Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 35

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. Communications

    1. Biocatalysis

      Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids

      Anna M. Rydzik, Ivanhoe K. H. Leung, Grazyna T. Kochan, Michael A. McDonough, Timothy D. W. Claridge and Prof. Christopher J. Schofield

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406125

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      Thinking outside the BBOX: γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate (2OG)-dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers.

    2. Li-Ion Batteries | Very Important Paper

      Sustainable Electrical Energy Storage through the Ferrocene/Ferrocenium Redox Reaction in Aprotic Electrolyte

      Dr. Yu Zhao, Yu Ding, Dr. Jie Song, Dr. Gang Li, Prof. Guangbin Dong, Prof. John B. Goodenough and Prof. Guihua Yu

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406135

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      The redox couple ferrocene/ferrocenium is applied for the construction of a liquid cathode Li-ion redox battery for electrical energy storage. The redox reaction is highly reversible and efficient. Even after 250 full charge/discharge cycles the capacity maintains ca. 90 % of the initial value and the Coulombic efficiency reaches 98–100 %.

  2. Reviews

    1. Natural Products

      Reactivity and Stability of Glucosinolates and their Breakdown Products in Foods

      Dr. Franziska S. Hanschen, Dr. Evelyn Lamy, Prof. Dr. Monika Schreiner and Prof. Dr. Sascha Rohn

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201402639

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      Vegetables such as broccoli contain a variety of cancer-preventing agents, among them glucosinolates. These sulfur-containing compounds are precursors to a variety of enzymatically or chemically formed breakdown products that affect the quality of food with regard to nutritional value, flavor, and beneficial health effects. This review provides an overview over the reactivity of glucosinolates and their breakdown products.

  3. Author Profiles

    1. Dongyuan Zhao

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406195

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      My biggest inspiration is nature. My favorite time of day is the evening.

  4. Communications

    1. Nanoparticle Imaging Agents

      You have full text access to this OnlineOpen article
      A “Schizophotonic” All-In-One Nanoparticle Coating for Multiplexed SE(R)RS Biomedical Imaging

      Dr. Pasquale Iacono, Dr. Hazem Karabeber and Prof. Dr. Moritz F. Kircher

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201403835

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      Split personality: A biocompatible polymeric surface coating gives rise to dual emissive SERS/NIRF behavior when bound to gold nanoparticles of varying sizes. These polymers allow the first synthesis of SERS nanoprobes with gold cores smaller than 20 nm. These nanoprobes are shown to be capable of multiplexed lymph-node imaging.

    2. 1,2-Oxaphosphetane Complexes

      Synthesis and Reaction of the First 1,2-Oxaphosphetane Complexes

      Andreas Wolfgang Kyri, Dr. Vitaly Nesterov, Dr. Gregor Schnakenburg and Prof. Dr. Rainer Streubel

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201404877

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      O-PIIIeration successful: The first 1,2-oxaphosphetane complexes II were synthesized by a formal P1 insertion into the C[BOND]O bond of different epoxides using the Li/Cl phosphinidenoid complex I (see scheme; R=CH(SiMe3)2, solv=solvent). The reaction of a mixture of II and trifluoromethane sulfonic acid/benzonitrile/triethylamine led to a ring expansion formation of the 1,3,4-oxazaphosphacyclohex-2-ene complex III.

    3. Photoelectrodes

      Switchable Charge-Transfer in the Photoelectrochemical Energy-Conversion Process of Ferroelectric BiFeO3 Photoelectrodes

      Dr. Dawei Cao, Dr. Zhijie Wang, Nasori, Liaoyong Wen, Yan Mi and Prof. Yong Lei

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406044

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      Poling station: The orientation of the BiFeO3 (BFO) band bending at the BFO/electrolyte in polycrystalline BFO photoelectrodes can be switched from upwards to downwards by poling pretreatments of +8 V or −8 V, respectively. It is thus possible to manipulate photoelectrochemical reactions on a single ferroelectric photoelectrode.

    4. Bioorthogonal Chemistry | Hot Paper

      Super-Resolution Imaging of Plasma Membrane Glycans

      Sebastian Letschert, Dr. Antonia Göhler, Christian Franke, Nadja Bertleff-Zieschang, Elisabeth Memmel, Priv.-Doz. Dr. Sören Doose, Prof. Dr. Jürgen Seibel and Prof. Dr. Markus Sauer

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406045

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      Glycan spotting: Click chemistry and super-resolution imaging was used to visualize and quantify ManNAc-, GalNAc-, and O-GlcNAc-modified glycans in the plasma membrane of mammalian cells with single-molecule sensitivity (see image). The data demonstrate that a single cell may easily contain more than ten million glycans, which are homogeneously distributed and do not form clusters or nanodomains.

    5. Bioconjugation | Hot Paper

      Dialdehydes Lead to Exceptionally Fast Bioconjugations at Neutral pH by Virtue of a Cyclic Intermediate

      Pascal Schmidt, Dr. Linna Zhou, Kiril Tishinov, Kaspar Zimmermann and Prof. Dr. Dennis Gillingham

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406132

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      For aldehydes, 1+1=500: Dialdehydes react with O-alkylhydroxylamines at rates of 500 M−1 s−1 at neutral pH values in the absence of catalysts. The key to these conjugations is an unusually stable cyclic intermediate, which ultimately undergoes dehydration to yield an oxime. The application of this method in bioconjugations and a mechanistic interpretation are outlined.

    6. RNA Targeting

      A Toxic RNA Catalyzes the In Cellulo Synthesis of Its Own Inhibitor

      Dr. Suzanne G. Rzuczek, Dr. HaJeung Park and Prof. Dr. Matthew D. Disney

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406465

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      Potent modulators of RNA function can be assembled in cellulo by using the cell as the reaction vessel and a disease-causing RNA as the catalyst. In particular, a Huisgen 1,3-dipolar cycloaddition reaction was used to template the synthesis of an RNA inhibitor in disease-affected cells.

    7. Receptor Targeting

      A Multivalent Ligand for the Mannose-6-Phosphate Receptor for Endolysosomal Targeting of an Activity-Based Probe

      Dr. Sascha Hoogendoorn, Dr. Gijs H. M. van Puijvelde, Prof. Dr. Johan Kuiper, Prof. Dr. Gijs A. van der Marel and Prof. Dr. Herman S. Overkleeft

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406842

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      On target: A synthetic glycopeptide (P) that contains six mannose-6-phosphate residues was covalently attached to a fluorescent activity-based probe for cathepsins. The construct was internalized in live cells through binding to the mannose-6-phosphate receptor (MPR), thus validating the cluster as an MPR-targeting ligand that can be used to deliver cargo into the endolysosomal pathway.

    8. C[BOND]H Oxidation

      Enantioselective Allylic Hydroxylation of ω-Alkenoic Acids and Esters by P450 BM3 Monooxygenase

      B.Sc. Katharina Neufeld, Birgit Henßen and Prof. Dr. Jörg Pietruszka

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201403537

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      Modern biocatalysts on the rise: The P450 BM3 monooxygenase mutant A74G/L188Q catalyzes the enantioselective allylic hydroxylation of ω-alkenoic acids and esters under mild conditions using O2 as an oxidant. This reaction offers access to important chiral building blocks for the synthesis of biologically active compounds and demonstrates the highest chemo- and enantioselectivity observed to date for the C[BOND]H oxidation of acyclic terminal olefins.

    9. Natural Products

      Total Synthesis of Myceliothermophins C, D, and E

      Prof. Dr. K. C. Nicolaou, Dr. Lei Shi, Dr. Min Lu, Dr. Manas R. Pattanayak, Dr. Akshay A. Shah, Dr. Heraklidia A. Ioannidou and Dr. Manjunath Lamani

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406815

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      Cascades: The total synthesis of the cytotoxic myceliothermophins C, D, and E have been achieved through a sequence involving a cascade bis(cyclization) of epoxide or aldehyde substrates to forge a trans-fused decalin precursor of the natural products.

