Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

October 26, 2009

Volume 48, Issue 45

Pages 8381–8579

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
    1. Cover Picture: The Lowest Singlet and Triplet States of the Oxyallyl Diradical (Angew. Chem. Int. Ed. 45/2009) (page 8381)

      Takatoshi Ichino, Stephanie M. Villano, Adam J. Gianola, Daniel J. Goebbert, Luis Velarde, Andrei Sanov, Stephen J. Blanksby, Xin Zhou, David A. Hrovat, Weston Thatcher Borden and W. Carl Lineberger

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200905074

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      Photodetachment of the oxyallyl radical anion leads to formation of the oxyallyl diradical, an elusive transient molecule involved in many organic reactions. As described by W. C. Lineberger et al. in their Communication on page 8509 ff., the photoelectron spectrum reveals that the oxyallyl ground state is singlet and the lowest triplet state is only 55 meV higher in energy. The spectral profile indicates that the planar singlet state is the transition state for ring-opening of cyclopropanone, whilst the CCC bending motion is activated upon photodetachment to the triplet state.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
    1. Inside Cover: Stable Pentavalent Uranyl Species and Selective Assembly of a Polymetallic Mixed-Valent Uranyl Complex by Cation–Cation Interactions (Angew. Chem. Int. Ed. 45/2009) (page 8382)

      Victor Mougel, Pawel Horeglad, Grégory Nocton, Jacques Pécaut and Marinella Mazzanti

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200905187

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      Oligomeric cation–cation complexes of actinyls are highly relevant for nuclear waste reprocessing and the migration of actinides in the environment. In their Communication on page 8477 ff., M. Mazzanti et al. show that the N,N′-bis(salicylidene)ethylenediamine (salen) ligand can stabilize uranium in the pentavalent state. A tetrametallic cation–cation complex shows stability towards disproportionation and hydrolysis, and an unambiguous antiferromagnetic coupling between the four oxo-bridged uranium centers.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
    1. You have free access to this content
      Asymmetric Total Synthesis of Soraphen A: A Flexible Alkyne Strategy (page 8396)

      Barry M. Trost, Joshua D. Sieber, Wei Qian, Rajiv Dhawan and Zachary T. Ball

      Version of Record online: 20 OCT 2009 | DOI: 10.1002/anie.200990231

      This article corrects:

      Asymmetric Total Synthesis of Soraphen A: A Flexible Alkyne Strategy1

      Vol. 48, Issue 30, 5478–5481, Version of Record online: 24 JUN 2009

  5. News

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
  6. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
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    1. Lawrence T. Scott (page 8402)

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200904777

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      “The biggest challenge facing scientists is the capture and utilization of solar energy. The secret of being a successful scientist is loving to solve problems and to share new findings with others …” This and more about Lawrence T. Scott can be found on page 8402.

  7. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
  8. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    14. Preview
    1. Fluorine in Medicinal Chemistry and Chemical Biology. Edited by Iwao Ojima. (pages 8404–8405)

      John T. Welch

      Version of Record online: 20 OCT 2009 | DOI: 10.1002/anie.200904312

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      Wiley-Blackwell, Chichester 2009. 640 pp., hardcover € 155.00.—ISBN 978-1405167208

    2. Silica-Based Materials for Advanced Chemical Applications. By Mario Pagliaro. (page 8405)

      Bénédicte Lebeau

      Version of Record online: 20 OCT 2009 | DOI: 10.1002/anie.200904266

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      Royal Society of Chemistry, Cambridge 2009. 192 pp., hardcover £ 70.00.—ISBN 978-1847558985

  9. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
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    1. Chemistry at Interfaces

      Interfacial Systems Chemistry: Towards the Remote Control of Surface Properties (pages 8406–8408)

      Christof Wöll

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200902974

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      Flexible linkers: Surface chemists have long strived to prepare surfaces with properties that can be adjusted by a external stimulus. In a new platform method a substrate-bound triacatriangulinium spacer provides the attached azobenzene molecule enough room so that it can change configurations upon irradiation (see picture).

