Chemistry - A European Journal

Cover image for Chemistry - A European Journal

December 14, 2012

Volume 18, Issue 51

Pages 16237–16579

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Chemical Adaptability: The Integration of Different Kinds of Matter into Giant Molecular Metal Oxides (Chem. Eur. J. 51/2012) (page 16237)

      Prof. Dr. Achim Müller, Dr. Alice Merca, Dr. Ahmed Jasim M. Al-Karawi, Somenath Garai, Dr. Hartmut Bögge, Dr. Guangfeng Hou, Prof. Dr. Lixin Wu, Dr. Erhard T. K. Haupt, Prof. Dr. Dieter Rehder, Fadi Haso and Prof. Dr. Tianbo Liu

      Article first published online: 7 DEC 2012 | DOI: 10.1002/chem.201290217

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      The term adaptability is often used in biology on organism and molecular level, but rather seldom in chemistry. In their Full Paper on page 16310 ff., A. Müller, E. T. K. Haupt et al. refer to a new phenomenon that they call “chemical adaptability”. Wheel-shaped molecular metal oxides can integrate different kinds of matter without changing their shapes and even cations and anions at the same positions. This can be explained by the unique properties of molybdenum oxide building blocks that “behave” similarly flexible to those in dynamic libraries; the latter scenario can lead to the huge variety of related well-known giant clusters.

  2. Graphical Abstract

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

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

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

      New Reactivity of the Uranyl(VI) Ion (pages 16258–16271)

      Dr. Robert J. Baker

      Article first published online: 14 NOV 2012 | DOI: 10.1002/chem.201203085

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      The unusual reactivity of the uranyl ion, [UO2]2+, reported during the past few years is highlighted. Organometallic and catalytic chemistry is reviewed and the use of uranyl in supramolecular assemblies emphasized. Oxygen functionalization and reduction to the pentavalent state is discussed.

  5. Communications

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

      An Extremely Redox-Active Air-Stable Neutral π Radical: Dicyanomethylene-Substituted Triangulene with a Threefold Symmetry (pages 16272–16276)

      Dr. Akira Ueda, Hideki Wasa, Dr. Shinsuke Nishida, Dr. Yuki Kanzaki, Prof. Dr. Kazunobu Sato, Prof. Dr. Daisuke Shiomi, Prof. Dr. Takeji Takui and Prof. Dr. Yasushi Morita

      Article first published online: 23 NOV 2012 | DOI: 10.1002/chem.201203755

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      Radically active: A redox-active air-stable neutral π radical (1.) with three dicyanomethylene groups introduced with threefold symmetry into a triangulene π skeleton instead of the oxygen atoms of TOT. was designed, synthesized, and characterized (see figure). The enhanced electron-accepting ability and extended π-electronic system of this chemical modification gave an extremely small SOMO–LUMO gap and significantly lowered the frontier orbital energies, leading to the remarkable increase in the redox stages.

    2. G-quadruplexes

      A Cyclometallated Platinum Complex as a Selective Optical Switch for Quadruplex DNA (pages 16277–16282)

      Dr. Kogularamanan Suntharalingam, Dr. Anna Łęczkowska, Mona A. Furrer, Yilei Wu, Dr. Marina K. Kuimova, Dr. Bruno Therrien, Dr. Andrew J. P. White and Prof. Ramon Vilar

      Article first published online: 20 NOV 2012 | DOI: 10.1002/chem.201202990

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      Hits the spot: A cyclometalled platinum(II) complex with a substituted phenanthroline ligand is reported. The complex has high in vitro affinity for quadruplex DNA and upon binding its emission is switched on. The complex can be easily delivered to the cell by using a metallo-cage as a carrier (see illustration). By means of confocal microscopy, it is shown that the complex is released inside the cell, penetrates the nucleus and localises in the nucleoli.