  5. Book Reviews

    1. Symmetry of Crystals & Molecules. By Mark Ladd.

      Werner Kaminsky

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407286

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      Oxford University Press, 2014. 464 pp., hardcover, £ 55.00.—ISBN 978-0199670888

  6. Cover Pictures

    1. Mononuclear and Terminal Zirconium and Hafnium Methylidenes

      Dr. Masahiro Kamitani, Balazs Pinter, Dr. Chun-Hsing Chen, Dr. Maren Pink and Prof. Dr. Daniel J. Mindiola

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408379

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      Kinetically stable methylidene complexes of zirconium and hafnium were prepared through photolysis-induced α-H abstraction from the corresponding complexes with aryloxide and two methyl ligands. In their Communication (DOI: 10.1002/anie.201405042), D. J. Mindiola and co-workers describe their quest for a kinetically more resistant system (structure on top of the compass) by taking advantage of prior systems (old map with drawings), thus finding the target molecule (inside the treasure chest).

  7. Communications

    1. Sythetic Methods

      Regioselective Radical Aminofluorination of Styrenes

      Hongwei Zhang, Yongcheng Song, Dr. Jinbo Zhao, Prof. Jingping Zhang and Prof. Qian Zhang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406797

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      Double agent: The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite to those of the palladium-catalyzed and noncatalyzed processes. NFSI reacts under N[BOND]F bond homolysis and is utilized as both a radical nitrogen source and radical fluorine source.

    2. [4+2] Cycloaddition

      Cobalt-Catalyzed Formal [4+2] Cycloaddition of α,α′-Dichloro-ortho-Xylenes with Alkynes

      Prof. Dr. Kimihiro Komeyama, Yuji Okamoto and Prof. Dr. Ken Takaki

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406807

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      Simple, but powerful: The title reaction leads to 1,4-dihydronaphthalenes with a wide substrate scope and high functional-group tolerance. Mechanistic investigation supports a benzyl cobaltation of alkyne, not the classical Diels–Alder reaction of ortho-quinodimethanes. This methodology provides a straightforward access to linearly expanded π-conjugated aromatics.

    3. Radical Chemistry

      Trans-Selective Radical Silylzincation of Ynamides

      Elise Romain, Carolin Fopp, Prof. Dr. Fabrice Chemla, Dr. Franck Ferreira, Dr. Olivier Jackowski, Prof. Dr. Martin Oestreich and Dr. Alejandro Perez-Luna

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407002

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      A radical­ transformation:­ Z-configured α,β-disubstituted enamides are obtained through a regio- and stereoselective silylzincation of terminal ynamides and subsequent sequential functionalization of the resulting Cinline image[BOND]Zn and Cinline image[BOND]Si bonds (see Scheme). The trans-selective silylzincation proceeds through a radical process combining organosilyl radical and radical Zn-atom transfer chemistry.

  8. Cover Pictures

    1. 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: 27 AUG 2014 | DOI: 10.1002/anie.201408162

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      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 with a quantum yield of 24 %. J. Kim and co-workers show in their Communication (10.1002/anie.201404490) that 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. Fluxionally Chiral DMAP Catalysts: Kinetic Resolution of Axially Chiral Biaryl Compounds

      Gaoyuan Ma, Dr. Jun Deng and Prof. Dr. Mukund P. Sibi

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408268

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      Place a pair of enantiomers in a box, wave a magic wand (a chiral catalyst), and two enantioenriched compounds pop out because of their differential interaction with the catalyst. In their Communication (DOI: 10.1002/anie.201406684), M. P. Sibi et al. demonstrate that a novel 4-dimethylaminopyridine catalyst having fluxional chirality is efficient in promoting acylative kinetic resolution of axially chiral biaryl compounds with selectivities of up to 51:1.

    3. Surface Polarization Matters: Enhancing the Hydrogen-Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures

      Song Bai, Dr. Chengming Wang, Dr. Mingsen Deng, Prof. Ming Gong, Yu Bai, Prof. Jun Jiang and Prof. Yujie Xiong

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408163

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      Surface charge states play an important role in tuning the catalytic performance of nanocrystals in various reactions. In their Communication (DOI: 10.1002/anie.201406468), Y. Xiong and co-workers demonstrate that the surface polarization effect can be induced on Pt surfaces in Pt–Pd–graphene stack structures as long as the Pt surface thickness is shrunk to a few layers. The surface polarization boosts the hydrogen evolution reaction activity as the thickness of the Pt layer decreases, opening the possibility to decrease the amount of Pt used.

  9. Communications

    1. Luminescent Frameworks

      Cluster Linker Approach: Preparation of a Luminescent Porous Framework with NbO Topology by Linking Silver Ions with Gold(I) Clusters

      Zhen Lei, Xiao-Li Pei, Zhan-Guo Jiang and Prof. Dr. Quan-Ming Wang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406761

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      Cluster linker: A luminescent gold(I) cluster prefunctionalized with pyrazinyl groups (left) was used as a cluster linker, similar to an organic linker, to connect silver ions in order to form a 3D framework. The intrinsic luminescence of the cluster was thus introduced into a bifunctional porous framework, which is characterized by an NbO topology and features 1D channels with a diameter of 1.1 nm.

    2. Mössbauer Spectroscopy

      Re-Appearance of Cooperativity in Ultra-Small Spin-Crossover [Fe(pz){Ni(CN)4}] Nanoparticles

      Haonan Peng, Dr. Simon Tricard, Gautier Félix, Dr. Gábor Molnár, Dr. William Nicolazzi, Dr. Lionel Salmon and Dr. Azzedine Bousseksou

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406710

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      Spin-crossover nanoparticles: Mössbauer spectroscopy was used to determine the variation of the Debye temperature (θD) for [Fe(pz){Ni(CN)4}] (py=pyrazine) spin-crossover nanoparticles ranging from 2 to 110 nm (see picture). The investigations explain the re-appearance of cooperativity in the smallest nanoparticles.

    3. Polyketide Biosynthesis

      An Unusual Dehydratase Acting on Glycerate and a Ketoreducatse Stereoselectively Reducing α-Ketone in Polyketide Starter Unit Biosynthesis

      Dr. Hai-Yan He, Dr. Hua Yuan, Dr. Man-Cheng Tang and Prof. Dr. Gong-Li Tang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406602

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      Biochemical characterization of a dehydratase and a ketoreductase-like domain (DH*-KR*) in the loading module of FR901464 polyketide synthase revealed that DH* catalyzes the dehydration of an acyl carrier protein (ACP)-tethered glycerate to an ACP-linked pyruvate. The KR* domain then carries out α-ketone reduction to yield L-lactyl-S-ACP, which serves as a starter unit for polyketide biosynthesis.

    4. DNA Demethylation

      Pyrene-Based Quantitative Detection of the 5-Formylcytosine Loci Symmetry in the CpG Duplex Content during TET-Dependent Demethylation

      Dr. Liang Xu, Ying-Chu Chen, Jenny Chong, Dr. Andrea Fin, Dr. Lisa S. McCoy, Dr. Jun Xu, Prof. Dr. Chao Zhang and Prof. Dr. Dong Wang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406220

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      Employing the unique fluorescence properties of the pyrene group, a sensitive fluorescence-based probe was designed and synthesized not only to target 5-formylcytosine (5fC) sites, but also to distinguish symmetric from asymmetric 5fC sites in the double-stranded DNA context during the TET-dependent 5mC oxidation process. Dominant levels of symmetric 5fC were revealed among total 5fC sites during in vitro TET-dependent 5mC oxidation.

    5. C[BOND]H Functionalization

      Combining Rhodium and Photoredox Catalysis for C[BOND]H Functionalizations of Arenes: Oxidative Heck Reactions with Visible Light

      M. Sc. David C. Fabry, Dipl.-Chem. Jochen Zoller, Dr. Sadiya Raja and Prof. Dr. Magnus Rueping

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201400560

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      Much milder and environmentally friendly reaction conditions can be used for oxidative Heck reactions through the combined use of rhodium and redox catalysis. This allows the rhodium complex to be catalytically regenerated. A broad range of substrates was tolerated in the reaction and afforded different amides in good to very good yields.

