scanning electrochemical microscopy tips to attain spatial resolution higher than that of ordinary atomic force microscopy imaging or super-resolution optical techniques. Electron transfer and catalytic hydrogen evolution at individual metal nanoparticles were visualized (HOPG=highly ordered pyrolytic graphite).

    3. Plasmonics

      Shedding Light on the Extinction-Enhancement Duality in Gold Nanostar-Enhanced Raman Spectroscopy

      Dr. Ming Li, Dr. Jeon Woong Kang, Dr. Ramachandra Rao Dasari and Prof. Ishan Barman

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409314

      Thumbnail image of graphical abstract

      Gold nanostars: The relationship between the enhancement by surface-enhanced Raman spectroscopy (SERS) and the localized surface plasmon resonance (LSPR) band is investigated (see picture). The competition between the field enhancement and the optical extinction causes the maximum enhancement factor occurring at a blue-shifted LSPR band from the excitation wavelength rather than at the on-resonance position.

    4. Electrocatalysts

      ZIF-8 Derived Graphene-Based Nitrogen-Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts

      Hai-xia Zhong, Jun Wang, Yu-wei Zhang, Wei-lin Xu, Prof. Wei Xing, Dan Xu, Prof. Dr. Yue-fei Zhang and Prof. Dr. Xin-bo Zhang

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408990

      Thumbnail image of graphical abstract

      Nitrogen-doped: A new oxygen reduction reaction electrocatalyst was obtained from ZIF-derived porous carbon and graphene. The catalyst exhibits high activity, superior tolerance to methanol, and good stability in comparison to commercial Pt/C catalyst.

    5. Imaging of Bacteria

      PET Imaging of Bacterial Infections with Fluorine-18-Labeled Maltohexaose

      Dr. Xinghai Ning, Dr. Wonewoo Seo, Dr. Seungjun Lee, Dr. Kiyoko Takemiya, Dr. Mohammad Rafi, Dr. Xuli Feng, Dr. Daiana Weiss, Dr. Xiaojian Wang, Larry Williams, Vernon M. Camp, Malveaux Eugene, Prof. W. Robert Taylor, Prof. Mark Goodman and Prof. Niren Murthy

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408533

      Thumbnail image of graphical abstract

      Highly sensitive: A positron emission tomography (PET) tracer composed of 18F-labeled maltohexaose (MH18F) can image bacteria in vivo with a sensitivity and specificity that are orders of magnitude higher than those of fluorodeoxyglucose. MH18F can detect early-stage infections composed of as few as 105 E. coli colony-forming units (CFUs), and can identify drug resistance in bacteria in vivo.

    6. Tumor Imaging

      Targeted Imaging and Proteomic Analysis of Tumor-Associated Glycans in Living Animals

      Ran Xie, Lu Dong, Rongbing Huang, Senlian Hong, Ruoxing Lei and Prof. Xing Chen

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408442

      Thumbnail image of graphical abstract

      Sweet target: A strategy for the targeted imaging of tumor-associated glycans is reported and makes use of ligand-targeted liposomes encapsulating azidosugars. The azidosugars were selectively incorporated into the melanoma glycans in a xenograft mouse model and were then reacted with fluorophores using copper-free click chemistry for in vivo imaging or with affinity tags for proteomic analysis.

    7. Heterogeneous Catalysis

      Efficient Coupling of Solar Energy to Catalytic Hydrogenation by Using Well-Designed Palladium Nanostructures

      Dr. Ran Long, Zhoulv Rao, Keke Mao, Yu Li, Chao Zhang, Qiliang Liu, Dr. Chengming Wang, Prof. Zhi-Yuan Li, Prof. Xiaojun Wu and Prof. Yujie Xiong

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407785

      Thumbnail image of graphical abstract

      Taking shape: A Ru3+-mediated synthesis has been developed for unique Pd concave nanostructures which can directly harvest UV-to-visible light for styrene hydrogenation (see figure). The catalytic efficiency under full-spectrum irradiation at room temperature turns out to be comparable to that of the thermally (70 °C) driven reaction. The yields are higher than those obtained using Pd nanocrystals such as nanocubes and octahedrons.

    8. Kinetic Resolution

      Tungsten-Catalyzed Regio- and Enantioselective Aminolysis of trans-2,3-Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols

      Dr. Chuan Wang and Prof. Dr. Hisashi Yamamoto

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408732

      Thumbnail image of graphical abstract

      The first enantioselective aminolysis of 2,3-epoxy alcohols is described and involves the use of a tungsten catalyst with a bis(hydroxamic acid) (BHA) ligand. A sequential reaction process combining epoxidation and ring opening (by kinetic resolution) provides a new method for the preparation of virtually enantiopure amino alcohols.

    9. Enzyme Catalysis

      A Dehydratase Domain in Ambruticin Biosynthesis Displays Additional Activity as a Pyran-Forming Cyclase

      Gesche Berkhan and Dr. Frank Hahn

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407979

      Thumbnail image of graphical abstract

      Two birds with one stone: Through reaction of the recombinant polyketide synthase domain AmbDH3 with synthetic substrate surrogates, this domain was shown to have an unprecedented dual role as a dehydratase and a pyran-forming cyclase. The domain shows high stereoselectivity and relaxed substrate specificity, thus making it a potential tool for the chemoenzymatic synthesis of chiral oxygen-containing heterocycles.