    3. Asymmetric Catalysis

      Asymmetric Counteranion-Directed Catalytic Hosomi–Sakurai Reaction (pages 16283–16287)

      Manuel Mahlau, Dr. Pilar García-García and Prof. Dr. Benjamin List

      Article first published online: 23 NOV 2012 | DOI: 10.1002/chem.201203623

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      Counteranion control enables the enantioselective, organo Lewis acid catalyzed Hosomi–Sakurai reaction of (hetero)aromatic aldehydes and allylsilanes using an easily handled disulfonimide precatalyst (see scheme). The key to the success of this system is to turn the usually undesired silylium ion catalysis into the desired catalytic regime and pair the cation with an enantiopure disulfonimide anion, thereby applying the concept of asymmetric counteranion-directed catalysis.

    4. Silicon Complexes

      Stable Five-Coordinate Silicon(IV) Complexes with SiN4X Skeletons (X=S, Se, Te) and Si[DOUBLE BOND]X Double Bonds (pages 16288–16291)

      Konstantin Junold, Johannes A. Baus, Dr. Christian Burschka, Dominic Auerhammer and Prof. Dr. Reinhold Tacke

      Article first published online: 22 NOV 2012 | DOI: 10.1002/chem.201202936

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      Silylenes: Reaction of the donor-stabilized silylene 1 with elemental sulfur, selenium, or tellurium led to the formation of 2 ac [SiN4X skeletons (X=S, Se, Te)], the first stable five-coordinate silicon(IV) compounds with silicon–chalcogen double bonds (see figure).

    5. Amides

      Dual Nucleophilic/Electrophilic Capture of In Situ Generated Iminium Ethers: Towards the Synthesis of Functionalized Amide Building Blocks (pages 16292–16296)

      Dr. Bo Peng, Dr. Daniel H. O'Donovan, Dr. Igor D. Jurberg and Dr. Nuno Maulide

      Article first published online: 14 NOV 2012 | DOI: 10.1002/chem.201203293

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      Rearranging its feathers: The transformation of simple linear amides into a diverse range of branched, functionalized products by conversion to iminium esters is followed by sequential treatment with nucleophiles and electrophiles (see scheme). The method takes advantage of a novel Claisen rearrangement and the use of aromatic substrates greatly facilitates the formation of the intermediate iminium ether.

    6. Organocatalysis

      Highly Enantioselective Intermolecular Stetter Reaction of Simple Acrylates: Synthesis of α-Chiral γ-Ketoesters (pages 16297–16301)

      Nathalie E. Wurz, Dr. Constantin G. Daniliuc and Prof. Dr. Frank Glorius

      Article first published online: 14 NOV 2012 | DOI: 10.1002/chem.201202432

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      Simple Stetter: A novel N-heterocyclic carbene (NHC) was designed by combining an electron-rich 2,6-dimethoxy substituent and an underestimated yet promising chiral motif. With this NHC in hand, a highly enantioselective intermolecular Stetter reaction of simple acrylates was developed, yielding versatile α-chiral γ-ketoesters. This represents the first catalytic asymmetric route towards these valuable compounds (see scheme).

  6. Full Papers

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

      Unusual Regenerable Porous Metal–Organic Framework Based on a New Triple Helical Molecular Necklace for Separating Organosulfur Compounds (pages 16302–16309)

      Dr. Shun-Li Li, Dr. Ya-Qian Lan, Dr. Hiroaki Sakurai and Prof. Dr. Qiang Xu

      Article first published online: 21 NOV 2012 | DOI: 10.1002/chem.201203093

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      Designer MOF necklace: By using rigidly designed carboxylate ligands, a new 3D porous metal–organic framework (MOF) involving an unusual triple molecular necklace-like helix has been constructed for the first time (see figure). It exhibits excellent adsorptive desulfurization properties with high stability, repeatability, and regenerability.

