Chemistry - A European Journal

Cover image for Vol. 19 Issue 26

June 24, 2013

Volume 19, Issue 26

Pages 8357–8683

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Enthalpy–Entropy Compensation Combined with Cohesive Free-Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives (Chem. Eur. J. 26/2013) (page 8357)

      Thibault Dutronc, Dr. Emmanuel Terazzi, Dr. Laure Guénée, Kerry-Lee Buchwalder, Aurore Spoerri, Dr. Daniel Emery, Dr. Jiri Mareda, Dr. Sébastien Floquet and Prof. Claude Piguet

      Article first published online: 14 JUN 2013 | DOI: 10.1002/chem.201390093

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      Lipophilic methyl-substituted cyanobiphenyls can be considered as molecular salmon that jump out of the condensed phase, but are limited by an increase in size of their rigid core. The concept of cohesive free-energy densities applied to melting processes correlates the molecular volumes of the constituents with the macroscopic enthalpic and entropic changes that accompany the phase transitions of the bulk materials. For more details see the Full Paper by E. Terazzi, C. Piguet et al. on page 8447 ff.

    2. You have free access to this content
      Back Cover: Fabrication of Regular ZnO/TiO2 Heterojunctions with Enhanced Photocatalytic Properties (Chem. Eur. J. 26/2013) (page 8688)

      Long Wu, Jun Xing, Yu Hou, Fang Yuan Xiao, Dr. Zhen Li and Prof. Dr. Hua Gui Yang

      Article first published online: 14 JUN 2013 | DOI: 10.1002/chem.201390096

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      Regular ZnO/TiO2 heterojunctions were synthesized with a facile wet-chemical method. In their Communication on page 8393 ff., H. G. Yang et al. report on the synthesis of ZnO/TiO2 heterojunctions in which uniform wurtzite ZnO nanorod arrays grow only on the eight {101} facets of TiO2, while the other two highly reactive {001} faces remain clean. The resulting ZnO/TiO2 heterojunctions exhibit enhanced photocatalytic performance.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Graphical Abstract: Chem. Eur. J. 26/2013 (pages 8360–8370)

      Article first published online: 14 JUN 2013 | DOI: 10.1002/chem.201390094

  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
  4. Concept

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Drug Delivery

      Transporting and Shielding Photosensitisers by Using Water-Soluble Organometallic Cages: A New Strategy in Drug Delivery and Photodynamic Therapy (pages 8378–8386)

      Prof. Bruno Therrien

      Article first published online: 4 JUN 2013 | DOI: 10.1002/chem.201301348

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      What's new under the sun? Hiding, protecting and shielding a photosensitiser in the cavity of a water-soluble arene-ruthenium metallacage (see figure) can provide a solution to eliminate skin photosensitivity, an important limitation to photodynamic treatments.

  5. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Click Chemistry

      Nanoparticles under the Light: Click Functionalization by Photochemical Thiol-yne Reaction, Towards Double Click Functionalization (pages 8388–8392)

      Paul Demay-Drouhard, Emilie Nehlig, Dr. Julie Hardouin, Prof. Laurence Motte and Dr. Erwann Guénin

      Article first published online: 6 JUN 2013 | DOI: 10.1002/chem.201300903

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      A light click away: The first application of the thiol-yne reaction to nanoparticle functionalization is described (see figure). This metal-free click chemistry approach is compatible with the addition of various molecules at the surface and can be combined with CuAAC methodology to perform chemoselective double functionalization.

    2. Photocatalysts

      Fabrication of Regular ZnO/TiO2 Heterojunctions with Enhanced Photocatalytic Properties (pages 8393–8396)

      Long Wu, Jun Xing, Yu Hou, Fang Yuan Xiao, Dr. Zhen Li and Prof. Dr. Hua Gui Yang

      Article first published online: 17 MAY 2013 | DOI: 10.1002/chem.201300849

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      Facet-selective growth: Regular ZnO/TiO2 heterojunctions have been successfully synthesized using a facile hydrothermal technique (see figure). Due to the interfacial lattice matching, wurtzite ZnO can only grow on the eight {101} facets of the anatase TiO2 single crystals, while the other two {001} facets are untouched. The as-prepared regular ZnO/TiO2 heterojunctions exhibited enhanced photocatalytic generation of .OH radicals and enhanced photodegradation of methyl orange when irradiated with UV light.