    2. Selenium Catalysts

      Green Chemistry with Selenium Reagents: Development of Efficient Catalytic Reactions (pages 8409–8411)

      Diana M. Freudendahl, Stefano Santoro, Sohail A. Shahzad, Claudio Santi and Thomas Wirth

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200903893

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      Selenium goes green! Recent advances in organoselenium chemistry clearly demonstrate that selenium-based catalysts can be used conveniently in a series of functional group transformations. Organoselenium compounds are promising “green catalysts” as they can transfer oxygen from environmentally friendly oxidants such as H2O2.

  10. Minireview

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
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    1. Asymmetric Materials

      Polymeric Janus Particles (pages 8412–8421)

      Frederik Wurm and Andreas F. M. Kilbinger

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200901735

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      One particle, two faces: The synthesis of Janus particles is an emerging area of research. Such particles resemble the two-faced Roman god Janus who, according to mythology, had a face on either side of his head (see picture). Polymeric asymmetric particles in particular have recently received significant attention. Synthetic strategies and potential applications of such Janus particles are described.

  11. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
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    1. Sustainable Chemistry

      Oxidative Halogenation with “Green” Oxidants: Oxygen and Hydrogen Peroxide (pages 8424–8450)

      Ajda Podgoršek, Marko Zupan and Jernej Iskra

      Version of Record online: 13 OCT 2009 | DOI: 10.1002/anie.200901223

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      The friendly approach: The use of hazardous molecular halogens can be avoided by applying an oxidative halogenation strategy. Hydrogen peroxide and oxygen are suitable oxidants to promote the oxidation of a halide, either in the presence of a catalyst or uncatalyzed, into an active halogenating species (see scheme). The uncatalyzed transformation occurs with 100 % halogen atom economy and can be improved further by using alternative reaction media.

  12. Communications

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Reviews
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    11. Minireview
    12. Review
    13. Communications
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    1. Drug Discovery

      Application of Fragment Growing and Fragment Linking to the Discovery of Inhibitors of Mycobacterium tuberculosis Pantothenate Synthetase (pages 8452–8456)

      Alvin W. Hung, H. Leonardo Silvestre, Shijun Wen, Alessio Ciulli, Tom L. Blundell and Chris Abell

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/anie.200903821

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      Two distinct strategies uncovered potent inhibitors of the title enzyme. X-ray crystallography and isothermal titration calorimetry guided the systematic elaboration of fragments identified from biophysical screens. The excellent inhibitor shown in the enzyme active site on the right was formed by connection of the lead fragments (left) with an acyl sulfonamide linker and resembles the best inhibitor discovered by the fragment-growing strategy.

    2. Nanobiosensing (1)

      Nanostructuring of Patterned Microelectrodes To Enhance the Sensitivity of Electrochemical Nucleic Acids Detection (pages 8457–8460)

      Leyla Soleymani, Zhichao Fang, Xuping Sun, Hong Yang, Bradford J. Taft, Edward H. Sargent and Shana O. Kelley

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200902439

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      Take the rough without the smooth: The electrodeposition of patterned metal microelectrodes on a chip-based platform led to biosensors with varying sensitivity according to the degree of surface nanostructuring, which could be controlled systematically (see picture). The sensitivity of microelectrodes with highly nanostructured surfaces was superior to that of smooth microelectrodes.

    3. Nanobiosensing (2)

      Direct, Electronic MicroRNA Detection for the Rapid Determination of Differential Expression Profiles (pages 8461–8464)

      Hong Yang, Angela Hui, George Pampalakis, Leyla Soleymani, Fei-Fei Liu, Edward H. Sargent and Shana O. Kelley

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200902577

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      In the time it takes for lunch: An electronic chip featuring nanostructured microelectrodes (NMEs) enables the analysis of microRNA expression profiles in just 30 min in small RNA samples without enzymatic amplification or sequence labeling. The multiplexed chip detects the hybridization of microRNA targets to NME surfaces and provides large electrocatalytic gain through the use of an ultrasensitive redox reporter system (see picture).