    10. Iron(IV) Complexes

      A cis-Divacant Octahedral and Mononuclear Iron(IV) Imide

      Keith Searles, Prof. Dr. Skye Fortier, Dr. Marat M. Khusniyarov, Dr. Patrick J. Carroll, Dr. Jörg Sutter, Prof. Dr. Karsten Meyer, Prof. Dr. Daniel J. Mindiola and Prof. Dr. Kenneth G. Caulton

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407156

      Thumbnail image of graphical abstract

      The iron-y of an imide: A rare low-spin FeIV imide complex [(pyrr2py)Fe[DOUBLE BOND]NAd] (pyrr2py2−=bis(pyrrolyl)pyridine; Ad= 1-adamantyl) confined to a cis-divacant octahedral geometry was prepared by reduction of N3Ad with the FeII precursor [(pyrr2py)Fe(OEt2)]. The complex exhibits temperature-independent paramagnetism. In comparison to an authentic FeIII complex, such as [(pyrr2py)FeCl], the pyrr2py2− ligand is virtually redox innocent.

    11. Metal Hydrides

      Orbital-Like Motion of Hydride Ligands around Low-Coordinate Metal Centers

      Manuel A. Ortuño, Dr. Pietro Vidossich, Dr. Salvador Conejero and Prof. Dr. Agustí Lledós

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407572

      Thumbnail image of graphical abstract

      Mobile hydrides: A new type of dynamic process involving hydrides in low-coordinate NHC-based complexes has been computationally characterized. This dynamics can be described as an orbital-like motion of hydride ligands around the metal center. This novel insight leads to a better interpretation of NMR spectra.

    12. Dinitrogen Conversion

      Catalytic Dinitrogen Reduction at the Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand

      Dr. Qian Liao, Dr. Nathalie Saffon-Merceron and Dr. Nicolas Mézailles

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408664

      Thumbnail image of graphical abstract

      Stoichiometric N2 reduction at a Mo center stabilized by bulky tetradentate phosphine ligand allowed the isolation of Mo–aminoimide and Mo–imido complexes. Both are suitable catalysts for the synthesis of NTMS3 from N2 and TMSCl through a mechanism involving a TMS radical.

    13. C[BOND]H Activation

      Highly Linear Selective Cobalt-Catalyzed Addition of Aryl Imines to Styrenes: Reversing Intrinsic Regioselectivity by Ligand Elaboration

      Wengang Xu and Prof. Naohiko Yoshikai

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408028

      Thumbnail image of graphical abstract

      Paired off: The title reaction has been achieved with cobalt-based catalytic systems featuring bis(2,4-dimethoxyphenyl)(phenyl)phosphine (L) and either 2-methoxypyridine or DBU (LB), thus affording a variety of 1,2-diarylethanes in good yields. Ligand screening and deuterium-labeling studies show the ligand and Lewis base to be important in the crucial C[BOND]C reductive elimination step. Cy=cyclohexyl, PMP=para-methoxyphenyl.

    14. Quinones and Deubiquitinases

      Harnessing the Oxidation Susceptibility of Deubiquitinases for Inhibition with Small Molecules

      Shimrit Ohayon, Maya Refua, Adi Hendler, Prof. Amir Aharoni and Prof. Ashraf Brik

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408411

      Thumbnail image of graphical abstract

      Rub a DUB style: Reactive oxygen species generated by small molecules such as ortho quinones rapidly deactivate deubiquitinases (DUBs) by selective and irreversible oxidiation of the catalytic cysteine residue. DTT=dithiothreitol.

    15. Liquid Crystals

      Supramolecular [60]Fullerene Liquid Crystals Formed By Self-Organized Two-Dimensional Crystals

      Xiaoyan Zhang, Dr. Chih-Hao Hsu, Dr. Xiangkui Ren, Yan Gu, Prof. Bo Song, Dr. Hao-Jan Sun, Prof. Shuang Yang, Prof. Erqiang Chen, Prof. Yingfeng Tu, Prof. Xiaohong Li, Prof. Xiaoming Yang, Prof. Yaowen Li and Prof. Xiulin Zhu

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408438

      Thumbnail image of graphical abstract

      Soft materials: A series of fullerene dyads self-organize to form two-dimensional crystals through π–π interactions between fullerenes. Lamellar packing of the 2D crystals gives rise to the formation of a new family of thermotropic supramolecular liquid crystals with hierarchical structures.

    16. H2 Production

      Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co-Catalyst

      Dr. Ning Liu, Christopher Schneider, Dr. Detlef Freitag, Dr. Umamaheswari Venkatesan, Dr. V. R. Reddy Marthala, Prof.Dr. Martin Hartmann, Benjamin Winter, Prof.Dr. Erdmann Spiecker, Dr. Andres Osvet, Eva M. Zolnhofer, Prof.Dr. Karsten Meyer, Dr. Tomohiko Nakajima, Xuemei Zhou and Prof.Dr. Patrik Schmuki

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408493

      Thumbnail image of graphical abstract

      Without a noble metal: The high-pressure hydrogenation of commercially available anatase or mixed-phase anatase/rutile TiO2 powder resulted in a highly effective and stable photocatalyst for H2 evolution without the need for an additional co-catalyst. This activation was not observed for rutile, but for anatase/rutile mixtures, a strong synergistic effect was found.

    17. Asymmetric Catalysis

      Rationally Designed Multifunctional Supramolecular Iminium Catalysis: Direct Vinylogous Michael Addition of Unmodified Linear Dienol Substrates

      Yun Gu, Dr. Yao Wang, Tian-Yang Yu, Prof. Dr. Yong-Min Liang and Prof. Dr. Peng-Fei Xu

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201406786

      Thumbnail image of graphical abstract

      Fall into line: The title catalysis strategy has been developed for addressing the long-standing problem of the direct vinylogous Michael addition of unmodified linear dienol substrates. The desired 1,7-dioxo compounds were obtained with good yields and excellent regio- and enantioselectivity. DCE=1,2-dichloroethane, TMS=trimethylsilyl.