    3. Drug Discovery

      A Detective Story in Drug Discovery: Elucidation of a Screening Artifact Reveals Polymeric Carboxylic Acids as Potent Inhibitors of RNA Polymerase (pages 8397–8400)

      Weixing Zhu, Dr. Matthias Groh, Dr. Jörg Haupenthal and Prof. Dr. Rolf W. Hartmann

      Article first published online: 16 MAY 2013 | DOI: 10.1002/chem.201301289

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      Chasing the active impurity: In the validation of a screening hit it was discovered that a polymeric trace impurity was responsible for the biological activity. Such a side product can be formed with similar compounds. During the investigations it was discovered that the negatively charged macromolecule interacts very efficiently with the protein surface of E. coli RNAP via electrostatic interactions.

    4. Asymmetric Synthesis

      Construction of Optically Active Indolines by Formal [4+1] Annulation of Sulfur Ylides and N-(ortho-Chloromethyl)aryl Amides (pages 8401–8404)

      Qing-Qing Yang, Qiang Wang, Jing An, Dr. Jia-Rong Chen, Dr. Liang-Qiu Lu and Prof. Dr. Wen-Jing Xiao

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300988

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      Get asymmetric! Asymmetric [4+1] annulation of sulfur ylides and N-(ortho-chloromethyl)aryl amides allowed the formation of the desired cycloadduct with moderate to high yields and enantioselectivities (see scheme). The described strategy, taking advantage of chiral sulfur ylides, represents a direct procedure to access chiral 2-substituted indolines.

    5. C[BOND]C Coupling

      Ni-Catalyzed Cascade Cyclization–Kumada Alkyl–Alkyl Cross-Coupling (pages 8405–8410)

      Manuel Guisán-Ceinos, Rita Soler-Yanes, Daniel Collado-Sanz, Dr. Vilas B. Phapale, Dr. Elena Buñuel and Prof. Diego J. Cárdenas

      Article first published online: 15 MAY 2013 | DOI: 10.1002/chem.201300882

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      Suggesting novel disconnections: A powerful Ni-catalyzed cascade reaction involving cyclization followed by cross-coupling allows the formation of up to three alkyl–alkyl bonds in a single operation by using alkene-containing alkyl iodides and Grignard reagents (see scheme; acac=acetylacetonate; TMEDA=N,N′,N′-tetramethyl ethylenediamine). Mechanistic experimental and computational studies suggest a NiI–NiII–NiIII catalytic cycle and the intermediacy of radicals.

    6. Cyclization

      Twofold Carbon–Carbon Bond Formation by Intra- and Intermolecular Radical Reactions of Aryl Diazonium Salts (pages 8411–8416)

      Dipl.-Chem. Hannelore Jasch, Prof. Dr. Yannick Landais and Prof. Dr. Markus R. Heinrich

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300354

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      Cascade reactions: A variety of novel cascade reactions can be performed when the known and well-studied radical 5- or 6-exo-cyclization of an aryl diazonium salt is conducted in the presence of alkenes and further optional scavengers (see scheme).

    7. Asymmetric Catalysis

      Rh-Catalyzed Direct Enantioselective Alkynylation of α-Ketiminoesters (pages 8417–8420)

      Kazuhiro Morisaki, Masanao Sawa, Jun-ya Nomaguchi, Dr. Hiroyuki Morimoto, Yosuke Takeuchi, Prof. Dr. Kazushi Mashima and Prof. Dr. Takashi Ohshima

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201301237

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      A green way to amino acids: α-Tetrasubstituted α-amino acid derivatives are formed in high yield and enantioselectivity by using a Rh-catalyzed enantioselective alkynylation of α-ketiminoesters. This reaction, which involves a proton transfer and can be conducted at room temperature, has high substrate scope (see scheme; Cbz=benzyloxycarbonyl, Fmoc=9-fluorenylmethyloxycarbonyl).