    4. Metal–Organic Polyhedra

      Metal–Organic Hendecahedra Assembled from Dinuclear Paddlewheel Nodes and Mixtures of Ditopic Linkers with 120 and 90° Bend Angles (pages 8465–8468)

      Jian-Rong Li and Hong-Cai Zhou

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200904722

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      Don't be square: The title cages were synthesized by cooperative assembly of four-connected units and mixtures of two bridging dicarboxylate ligands (see picture). This work may open a new synthetic path towards complex coordination polyhedra that are inaccessible through reported synthetic procedures.

    5. Chirality

      A Multinuclear Coordination System of L-Cysteine and L-Penicillamine That Induce Opposite Chiralities at Metal Centers (pages 8469–8472)

      Yuko Sameshima, Nobuto Yoshinari, Kiyoshi Tsuge, Asako Igashira-Kamiyama and Takumi Konno

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200904635

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      Same but different: L-Cysteine (L-cys) and L-penicillamine (L-pen) ligands are incorporated in similar pentanuclear AuI3M2 (M=NiII, CoIII) structures with, however, opposite stereochemical configurations. This phenomenon is explained in terms of intramolecular hydrogen bonding and steric interactions, which may provide insight into why D-penicillamine behaves like L-cysteine in nature.

    6. Strained Molecules

      Foregoing Rigidity to Achieve Greater Intimacy (pages 8473–8476)

      Alexander S. Filatov, Edward A. Jackson, Lawrence T. Scott and Marina A. Petrukhina

      Version of Record online: 5 OCT 2009 | DOI: 10.1002/anie.200903427

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      Close encounters: Bending a flat molecule to make better contact with the surface of a curved molecule introduces strain. If the curved molecule can flatten somewhat (see picture), the overall energy cost of maximizing the surface contact is shared by both partners. X-ray crystal structures illustrate this geometrical mutual adaptation phenomenon.

    7. Uranium Clusters

      Stable Pentavalent Uranyl Species and Selective Assembly of a Polymetallic Mixed-Valent Uranyl Complex by Cation–Cation Interactions (pages 8477–8480)

      Victor Mougel, Pawel Horeglad, Grégory Nocton, Jacques Pécaut and Marinella Mazzanti

      Version of Record online: 8 SEP 2009 | DOI: 10.1002/anie.200903457

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      Useful connection: The self-assembly of four salen complexes of pentavalent uranyl ions by mutual coordination affords a tetrametallic complex that is highly stable toward disproportionation and hydrolysis, and shows an unambiguous antiferromagnetic coupling between the four oxo-bridged uranium centers (see picture; O red, U green). The first mixed-valent UV3/UVI compound has been selectively synthesized from this complex.

    8. Heterogeneous Catalysis

      Nanofaceted Pd[BOND]O Sites in Pd[BOND]Ce Surface Superstructures: Enhanced Activity in Catalytic Combustion of Methane (pages 8481–8484)

      Sara Colussi, Arup Gayen, Matteo Farnesi Camellone, Marta Boaro, Jordi Llorca, Stefano Fabris and Alessandro Trovarelli

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200903581

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      An open superstructure: A Pd/CeO2 catalyst prepared by solution combustion synthesis is three to five times more active for CH4 combustion than the best conventional palladium-based systems. The catalyst contains an ordered, stable Pd-O-Ce surface superstructure (see picture; cyan arrow is a square-planar Pd site, red arrow is an undercoordinated O atom) and is an example of ultra-highly dispersed, stable Pd[BOND]O within an oxide carrier.

    9. Medicinal Chemistry

      Polyelectrolyte Microcapsules as Antigen Delivery Vehicles To Dendritic Cells: Uptake, Processing, and Cross-Presentation of Encapsulated Antigens (pages 8485–8489)

      Stefaan De Koker, Bruno G. De Geest, Satwinder K. Singh, Riet De Rycke, Thomas Naessens, Yvette Van Kooyk, Jo Demeester, Stefaan C. De Smedt and Johan Grooten

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200903769

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      Stand and deliver: Degradable polyelectrolyte microcapsules (PMs; see picture) as antigen delivery vehicles are taken up by dendritic cells (DCs) by macropinocytosis. Following uptake, the shell of the microcapsules ruptures, resulting in the invasion of the capsules by the cellular cytoplasm, thus allowing DCs to efficiently process encapsulated antigen.