    2. Chemical Adaptability

      Chemical Adaptability: The Integration of Different Kinds of Matter into Giant Molecular Metal Oxides (pages 16310–16318)

      Prof. Dr. Achim Müller, Dr. Alice Merca, Dr. Ahmed Jasim M. Al-Karawi, Somenath Garai, Dr. Hartmut Bögge, Dr. Guangfeng Hou, Prof. Dr. Lixin Wu, Dr. Erhard T. K. Haupt, Prof. Dr. Dieter Rehder, Fadi Haso and Prof. Dr. Tianbo Liu

      Article first published online: 23 NOV 2012 | DOI: 10.1002/chem.201203186

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      Integration without changing shape: {Mo11}n (n=14, 16)-type molybdenum oxide clusters allow integration of matter—without changing their wheel shapes—like cations and anions positioned at the same places as well as “salt-like” {M(SO4)}16 rings (M= K, NH4), caused by unique flexible building block properties similar to those present in related dynamic libraries which lead to a variety of giant clusters.

    3. Conformation Analysis

      Effect of the Substituents of the Neighboring Ring in the Conformational Equilibrium of Iduronate in Heparin-like Trisaccharides (pages 16319–16331)

      Juan Carlos Muñoz-García, Dr. Javier López-Prados, Dr. Jesús Angulo, Irene Díaz-Contreras, Dr. Niels Reichardt, Dr. José L. de Paz, Prof. Manuel Martín-Lomas and Dr. Pedro M. Nieto

      Article first published online: 9 NOV 2012 | DOI: 10.1002/chem.201202770

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      The sulfation pattern of the neighboring ring drives the conformational equilibrium of iduronate in heparin trisaccharides. A library of heparin-like trisaccharides incorporating sulfate groups in key positions has been prepared. The conformational equilibrium of the central iduronate ring has been analyzed and the populations were calculated by combining NMR and molecular dynamics (see figure).

    4. Reaction Mechanisms

      CPMD Simulation of a Bimolecular Chemical Reaction: Nucleophilic Attack of a Disulfide Bond under Mechanical Stress (pages 16332–16338)

      M. Sc. Florian Hofbauer and Prof. Dr. Irmgard Frank

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201202065

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      Breaking disulfide bonds: Disulfide bonds are destabilized by steric or mechanical strain. In a basic environment, they may be broken through nucleophilic attack. Car–Parrinello molecular dynamics (CPMD) simulations allow the analysis of the mechanism of this reaction and of side reactions for comparison with AFM experiments (see figure).

    5. Dyes/Pigments

      Phosphorylated 3-Heteroarylcoumarins and Their Use in Fluorescence Microscopy and Nanoscopy (pages 16339–16348)

      Dr. Shamil Nizamov, Dr. Katrin I. Willig, Dipl.-Chem. Maksim V. Sednev, Dr. Vladimir N. Belov and Prof. Stefan W. Hell

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201202382

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      A green light for bright ideas! 3-Heteroarylcoumarins with a CH2OP(O)(OH)2 group attached to the 2,2,4-trimethyl-1,2-dihydroquinoline residue absorb at 410–440 nm and emit at 500–515 nm (see figure). Large fluorescence quantum yields and low cross-talk in two-color imaging (with xanthene dyes) were observed. In stimulated emission depletion (STED) nanoscopy, these phosphorylated dyes with large Stokes shifts allow an optical resolution of 40–60 nm.

    6. Photolysis

      IR-Monitored Photolysis of CO-Inhibited Nitrogenase: A Major EPR-Silent Species with Coupled Terminal CO Ligands (pages 16349–16357)

      Lifen Yan, Dr. Vladimir Pelmenschikov, Christie H. Dapper, Aubrey D. Scott, Prof. William E. Newton and Prof. Stephen P. Cramer

      Article first published online: 7 NOV 2012 | DOI: 10.1002/chem.201202072

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      Fischer–Tropsch chemistry: Fourier transform infrared (FTIR) spectroscopy has been used to study the photochemistry of a new EPR-silent CO-inhibited form of α-H195Q nitrogenase from Azotobacter vinelandii. DFT calculations helped to assign the observed species as terminal CO molecules bound to the FeMo-cofactor active site (see figure).