    8. Asymmetric Organocatalysis

      Dual Organocatalytic Activation of Isatins and Formaldehyde tert-Butyl Hydrazone: Asymmetric Synthesis of Functionalized 3-Hydroxy-2-oxindoles (pages 8421–8425)

      Dr. David Monge, Ana M. Crespo-Peña, Dr. Eloísa Martín-Zamora, Dr. Eleuterio Álvarez, Prof. Rosario Fernández and Dr. José M. Lassaletta

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201301351

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      Two is better than one! Dual activation of isatins and formaldehyde tert-butyl hydrazone by 2,2′-diamino-1,1′-binaphthalene (BINAM)-derived bis(ureas) is the key to achieve high reactivity and excellent enantioselectivities in the synthesis of azo- and azoxy-functionalized 3-hydroxy-2-oxindoles (see scheme).

    9. Asymmetric Catalysis

      Catalytic Enantioselective Synthesis of Tetrahydroisoquinolines and Their Analogues Bearing a C4 Stereocenter: Formal Synthesis of (+)-(8S,13R)-Cyclocelabenzine (pages 8426–8430)

      Zhilong Chen, Zhaobin Wang and Prof. Jianwei Sun

      Article first published online: 15 MAY 2013 | DOI: 10.1002/chem.201301065

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      A one-pot wonder: 1,2,3,4-Tetrahydroisoquinolines with a C4 stereocenter can be formed by using a one-pot multicomponent chiral phosphoric acid catalyzed transformation of a mixture of oxetane-tethered benzaldehydes, amines, and the dimethyl ester derivative of the Hantzsch ester (see scheme). This transformation can be used to prepare the spermidine alkaloid (+)-(8S,13R)-cyclocelabenzine.

    10. Natural Products

      Total Synthesis of Jadomycins B, S, T, and ILEVS1080 (pages 8431–8434)

      Dr. Xiaoyu Yang and Prof. Biao Yu

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201301297

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      Sweetening up jadomycin A: The first total synthesis of jadomycins B, S, T, and ILEVS1080 has been achieved, featuring construction of the unique 8H-benz[b]oxazolo[3,3-f]phenanthridine skeleton by biomimetic condensation of a quinone aldehyde with amino acid sodium salts and elaboration of the glycosides by Mitsunobu condensation (see figure).

  6. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. Cuprate Chemistry

      Heterobimetallic Cuprates Consisting of a Redox-Switchable, Silicon-Based Metalloligand: Synthesis, Structures, and Electronic Properties (pages 8436–8446)

      Dipl.-Chem. Steffen Styra, Dr. Sandra González-Gallardo, Dr. Felix Armbruster, Dr. Pascual Oña-Burgos, Dipl.-Chem. Eric Moos, Dr. Matthias Vonderach, Priv.-Doz. Dr. Patrick Weis, Priv.-Doz. Dr. Oliver Hampe, Dipl.-Chem. Anneken Grün, Dipl.-Chem. Yvonne Schmitt, Prof. Dr. Markus Gerhards, Dipl.-Chem. Fabian Menges, Dipl.-Chem. Maximilian Gaffga, Prof. Dr. Gereon Niedner-Schatteburg and Prof. Dr. Frank Breher

      Article first published online: 4 JUN 2013 | DOI: 10.1002/chem.201300586

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      Putting metals together: The preparation, structures, and electronic properties of bimetallic silyl halido cuprates consisting of an anionic silicon-based metalloligand are reported, together with detailed studies on their gas-phase properties and their fluorescence and redox behavior in solution (see figure).

    2. Intermolecular Interactions

      Enthalpy–Entropy Compensation Combined with Cohesive Free-Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives (pages 8447–8456)

      Thibault Dutronc, Dr. Emmanuel Terazzi, Dr. Laure Guénée, Kerry-Lee Buchwalder, Aurore Spoerri, Dr. Daniel Emery, Dr. Jiri Mareda, Dr. Sébastien Floquet and Prof. Claude Piguet

      Article first published online: 21 MAY 2013 | DOI: 10.1002/chem.201300587

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      In tune with temperature! The transformation of the melting thermodynamic parameters into cohesive free-energy densities (CFED) for 4′-(n-oxy)-i′-methyl-j-methyl-4-cyanobiphenyl (CnLi,j) provides a novel linear correlation for predicting melting temperatures in a simple way.