    10. Emulsions

      High Internal Phase Emulsions Stabilized Solely by Microgel Particles (pages 8490–8493)

      Zifu Li, Tian Ming, Jianfang Wang and To Ngai

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200902103

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      Smart microgels: High internal phase emulsions (HIPEs) with a volume fraction up to 0.9 are prepared using soft microgel particles as stabilizer. Adsorption of microgels at the interface can effectively hinder droplet coalescence, and the excess particles form a gel in the continuous phase to inhibit creaming and phase inversion. Drying such HIPEs in air leads to porous materials.

    11. DNA Nanotechnology

      Template-Directed Nucleation and Growth of Inorganic Nanoparticles on DNA Scaffolds (pages 8494–8496)

      Linda A. Stearns, Rahul Chhabra, Jaswinder Sharma, Yan Liu, William T. Petuskey, Hao Yan and John C. Chaput

      Version of Record online: 30 SEP 2009 | DOI: 10.1002/anie.200903319

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      DNA origami: A DNA nanotube containing gold-binding peptides can nucleate nanoparticles of a discrete size from soluble chemical precursors. The peptide–DNA nanostructure was used to direct the assembly of an inorganic nanostructure, with gold nanoparticles distributed along the surface of the DNA nanotube (see picture). The resulting nanostructure is an important step forward in the synthesis of programmable inorganic materials by self-assembly.

    12. Platinum Antitumor Agents

      Methionine Can Favor DNA Platination by trans-Coordinated Platinum Antitumor Drugs (pages 8497–8500)

      Chan Li, Zhanyong Li, Einar Sletten, Fabio Arnesano, Maurizio Losacco, Giovanni Natile and Yangzhong Liu

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200902948

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      It happens at the Met: The DNA platination rate is substantially enhanced by methionine binding to trans-coordinated platinum antitumor drugs (see scheme). Platinum–methionine intermediates were also formed in a cell system and could play a major role in the mechanism of action of trans compounds.

    13. Molecular Devices

      Molecular Monolayer Nonvolatile Memory with Tunable Molecules (pages 8501–8504)

      Junghyun Lee, Hojong Chang, Sangkwan Kim, Gyeong Sook Bang and Hyoyoung Lee

      Version of Record online: 30 SEP 2009 | DOI: 10.1002/anie.200902990

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      An unforgettable monolayer: Dialkylthiolate-tethered metal complex self-assembled monolayers (see picture; thickness 3 nm) provide stable and reproducible molecular monolayer nonvolatile memory (MMNVM) characterized by its hysteretic current–voltage (IV) properties and retention time for write–multiple read–erase–multiple read pulse cycles. This is the first known voltage-driven MMNVM using only a molecular monolayer.

    14. Crystal Polymorphism

      Unmasking a Third Polymorph of a Benchmark Crystal-Structure-Prediction Compound (pages 8505–8508)

      Saikat Roy and Adam J. Matzger

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200903285

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      Polymorph hunting: The crystal structure of a third polymorph (form III; see picture: N blue, S yellow, O red) of 6-amino-2-phenylsulfonylimino-1,2-dihydropyridine, a crystal-structure-prediction blind-test molecule, was obtained using polymer-induced heteronucleation. Experimental stability determination finds that the in silico predicted thermodynamically stable form (form II) is actually least stable among the three polymorphs.