    7. Spin-State Switching

      Light-Driven Coordination-Induced Spin-State Switching: Rational Design of Photodissociable Ligands (pages 16358–16368)

      Dr. Steffen Thies, Hanno Sell, Dr. Claudia Bornholdt, Christian Schütt, Dr. Felix Köhler, Prof. Dr. Felix Tuczek and Prof. Dr. Rainer Herges

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201201698

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      Turn the spin: Nickel–porphyrins with appropriately designed axial photochromic ligands change their coordination number and consequently their spin state reversibly upon irradiation. Rational design led to a substituted 3-phenylazopyridine as a photodissociable ligand with a switching efficiency of 40 % (see figure). Thus, the magnetic susceptibility of a homogeneous solution was switched by a factor of more than two at room temperature.

    8. Supported Catalysts

      A Fast-Initiating Ionically Tagged Ruthenium Complex: A Robust Supported Pre-catalyst for Batch-Process and Continuous-Flow Olefin Metathesis (pages 16369–16382)

      Dr. Etienne Borré, Dr. Mathieu Rouen, Isabelle Laurent, Magaly Magrez, Dr. Fréderic Caijo, Dr. Christophe Crévisy, Dr. Wladimir Solodenko, Loic Toupet, René Frankfurter, Prof. Dr. Carla Vogt, Prof. Dr. Andreas Kirschning and Dr. Marc Mauduit

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201201589

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      Tag! You′re it! A pyridinium-tagged Ru complex (see figure) that was anchored to sulfonated silica formed a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions with low ruthenium leaching.

    9. DNA Condensation

      Efficient DNA Condensation Induced by Ruthenium(II) Complexes of a Bipyridine-Functionalized Molecular Clip Ligand (pages 16383–16392)

      Dr. Satish S. Bhat, Prof. Avinash S. Kumbhar, Dr. Anupa A. Kumbhar and Dr. Ayesha Khan

      Article first published online: 23 OCT 2012 | DOI: 10.1002/chem.201200407

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      Carriers for DNA delivery: A series of mixed-ligand ruthenium(II) polypyridyl complexes of a bipyridine-functionalized molecular clip has been synthesized and characterized. These complexes rapidly condense free DNA into globular nanoparticles of various sizes. The DNA condensation induced by these complexes has been investigated by an electrophoretic mobility assay, dynamic light scattering, and transmission electron microscopy (see the respective images). The cellular uptake of complex–DNA condensates and the low cytotoxicity of these complexes satisfy the requirements of a gene vector.

    10. Thin Films

      Assembly of Graphene Nanosheets and SiO2 Nanoparticles Towards Transparent, Antireflective, Conductive, and Superhydrophilic Multifunctional Hybrid Films (pages 16393–16401)

      Jiayi Zhu, Ligang Xu and Prof. Dr. Junhui He

      Article first published online: 23 OCT 2012 | DOI: 10.1002/chem.201202494

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      One film, multiple functions: A new graphene/SiO2 hybrid film with a self-antireflective structure was fabricated by layer-by-layer assembly of graphene nanosheets and SiO2 nanoparticles. The self-antireflective structure could enhance the transmittance of hybrid films. The transparent, conductive, and superhydrophilic graphene/SiO2 hybrid film showed excellent antireflective, antistatic, and antifogging behaviors (see figure).

    11. Radical Reactions

      Synthesis and Characterization of New 5-Linked Pinoresinol Lignin Models (pages 16402–16410)

      Dr. Fengxia Yue, Dr. Fachuang Lu, Prof. Dr. Runcang Sun and Prof. Dr. John Ralph

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201201506

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      Super model: In this study, aimed at helping to better understand 5-linked pinoresinol structures by providing the required data for NMR structural characterization, new lignin model pinoresinol compounds were synthesized through biomimetic peroxidase-mediated oxidative coupling between pre-formed (free-phenolic) 5-5′- or 5-O-4′-linked coniferyl alcohol dimers and a coniferyl alcohol monomer (examples with 5-O-4′-linked dimers are shown in the scheme).