  10. Minireviews

    1. Natural Product Synthesis

      The Total Synthesis of Isodon Diterpenes

      Dr. Kiel E. Lazarski, Dr. Benjamin J. Moritz and Prof. Regan J. Thomson

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201404482

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      An interesting family: Complex polycyclic diterpenes can be isolated from the plants of the Isodon genus. This Minireview gives a concise summary of recent synthetic efforts that have culminated in the successful total synthesis of these diterpenes.

  11. Communications

    1. Total Synthesis

      A Biomimetic Synthesis of (±)-Basiliolide B

      Long Min, Yang Zhang, Xuefeng Liang, Junrong Huang, Wenli Bao and Dr. Chi-Sing Lee

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405770

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      O-Acylation or O-methylation? The biosynthetic origin of the C ring of the basiliolide/transtaganolide framework has been elucidated by studying the proposed biosynthetic pathways, namely O-acylation and O-methylation. The intramolecular O-acylation of the seco acid derivative gave (±)-basiliolide B in 92 % yield. This indicates that the seco acid derivative is likely a biosynthetic precursor of basiliolide B instead of a biosynthetic dead end.

    2. Enzymatic Activity

      Multiple Stable Conformations Account for Reversible Concentration-Dependent Oligomerization and Autoinhibition of a Metamorphic Metallopeptidase

      Mar López-Pelegrín, Dr. Núria Cerdà-Costa, Dr. Anna Cintas-Pedrola, Fátima Herranz-Trillo, Pau Bernadó, Dr. Juan R. Peinado, Dr. Joan L. Arolas and Prof. Dr. F. Xavier Gomis-Rüth

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405727

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      Shape shifting: A minimal metamorphic, selective, and specific caseinolytic metallopeptidase, selecase, reversibly transits between several different states of defined three-dimensional structure (monomer and tetramer represented in picture). The competent conformation is sequestered in incompetent but structured dimers, tetramers, and octamers, which are associated with loss of enzymatic activity due to autoinhibition.

    3. Luminescence

      A Phosphorescent Molecular “Butterfly” that undergoes a Photoinduced Structural Change allowing Temperature Sensing and White Emission

      Dr. Mingu Han, Yu Tian, Dr. Zhao Yuan, Prof. Lei Zhu and Prof. Biwu Ma

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405293

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      The white brothers: A molecular “butterfly”, that is, a phosphorescent PtII binuclear complex, can flap its “wings” and generate dual (white) emission upon photoexcitation. This photoinduced molecular structure change results from the shorterning of the Pt–Pt distance in the excited state and is phase-dependent allowing application of the complex as a self-referenced luminescent sensor for phase change, temperature, and viscosity.

    4. Flavin Redox Bifurcation

      Flavin Redox Bifurcation as a Mechanism for Controlling the Direction of Electron Flow during Extracellular Electron Transfer

      Dr. Akihiro Okamoto, Prof. Dr. Kazuhito Hashimoto and Prof. Dr. Kenneth H. Nealson

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201407004

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      The iron-reducing bacterium­ Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). The redox bifurcation of the cell-secreted riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell–electrode interface to drive either bacterial electrode reduction or oxidation reactions. Sq=semiquinone, Hq=hydroquinone.

    5. Wearable Solar Cells | Very Important Paper

      A Lightweight Polymer Solar Cell Textile that Functions when Illuminated from Either Side

      Zhitao Zhang, Xueyi Li, Guozhen Guan, Shaowu Pan, Zhengju Zhu, Dayong Ren and Prof. Huisheng Peng

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201407688

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      A polymer solar cell textile has been developed by sandwiching a metal textile electrode between two ultrathin, transparent, and conducting carbon nanotube sheets. Because of its unique structure, the resulting solar cell textile shows the same energy conversion efficiency regardless of which side it is irradiated from. Furthermore, its energy conversion efficiencies were maintained even after 200 bending cycles.

  12. News

  13. Communications

    1. Nanoparticle Catalysts

      Palladium Nanoparticles Embedded in the Inner Surfaces of Carbon Nanotubes: Synthesis, Catalytic Activity, and Sinter Resistance

      Prof. Dr. Hongyang Liu, Dr. Liyun Zhang, Prof. Dr. Ning Wang and Prof. Dr. Dang Sheng Su

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406490

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      Inside out: A facile and versatile synthesis using a template-based procedure gives Pd nanoparticles uniformly embedded in the inner surfaces of carbon nanotubes (see picture). The nanocomposite is catalytically more active and sinter-resistant, than traditional carbon-nanotube-supported Pd catalysts.

    2. Nanostructures

      Surface Polarization Matters: Enhancing the Hydrogen-Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures

      Song Bai, Dr. Chengming Wang, Dr. Mingsen Deng, Prof. Ming Gong, Yu Bai, Prof. Jun Jiang and Prof. Yujie Xiong

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406468

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      Less is more: Pt–Pd–graphene stack structures (see picture) are prepared by a new method that allows control of the thickness of the Pt shell. This thickness correlates with performance in the hydrogen-evolution reaction (HER). As a result of surface polarization, the HER activity actually increases with decreasing Pt thickness, opening possibilities of using less Pt.

    3. Radicals

      An Amphoteric Switch to Aromatic and Antiaromatic States of a Neutral Air-Stable 25π Radical

      Tullimilli Y. Gopalakrishna, Dr. J. Sreedhar Reddy and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406893

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      Super stable: A 25π radical of an expanded isophlorin undergoes reversible one-electron oxidation to form 24π antiaromatic species and one-electron reduction to form 26π aromatic species, confirming its amphoteric behavior. All of the three oxidation states of the macrocycle have been characterized in solution and solid state to confirm their stability under ambient conditions.

  14. Reviews

    1. Nanostructures

      Formation of Nanoparticles and Nanostructures—An Industrial Perspective on CaCO3, Cement, and Polymers

      Dr. Jens Rieger, Dr. Matthias Kellermeier and Dr. Luc Nicoleau

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201402890

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      Intermediate nanostructures occurring during crystallization reactions play an important role in understanding and controlling the formation of particles and hybrid materials. The use of polymers allows the range of achievable properties to be broadened through their specific effects at the nanoscale—as is exemplified in this Review with calcium carbonate, zinc oxide, and cementitious systems.

  15. Communications

    1. Electrocatalysis | Very Important Paper

      Core/Shell Au/MnO Nanoparticles Prepared Through Controlled Oxidation of AuMn as an Electrocatalyst for Sensitive H2O2 Detection

      Huiyuan Zhu, Aruna Sigdel, Dr. Sen Zhang, Dr. Dong Su, Zheng Xi, Dr. Qing Li and Prof. Shouheng Sun

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406281

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      Cell sensing: AuMn alloy nanoparticles were synthesized through hydride reduction of manganese acetylacetonate in the presence of Au nanoparticles and were subsequently converted into Au/MnO nanoparticles through air annealing. The Au/MnO nanoparticles are active catalysts for the electrochemical reduction of H2O2 and can be used to measure the H2O2 levels from different types of cells for cancer detection.

    2. Isotopic Labeling

      A Universal Procedure for the [18F]Trifluoromethylation of Aryl Iodides and Aryl Boronic Acids with Highly Improved Specific Activity

      Dion van der Born, Claudia Sewing, Dr. J. (Koos) D. M. Herscheid, Prof. Dr. Albert D. Windhorst, Prof. Dr. Romano V. A. Orru and Dr. Danielle J. Vugts

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406221

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      A quality label: Tracers for positron emission tomography (PET) with a [18F]CF3 group directly attached to an arene were synthesized with improved specific activity by the trifluoromethylation of aryl iodides and aryl boronic acids with [18F]trifluoromethane (see scheme). In particular, the trifluoromethylation of aryl boronic acids proceeded rapidly under mild reaction conditions, thus making this method highly suitable for PET-tracer production.