    15. Diradicals

      The Lowest Singlet and Triplet States of the Oxyallyl Diradical (pages 8509–8511)

      Takatoshi Ichino, Stephanie M. Villano, Adam J. Gianola, Daniel J. Goebbert, Luis Velarde, Andrei Sanov, Stephen J. Blanksby, Xin Zhou, David A. Hrovat, Weston Thatcher Borden and W. Carl Lineberger

      Version of Record online: 8 SEP 2009 | DOI: 10.1002/anie.200904417

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      Small S–T splitting: The photoelectron spectrum of the oxyallyl radical anion (see picture) reveals that the electronic ground state of oxyallyl is singlet, and the lowest triplet state is separated from the singlet state by only (55±2) meV in adiabatic energy.

    16. Nanoparticles

      Direct Synthesis of H2O2 from H2 and O2 over Gold, Palladium, and Gold–Palladium Catalysts Supported on Acid-Pretreated TiO2 (pages 8512–8515)

      Jennifer K. Edwards, Edwin Ntainjua N, Albert F. Carley, Andrew A. Herzing, Christopher J. Kiely and Graham J. Hutchings

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200904115

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      Palladium-ringed gold: The acid-pretreated Au–Pd catalysts supported on TiO2 have a well-defined gold-rich core (blue) and palladium-rich shell (green). This type of core and shell enhances the catalytic activity of the catalyst for the direct synthesis of H2O2 from H2 and O2.

    17. Molecular Logic

      Old Molecules, New Concepts: [Ru(bpy)3]2+ as a Molecular Encoder–Decoder (pages 8516–8518)

      Paola Ceroni, Giacomo Bergamini and Vincenzo Balzani

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/anie.200904764

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      Totally logical: The well-known complex [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) can perform as both a 4-to-2 encoder and a 2-to-4 decoder (see picture; gray C, blue N, red Ru) by a combination of electronic and photonic inputs and outputs. The system can be reset in situ without the addition of chemical reagents. This approach is considered as an alternative route to solid-state molecular electronics and the design and construction of chemical computers.

    18. Methylmercury Determination

      The Determination of Methylmercury in Real Samples Using Organically Capped Mesoporous Inorganic Materials Capable of Signal Amplification (pages 8519–8522)

      Estela Climent, M. Dolores Marcos, Ramón Martínez-Máñez, Félix Sancenón, Juan Soto, Knut Rurack and Pedro Amorós

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200904243

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      The affinity of methylmercury towards capping leuko-squaraine groups (see picture, white) induces the opening of the pores of a capped mesoporous hybrid material and the release of entrapped safranine dyes (orange), thus allowing the selective optical detection of methylmercury in complex biological samples.

    19. Membrane Proteins

      Cross-Linking of Transmembrane Helices Reveals a Rigid-Body Mechanism in Bacteriorhodopsin Transport (pages 8523–8525)

      Rosana Simón-Vázquez, Tzvetana Lazarova, Alex Perálvarez-Marín, José-Luis Bourdelande and Esteve Padrós

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200904031

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      A flashy protein: The flash-induced transient protonation of pyranine has been studied in the presence of the cross-linked double mutant E166C/A228C (red trace), a reduced mutant (blue trace), and wild-type bacteriorhodopsin (gray traces). If helices F and G are cross-linked, there is a delay in both proton release (extracellular side) and proton uptake (cytoplasmic side). Together with flash photolysis and FTIR studies, these data support a rigid-body mechanism of bacteriorhodopsin proton transport.

    20. Peptide Activation

      Infrared Photoactivation Reduces Peptide Folding and Hydrogen-Atom Migration following ETD Tandem Mass Spectrometry (pages 8526–8528)

      Aaron R. Ledvina, Graeme C. McAlister, Myles W. Gardner, Suncerae I. Smith, James A. Madsen, Jae C. Schwartz, George C. Stafford Jr., John E. P. Syka, Jennifer S. Brodbelt and Joshua J. Coon

      Version of Record online: 30 SEP 2009 | DOI: 10.1002/anie.200903557

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      Peptides see the light: The photoactivation of peptide precursor cations during electron transfer dissociation (ETD) led to the generation of isotopic cluster peaks that more closely resembled theoretically predicted product-ion distributions. This method should enable the application of ETD to low-charge-density peptide precursors, the gas-phase secondary structure of which prevents the direct formation of c- and z.-type fragment ions.