    12. Biosensors

      A New Signal-On Photoelectrochemical Biosensor Based on a Graphene/Quantum-Dot Nanocomposite Amplified by the Dual-Quenched Effect of Bipyridinium Relay and AuNPs (pages 16411–16418)

      Dr. Xiaoru Zhang, Yunpeng Xu, Prof. Yanqiang Yang, Xia Jin, Sujuan Ye, Prof. Shusheng Zhang and Dr. Lilin Jiang

      Article first published online: 5 NOV 2012 | DOI: 10.1002/chem.201202213

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      PECking order! A new photoelectrochemical (PEC) biosensor was developed by using carboxyl-functionalized graphene and CdSe nanoparticles (NPs). This sensitive interface was successfully applied to detection of thrombin based on the dual-quenched effect of a PEC nanoparticle, which relied on the electron transfer of a bipyridinium relay and energy transfer of AuNPs (see figure). After recognition with an aptamer, the PEC nanoparticle was removed and a signal-on PEC biosensor was obtained. (TEOA=triethanolamine.)

    13. Self-Assembly

      Self-Assembly of a Mononuclear [FeIII(L)(EtOH)2] Complex Bearing an n-Dodecyl Chain on Solid Highly Oriented Pyrolytic Graphite Surfaces (pages 16419–16425)

      Dr. Ayuk M. Ako, Dr. Mohammad Sahabul Alam, Mostafizur Rahman, Dr. Jonathan P. Hill, Dr. Noelia M. Sanchez-Ballester, Dr. Katsuhiko Ariga, Dr. Gernot Buth, Dr. Christopher E. Anson and Prof. Dr. Annie K. Powell

      Article first published online: 5 NOV 2012 | DOI: 10.1002/chem.201202858

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      Iron lines up: An amphiphilic iron(III) coordination complex assembles into a nanowire on a highly oriented pyrolytic graphite surface (see figure). Scanning tunneling microscopy and current imaging tunneling spectroscopy measurements reveal that molecules of the complex form ordered 1D self-assembled domains with iron atoms located at well-defined positions within the structures.

    14. Exchange Reactions

      Dissociation Kinetics of Open-Chain and Macrocyclic Gadolinium(III)-Aminopolycarboxylate Complexes Related to Magnetic Resonance Imaging: Catalytic Effect of Endogenous Ligands (pages 16426–16435)

      Dr. Zsolt Baranyai, Zoltán Pálinkás, Dr. Fulvio Uggeri, Dr. Alessandro Maiocchi, Prof. Silvio Aime and Prof. Ernő Brücher

      Article first published online: 8 NOV 2012 | DOI: 10.1002/chem.201202930

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      Transmetalation reactions of Gd(DTPA)2− and Gd(DTPA-BMA) with Cu2+ occur through the dissociation of complexes catalyzed by endogenous citrate, phosphate, and carbonate ions. The dissociation of Gd(DTPA-BMA) is catalyzed mainly by CO32− ions. The reactions of Gd(DOTA) and Gd(HP-DO3A) with Cu2+ take place through the proton-assisted dissociation of complexes and the endogenous ligands do not affect the dissociation rates (see figure).

    15. Deuterium Labeling

      Stereo- and Regioselective Direct Multi-Deuterium-Labeling Methods for Sugars (pages 16436–16442)

      Dr. Yoshinari Sawama, Yuki Yabe, Hiroki Iwata, Dr. Yuta Fujiwara, Dr. Yasunari Monguchi and Prof. Dr. Hironao Sajiki

      Article first published online: 13 NOV 2012 | DOI: 10.1002/chem.201202852

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      Branding sugars: An efficient chemo- and stereoselective synthetic route to multi-deuterated sugars by using non-labeled sugars as starting materials and their Ru/C-catalyzed H–D-exchange reaction in D2O has been developed. The exchange reaction takes place selectively on carbons adjacent to the free hydroxyl groups to perform the deuterium labeling of various pyranosides (such as glucose disaccharide etc.), as well as furanosides, represented by ribose and deoxyribose (see scheme).