    3. Molecular Recognition

      Three-Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks (pages 8457–8465)

      Dennis Cao, Dr. Michal Juríček, Zachary J. Brown, Dr. Andrew C.-H. Sue, Dr. Zhichang Liu, Juying Lei, Anthea K. Blackburn, Dr. Sergio Grunder, Dr. Amy A. Sarjeant, Prof. Ali Coskun, Prof. Cheng Wang, Prof. Omar K. Farha, Prof. Joseph T. Hupp and Prof. J. Fraser Stoddart

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300762

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      Playing the hand-stacking game: The reaction of [2]catenane-containing struts with Cu(NO3)2 produces extended frameworks, from whence both co-conformational selection and diastereoselection are observed following crystallization. Solid-state structures reveal the selective formation of stereoregular π–π stacks of enantiomeric pairs of donor–acceptor catenanes, despite the presence in solution of up to eight co-conformational and stereoisomers exhibiting planar chirality (see figure).

    4. Computer Chemistry

      QM/MM Study on the Light Emitters of Aequorin Chemiluminescence, Bioluminescence, and Fluorescence: A General Understanding of the Bioluminescence of Several Marine Organisms (pages 8466–8472)

      Dr. Shu-Feng Chen, Prof. Nicolas Ferré and Prof. Ya-Jun Liu

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300678

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      See jellyfish in a new light: The origin and differences in the chemiluminescence, bioluminescence, and fluorescence of the proteins of the aequorin jellyfish were theoretically investigated by using hybrid quantum mechanics and molecular mechanics methods combined with a molecular dynamics method. The findings are important for understanding the bioluminescence of jellyfish and other marine organisms (see figure).

    5. Photochemistry

      A Versatile Dithienylethene-Functionalized Ph-Diazabutadiene (DAB) Ligand: From Photoswitchable Main-Group Molecules to Photochromic Polymers (pages 8473–8477)

      Jacquelyn T. Price and Prof. Paul J. Ragogna

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201301086

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      Switching it up! A versatile redox-active diazabutadiene (DAB) ligand containing photochromic dithienylethene rings in the backbone has been synthesized. The coordination of both BIII and PIII has been demonstrated, along with the facile functionalization of the PIII heterocycle with a polymerizable group and the synthesis of a photochromic side-chainfunctionalized polymer (see figure).

    6. Cluster Compounds

      Well-Defined Molecular Magnesium Hydride Clusters: Relationship between Size and Hydrogen-Elimination Temperature (pages 8478–8489)

      Julia Intemann, Dr. Jan Spielmann, Dr. Peter Sirsch and Prof. Dr. Sjoerd Harder

      Article first published online: 9 MAY 2013 | DOI: 10.1002/chem.201300684

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      Size matters: The temperature that is required for the elimination of H2 in magnesium hydride clusters is dependent on the cluster size (see scheme). Detailed experimental and/or theoretical data for magnesium hydride and magnesium(I) clusters are reported.

    7. Fluorophores

      The Photophysics of Pyridine-Derivatized ortho-, meta-, and para-Dibutylamino Cruciforms (pages 8490–8496)

      Dipl.-Chem. Florian Hinderer and Prof. Dr. Uwe H. F. Bunz

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300211

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      Position is everything: The position of the nitrogen atoms and groups of cruciforms containing both pyridine and N,N-dimethylaniline moieties has a profound effect on the photophysical properties (solvatochromism, fluorescence quantum yields, fluorescence lifetimes, and their response to a change in the pH of the environment) of these compounds. This effect is in part due to the meta-positioned nitrogen atoms and groups of the excited states having surprisingly large orbital coefficients in the HOMO (see picture). Additionally, these compounds show promise as pH sensors.