    21. Metal Synthesis

      Sol–Gel Autocombustion Synthesis of Metals and Metal Alloys (pages 8529–8531)

      Yuwen Jiang, Shaoguang Yang, Zhenghe Hua and Hongbo Huang

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200903444

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      Go for the burn! Sol–gel autocombustion is an energy-efficient approach to synthesizing metals, such as Co, Ni, Cu, Ag, Bi, and Co–Ni alloy. Based on differential thermal analysis (DTA) and mass spectrometry measurements (see picture for Ni gel), a reaction mechanism is proposed that leads to the formation of metals and metal alloys instead of metal oxides.

    22. Molecular Devices

      A Rapidly Shuttling Copper-Complexed [2]Rotaxane with Three Different Chelating Groups in Its Axis (pages 8532–8535)

      Jean-Paul Collin, Fabien Durola, Jacques Lux and Jean-Pierre Sauvage

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200903311

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      Fast and furious: The mobile ring of a copper-complexed [2]rotaxane incorporates an endocyclic but nonsterically hindering bidentate chelate. The rotaxane axis contains three different chelates (see picture), and both terminal coordination sites are separated by about 23 Å. The shuttling motion is triggered by oxidation or reduction of the copper center and is as fast as that in a related two-station rotaxane whose terminal stations are 10 Å apart.

    23. Silicon Chemistry

      A Remarkable Base-Stabilized Bis(silylene) with a Silicon(I)–Silicon(I) Bond (pages 8536–8538)

      Sakya S. Sen, Anukul Jana, Herbert W. Roesky and Carola Schulzke

      Version of Record online: 2 OCT 2009 | DOI: 10.1002/anie.200902995

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      Singles party: A compound with a SiI[BOND]SiI bond was prepared by the reduction of amidinatotrichlorosilane with potassium graphite. There is no multiple-bond character in the Si[BOND]Si bond, and the X-ray structural analysis (see picture) shows that this bis(silylene) possesses a gauche-bent geometry.

    24. Time-Resolved Diffraction

      In Situ Time-Resolved Neutron Diffraction Investigation during Oxygen Exchange in Layered Cobaltite Cathode Materials (pages 8539–8542)

      Lorenzo Malavasi, Cristina Tealdi and Clemens Ritter

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200902622

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      Keep your eye on the oxygen: In situ time-resolved neutron diffraction measurements can be used to study the structural changes occurring during oxygen exchange in a material (see graph of the increase in oxygen content when the gas flux is switched from Ar to O2). The method is demonstrated for a layered cobaltite, which is a promising cathode material for intermediate-temperature fuel cells.

    25. Natural Products

      A Concise Ring-Expansion Route to the Compact Core of Platensimycin (pages 8543–8546)

      Nicholas A. McGrath, Emily S. Bartlett, Satapanawat Sittihan and Jon T. Njardarson

      Version of Record online: 1 OCT 2009 | DOI: 10.1002/anie.200903347

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      Oxatropanes from oxiranes: An expedient assembly of the compact platensimycin core is described. The synthetic approach relies on a Suzuki cross-coupling, a late-stage dearomatization reaction, and a copper-catalyzed vinyl oxirane ring expansion for accessing the oxatropane moiety of the natural product.

    26. Synthesis Design

      The Continuous-Flow Synthesis of Ibuprofen (pages 8547–8550)

      Andrew R. Bogdan, Sarah L. Poe, Daniel C. Kubis, Steven J. Broadwater and D. Tyler McQuade

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200903055

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      Let relief flow forth! A three-step, continuous-flow synthesis of ibuprofen was accomplished using a simplified microreactor. By designing a synthesis in which excess reagents and byproducts are compatible with downstream reactions, no intermediate purification or isolation steps are required.