    16. Coordination Frameworks

      Reversible Phase Transformation and Luminescence of Cadmium(II)–Dipyridylamide-Based Coordination Frameworks (pages 16443–16449)

      Prof. Biing-Chiau Tzeng, Sheng-Luen Wei and Dr. Tsung-Yi Chang

      Article first published online: 22 NOV 2012 | DOI: 10.1002/chem.201202916

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      Zig and zag: The effect of a metal on the interconversion between 1D double-zigzag and 2D polyrotaxane frameworks of CdII–papo by heating and grinding was investigated by X-ray diffraction (see figure; papo=N,N′-bis(pyridylcarbonyl)-4,4′-diaminodiphenyl ether).

    17. Chromophores

      From Graftable Biphotonic Chromophores to Water-Soluble Organic Nanodots for Biophotonics: The Importance of Environmental Effects (pages 16450–16462)

      Dr. Cédric Rouxel, Dr. Marina Charlot, Dr. Olivier Mongin, Dr. Tathavarathy Rama Krishna, Dr. Anne-Marie Caminade, Dr. Jean-Pierre Majoral and Dr. Mireille Blanchard-Desce

      Article first published online: 8 NOV 2012 | DOI: 10.1002/chem.201202832

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      Branching out: The photophysical properties of model and graftable biphotonic quadrupolar chromophores were compared with that of a chromophore embedded into the core of a water-soluble dendrimer (see figure). The environment polarity modulates the fluorescence and the two-photon absorption (TPA). The dendritic branches behave like a cybotactic environment, which creates a local setting favorable to TPA response.

    18. Radical Reactions

      Hydrogen Transfer in SAM-Mediated Enzymatic Radical Reactions (pages 16463–16472)

      Johnny Hioe and Prof. Dr. Hendrik Zipse

      Article first published online: 8 NOV 2012 | DOI: 10.1002/chem.201202869

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      The thermodynamics of hydrogen-transfer reactions involving adenosyl radicals have been quantified for selected S-adenosylmethionine (SAM)-dependent enzymes by using a combination of theoretical and experimental bond dissociation energy data. These reactions use SAM both in a stoichiometric and in a catalytic fashion. All reactions known to use SAM as a co-substrate involve exothermic hydrogen-transfer reactions (see figure).

    19. C[BOND]C Bond Formation

      Direct sp3 C[BOND]H Amination of Nitrogen-Containing Benzoheterocycles Mediated by Visible-Light-Photoredox Catalysts (pages 16473–16477)

      Dr. Yoshihiro Miyake, Kazunari Nakajima and Assoc. Prof. Dr. Yoshiaki Nishibayashi

      Article first published online: 13 NOV 2012 | DOI: 10.1002/chem.201203066

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      Amination sees the light: Visible-light-mediated direct sp3 C[BOND]H amination of benzocyclic amines via α-aminoalkyl radicals by using photoredox catalysts is described here (see scheme). The obtained N,N-acetals were also successfully applied for carbon–carbon bond-forming reactions with carbon nucleophiles. The procedure is suitable for a late-stage modification of C[BOND]H bonds to C[BOND]C bonds.

    20. Rearrangement Reactions

      Lithium Choreography: Intramolecular Arylations of Carbamate-Stabilised Carbanions and Their Mechanisms Probed by In Situ IR Spectroscopy and DFT Calculations (pages 16478–16490)

      Anne M. Fournier, Dr. Christopher J. Nichols, Dr. Mark A. Vincent, Prof. Ian H. Hillier and Prof. Jonathan Clayden

      Article first published online: 23 OCT 2012 | DOI: 10.1002/chem.201201761

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      Dancing to lithium's tune: In situ IR spectroscopy and DFT calculations allow the detailed pathways of aryl migrations taking place in lithiated carbamates to be characterised (see scheme).

    21. Nanostructures

      Template-Free Fabrication of Bi2O3 and (BiO)2CO3 Nanotubes and Their Application in Water Treatment (pages 16491–16497)

      Fan Qin, Guangfang Li, Runming Wang, Jiliang Wu, Prof. Hongzhe Sun and Prof. Rong Chen

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201201989

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      Uniform Bi2O3 and (BiO)2CO3 nanotubes were synthesized by a solvothermal method without involving any surfactants or templates. The synergistic effect of ethylene glycol and urea played a critical role in the formation of the tubular structure. The Bi2O3 and (BiO)2CO3 nanostructures not only exhibited excellent CrVI-removal capacity, but also displayed high photocatalytic efficiency for the degradation of Rhodaine B under visible-light irradiation (see figure).