    18. Diagnostic GPI

      Diagnosis of Toxoplasmosis Using a Synthetic Glycosylphosphatidylinositol Glycan

      Dr. Sebastian Götze, Dr. Nahid Azzouz, Dr. Yu-Hsuan Tsai, Prof. Dr. Uwe Groß, Anika Reinhardt, Dr. Chakkumkal Anish, Prof. Dr. Peter H. Seeberger and Dr. Daniel Varón Silva

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201406706

      Thumbnail image of graphical abstract

      Good news for cat lovers! A glycosylphosphatidylinositol (GPI) glycan resembling an antigen on the parasite T. gondii was synthesized and immobilized on a microarray. This setup can be used to diagnose toxoplasmosis. Latent and acute toxoplasmosis can be readily distinguished.

    19. Total Synthesis | Hot Paper

      A Cascade Strategy Enables a Total Synthesis of (−)-Gephyrotoxin

      Shuyu Chu, Dr. Stephen Wallace and Prof. Dr. Martin D. Smith

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201409038

      Thumbnail image of graphical abstract

      The concise synthesis of (−)-gephyrotoxin from L-pyroglutaminol involves a diastereoselective intramolecular enamine/Michael cascade reaction that forms two rings and two stereocenters and generates a stable tricyclic iminium cation. A hydroxy-directed reduction of this intermediate plays a key role in establishing the required cis-configured decahydroquinoline ring system.

    20. Isomer Separation

      C60-Mediated Molecular Shape Sorting: Separation and Purification of Geometrical Isomers

      Moumita Rana, R. Bharathanatha Reddy, Bibhuti Bhusan Rath and Dr. Ujjal K. Gautam

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408981

      Thumbnail image of graphical abstract

      Pick and choose: The ability of C60 to form crystals with molecules of a suitable geometry under ambient conditions was used to develop a method to separate geometrical isomers of molecules such as xylene and trimethylbenzene. The versatility of this approach is demonstrated by preparing a C60–trimethylbenzene solvate crystal, where the purity of the separated isomers is much higher than the commercially available products.

    21. Cooperative Effects

      Synthesis and Ligand Modification Chemistry of a Molybdenum Dinitrogen Complex: Redox and Chemical Activity of a Bis(imino)pyridine Ligand

      Grant W. Margulieux, Zoë R. Turner and Prof. Paul J. Chirik

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408725

      Thumbnail image of graphical abstract

      Good golly Miss ‘Moly’: A molybdenum dinitrogen complex supported by a redox-active bis(imino)pyridine ligand has been synthesized and structurally characterized. Unique N[BOND]H addition chemistry involving metal–ligand cooperativity has been observed with ammonia and aryl hydrazines, as well as primary and secondary amines. Such transformations are of relevance for synthetic schemes for the interconversion of ammonia and its elements.

    22. Porphyrinoids

      Neo-Fused Hexaphyrin: A Molecular Puzzle Containing an N-Linked Pentaphyrin

      Pingchun Wei, Kai Zhang, Dr. Xin Li, Deying Meng, Prof. Dr. Hans Ågren, Prof. Dr. Zhongping Ou, Prof. Dr. Seikweng Ng, Prof. Dr. Hiroyuki Furuta and Prof. Dr. Yongshu Xie

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408307

      Thumbnail image of graphical abstract

      Fusion, confusion? Ring fusion of neo-confused hexaphyrin (1.1.1.1.1.0) 1 led to the bicyclic neo-fused hexaphyrin 2, and subsequent CuII coordination triggered a ring opening reaction to afford a contracted N-linked pentaphyrin 3. The reactive N[BOND]C bonds in the porphyrinoid macrocycles play an important role.

    23. Natural Product Synthesis | Hot Paper

      Total Synthesis of the Tetracyclic Antimalarial Alkaloid (±)-Myrioneurinol

      Anthony J. Nocket and Prof. Dr. Steven M. Weinreb

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407810

      Thumbnail image of graphical abstract

      Malaria’s worst nightmare: A total synthesis of the tetracyclic antimalarial Myrioneuron alkaloid (±)-myrioneurinol features three highly diastereoselective reactions as the key steps: an intramolecular Michael addition of a lactam titanium enolate to an α,β-unsaturated ester, a conjugate addition of a malonate enolate to a nitrosoalkene, and an intramolecular aza-Sakurai reaction.

    24. Boron Compounds

      Isolation of a Three-Coordinate Boron Cation with a Boron–Sulfur Double Bond

      Dr. Daniel Franz, Dr. Elisabeth Irran and Prof. Dr. Shigeyoshi Inoue

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407809

      Thumbnail image of graphical abstract

      A healthy relationship: The first three-coordinate boron cation with a boron–sulfur double bond has the shortest B[BOND]S distance reported for a molecular complex. In the calculated LUMO, the contribution from the boron center confirms that the compound is a boron-centered cation. The HOMO−1 reveals the π interaction which is the cause of the close contact between B and S.

    25. Semihydrogenation

      A Palladium Nanoparticle–Nanomicelle Combination for the Stereoselective Semihydrogenation of Alkynes in Water at Room Temperature

      Eric D. Slack, Christopher M. Gabriel and Prof. Dr. Bruce H. Lipshutz

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407723

      Thumbnail image of graphical abstract

      Nano, meet nano! The addition of NaBH4 to Pd(OAc)2 in water containing nanomicelles leads to generation of H2 and Pd nanoparticles. This combination leads to clean and highly selective conversion of alkynes to Z-alkenes at room temperature. The aqueous mixture is smoothly recycled without loss of reagent activity, stereochemical outcome, or yield. Furthermore, many functional groups are tolerated under these green conditions.