    3. C[BOND]H Activation | Hot Paper

      Aldehyde-Assisted Ruthenium(II)-Catalyzed C[BOND]H Oxygenations

      M. Sc. Fanzhi Yang, Karsten Rauch, M. Sc. Katharina Kettelhoit and Prof. Dr. Lutz Ackermann

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201405647

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      The weakest link: Challenging aryl C[BOND]H oxygenations with very weakly coordinating aldehydes proceed chemoselectively in the presence of versatile ruthenium(II) catalysts under mild reaction conditions. This transformation features an ample substrate scope and excellent positional selectivity.

    4. Protein Design

      Optogenetic Engineering: Light-Directed Cell Motility

      Prof. Dr. Robert M. Hughes and Prof. Dr. David S. Lawrence

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404198

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      Shine a light: A straightforward strategy for the acquisition of genetically encoded, light-activatable proteins is based upon the principles set forth in the 100 year old Michaelis–Menten equation. Photoactivation of a light-responsive cofilin mediates cytoskeleton remodelling, lamellipodia and filopodia formation, and directed cell motility.

    5. Collective Tunneling | Very Important Paper

      Exceptional Isotopic-Substitution Effect: Breakdown of Collective Proton Tunneling in Hexagonal Ice due to Partial Deuteration

      Dr. Christof Drechsel-Grau and Prof. Dr. Dominik Marx

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201405989

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      Ab initio simulations clarify the effects of H/D isotopic substitution on the mechanism of the collective tunneling of six protons within proton-ordered cyclic water hexamers that are contained in proton-disordered ice. At the transition state, isotopic substitution leads to a Zundel-like [HO⋅⋅⋅D⋅⋅⋅OH] complex with localized ionic defects and thus inhibits perfectly correlated proton tunneling.

    6. Electrocatalysis | Hot Paper

      Controlling Selectivity in the Chlorine Evolution Reaction over RuO2-Based Catalysts

      Kai S. Exner, Josef Anton, Timo Jacob and Herbert Over

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406112

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      Being selective: The selectivity in the industrially important Chlor-Alkali process has been elucidated on the microscopic level through a combination of DFT calculations and volcano plots. A single layer of TiO2(110) grown on RuO2(110) increases the selectivity between the chlorine and oxygen evolution reactions (CER and OER, respectively) by several orders of magnitude, while keeping the high activity for CER practically constant.

    7. Cycloadditions

      The Trapping of Phenyldiazenes in Cycloaddition Reactions

      M. Sc. Stefanie K. Fehler, Dr. Gerald Pratsch and Prof. Dr. Markus R. Heinrich

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406175

      Thumbnail image of graphical abstract

      Catch me if you can! Phenyldiazenes were intensively investigated in the late 1960s. But only recently was it possible to finally trap these reactive intermediates in cycloaddition reactions leading to pyridazinium salts (see scheme).

    8. Photocatalysis

      Photocatalytic Synthesis of Dihydrobenzofurans by Oxidative [3+2] Cycloaddition of Phenols

      Travis R. Blum, Dr. Ye Zhu, Sarah A. Nordeen and Prof. Tehshik P. Yoon

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406393

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      In a good light: The versatile photoredox properties of RuII chromophores offer a strategy to couple powerful oxidative transformations to benign inorganic peroxysulfate oxidants. In this example, the photocatalytic [3+2] cycloaddition of phenols and electron-rich styrenes for the synthesis of diverse dihydrobenzofurans is presented.

    9. Controlled Drug Delivery

      Molecularly Precise Dendrimer–Drug Conjugates with Tunable Drug Release for Cancer Therapy

      Dr. Zhuxian Zhou, Dr. Xinpeng Ma, Dr. Caitlin J. Murphy, Dr. Erlei Jin, Dr. Qihang Sun, Prof. Youqing Shen, Edward A. Van Kirk and Prof. William J. Murdoch

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406442

      Thumbnail image of graphical abstract

      Camptothecine core: Polylysine dendrimers with the conjugated drug in the core were synthesized for cancer therapy. The release rates of the camptothecine conjugates were easily tunable by adjusting the dendrimer generation and the peripheral functional groups as well as the pH. Conjugates showing a fast drug release also exhibited a high anticancer activity against intraperitoneal and subcutaneous tumors.

    10. Photochemistry

      Metal-Free C[BOND]H Bond Activation of Branched Aldehydes with Hypervalent Iodine(III) Catalyst under Visible-Light Photolysis: Successful Trapping with Electron-Deficient Olefins

      Dr. Shin A. Moteki, Asuka Usui, Dr. Sermadurai Selvakumar, Dr. Tiexin Zhang and Prof. Dr. Keiji Maruoka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406513

      Thumbnail image of graphical abstract

      A radical approach: The mild photocatalyzed activation of the C(O)[BOND]H bond in branched aldehydes offers easy access to acyl radicals and, without decarbonylation, allowed the efficient synthesis of unsymmetrical ketones by trapping with electrophilic olefins. A characteristic feature of this approach is the catalytic use of a hypervalent iodine(III) reagent to generation of radicals.

    11. Cross-Coupling

      Gold(I)-Catalyzed Diazo Coupling: Strategy towards Alkene Formation and Tandem Benzannulation

      Daming Zhang, Guangyang Xu, Dong Ding, Chenghao Zhu, Dr. Jian Li and Prof. Dr. Jiangtao Sun

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406712

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      Crossing paths: A gold(I)-catalyzed cross-coupling of diazo compounds to afford tetrasubstituted alkenes has been developed. In addition, a gold(I)-initiated benzannulation has been achieved in a tandem reaction involving cross-coupling of the vinyldiazoacetates, sequential 6π electrocyclization, and oxidative aromatization.

    12. Metal–Organic Supercontainers

      pH-Modulated Molecular Assemblies and Surface Properties of Metal–Organic Supercontainers at the Air–Water Interface

      Nathan L. Netzer, Dr. Feng-Rong Dai, Prof. Zhenqiang Wang and Prof. Chaoyang Jiang

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406733

      Thumbnail image of graphical abstract

      MOSC thin films: The molecular assemblies of metal–organic supercontainers (MOSCs) were studied at the air–water interface. Variation in the pH values of the subphases causes significant changes in the molecular orientation in the Langmuir films. The uniform MOSC structures in Langmuir–Blodgett films show tunable surface properties that can be precisely controlled by fabricating conditions.

    13. Cyclization

      Mild ArI-Catalyzed C(sp2)[BOND]H or C(sp3)[BOND]H Functionalization/C[BOND]O Formation: An Intriguing Catalyst-Controlled Selectivity Switch

      Xueqiang Wang, Joan Gallardo-Donaire and Prof. Ruben Martin

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407011

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      Who controls the switch? I! A tandem C(sp2)[BOND]H or C(sp3)[BOND]H functionalization/C[BOND]O bond-forming reaction catalyzed by IIII reagents generated in situ has been developed. The transformation shows broad scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the nature of the iodine catalyst employed (see scheme; HFIP=1,1,1,3,3,3-hexafluoro-2-propanol).

    14. Cross-Coupling

      Synthesis of Direct β-to-β Linked Porphyrin Arrays with Large Electronic Interactions: Branched and Cyclic Oligomers

      Hao Cai, Keisuke Fujimoto, Dr. Jong Min Lim, Chaojie Wang, Weiming Huang, Yutao Rao, Senmiao Zhang, Hui Shi, Dr. Bangshao Yin, Prof. Dr. Bo Chen, Prof. Dr. Ming Ma, Prof. Dr. Jianxin Song, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407032

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      Molecular twine: The title porphyrin trimers and pentamers have been synthesized by Suzuki–Miyaura coupling of β-boryl-porphyrins and β-bromoporphyrins. The cyclic porphyrin trimer, the smallest directly linked cyclic porphyrin, and its twined pentamer exhibit small HOMO–LUMO gaps, broad nonsplit Soret bands, red-shifted Q-bands, and efficient excitation-energy hopping.