    22. Absolute Alkynylation

      Development of Zn–ProPhenol-Catalyzed Asymmetric Alkyne Addition: Synthesis of Chiral Propargylic Alcohols (pages 16498–16509)

      Prof. Barry M. Trost, Mark J. Bartlett, Dr. Andrew H. Weiss, Dr. Axel Jacobi von Wangelin and Dr. Vincent S. Chan

      Article first published online: 23 OCT 2012 | DOI: 10.1002/chem.201202085

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      A precious few: A general and practical zinc-catalyzed enantioselective alkyne addition methodology is reported (see scheme). New insights into the mechanism of this reaction have resulted in a significant reduction in reagent stoichiometry, enabling the use of precious alkynes and avoiding the use of excess dimethylzinc. This methodology has enabled the efficient synthesis of several complex natural products.

    23. Reaction Mechanisms

      Studies on the Amination of Aryl Chlorides with a Monoligated Palladium Catalyst: Kinetic Evidence for a Cooperative Mechanism (pages 16510–16516)

      Dr. Ciril Jimeno, Dr. Ute Christmann, Eduardo C. Escudero-Adán, Prof. Ramon Vilar and Prof. Miquel A. Pericàs 

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201202140

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      Two cycles for catalytic amination: Combined spectroscopic, crystallographic, and kinetic studies on the amination of p-chlorotoluene with p-toluidine with a monoligated Pd catalyst have revealed overlapping, yet cooperative, mechanistic scenarios, the relative weights of which are strongly influenced by the products formed as the reaction proceeds (see scheme; L=2′-methyl-[1,1′-biphenyl]-2-yl).

    24. Drug Delivery

      Hollow-Core Magnetic Colloidal Nanocrystal Clusters with Ligand-Exchanged Surface Modification as Delivery Vehicles for Targeted and Stimuli-Responsive Drug Release (pages 16517–16524)

      Dian Li, Jing Tang, Jia Guo, Prof. Shilong Wang, Deeptangshu Chaudhary and Prof. Changchun Wang

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201202249

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      A hollow victory: Hollow-core magnetic colloidal nanocrystal clusters (HMCNCs) with controllable chambers and tunable porous shells are endowed with pH-stimulated drug-release and targeting capability through a ligand-exchange method (see scheme, PAA= poly(acrylic acid)). Folate-HMCNCs with doxorubicin in the core showed higher cytotoxicity towards HeLa cells than free doxorubicin.

    25. Cage Compounds

      C3i-Symmetric Octanuclear Cadmium Cages: Double-Anion-Templated Synthesis, Formation Mechanism, and Properties (pages 16525–16530)

      Dr. Jie Sun , Dr. Di Sun , Shuai Yuan, Dr. Dongxu Tian, Liangliang Zhang, Prof. Xingpo Wang and Prof. Dr. Daofeng Sun

      Article first published online: 4 OCT 2012 | DOI: 10.1002/chem.201200980

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      Metal–organic coordination cages: A series of C3i-symmetric bicapped trigonal-antiprismatic Cd8 cages, doubly anion templated by different anions, have been solvothermally synthesized by using a flexible ligand. The templating abilities of these anions in the formation of the cages (see figure) have been experimentally studied.

    26. Asymmetric Hydrogenation

      Ruthenium-Catalyzed Asymmetric Hydrogenation of 3-Oxoglutaric Acid Derivatives: A Study of Unconventional Solvent and Substituent Effects (pages 16531–16539)

      Wanfang Li, Xiaoming Tao, Xin Ma, Weizheng Fan, Xiaoming Li, Mengmeng Zhao, Xiaomin Xie and Prof. Zhaoguo Zhang

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201202614

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      Pronounced solvent effects: 3-Oxoglutaric acid derivatives have been hydrogenated in various solvents with high enantioselectivities (see scheme). Inversions of the product configuration were observed when the solvent was changed. Mixed solvent systems can give better enantioselectivities than a single solvent.