    26. Chirality Transfer

      Supramolecular Architectures from Bent-Core Dendritic Molecules

      Dr. Miguel Cano, Dr. Antoni Sánchez-Ferrer, Prof. Dr. José Luis Serrano, Dr. Nélida Gimeno and Prof. Dr. M. Blanca Ros

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407705

      Thumbnail image of graphical abstract

      Twist of fate: Achiral, ionic bent-core dendrimers can not only lead to different bent-core liquid crystals (BCLCs) but also to a variety of aggregates in water, such as rods, spheres, nontwisted, or twisted fibers, and helical ribbons that lead to tubules. The conformational chirality of bent-core molecules in BCLCs can also be translated to chiral supramolecular architectures in the presence of a solvent.

    27. Circular Helicates

      Formation of a Dimer of Trinuclear Helicates which Encapsulates an Array of Six Hydrogen-Bonded Anions

      Robert A. Faulkner, Dr. Lindsay P. Harding, Joshua Higginson, Prof. Craig R. Rice and Christopher Slater

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407645

      Thumbnail image of graphical abstract

      Cu does the twist: Cu2+ ions react with ligand L, containing two bidentate pyridyl-thiazole units linked by 1,3-diaminophenylene, to form a dinuclear double helicate [Cu2L2]4+. [Cu2L2]4+ reacts with OPO3H2 ions (0.5 equiv) to give the unsaturated double helicate [Cu2L2(OPO3H2)]3+. Further reaction of [Cu2L2(OPO3H2)]3+ with OPO3H2 yields a trinuclear circular helicate which self-assembles into a hexameric cluster [{Cu3L3(OPO3H2)3}2]6+ (see structure).

    28. Self-Healing Materials

      A Rapidly Self-Healing Supramolecular Polymer Hydrogel with Photostimulated Room-Temperature Phosphorescence Responsiveness

      Hui Chen, Prof. Xiang Ma, Dr. Shuaifan Wu and Prof. He Tian

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407402

      Thumbnail image of graphical abstract

      A supramolecular polymeric hydrogel forms by host–guest recognition between a β-cyclodextrin polymer and an α-bromonaphthalene polymer without any additional gelators. This hydrogel can self-heal within only about one minute under ambient atmosphere without any additive, and can be excited to engender photostimulated room temperature phosphorescence (RTP) emission when azobenzene polymer is introduced.

  15. Essays

    1. History of Science

      Theodore William Richards: Apostle of Atomic Weights and Nobel Prize Winner in 1914

      Prof. Dr. Dudley R. Herschbach

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407464

      Thumbnail image of graphical abstract

      In recognition of his exact determinations of the atomic weights of a large number of the chemical elements, T. W. Richards received the Nobel Prize in Chemistry in 1914. His meticulous techniques resulted in “a degree of accuracy never before attained”. This Essay follows Richards from his precocious youth to becoming a celebrated chemist and emphasizes his dedication to foresee likely sources of error and how to avoid them.

  16. Highlights

    1. Photoredox Catalysis

      Oxidative Photoredox-Catalytic Activation of Aliphatic Nucleophiles for C(sp3)–C(sp2) Cross-Coupling Reactions

      Dr. Emanuela Jahn and Dr. Ullrich Jahn

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408748

      Thumbnail image of graphical abstract

      In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  17. Communications

    1. Metalloenzymes

      Iron(III) Located in the Dinuclear Metallo-β-Lactamase IMP-1 by Pseudocontact Shifts

      Thomas J. Carruthers, Dr. Paul D. Carr, Dr. Choy-Theng Loh, Dr. Colin J. Jackson and Prof. Gottfried Otting

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408693

      Thumbnail image of graphical abstract

      Metal detector: Pseudocontact shifts measured by NMR spectroscopy allow the accurate determination of the location of paramagnetic metal ions in the active site of dinuclear metalloenzymes. Using this method a [FeZn]-complex of the metallo-β-lactamase IMP-1 could be identified and characterized.

    2. Metal Atom Wires

      A Motif for Infinite Metal Atom Wires

      Xi Yin, Steven A. Warren, Yung-Tin Pan, Kai-Chieh Tsao, Dr. Danielle L. Gray, Dr. Jeffery Bertke and Prof.Dr. Hong Yang

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408461

      Thumbnail image of graphical abstract

      Totally wired: A new motif for the synthesis of 1D metal atom wire crystal is described in which Pd/Pt heterometallic and Pd atom chain structures were formed. The picture depicts an SEM micrograph of a needle-like crystal of the metal atom wire compound and representations of its molecular building blocks.

    3. Organocatalysis

      Lewis Base Catalyzed Aerobic Oxidative Intermolecular Azide–Zwitterion Cycloaddition

      Wenjun Li and Prof. Dr. Jian Wang

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408265

      Thumbnail image of graphical abstract

      The works: The discovery of a novel aerobic oxidative intermolecular azide–zwitterion reaction catalyzed by an organocatalyst is presented. It is demonstrated that the merger of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and electron-deficient olefins generates reactive zwitterion intermediates, which readily participate in cycloaddition reactions with an array of azides, thus providing facile entry to fully or highly substituted 1,2,3-triazole frameworks.

    4. Helical Structures

      Construction of a Highly Distorted Benzene Ring in a Double Helicene

      Dr. Sigma Hashimoto, Soichiro Nakatsuka, Prof. Dr. Masaharu Nakamura and Prof. Dr. Takuji Hatakeyama

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408390

      Thumbnail image of graphical abstract

      Bent on helices: A P-fused double helicene consisting of a highly distorted benzene, with a bending angle of 23°, has been synthesized by a tandem intramolecular phospha-Friedel–Crafts reaction. Despite distortion and reduced aromaticity, the proposed molecule shows thermal and chemical stability, and can be converted into the corresponding C2-symmetric bis(phosphine).