    15. Synthetic Methods | Very Important Paper

      Highly Diastereoselective and Enantiospecific Allylation of Ketones and Imines Using Borinic Esters: Contiguous Quaternary Stereogenic Centers

      Dr. Jack L.-Y. Chen and Prof. Dr. Varinder K. Aggarwal

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407127

      Thumbnail image of graphical abstract

      Goldilocks reactivity: 3,3-Disubstituted allylic borinic esters possess the perfect balance between reactivity and configurational stability to react with both ketones and ketimines, allowing facile access to adjacent quaternary stereocenters with full stereocontrol. Synthesis of all possible stereoisomers of a quaternary-quaternary motif is demonstrated. TFAA=trifluoroacetic anhydride.

  16. Minireviews

    1. Chiral-at-Metal Complexes

      Asymmetric Catalysis Mediated by the Ligand Sphere of Octahedral Chiral-at-Metal Complexes

      Dr. Lei Gong, B.Sc. Liang-An Chen and Prof. Dr. Eric Meggers

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404305

      Thumbnail image of graphical abstract

      “Organocatalysis” with metal complexes: Inert octahedral metal complexes are an emerging class of catalysts for asymmetric synthesis. In these compounds the globular, rigid nature and stereochemical options of octahedral compounds are exploited. Complexes like those shown promise new opportunities in the field of catalysis.

  17. Communications

    1. Drug Delivery

      Cell-Mediated Assembly of Phototherapeutics

      Weston J. Smith, Nathan P. Oien, Dr. Robert M. Hughes, Christina M. Marvin, Zachary L. Rodgers, Junghyun Lee and Prof. David S. Lawrence

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201406216

      Thumbnail image of graphical abstract

      Window of opportunity: A wavelength-encoded drug-delivery strategy operates within the optical window of tissue. The photoresponsive system is acquired by the assembly of lipid-cobalamin-drug and lipid-fluorophore constructs on the surface of erythrocytes. The desired wavelength of cobalamin-drug photocleavage is “dialed-in” by simply choosing the appropriate lipid-fluorophore “antenna”.

    2. Analytical Methods

      Lysosomal pH Rise during Heat Shock Monitored by a Lysosome-Targeting Near-Infrared Ratiometric Fluorescent Probe

      Dr. Qiongqiong Wan, Prof. Dr. Suming Chen, Prof. Dr. Wen Shi, Lihong Li and Prof. Dr. Huimin Ma

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201405742

      Thumbnail image of graphical abstract

      Feeling hot, hot, hot: A near-infrared ratiometric pH probe with a stable semicyanine skeleton is developed for lysosomal pH measurements. The readily preparable probe shows an excellent lysosome-targeting ability and high photostability. The probe is used to investigate the change of lysosomal pH with temperature, revealing for the first time that lysosomal pH values rise during heat shock and the process is irreversible.

  18. Highlights

    1. Arenes

      Organocatalytic Enantioselective Construction of Polyaromatic Architectures

      Ophélie Quinonero, Dr. Cyril Bressy and Dr. Xavier Bugaut

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406263

      Thumbnail image of graphical abstract

      Aromatics in 3D. Organocatalysis is now reaching beyond the control of stereogenic centers and opens new possibilities for the construction of complex polyaromatic structures with either helical or axial chirality.

  19. Communications

    1. Organic Photovoltaics

      Polymerization of Tellurophene Derivatives by Microwave-Assisted Palladium-Catalyzed ipso-Arylative Polymerization

      Dr. Young S. Park, Dr. Qin Wu, Dr. Chang-Yong Nam and Prof. Robert B. Grubbs

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406068

      Thumbnail image of graphical abstract

      Telluric rings: The tellurophene-containing low-bandgap polymer PDPPTe2T, prepared by microwave-assisted ipso-arylative polymerization, exhibited red-shifted absorption spectra compared to the thiophene analogue. Bulk heterojunction solar-cell devices from PDPPTe2T and PC71BM reach a power conversion efficiency of 4.4 % and produce photocurrent at wavelengths up to 1 µm.

    2. Drug Delivery

      An Aptamer Intrinsically Comprising 5-Fluoro-2′-deoxyuridine for Targeted Chemotherapy

      Dipl.-Chem. Sven Kruspe and Prof. Dr. Ulrich Hahn

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405778

      Thumbnail image of graphical abstract

      A trojan chemotherapeutic: An aptamer intrinsically comprising multiple units of the nucleoside analogue 5-fluoro-2′-deoxyuridine can exert a direct cytostatic effect on certain cells. The aptamer, which can be synthesized in a single enzymatic step, binds to a cell surface receptor that is conveyed into the lysosome. Upon lysosomal degradation of the aptamer by intracellular nucleases, the active drug is released within the targeted cells exclusively.

    3. Natural Product Synthesis

      A Multitasking Vanadium-Dependent Chloroperoxidase as an Inspiration for the Chemical Synthesis of the Merochlorins

      Dr. Stefan Diethelm, Dr. Robin Teufel, Dr. Leonard Kaysser and Prof. Dr. Bradley S. Moore

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405696

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      Naturally inspiring: The vanadium- dependent chloroperoxidase Mcl24 was found to mediate a complex series of transformations in the biosynthesis of the merochlorins, in particular, a site-selective naphthol chlorination and an oxidative dearomatization/terpene cyclization sequence to build up the stereochemically complex carbon framework. Inspired by the enzyme reactivity, a chemical chlorination protocol paralleling the biocatalytic process was developed.

    4. Halogenation

      You have full text access to this OnlineOpen article
      Regioselective Dihalohydration Reactions of Propargylic Alcohols: Gold-Catalyzed and Non-Catalyzed Reactions

      Jarryl M. D'Oyley, Dr. Abil E. Aliev and Dr. Tom D. Sheppard

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405348

      Thumbnail image of graphical abstract

      With or without gold: Propargylic alcohols were converted into α,α-diiodo-β-hydroxyketones by treatment with N-iodosuccinimide in the presence of a gold catalyst. α,α-Dichloro-β-hydroxyketones were prepared without a catalyst by reaction of propargylic alcohols with trichloroisocyanuric acid. Mechanistic studies suggest that both of these reactions proceed via the formation of 5-halooxazines, formed by participation of the acetonitrile solvent.

    5. Microwave Spectroscopy

      Tautomerism in Neutral Histidine

      Celina Bermúdez, Santiago Mata, Dr. Carlos Cabezas and Prof. José L. Alonso

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405347

      Thumbnail image of graphical abstract

      Conformational analysis: Neutral histidine has been generated in the gas phase by laser ablation of solid samples and its NεH tautomeric form has been unraveled through its rotational spectrum (see picture). The quadrupole hyperfine structure, arising from the existing three 14N nuclei, constituted a site-specific probe for revealing the tautomeric form as well as the side-chain configuration of this proteogenic amino acid.

  20. Book Reviews

    1. Bioinorganic Chemistry. By Dieter Rehder.

      Felix Zelder

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406318

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      Oxford University Press, Oxford, 2014. 240 pp., hardcover, £ 34.99.—ISBN 978-0199655199

  21. Communications

    1. Carbenoids

      C[BOND]H Functionalization/Asymmetric Michael Addition Cascade Enabled by Relay Catalysis: Metal Carbenoid used for C[BOND]C Bond Formation

      Dr. Dian-Feng Chen, Feng Zhao, Yue Hu and Prof. Dr. Liu-Zhu Gong

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406098

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      Square deal: A combination of either ruthenium(II) or rhodium(II) complexes and quinine-derived squaramide enables 3-diazooxindoles, indole, and nitroalkenes to undergo a highly efficient asymmetric three-component reaction. Based on this metal/organo relay catalysis, a total synthesis of (−)-folicanthine was accomplished in seven steps with 14.5 % overall yield.