    8. Sensors

      Leveraging Material Properties in Fluorescence Anion Sensor Arrays: A General Approach (pages 8497–8506)

      Prof. Pavel Anzenbacher Jr., Dr. Yuanli Liu, Dr. Manuel A. Palacios, Dr. Tsuyoshi Minami, Dr. Zhuo Wang and Dr. Ryuhei Nishiyabu

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201204188

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      One for all, all for one: A single fluorescent probe is shown to recognize eight different aqueous anions and eight urine samples when embedded in ten different polyurethanes in an array that displays 100 % classification accuracy (see figure). To demonstrate the potential of the concept for quantitative studies, an estimation of non-steroidal anti-inflammatory drugs, ibuprofen and diclofenac, in water and in saliva was performed.

    9. Nanomaterials

      Organic–Inorganic Hybrid Supermicroporous Iron(III) Phosphonate Nanoparticles as an Efficient Catalyst for the Synthesis of Biofuels (pages 8507–8514)

      Malay Pramanik and Prof. Dr. Asim Bhaumik

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300128

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      Iron brews biofuels: Highly crystalline, supermicroporous iron(III) phosphonate nanoparticles have been synthesized through a hydrothermal reaction between benzene-1,3,5-triphosphonic acid and FeCl3. The resulting material was used as an efficient and recyclable catalyst for the synthesis of biofuels under mild reaction conditions (see scheme).

    10. Total Synthesis

      Total Synthesis, Proof of Absolute Configuration, and Biosynthetic Origin of Stylopsal, the First Isolated Sex Pheromone of Strepsiptera (pages 8515–8524)

      Dr. Roman Lagoutte, Ing. Petr Šebesta, Dr. Pavel Jiroš, Dr. Blanka Kalinová, Dr. Anna Jirošová, Dr. Jakub Straka, Kateřina Černá, Dr. Jan Šobotník, Dr. Josef Cvačka and Dr. Ullrich Jahn

      Article first published online: 29 APR 2013 | DOI: 10.1002/chem.201204196

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      Love at first…smell: An asymmetric total synthesis, gas chromatographic analyses, and field tests confirm the structure of the first isolated sex pheromone of a twisted-wing parasite Stylops muelleri (see figure). Its biosynthetic origin and complexity demonstrate the considerable efforts undertaken by the motionless and fully host-dependant female to attract the very short-lived free-living male, thus securing success in the perpetuation of the species.

    11. Cluster Compounds

      Connecting Discrete Stereoclusters by Using DFT and NMR Spectroscopy: The Case of Nivariol (pages 8525–8532)

      Dr. Francisco Cen-Pacheco, Prof. Jaime Rodríguez, Prof. Manuel Norte, Prof. José J. Fernández and Dr. Antonio Hernández Daranas

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201204272

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      Never say nivariol again: The interpretation of NMR coupling constants and chemical shifts with the aid of DFT calculations allowed the structural determination of a complex polyether triterpene (see figure). This approach is of particular importance when studying chiral quaternary carbon centers or distant stereoclusters.

    12. Zeolites

      Large Zeolite H-ZSM-5 Crystals as Models for the Methanol-to-Hydrocarbons Process: Bridging the Gap between Single-Particle Examination and Bulk Catalyst Analysis (pages 8533–8542)

      Dr. Jan P. Hofmann, Dr. Davide Mores, Luis R. Aramburo, Shewangizaw Teketel, Dr. Marcus Rohnke, Prof. Dr. Jürgen Janek, Prof. Dr. Unni Olsbye and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201203351

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      Death of the coffins: Large coffin-shaped H-ZSM-5 zeolite crystals were used as model catalysts for the methanol-to-hydrocarbons reaction (see figure). Their activity and deactivation behavior were tested by the combined use of fixed-bed reactor and optical microspectroscopy experiments. Deactivation by carbonaceous deposit formation was studied by an integral approach to result in a comprehensive coking model.

    13. Nanostructures

      Fabrication of Ag Nanoparticles Embedded in TiO2 Nanotubes: Using Electrospun Nanofibers for Controlling Plasmonic Effects (pages 8543–8549)

      Dr. Mi-Hee Jung, Dr. Yong Ju Yun, Dr. Moo-Jung Chu and Dr. Man Gu Kang

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300834

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      Plasmon-enhanced solar cells were fabricated by using polycrystalline TiO2 nanotubes (NTs) with embedded Ag nanoparticles (NPs), obtained by coating composites of electrospun poly(ethylene oxide) and Ag NPs with TiO2 by atomic layer deposition (ALD), as the photoanode. Their plasmon effect can be controlled by varying the thickness of a dielectric Al2O3 spacer between the Ag NPs and dye molecules by means of the ALD process (see figure).