    5. Oxygen Storage | Hot Paper

      Metal–Organic Frameworks for Oxygen Storage

      Dr. Jared B. DeCoste, Dr. Mitchell H. Weston, Patrick E. Fuller, Trenton M. Tovar, Gregory W. Peterson, Dr. M. Douglas LeVan and Dr. Omar K. Farha

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408464

      Thumbnail image of graphical abstract

      MOFs store oxygen too: Two metal–organic frameworks with open metal sites store oxygen at capacities far greater than that of an empty cylinder and are comparable to the state-of-the-art oxygen storage materials. Self-assembled materials allow for rational design of materials for adsorption of specific gases.

    6. Supported Catalysts

      Bulky Aryloxide Ligand Stabilizes a Heterogeneous Metathesis Catalyst

      Dr. Matthew P. Conley, Dr. William P. Forrest, Dr. Victor Mougel, Prof. Dr. Christophe Copéret and Prof. Dr. Richard R. Schrock

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408880

      Thumbnail image of graphical abstract

      Like a rock: Grafting a W-oxo alkylidene, containing bulky adamantyl-substituted phenoxy ligands, onto partially dehydroxylated silica generates a very active and stable metathesis catalyst. This large ligand allows efficient terminal alkene homocoupling with a turnover number (TON) exceeding 75 000.

    7. Bioimaging

      Mitochondria-Targeted Cancer Therapy Using a Light-Up Probe with Aggregation-Induced-Emission Characteristics

      Dr. Qinglian Hu, Dr. Meng Gao, Guangxue Feng and Prof.Dr. Bin Liu

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408897

      Thumbnail image of graphical abstract

      Lighting up mitochondria: A mitochondria-targeting probe (AIE-mito-TPP) has been developed, comprising a triphenylphosphine (TPP) moiety conjugated to a fluorogen, which can undergo aggregation-induced emission (AIE). The preferential aggregation and subsequent emission of AIE-mito-TPP within cancer-cell mitochondria makes them a potential agent for cancer-cell imaging and therapy.

  18. Cover Pictures

    1. Membrane-Spanning DNA Nanopores with Cytotoxic Effect

      Dr. Jonathan R. Burns, Noura Al-Juffali, Dr. Sam M. Janes and Dr. Stefan Howorka

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201409587

      Thumbnail image of graphical abstract

      Reducing the viability of cancerous tissues is relevant in biomedicine and basic research. In their Communication (DOI: 10.1002/anie.201405719), S. Howorka et al. show that cancer cells can be killed by rupturing their plasma membrane with DNA nanopores. The piercing of cells only occurs when the DNA pores carry an outer hydrophobic belt for bilayer insertion. Future development will pave the way for targeting specific cancer types or for the more general shuttling of drugs into cells.

  19. Communications

    1. C[BOND]H Functionalization | Very Important Paper

      Ruthenium–Porphyrin-Catalyzed Diastereoselective Intramolecular Alkyl Carbene Insertion into C[BOND]H Bonds of Alkyl Diazomethanes Generated In Situ from N-Tosylhydrazones

      Annapureddy Rajasekar Reddy, Cong-Ying Zhou, Zhen Guo, Jinhu Wei and Prof. Dr. Chi-Ming Che

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408102

      Thumbnail image of graphical abstract

      Nose to tail: With a ruthenium–porphyrin catalyst, alkyl diazomethanes generated in situ from N-tosylhydrazones underwent efficient intramolecular C(sp3)[BOND]H insertion to give substituted tetrahydrofurans and pyrrolidines (see scheme) in a reaction that can be viewed as a reductive coupling between C[DOUBLE BOND]O and C[BOND]H bonds to form a new C[BOND]C bond. This transformation was applied in a concise synthesis of (±)-pseudoheliotridane.

    2. Iron Catalysis

      Iron-Induced Regio- and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

      Dr. Masayuki Iwasaki, Tomoya Fujii, Prof. Dr. Kiyohiko Nakajima and Prof. Dr. Yasushi Nishihara

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408121

      Thumbnail image of graphical abstract

      Radical action: Regio- and stereoselective chlorothiolation of alkynes is achieved with an inexpensive and abundant iron catalyst. The reaction simultaneously installs chloro and sulfenyl moieties on terminal and internal alkynes, providing synthetically useful tri- and tetrasubstituted alkenes with excellent selectivity by a radical pathway. The utility of the reaction is shown by transformations of the adducts using cross-coupling reactions.

    3. Kinase Sensing

      Differential Sensing of MAP Kinases Using SOX-Peptides

      Dr. Diana Zamora-Olivares, Dr. Tamer S. Kaoud, Dr. Jiney Jose, Prof. Andrew Ellington, Prof. Kevin N. Dalby and Prof. Eric V. Anslyn

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408256

      Thumbnail image of graphical abstract

      SOX it to the kinases: Five SOX peptides are used to classify groups of mitogen-activated protein kinases (MAPK) and their isoforms using chemometrics. The score plots show excellent classification and accuracy, while support vector machine analysis serves to quantify ERK and an ERK inhibitor concentration in kinase mixtures. Examination of the loading plots reveals cross-reactivity among the peptides, and some unexpected results.