    2. Trifluoromethylation | Hot Paper

      Vanadium-Catalyzed Solvent-Free Synthesis of Quaternary α-Trifluoromethyl Nitriles by Electrophilic Trifluoromethylation

      Natalja Früh and Prof. Dr. Antonio Togni

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406181

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      Not only copper! Oxovanadium(IV) complexes catalyze the trifluoromethylation of silyl ketene imines with hypervalent iodine reagents to form quaternary α-trifluoromethyl nitriles under solvent-free conditions. The products, formed in up to 93 % yield, may be further transformed into useful synthetic building blocks for organofluorine chemistry.

    3. Asymmetric Catalysis

      Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols through NHC-Catalyzed Atroposelective Acylation

      Dr. Shenci Lu, Si Bei Poh and Prof. Yu Zhao

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406192

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      BINOL and NOBIN derivatives are obtained in high enantioselectivities of ≥99 % ee through NHC-catalyzed kinetic resolution. This method presents the first highly enantioselective catalytic acylation of axially chiral alcohols.

  22. Cover Pictures

    1. Opposite-Face Sensitivity of Cerium(IV) Oxide in Hydrogenation and Oxidation Catalysis

      Gianvito Vilé, Dr. Sara Colussi, Dr. Frank Krumeich, Prof. Alessandro Trovarelli and Prof. Javier Pérez-Ramírez

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201408165

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      Structure–performance relationships of ceria in heterogeneous reactions are revealed by J. Pérez-Ramírez, A. Trovarelli, et al. in their Communication (DOI: 10.1002/anie.201406637). The (111) surface prevalent in conventional polyhedral CeO2 particles outperforms in hydrogenation, while the (100) surface that is exposed in nanocubes dominates in oxidation. Artwork: Amalia Gallardo (ArteLi) and Marcel Reich.

    2. An All-Halogen Bonding Rotaxane for Selective Sensing of Halides in Aqueous Media

      Benjamin R. Mullaney, Dr. Amber L. Thompson and Prof. Paul D. Beer

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201408031

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      Combining halogen bonding with an optical probe in an interlocked host design leads to a potent anion sensory system. As P. D. Beer et al. show in their Communication (DOI: 10.1002/anie.201403659), an all-halogen bonding rotaxane host with a photoactive rhenium(I) bipyridyl center in the macrocyclic component can optically sense halide anions by luminescence, with a high binding affinity and selectivity for iodide ions. Image: Dr. Karl Harrison.

    3. Long-Lived Trifluoromethide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations

      Prof. Dr. G. K. Surya Prakash, Dr. Fang Wang, Zhe Zhang, Prof. Dr. Ralf Haiges, Dr. Martin Rahm, Prof. Dr. Karl O. Christe, Dr. Thomas Mathew and Prof. Dr. George A. Olah

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201407930

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      CF3 is a long-lived species! For more than six decades, CF3 was believed to exist only as a short-lived and kinetically unstable species in the condensed phase. In their Communication (DOI: 10.1002/anie.201406505), G. K. S. Prakash et al. have obtained the first direct evidence for the persistence of the trifluoromethide anion in THF by NMR spectroscopy. The experiments explicitly show that CF3 with the [K(18-crown-6)]+ counterion is quite stable at low temperatures.

  23. Communications

    1. Energy Conversion

      Platinum-Free Binary Co-Ni Alloy Counter Electrodes for Efficient Dye-Sensitized Solar Cells

      Xiaoxu Chen, Prof. Qunwei Tang, Dr. Benlin He, Dr. Lin Lin and Prof. Liangmin Yu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406982

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      A mild hydrothermal reduction strategy has been used to generate Pt-free binary Co-Ni alloys for use as counter electrode (CE) materials in dye-sensitized solar cells (DSSCs). These materials offer high electrocatalytic activity toward I3, good electron-conduction, as well as cost-effectiveness. A conversion efficiency of 8.39 % was measured under one sun irradiation, which is much higher than the 6.96 % from platinum-based DSSCs.

    2. Crystal Morphology

      Opposite Face Sensitivity of CeO2 in Hydrogenation and Oxidation Catalysis

      Gianvito Vilé, Dr. Sara Colussi, Dr. Frank Krumeich, Prof. Alessandro Trovarelli and Prof. Javier Pérez-Ramírez

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406637

      Thumbnail image of graphical abstract

      Shape and face matter: The design of ceria catalysts for oxidation and hydrogenation reactions is governed by opposite criteria. Whereas oxygen vacancies, maximized on (100) nanocubes, promote oxidation, hydrogenation is favored by their minimization, requiring (111) face-enclosed polyhedral particles.

    3. Reactive Intermediates | Very Important Paper

      Long-Lived Trifluoromethanide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations

      Prof. Dr. G. K. Surya Prakash, Dr. Fang Wang, Zhe Zhang, Prof. Dr. Ralf Haiges, Dr. Martin Rahm, Prof. Dr. Karl O. Christe, Dr. Thomas Mathew and Prof. Dr. George A. Olah

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406505

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      Rather persistent: For more than 60 years, the trifluoromethanide anion has been widely believed to exist only as an extremely transient species in the condensed phase, and to undergo swift decomposition to difluorocarbene and fluoride. The trifluoromethanide anion has now been successfully prepared, observed, and characterized for the first time in solution. Contrary to previous assumptions, the anion possesses considerable lifetime at subambient temperatures.

    4. Boride Magnets | Hot Paper

      Unexpected Synergy between Magnetic Iron Chains and Stacked B6 Rings in Nb6Fe1−xIr6+xB8

      Dipl.-Chem. Mohammed Mbarki, M.Sc. Rachid St. Touzani and Priv.-Doz. Dr. Boniface P. T. Fokwa

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406397

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      A mutual dependency between ferromagnetic iron chains and stacked B6 rings (see picture) is found in the new ferromagnetic material, Nb6Fe1−xIr6+xB8 (TC=350 K) by combining experiment and density functional theory (DFT). The strong magnetic Fe–Fe interactions found in the iron chains induce an unexpected strengthening of the B–B interactions in the B6 rings.

    5. Nanostructure Assembly

      Recrystallization-Induced Self-Assembly for the Growth of Cu2O Superstructures

      Yang Shang, Yi-Ming Shao, Prof. Dr. Dong-Feng Zhang and Prof. Dr. Lin Guo

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406331

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      A recrystallization-induced self-assembly (RISA) strategy was proposed for the growth of 3D Cu2O superstructures and employs Cu2O mesoporous spheres (diameters ca. 300 nm) as the building blocks. Balancing the hydrolysis and recrystallization rates of the CuCl precursors is key to the successful assembly. Furthermore, the shape of the superstructures can be tuned to obtain either cubes or tetrahedra.

    6. Heterocycle Synthesis

      Dearomative Indole [5+2] Cycloaddition Reactions: Stereoselective Synthesis of Highly Functionalized Cyclohepta[b]indoles

      Guangjian Mei, Hao Yuan, Yueqing Gu, Wei Chen, Prof. Dr. Lung Wa Chung and Prof. Dr. Chuang-chuang Li

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406278

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      Bridge construction: The title reaction with an oxidopyrylium ylide resulted in efficient and diastereoselective construction of highly functionalized oxacyclohepta[b]indoles. The protocol proceeded under very mild reaction conditions, thus enabling high functional-group tolerance and endo selectivity. TBS=tert-butyldimethylsilyl, Tf=trifluoromethanesulfonyl.

    7. Dinuclear Metal Complexes

      Facile C[BOND]H Bond Formation by Reductive Elimination at a Dinuclear Metal Site

      Dr. Richard D. Adams, Dr. Vitaly Rassolov and Yuen Onn Wong

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406219

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      The electronically unsaturated dirhenium complex [Re2(CO)8(µ-AuPPh3)(µ-Ph)] was obtained from the reaction of [Re2(CO)8{µ-η2-C(H)[DOUBLE BOND]C(H)nBu}(µ-H)] with [Au(PPh3)Ph] and by reaction with HSnPh3 was converted into [Re2(CO)8(µ-H)(µ-Ph)] (see picture). This hydrido-bridged complex reductively eliminates benzene upon addition of NCMe.