    14. Sensors

      Formation and Properties of Self-Assembly-Driven Fluorescent Nanoparticle Sensors (pages 8550–8557)

      Dr. Kun Cui, Dr. Xuemin Lu, Junfang Guan, Prof. Qinghua Lu, Dr. Zhaofu Fei and Prof. Paul J. Dyson

      Article first published online: 2 MAY 2013 | DOI: 10.1002/chem.201204349

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      Self-assembly makes good sense: Fluorescent nanoparticles were prepared by two main supramolecular interactions: ionic bonding and hydrophobic/hydrophilic interactions. The fluorescence of the nanoparticles is sensitive to a quenching effect by various ions with high selectivity (see figure).

    15. Gels

      Chiral Hexa- and Nonamethylene-Bridged Bis(L-Leu-oxalamide) Gelators: The First Oxalamide Gels Containing Aggregates with a Chiral Morphology (pages 8558–8572)

      Dr. Nataša Šijaković Vujičić, Dr. Zoran Glasovac, Dr. Niek Zweep, Prof. Jan H. van Esch, Dr. Marijana Vinković, Dr. Jasminka Popović and Prof. Mladen Žinić

      Article first published online: 7 MAY 2013 | DOI: 10.1002/chem.201300642

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      Mix/morph gelators: Chiral dioxalamide dimethyl esters and dicarboxylic acid derivatives (containing flexible methylene bridges with an odd (n=7) and even (n=4) number of methylene groups) are good gelators of polar and lipophilic organic solvents. They are capable of forming diverse gel aggregates of chiral and achiral morphologies, sometimes simultaneously present in the same gel system.

    16. Hydride Complexes

      Unusual Structure, Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN[DOUBLE BOND])Mo(H)(SiH2Ph)(PMe3)3] (pages 8573–8590)

      Dr. Andrey Y. Khalimon, Prof. Dr. Stanislav K. Ignatov, Andrey I. Okhapkin, Dipl.-Ing. Razvan Simionescu, Prof. Dr. Lyudmila G. Kuzmina, Prof. Dr. Judith A. K. Howard and Dr. Georgii I. Nikonov

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300376

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      Rule breakers: Silyl hydride complex [(ArN)Mo(H)(SiH2Ph)(PMe3)3] undergoes a silane-assisted exchange of coordinated and free phosphines and catalyzes the hydrosilylation of carbonyl groups through an unexpected mechanism (see scheme), as studied by using DFT.

    17. Asymmetric Catalysis

      Highly Stereoselective Conjugate Addition and α-Alkynylation Reaction with Electron-Deficient Alkynes Catalyzed by Chiral Scandium(III) Complexes (pages 8591–8596)

      Zhen Wang, Zuliang Zhang, Qian Yao, Prof. Dr. Xiaohua Liu, Yunfei Cai, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300816

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      A highly Z-selective asymmetric conjugate addition of alkynyl carbonyl compounds with 3-substituted oxindoles has been developed by using scandium complexes of chiral N,N′-dioxides (L) under mild conditions. The products were obtained in excellent yields and high enantiomeric and geometric control. The catalyst was also found to be effective in the asymmetric acetylenic substitution reaction of 3-substituted oxindoles, giving excellent enantioselectivities (see scheme).

    18. Electrochemical Cells

      Efficient Green-Light-Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone-Containing Cyclometalating Ligands (pages 8597–8609)

      Daniel Tordera, Andreas M. Bünzli, Antonio Pertegás, Dr. José M. Junquera-Hernández, Prof. Edwin C. Constable, Dr. Jennifer A. Zampese, Prof. Catherine E. Housecroft, Prof. Enrique Ortí and Dr. Henk J. Bolink

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300457

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      Green enlightenment: Electron-withdrawing sulfone groups introduced into the cyclometalating phenylpyrazole ligands lead to very efficient green-emitting ionic iridium complexes. Green electroluminescence from efficient light-emitting chemical cells is obtained (see figure).