    4. Biocatalysis

      Artificial Multienzyme Supramolecular Device: Highly Ordered Self-Assembly of Oligomeric Enzymes In Vitro and In Vivo

      Dr. Xin Gao, Shuai Yang, Chengcheng Zhao, Prof. Yuhong Ren and Prof. Dongzhi Wei

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201405016

      Thumbnail image of graphical abstract

      The more the merrier: A two-dimensional layer-like supramolecular assembly of octameric leucine dehydrogenase and dimeric formate dehydrogenase was generated in vitro and in vivo by combining enzyme oligomerization and protein–protein interaction properties. This multienzyme structure had greater stability and higher NAD(H) recycling efficiency than unassembled enzymes when applied to a coenzyme recycling system.

    5. Antitumor Vaccines

      A Fully Synthetic Four-Component Antitumor Vaccine Consisting of a Mucin Glycopeptide Antigen Combined with Three Different T-Helper-Cell Epitopes

      Dipl.-Chem. Björn Palitzsch, Dipl.-Chem. Sebastian Hartmann, Dipl.-Chem. Natascha Stergiou, Dipl.-Chem. Markus Glaffig, Prof. Dr. Edgar Schmitt and Prof. Dr. Horst Kunz

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201406843

      Thumbnail image of graphical abstract

      The criss-cross formation of squaric acid diamides was used in the synthesis of anticancer vaccines in which a tumor-associated MUC1 glycopeptide antigen is combined with three different bacterial T-helper-cell epitopes. Without support by complete Freund’s adjuvant, the four-component vaccine elicits strong a immune responses in mice and predominantly protective IgG antibodies that recognize human breast cancer cells.

    6. Coordination Complexes

      Synthesis of Square-Planar Aluminum(III) Complexes

      Emily J. Thompson, Thomas W. Myers and Louise A. Berben

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201407098

      Thumbnail image of graphical abstract

      On a plain: Two square-planar complexes of aluminum(III) with chloride and hydride ligands have been synthesized (see picture; C gray, N blue, Al crimson, Cl green). These are supported by tridentate bis(imino)pyridine ligands that are reduced by two electrons. The AlIII ion in each is Lewis acidic enough to bind 2,6-lutidine.

    7. Nanostructures

      Size-Controlled Synthesis of Conjugated Polymer Nanoparticles in Confined Nanoreactors

      Sheng Deng, Dr. Jian Zhi, Xianmei Zhang, Qingqing Wu, Dr. Yun Ding and Prof. Aiguo Hu

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201407387

      Thumbnail image of graphical abstract

      Size matters: Soluble conjugated polymeric nanoparticles are synthesized by Suzuki-type polycondensation of two monomers in the channel of ordered mesoporous silica-supported carbon nanomembranes. These synthesized soluble conjugated microporous polymers (SCMPs) exhibit uniform particle-size distributions and well-controlled particle sizes. The SCMPs are particularly attractive in light-emitting and other optoelectronic applications.

    8. Analytical Methods

      Complementary Standoff Chemical Imaging to Map and Identify Artist Materials in an Early Italian Renaissance Panel Painting

      Dr. Kathryn A. Dooley, Damon M. Conover, Dr. Lisha Deming Glinsman and Dr. John K. Delaney

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201407893

      Thumbnail image of graphical abstract

      Technical art history: Visible-to-near-infrared reflectance imaging spectroscopy (RIS) and X-ray fluorescence (XRF) imaging spectroscopy were used as complementary chemical imaging methods to provide a robust spatial distribution of pigments. Hyperspectral RIS analysis allowed the isolation of the preparatory drawing from both the overlying original paint of the artist and the inpaint of the conservator.

    9. Carbon Clusters | Hot Paper

      The Structure and Stability of Magic Carbon Clusters Observed in Graphene Chemical Vapor Deposition Growth on Ru(0001) and Rh(111) Surfaces

      Dr. Junfeng Gao and Prof. Feng Ding

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201406570

      Thumbnail image of graphical abstract

      Nucleation of graphene: A new carbon cluster, composed of a C21 core and three dangling carbon atoms, is found to be exceptionally stable (see picture). This cluster is the most probable carbon cluster observed during the growth of graphene on Ru(0001) and Rh(111) surfaces by chemical vapor deposition.

  20. Highlights

    1. Heterogeneous Catalysis

      Heterogeneous Catalysis of CO2 Conversion to Methanol on Copper Surfaces

      Prof. Dr. Malte Behrens

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201409282

      Thumbnail image of graphical abstract

      Combined experimental and theoretical approaches resulted in a better understanding of the hydrogenation of CO2 to methanol on copper-based catalysts. These results highlight the important role of the reducible oxide promoter for CO2 activation.

  21. Communications

    1. Electrolytes for Li-Ion Batteries

      Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries

      Dr. Santanab Giri, Swayamprabha Behera and Prof. Puru Jena

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408648

      Thumbnail image of graphical abstract

      Halogen-free electrolytes: An in-depth study based on first-principles calculations shows that the anions of commercially available electrolytes for Li-ion batteries are all superhalogens. With this knowledge, several halogen-free superhalogen electrolytes with comparable characteristics are identified.

    2. Oxetanes

      Synthesis of Di-, Tri-, and Tetrasubstituted Oxetanes by Rhodium-Catalyzed O[BOND]H Insertion and C[BOND]C Bond-Forming Cyclization

      Owen A. Davis and Dr. James A. Bull

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408928

      Thumbnail image of graphical abstract

      It only takes two (steps): Highly substituted oxetanes and fused oxetane bicycles were generated by a mild, functional-group-tolerant O[BOND]H insertion and cyclization strategy. Enantioenriched oxetanes were obtained with complete retention of configuration from enantioenriched bromohydrins. These oxetanes present interesting building blocks for medicinal chemistry and were further functionalized, while the oxetane ring remained intact.