  24. Reviews

    1. Polyolefins

      Post-Metallocenes in the Industrial Production of Polyolefins

      M. Sc. Moritz C. Baier, Dr. Martin A. Zuideveld and Prof. Dr. Stefan Mecking

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201400799

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      “Post-metallocene” polymerization catalysis research ranges from fundamental mechanistic studies via catalyst design to material properties of polyolefins. A common goal of these studies is the creation of practically useful new materials or processes. A comprehensive overview of post-metallocene polymerization catalysts that have been put into practice is provided. The decisive properties for this success of a given catalyst structure are delineated.

  25. Communications

    1. CO2 Utilization | Hot Paper

      Ruthenium-Catalyzed Reductive Methylation of Imines Using Carbon Dioxide and Molecular Hydrogen

      Dr. Kassem Beydoun, Ghazi Ghattas, Katharina Thenert, Prof. Dr. Jürgen Klankermayer and Prof. Dr. Walter Leitner

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201403711

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      Tertiary N-methyl amines were obtained in good to excellent yields through the reductive methylation of imines (used as such or formed in situ from amines and aldehydes, see scheme). Apart from the well-defined [Ru(triphos)(tmm)] catalyst, CO2 was used as C1 source, and H2 as reducing agent. This method enabled the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis.

    2. Multidomain Gels

      Multidomain Hybrid Hydrogels: Spatially Resolved Photopatterned Synthetic Nanomaterials Combining Polymer and Low-Molecular-Weight Gelators

      Daniel J. Cornwell, Babatunde O. Okesola and Prof. David K. Smith

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405098

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      The best of both worlds: Forming polymer gel networks embedded within a low-molecular-weight gel matrix using photoirradiation allows the generation of multicomponent nanoscale soft materials. The different gel domains have different properties, for example, with regard to the diffusion of small molecules, such as dyes, depending on which nanoscale networks they contain (see picture).

    3. Asymmetric Catalysis

      Asymmetric Alkynylation/Lactamization Cascade: An Expeditious Entry to Enantiomerically Enriched Isoindolinones

      Dr. Vishnumaya Bisai, Arun Suneja and Prof. Dr. Vinod K. Singh

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405074

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      Simple and effective: A highly enantioselective domino alkynylation/lactamization involving the formation of one C[BOND]C and two C[BOND]N bonds was developed for the synthesis of diversely substituted isoindolinones (see scheme). The methodology was further extended to the synthesis of tetrahydroisoquinoline scaffolds found in a variety of biologically active natural products by a remarkably selective two-step procedure (up to 94 % ee).

    4. Nanostructures

      Formation of Polydopamine Nanofibers with the Aid of Folic Acid

      Xiang Yu, Hailong Fan, Le Wang and Prof. Dr. Zhaoxia Jin

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201404947

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      The magic of folic acid: When the oxidative self-polymerization of dopamine (turquoise) was conducted in the presence of folic acid (yellow), novel aggregated nanostructures of polydopamine (PDA) were generated: nanobelts and nanofibers (see SEM image). Supramolecular interactions between folic acid and protomolecules of PDA, such as π–π interactions and hydrogen bonding, appear to contribute to the formation of the nanobelts and nanofibers.

    5. Alkyne Metathesis

      A Tetrameric Cage with D2h Symmetry through Alkyne Metathesis

      Qi Wang, Chenxi Zhang, Dr. Bruce C. Noll, Dr. Hai Long, Dr. Yinghua Jin and Prof. Dr. Wei Zhang

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201404880

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      Clever cages: A tetrameric cage with a D2h symmetry was prepared from a C3-symmetric triyne monomer through a one-step alkyne metathesis. The tetramer consisting of two macrocyclic panels has a large internal cavity, which can selectively host C70 over C60.

    6. Single-Molecule Studies

      Direct Observation of Dynamic Mechanical Regulation of DNA Condensation by Environmental Stimuli

      Amy Lee, Adam Karcz, Ryan Akman, Tai Zheng, Sara Kwon, Szu-Ting Chou, Sarah Sucayan, Dr. Lucas J. Tricoli, Jason M. Hustedt, Dr. Qixin Leng, Prof. Jason D. Kahn, Prof. A. James Mixson and Prof. Joonil Seog

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201403499

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      Optical tweezers were used to directly measure single-molecule mechanical properties of DNA condensed using 19-mer poly-L-lysine (PLL) or branched histidine–lysine (HK) peptides. Force–extension profiles indicate that both carriers condense DNA actively. As the carrier concentration, pH, and the presence of zinc ions changes, DNA:HK complexes showed dynamically regulated mechanical properties at multiple force levels.

    7. Single Layer Materials

      Surface-Confined Single-Layer Covalent Organic Framework on Single-Layer Graphene Grown on Copper Foil

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

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201400273

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

    8. Biocatalysis | Very Important Paper

      Chiral Amine Synthesis Using ω-Transaminases: An Amine Donor that Displaces Equilibria and Enables High-Throughput Screening

      Dr. Anthony P. Green, Prof. Nicholas J. Turner and Dr. Elaine O'Reilly

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406571

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      ω-Transaminases (ω-TA) are employed as biocatalysts in a simple and efficient process for the synthesis of chiral amines. A dual-function diamine donor (ortho-xylylenediamine) serves to displace challenging reaction equilibria towards product formation whilst generating intensely colored by-products, which have allowed the development of liquid-phase and colony-based assays.

  26. Highlights

    1. Nanomembranes

      Converting Molecular Monolayers into Functional Membranes

      Prof. Dr. Dario Anselmetti and Prof. Dr. Armin Gölzhäuser

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406789

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      Carbon nanomembranes are constructed from monolayers of molecular amphiphiles assembled on a water surface. The floating molecular film is cross-linked to form a mechanically stable nanomembrane. By varying the type of molecules, the surface area, and the exposure condition, the membrane’s stiffness, thickness, and permeability can be tailored.

  27. Cover Pictures

    1. Harvesting Solar Light with Crystalline Carbon Nitrides for Efficient Photocatalytic Hydrogen Evolution

      Dr. Manas K. Bhunia, Dr. Kazuo Yamauchi and Prof. Kazuhiro Takanabe

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201407927

      Thumbnail image of graphical abstract

      Metal-free photocatalysts for visible-light-driven H2 evolution that are inexpensive are coveted for energy production. K. Takanabe and co-workers show in their Communication (10.1002/anie.201405161) that a family of crystalline carbon nitrides (CNs) obtained by supramolecular aggregation and ionic melt polycondensation gives excellent photocatalytic H2 evolution. Controlling the amount and arrangements of dopants in the CN structure enables a substantial amount of visible light to be harvested and enhances the photocatalytic performance.

  28. Communications

    1. Nanoparticle Architectures | Hot Paper

      Planet–Satellite Nanostructures Made To Order by RAFT Star Polymers

      Christian Rossner and Prof. Dr. Philipp Vana

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406854

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      Small world: Gold nanoparticles decorated with RAFT star polymers of different molecular weights can be used as scaffolds for the attachment of functional units at defined distances from the central core. This approach can result in planet–satellite nanostructures.

    2. Bioconjugation

      Double-Clicking Peptides onto Phosphorothioate Oligonucleotides: Combining Two Proapoptotic Agents in One Molecule

      Frank Abendroth and Prof. Dr. Oliver Seitz

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406674

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      A stone for two birds is accessed through a combination of oxime ligation and strain-promoted [2+3] cycloaddition. This method was used to conjugate phosphorothioate antisense oligonucleotides (PSAOs) with peptide-based drugs. The activity of a PSAO sequence targeted against mRNA from c-Flip can be enhanced by conjugation with a peptide mimetic designed to inhibit the X-linked inhibitor of apoptosis protein (XIAP).