    27. Cancer

      Synthesis and Immunological Evaluation of Self-Assembling and Self-Adjuvanting Tricomponent Glycopeptide Cancer-Vaccine Candidates (pages 16540–16548)

      Dr. Brendan L. Wilkinson, Dr. Stephanie Day, Dr. Robert Chapman, Prof. Sébastien Perrier, Prof. Vasso Apostolopoulos and Dr. Richard J. Payne

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201202629

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      Just add water! The synthesis of a number of tricomponent glycopeptide cancer-vaccine candidates is described. These vaccines contain a tumor-associated peptide or glycopeptide antigen covalently linked to a universal T-cell helper peptide and an immunoadjuvant. These vaccines spontaneously self-assembled in aqueous media to form stable nanoparticles and elicited a strong humoral immune response in mice models without the addition of an external adjuvant (see figure).

    28. Zeolites

      A Simple Route to Synthesize Mesoporous ZSM-5 Templated by Ammonium-Modified Chitosan (pages 16549–16555)

      Dr. Junjiang Jin, Xingdi Zhang, Prof. Yongsheng Li, Dr. Hua Li, Wei Wu, Yunlong Cui, Qian Chen, Dr. Liang Li, Dr. Jinlou Gu, Dr. Wenru Zhao and Prof. Jianlin Shi

      Article first published online: 5 NOV 2012 | DOI: 10.1002/chem.201201614

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      Mesoporous zeolite: Ammonium-modified chitosan served as a mesoporogen in the hydrothermal synthesis of mesoporous zeolite Socony Mobil (ZSM)-5, self-assembling with the zeolite precursor through strong static interactions (see figure; TPA=tetrapropylammonium, HTCC=N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride).

    29. Carbon Nanotubes

      Turn-On Fluorescence Sensor Based on Single-Walled-Carbon-Nanohorn–Peptide Complex for the Detection of Thrombin (pages 16556–16561)

      Shuyun Zhu, Zhongyuan Liu, Lianzhe Hu, Yali Yuan and Prof. Guobao Xu

      Article first published online: 4 OCT 2012 | DOI: 10.1002/chem.201201468

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      What a turn-on! A carbon-nanotube-based biosensing platform for proteases that uses peptide as a fluorescence probe has been developed. This biosensor exhibits high sensitivity and selectivity toward thrombin with a detection limit of 100 pM (see scheme; SWCNHs=Single-walled carbon nanohorns, FAM=fluorescein-based dye).

    30. Energetic Materials

      Synthesis and Promising Properties of a New Family of High-Nitrogen Compounds: Polyazido- and Polyamino-Substituted N,N′-Azo-1,2,4-triazoles (pages 16562–16570)

      Dr. Cai Qi, Dr. Sheng-Hua Li, Dr. Yu-Chuan Li, Dr. Yuan Wang, Dr. Xiu-Xiu Zhao and Prof. Dr. Si-Ping Pang

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201202428

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      Showing some backbone: The N,N′-azo heteroaromatic backbone could be used to develop new high-nitrogen compounds with promising properties. Polyazido and polyamino compounds 1 and 2, respectively, were efficiently synthesized in a safe and convenient manner (see figure).

    31. Nanoparticles

      Controlled Preparation and Reactive Silver-Ion Sorption of Electrically Conductive Poly(N-butylaniline)–Lignosulfonate Composite Nanospheres (pages 16571–16579)

      Dr. Qiu-Feng Lü, Jia-Yin Zhang and Zhi-Wei He

      Article first published online: 25 OCT 2012 | DOI: 10.1002/chem.201202203

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      Silver nanospheres: Lignosulfonate (LS) as a dispersant has been exploited to generate poly(N-butylaniline)–LS composite nanospheres with controllable size and silver-ion adsorptivity (see figure). The non-monotonic variation of the silver-ion adsorption capacity with LS content indicates the existence of a synergistic effect of the functional groups on the composite chains.

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