  22. News

  23. Author Profiles

    1. David Scheschkewitz

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201409127

      Thumbnail image of graphical abstract

      The best advice I have ever been given is to be prepared for the unexpected. The worst advice I have ever been given was not to try something because it had been tried before.

  24. Book Reviews

    1. Multicomponent Reactions. Volumes 1 and 2. Science of Synthesis Workbench Edition. Edited by Thomas J. J. Müller.

      Romano V. A. Orru

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408144

      Thumbnail image of graphical abstract

      Thieme, Stuttgart, 2014. 1278 pp., softcover, € 549.00.—ISBN 978-3131765611

  25. Communications

    1. Bioorthogonal Chemistry

      Coumarin-Based Fluorogenic Probes for No-Wash Protein Labeling

      Yingche Chen, Christopher M. Clouthier, Kelvin Tsao, Miroslava Strmiskova, Hugo Lachance and Prof. Jeffrey W. Keillor

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408015

      Thumbnail image of graphical abstract

      Labeling with FlARe: A coumarin-based dimaleimide labeling agent bearing substituted maleimide groups was prepared. Methoxy substituents were sufficient to attenuate reactivity with glutathione without adversely affecting reactivity with the dithiol target tag (dC10α; red). This kinetic selectivity enables the specific fluorescent labeling of a protein of interest (POI) in living cells through a fluorogenic addition reaction (FlARe).

    2. Hydrogen Production | Hot Paper

      A Molecular Copper Catalyst for Electrochemical Water Reduction with a Large Hydrogen-Generation Rate Constant in Aqueous Solution

      Peili Zhang, Prof. Mei Wang, Yong Yang, Tianyi Yao and Prof. Licheng Sun

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408266

      Thumbnail image of graphical abstract

      Acidic electrolysis: An ionic copper amine-pyridine complex displayed a hydrogen-generation rate constant (kobs) of over 10000 s−1 in pH 2.5 buffer solutions. A turnover frequency of 7000 h−1 cm−2 and a Faradaic efficiency of 96 % were measured in an extended controlled potential electrolysis experiment at −0.90 V versus the standard hydrogen electrode over two hours using a glassy carbon electrode.

    3. Asymmetric Synthesis | Hot Paper

      Organocatalytic and Scalable Synthesis of the Anti-Influenza Drugs Zanamivir, Laninamivir, and CS-8958

      Dr. Junshan Tian, Jiankang Zhong, Yunsheng Li and Prof. Dr. Dawei Ma

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408138

      Thumbnail image of graphical abstract

      A strategy to combat the flu: The anti-influenza drugs zanamivir and laninamivir (see structures) were synthesized in only 13 steps from inexpensive D-araboascorbic acid by the use of an organocatalytic Michael addition and a metal-catalyzed anti-selective Henry reaction as key transformations. This cost-effective, straightforward, and efficient approach enabled the synthesis of more than 3.5 g of zanamivir.

    4. Biosensors | Hot Paper

      Photocaged DNAzymes as a General Method for Sensing Metal Ions in Living Cells

      Kevin Hwang, Peiwen Wu, Taejin Kim, Lei Lei, Shiliang Tian, Prof. Yingxiao Wang and Prof. Yi Lu

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408333

      Thumbnail image of graphical abstract

      The attachment of a photolabile protecting group (PG) to a DNAzyme allows its delivery into cells, where irradiation with light restores its activity, thus allowing temporal control over the sensing of metal ions. F=fluorophore, Q=quencher.

    5. Protein Folding

      Reversible Unfolding–Refolding of Rubredoxin: A Single-Molecule Force Spectroscopy Study

      Dr. Peng Zheng, Dr. Yanyan Wang and Prof. Dr. Hongbin Li

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201408105

      Thumbnail image of graphical abstract

      Folding technique: A study employing single-molecule force spectroscopy showed that a metastable Fe(SCys)2 intermediate is key to the refolding of holo-rubredoxin and the reconstitution of the FeS4 center. The study also provides experimental evidence for the iron-priming mechanism for the folding of rubredoxin.

    6. Rhodium Catalysis | Hot Paper

      A Complete Switch of the Directional Selectivity in the Annulation of 2-Hydroxybenzaldehydes with Alkynes

      Dr. Huiying Zeng and Prof. Dr. Chao-Jun Li

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201407589

      Thumbnail image of graphical abstract

      Rodeo rhodium: Different natural product skeletons can be obtained from the same simple starting materials by using different catalytic systems. The gold-catalyzed annulation of terminal alkynes and salicylaldehydes yielded isoflavanones, whereas the rhodium-catalyzed version led to coumarin skeletons.

    7. Asymmetric Catalysis

      Asymmetric Triple Relay Catalysis: Enantioselective Synthesis of Spirocyclic Indolines through a One-Pot Process Featuring an Asymmetric 6π Electrocyclization

      Xiao-Ping Yin, Xing-Ping Zeng, Yun-Lin Liu, Fu-Min Liao, Jin-Sheng Yu, Dr. Feng Zhou and Prof. Dr. Jian Zhou

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201407677

      Thumbnail image of graphical abstract

      Oxindole-based spirocyclic indolines were prepared through a one-pot process that involved the hydrogenation of nitroarenes, ketimine formation, and an asymmetric [1,5] electrocyclic reaction. This final step was catalyzed by a bifunctional chiral tertiary amine that also featured a hydrogen bond donor moiety.