    3. Inclusion Compounds

      Observation of Interstitial Molecular Hydrogen in Clathrate Hydrates

      R. Gary Grim, Dr. Brian C. Barnes, Dr. Patrick G. Lafond, Dr. Winfred A. Kockelmann, Dr. David A. Keen, Dr. Alan K. Soper, Masaki Hiratsuka, Dr. Kenji Yasuoka, Dr. Carolyn A. Koh and Dr. Amadeu K. Sum

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406546

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      Breaking the boundaries: In the presence of molecular hydrogen, interstitial occupancy is observed in the type VI clathrate hydrate (see picture; tBuNH2 in interstices (red) with H2 (green)). This observation revises the definition of clathrate hydrate guest occupancy that assumes all guests are contained within the interior of the host water lattice.

    4. Synthetic Methods

      Copper-Mediated C6-Selective Dehydrogenative Heteroarylation of 2-Pyridones with 1,3-Azoles

      Riko Odani, Dr. Koji Hirano, Prof. Dr. Tetsuya Satoh and Prof. Dr. Masahiro Miura

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406228

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      Appointment of a temporary director: A copper-mediated C6-selective dehydrogenative arylation of 2-pyridones with 1,3-azoles was developed with the aid of an attachable/detachable pyridine-based directing group (see scheme). The reaction proceeded effectively without a noble metal, and in some cases molecular oxygen in air rendered the process catalytic in copper.

    5. Supramolecular Chemistry

      Palladium-Templated Subcomponent Self-Assembly of Macrocycles, Catenanes, and Rotaxanes

      Colm Browne, Dr. Tanya K. Ronson and Prof. Jonathan R. Nitschke

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406164

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      Mix and match: A range of different metallosupramolecular structures were obtained, including macrocycles (see picture) and host–guest systems, by combining PdII ions with 2,6-diformylpyridine and a variety of amines. Adding pyridine-based macrocyclic ligands allowed interlocked structures to be generated, such as rare examples of a doubly threaded [3]pseudorotaxane and [3]rotaxane.

    6. Colloidal Particles | Very Important Paper

      Reconfigurable Swarms of Nematic Colloids Controlled by Photoactivated Surface Patterns

      Sergi Hernàndez-Navarro, Dr. Pietro Tierno, Prof. Joan Anton Farrera, Prof. Jordi Ignés-Mullol and Prof. Francesc Sagués

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406136

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      Swarming into focus: The assembly and transport of large ensembles of colloidal particles or droplets that are dispersed in a film of anisotropic fluid can be directly controlled by means of AC electrophoresis. Individual or collective particle steering is independently achieved by elastic modulation of the host nematic liquid crystal on a photosensitive confining surface.

    7. Organocatalysis

      Phosphine-Catalyzed Annulations of 4,4-Dicyano-2-Methylenebut-3-enoates with Maleimides and Maleic Anhydride

      Xiao-Nan Zhang, Gen-Qiang Chen, Dr. Xiang-Ying Tang, Dr. Yin Wei and Dr. Min Shi

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201406100

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      Formalities: Novel phosphine-catalyzed [4+1] and formal [3+2] annulations of 4,4-dicyano-2-methylenebut-3-enoates with maleimides and maleic anhydride, respectively, have been developed. Maleimides serve as C1 synthons and maleic anhydride behaved as a C3 synthon to afford the corresponding compounds. A phosphinium-containing zwitterion is the key intermediate in both annulations.

    8. Artificial Spores

      A Cytoprotective and Degradable Metal–Polyphenol Nanoshell for Single-Cell Encapsulation

      Ji Hun Park, Kyunghwan Kim, Juno Lee, Ji Yu Choi, Daewha Hong, Prof. Sung Ho Yang, Prof. Frank Caruso, Prof. Younghoon Lee and Prof. Insung S. Choi

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201405905

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      Cell shells: A cytoprotective tannic acid/FeIII nanoshell was formed on individual yeast cells. Cell division was halted by formation and restarted by degradation of the nanoshell. The shell protected the cell from lytic enzymes, silver nanoparticles, and UV-C (λ: 100 to 280 nm) irradiation.

    9. DNA Structures

      Structural Basis for the Identification of an i-Motif Tetraplex Core with a Parallel-Duplex Junction as a Structural Motif in CCG Triplet Repeats

      Dr. Yi-Wen Chen, Cyong-Ru Jhan, Dr. Stephen Neidle and Dr. Ming-Hon Hou

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201405637

      Thumbnail image of graphical abstract

      Too close for comfort: CCG-repeat DNA was found by X-ray crystallography to form a tetraplex combined with a parallel duplex, either by the association of hairpins or via a triplex intermediate (see picture). The observation of this i-motif structure suggests a possible molecular-level pathological consequence of CCG-triplet-repeat expansion with regard to neurological disease.

    10. Nanoparticle Surfaces

      Revealing the Distribution of the Atoms within Individual Bimetallic Catalyst Nanoparticles

      Dr. Peter Felfer, Dr. Paul Benndorf, Prof. Anthony Masters, Prof. Thomas Maschmeyer and Prof. Julie M. Cairney

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201405043

      Thumbnail image of graphical abstract

      Atomic cartography: Atom-probe tomography reveals the atomic structure of Au@Ag nanoparticles. The atomic arrangement of the particle is reconstructed with a resolution of ±0.5 nm and shows that the surface coverage of Ag is influenced by the presence of residues from the synthesis. There is also a relationship between the particle’s surface curvature and the Ag surface coverage (surface excess, ΓAg).

    11. Contrast Agents | Hot Paper

      Phosphonated Near-Infrared Fluorophores for Biomedical Imaging of Bone

      Dr. Hoon Hyun, Dr. Hideyuki Wada, Dr. Kai Bao, Dr. Julien Gravier, Dr. Yogesh Yadav, Dr. Matt Laramie, Dr. Maged Henary, Dr. John V. Frangioni and Dr. Hak Soo Choi

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201404930

      Thumbnail image of graphical abstract

      Bifunctional molecules with high-affinity binding to bone minerals as well as bright near-infrared fluorescence were obtained by attaching low-affinity pendant groups to the non-delocalized backbone of polymethines. These agents enable the noninvasive assessment of bone development over the course of weeks in living animals.

    12. Natural Product Synthesis

      Coupling of Sterically Hindered Trisubstituted Olefins and Benzocyclobutenones by C[BOND]C Activation: Total Synthesis and Structural Revision of Cycloinumakiol

      Dr. Tao Xu and Prof. Dr. Guangbin Dong

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201404802

      Thumbnail image of graphical abstract

      The mystery is solved: The first total synthesis of the proposed structure of cycloinumakiol is achieved by rhodium catalysis. In the key step, the coupling of a trisubstituted olefin with a benzocyclobutenone through C[BOND]C activation yields the tetracyclic core skeleton. Comparison of the synthetic product to natural cycloinumakiol revealed a misassignment and the natural compound was unambiguously identified as 19-hydroxytotarol.

    13. Bioorthogonal Catalysis

      Progress towards Bioorthogonal Catalysis with Organometallic Compounds

      Timo Völker, Dr. Felix Dempwolff, Prof. Dr. Peter L. Graumann and Prof. Dr. Eric Meggers

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201404547

      Thumbnail image of graphical abstract

      Organometallic ruthenium complexes have been developed for bioorthogonal catalysis under biologically relevant conditions as well as inside living mammalian cells. The catalysts activate allyl carbamate protected amines with unprecedented high catalytic activity. A fluorescence probe and a caged anticancer drug were efficiently activated within the cellular cytoplasm.

    14. Switchable Molecular Magnets

      Ultrafast Photoswitching in a Copper-Nitroxide-Based Molecular Magnet

      Dr. Wawrzyniec Kaszub, Andrea Marino, Dr. Maciej Lorenc, Prof. Eric Collet, Prof. Elena G. Bagryanskaya, Prof. Evgeny V. Tretyakov, Prof. Victor I. Ovcharenko and Prof. Matvey V. Fedin

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201403672

      Thumbnail image of graphical abstract

      Almost instant: It takes less than 50 fs to switch the spin state of a copper-nitroxide-based molecular magnet using light. The timescale of the phenomenon and its mechanism are investigated by using femtosecond optical spectroscopy. This type of photoswitching is promising for developing ultrafast photo-magnetic materials.

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