    19. Total Synthesis

      Enantioselective Total Synthesis of (−)-Blennolide A (pages 8610–8614)

      Prof. Dr. Lutz F. Tietze, Dr. Ling Ma, Johannes R. Reiner, Stefan Jackenkroll and Sven Heidemann

      Article first published online: 3 MAY 2013 | DOI: 10.1002/chem.201300479

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      Domino effect: An enantioselective domino-Wacker/carbonylation/methoxylation process and an enantioselective Wacker oxidation are the key steps in the first total synthesis of the fungal metabolite blennolide A (see scheme).

    20. RNA

      Liquid-Phase RNA Synthesis by Using Alkyl-Chain-Soluble Support (pages 8615–8620)

      Dr. Shokaku Kim, Masanori Matsumoto and Prof. Dr. Kazuhiro Chiba

      Article first published online: 9 MAY 2013 | DOI: 10.1002/chem.201300655

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      The assembly of RNA oligomers relies principally on solid-phase approaches, although some alternative methods have been developed to date. A highly efficient and practical method of liquid-phase synthesis for RNA oligomers by using an alkyl-chain-type soluble support is reported. The utility of the liquid-phase method through 21-mer RNA synthesis on a gram scale is described (see scheme).

    21. Lithium–Sulfur Batteries

      Fast, Reversible Lithium Storage with a Sulfur/Long-Chain-Polysulfide Redox Couple (pages 8621–8626)

      Yu-Sheng Su, Dr. Yongzhu Fu, Dr. Bingkun Guo, Dr. Sheng Dai and Prof. Arumugam Manthiram

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300886

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      More juice: The kinetics of the sulfur/long-chain polysulfide redox couple (S8[LEFT RIGHT ARROW]Li2S4; theoretical capacity= 419 mA h g−1) are experimentally demonstrated to be very fast in the Li–S system. A Li–S battery with a blended-carbon interlayer retains excellent cycle stability and high discharge capacity over 250 cycles at 10 C and 15 C rates. The meso-/micropores in the interlayer are responsible for storing the migrating polysulfides and offering sufficient electrolyte accessibility.

    22. Catalysis

      Iron(III) Triflimide as a Catalytic Substitute for Gold(I) in Hydroaddition Reactions to Unsaturated Carbon–Carbon Bonds (pages 8627–8633)

      Jose R. Cabrero-Antonino, Dr. Antonio Leyva-Pérez and Prof. Dr. Avelino Corma

      Article first published online: 13 MAY 2013 | DOI: 10.1002/chem.201300386

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      Lewis and Brønsted catalysis: It is shown that iron(III) catalyses as efficiently as gold(I) the hydroaddition of a wide array of nucleophiles, including water, alcohols, thiols, amines, alkynes, and alkenes, to multiple C[BOND]C bonds (see scheme).

    23. Dual-Activation Catalysis

      Gold-Catalyzed Synthesis of Iodofulvenes (pages 8634–8641)

      Dipl.-Chem. Pascal Nösel, M.Sc. Tobias Lauterbach, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 7 MAY 2013 | DOI: 10.1002/chem.201300507

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      Iodine/gold exchange: A gold-catalyzed iodine transfer allows the efficient synthesis of benzofulvenes with iodo substituents on the fulvene core (see scheme). The new dual-activation catalysts are efficient catalysts for this new type of cycloisomerization.

    24. Supramolecular Polymers

      Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers (pages 8642–8649)

      Dr. Tristan Mes, Dr. Seda Cantekin, Dirk W. R. Balkenende, Martijn M. M. Frissen, Martijn A. J. Gillissen, Bas F. M. De Waal, Dr. Ilja K. Voets, Prof. Dr. E. W. Meijer and Dr. Anja R. A. Palmans

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201204273

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      Thioamide bonds: The polymerisation of a thioamide-based supramolecular motif is elucidated by combining depolarised dynamic light scattering and temperature-dependent spectroscopic measurements (see figure). A cooperative polymerisation mechanism and strong amplification of chirality makes this a highly versatile structuring motif.