    8. Supramolecular Chemistry

      A Simple and Highly Effective Ligand System for the Copper(I)-Mediated Assembly of Rotaxanes

      Dr. Christopher J. Campbell, Prof. David A. Leigh, Dr. Inigo J. Vitorica-Yrezabal and Steffen L. Woltering

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201407817

      Thumbnail image of graphical abstract

      The Cu(I)prit: A [2]rotaxane was produced through the assembly of a picolinaldehyde, an amine, and a bipyridine macrocycle (blue rings) around a CuI template by imine bond formation in close-to-quantitative yield. An analogous [3]rotaxane was obtained in excellent yield by replacing the amine with a diamine, thus showing the suitability of the system for the construction of higher order interlocked structures.

    9. Bacteria Identification | Hot Paper

      Identification of Bacteria in Water by a Fluorescent Array

      Wenwen Chen, Prof. Qizhai Li, Wenshu Zheng, Fang Hu, Prof. Guanxin Zhang, Prof. Zhuo Wang, Prof. Deqing Zhang and Prof. Xingyu Jiang

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201407606

      Thumbnail image of graphical abstract

      What's this bug? Probes with special fluorescent characteristics are used to fabricate an array (F-array) for bacteria identification with the assistance of statistical methods. Eight kinds of bacteria are discriminated successfully; even normal bacteria and multidrug-resistant bacteria can be distinguished. The method is easy to perform, fast, and effective.

    10. Enzymatic Mechanisms | Hot Paper

      Direct Evidence for a Peroxide Intermediate and a Reactive Enzyme–Substrate–Dioxygen Configuration in a Cofactor-free Oxidase

      Dr. Soi Bui, Dr. David von Stetten, Dr. Pablo G. Jambrina, Prof. Thierry Prangé, Dr. Nathalie Colloc'h, Dr. Daniele de Sanctis, Dr. Antoine Royant, Dr. Edina Rosta and Dr. Roberto A. Steiner

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201405485

      Thumbnail image of graphical abstract

      Peroxide intermediate: X-ray crystallography supported by in crystallo Raman spectroscopy and QM/MM methods reveals that the archetypical cofactor-free uricase catalyzes urate degradation via a C5(S)-peroxide intermediate. X-rays break the peroxide C5[BOND]OO(H) carbon–oxygen bond releasing dioxygen in situ, affording exquisite insight into the reactants′ configuration leading to the peroxo intermediate.

    11. Main-Group Chemistry

      Dilithium Hexaorganostannate(IV) Compounds

      M. Sc. Ireen Schrader, Dr. Kornelia Zeckert and Dr. Stefan Zahn

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201406260

      Thumbnail image of graphical abstract

      Add in to tin: Tin can readily accommodate more ligands than necessary to complete its Lewis octet. This ability allows it to host six carbon ligands to give the first hexaaryltin(IV) compounds of type [Sn(2-pyR)6]2− (see figure). The intramolecular coordination of the Li+ counterions stabilizes the reactive dianion.

    12. Noble-Gas Compounds

      Xenon(II) Polyfluoridotitanates(IV): Synthesis and Structural Characterization of [Xe2F3]+ and [XeF]+ Salts

      Kristian Radan, Dr. Evgeny Goreshnik and Prof. Boris Žemva

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201406404

      Thumbnail image of graphical abstract

      Stronger together: The molecule TiF4 is unable to efficiently remove fluoride from XeF2. However, at elevated temperatures, the large polytitanate species formed have an enhanced fluoride affinity, comparable to that of the strongest Lewis acids. Thermal reaction between XeF2 and TiF4 afforded colorless crystals the XeII species [Xe2F3][Ti8F33] (see picture) and [XeF]2[Ti9F38] which were isolated and structurally characterized.

    13. Photocatalysis

      Molecular-Level Understanding of the Photocatalytic Activity Difference between Anatase and Rutile Nanoparticles

      Dr. Wooyul Kim, Prof. Takashi Tachikawa, Gun-hee Moon, Prof. Tetsuro Majima and Prof. Wonyong Choi

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201406625

      Thumbnail image of graphical abstract

      Diffusing free hydroxyl radicals (.OHf) in water are responsible for the higher activity of anatase compared to rutile. A single-molecule detection system was used to directly observe the diffusion of .OHf from the anatase surface to the solution bulk. In contrast, rutile did not create .OHf at all.

    14. Polymerization | Very Important Paper

      Preparation of Stereoregular Isotactic Poly(mandelic acid) through Organocatalytic Ring-Opening Polymerization of a Cyclic O-Carboxyanhydride

      Dr. Antoine Buchard, Dr. David R. Carbery, Prof. Matthew G. Davidson, Dr. Petya K. Ivanova, Dr. Ben J. Jeffery, Dr. Gabriele I. Kociok-Köhn and Dr. John P. Lowe

      Article first published online: 14 OCT 2014 | DOI: 10.1002/anie.201407525

      Thumbnail image of graphical abstract

      Controlling tactic(s): The use of pyridine alone as organocatalyst of the ring-opening polymerization (ROP) of a cyclic O-carboxyanhydride resulted in atactic poly(mandelic acid) (PMA), however, a well-defined pyridine/mandelic acid adduct enabled excellent control over the ROP, providing highly isotactic chiral PMA with an enhanced heat resistance. Tg=glass-transition temperature.

  26. Reviews

    1. Analytical Methods

      Microfluidic Isolation of Nucleic Acids

      Sarah J. Reinholt and Prof. Antje J. Baeumner

      Article first published online: 13 OCT 2014 | DOI: 10.1002/anie.201309580

      Thumbnail image of graphical abstract

      It′s a small world: Many nucleic acid isolation techniques have been miniaturized and integrated into microfluidic devices, each having their own advantages and disadvantages, as well as (potential) applications. The techniques presented include using silica-based surfaces, functionalized paramagnetic beads, oligonucleotide-modified polymer surfaces, pH-dependent charged surfaces, and aluminum oxide membranes.

SEARCH

SEARCH BY CITATION