    25. Lithium-Ion Batteries

      Highly Reversible Lithium Storage in Hierarchical Ca2Ge7O16 Nanowire Arrays/Carbon Textile Anodes (pages 8650–8656)

      Wenwu Li, Xianfu Wang, Bin Liu, Dr. Sijun Luo, Zhe Liu, Xiaojuan Hou, Qingyi Xiang, Prof. Di Chen and Prof. Guozhen Shen

      Article first published online: 9 MAY 2013 | DOI: 10.1002/chem.201300115

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      Batteries not included: A hierarchical flexible electrode that consisted of aligned Ca2Ge7O16 nanowire arrays on carbon textile (see figure) exhibited a highly reversible capacity, remarkable cycling stability, and good rate capability.

    26. Synthetic Methods

      1,2,3,4-Tetrasubstituted Cyclopentadienes and Their Applications for Metallocenes: Efficient Synthesis through Zirconocene- and CuCl-Mediated Intermolecular Coupling of Two Alkynes and One Diiodomethane (pages 8657–8664)

      Weizhi Geng, Dr. Chao Wang, Jie Guang, Wei Hao, Dr. Wen-Xiong Zhang and Prof. Dr. Zhenfeng Xi

      Article first published online: 2 MAY 2013 | DOI: 10.1002/chem.201300416

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      Ringing in the changes: A one-pot synthesis of 1,2,3,4-tetrasubstituted cyclopentadienes by zirconocene- and CuCl-mediated intermolecular coupling of two alkynes and diiodomethane (see scheme; Cp=η5-C5H5; DMPU=1,3-dimethyl-3,4,5,6-tetrahydro-2(1 H)-pyrimidinone) gave products that were successfully applied for the synthesis of the corresponding zirconocene derivatives.

    27. Total Synthesis

      Total Syntheses of (±)-Fawcettimine, (±)-Fawcettidine, (±)-Lycoflexine, and (±)-Lycoposerramine-Q (pages 8665–8672)

      Naoya Itoh, Takashi Iwata, Hiromi Sugihara, Dr. Fuyuhiko Inagaki and Prof. Dr. Chisato Mukai

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300364

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      Fawcettimine alkaloids: The total syntheses of four fawcettimine-related Lycopodium alkaloids, (±)-fawcettimine, (±)-fawcettidine, (±)-lycoposerramine-Q, and (±)-lycoflexine, are described. The key steps in these syntheses are the Pauson–Khand reaction of 4-methylidene-6-siloxyoct-1-en-7-yne followed by regio- and stereoselective hydrogenation to provide the bicyclo[4.3.0]nonenone intermediate bearing a methyl group with the required stereochemistry (see scheme).

    28. Click Chemistry

      Thiol–Yne Click Reactions on Alkynyl–Dopamine-Modified Reduced Graphene Oxide (pages 8673–8678)

      Izabela Kaminska, Wang Qi, Alexandre Barras, Janusz Sobczak, Joanna Niedziolka-Jonsson, Patrice Woisel, Joel Lyskawa, William Laure, Marcin Opallo, Musen Li, Rabah Boukherroub and Sabine Szunerits

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201300225

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      Modified graphene oxide: A simple method has been developed for the simultaneous exfoliation and reduction of graphene oxide (GO) to reduced GO (rGO) by using alkynyl-terminated dopamine as the reducing agent. The reaction was performed under mild conditions to yield rGO functionalized with the dopamine derivative (see figure). The chemical reactivity of the alkynyl function was demonstrated and the surfaces of the rGO characterized by a variety of techniques.

    29. Lithium Batteries

      Catalytic Disproportionation of the Superoxide Intermediate from Electrochemical O2 Reduction in Nonaqueous Electrolytes (pages 8679–8683)

      Dr. Dong Zheng, Dr. Qiang Wang, Dr. Hung-Sui Lee, Dr. Xiao-Qing Yang and Prof. Deyang Qu

      Article first published online: 6 MAY 2013 | DOI: 10.1002/chem.201204506

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      For a rechargeable Li–air battery an efficient catalyst for rapid superoxide (O2) disproportionation is important. Tris(pentafluorophenyl)borane was found to catalyse the disproportionation reaction efficiently. The negative impact of the reaction between the electrolyte and O2 produced by the O2 reduction was minimized (see scheme).

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