    27. Organofluorine Chemistry

      Trifluoromethanesulfanylamides as Easy-to-Handle Equivalents of the Trifluoromethanesulfanyl Cation (CF3S+): Reaction with Alkenes and Alkynes (pages 8551–8555)

      Aurélien Ferry, Thierry Billard, Bernard R. Langlois and Eric Bacqué

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200903387

      Thumbnail image of graphical abstract

      Making introductions: The CF3S unit can be added in an electrophilic fashion to alkenes and alkynes in reactions with trifluoromethanesulfanylamide reagents (see scheme; Ts=toluene-4-sulfonyl). The products obtained may be of interest, for example, in pharmaceutical chemistry and materials science.

    28. Photochromic Complexes

      Two-Color Reversible Switching in a Photochromic Ruthenium Sulfoxide Complex (pages 8556–8558)

      Beth Anne McClure and Jeffrey J. Rack

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200903553

      Thumbnail image of graphical abstract

      On the flipside: A reversible photochromic mechanism for the complex [Ru(bpy)2(pySO)]2+ (bpy=2,2′-bipyridine, pySO=2-(isopropylsulfinylmethyl)pyridine) is presented. Isomerization from the S-bonded (see picture; blue) to the O-bonded form (red) occurs upon excitation with UV light with a time constant τ of 1.5 ns (Φ=0.11), for the reverse process τ=6.3 ns (Φ=0.027).

    29. Electrochemistry

      LiMn0.8Fe0.2PO4: An Advanced Cathode Material for Rechargeable Lithium Batteries (pages 8559–8563)

      Surendra K. Martha, Judith Grinblat, Ortal Haik, Ella Zinigrad, Thierry Drezen, James H. Miners, Ivan Exnar, Andreas Kay, Boris Markovsky and Doron Aurbach

      Version of Record online: 30 SEP 2009 | DOI: 10.1002/anie.200903587

      Thumbnail image of graphical abstract

      Capable and efficient: Carbon-coated nanoparticles of LiMn0.8Fe0.2PO4 (see TEM image) synthesized by a solid-state reaction were found to be an excellent cathode material for lithium-ion batteries: A stable reversible capacity of up to 165 mA h g−1 was observed, along with excellent cycling, very fast rate capabilities, excellent thermal stability, and very low surface reactivity in lithium-battery electrolyte solutions.

    30. Depsipeptides

      Siamese Depsipeptides: Constrained Bicyclic Architectures (pages 8564–8567)

      Javier Ruiz-Rodríguez, Jan Spengler and Fernando Albericio

      Version of Record online: 6 OCT 2009 | DOI: 10.1002/anie.200904135

      Thumbnail image of graphical abstract

      The first members of a new class of depsipeptides with tartaric acid as the core unit, called Siamese depsipeptides, are described. These compounds were synthesized from a branched precursor in only one cyclization step. The structural manipulation of a natural bioactive depsipeptide (sansalvamide A) gives analogues with greater activity, and thereby provides additional information on structure–activity relationships (see structures).

    31. Bond Cleavage

      Nickel and Palladium Silyl Pincer Complexes: Unusual Structural Rearrangements that Involve Reversible Si[BOND]C(sp3) and Si[BOND]C(sp2) Bond Activation (pages 8568–8571)

      Samuel J. Mitton, Robert McDonald and Laura Turculet

      Version of Record online: 30 SEP 2009 | DOI: 10.1002/anie.200904570

      Thumbnail image of graphical abstract

      Feeling the pinch: Remarkably facile Si[BOND]C(sp3) and Si[BOND]C(sp2) bond cleavage processes occur in [(Cy[BOND]PSiP)M(alkyl)] species (M=Ni, Pd; see picture); in the case of Ni, these Si[BOND]C bond activation processes are reversible on the NMR timescale in solution. Such examples of metal-mediated cleavage of an unstrained Si[BOND]C(sp3) bond are extremely rare and are unprecedented for Ni.

    32. Asymmetric Catalysis

      Brønsted Acid Catalyzed Enantioselective Semipinacol Rearrangement for the Synthesis of Chiral Spiroethers (pages 8572–8574)

      Qing-Wei Zhang, Chun-An Fan, Hai-Jun Zhang, Yong-Qiang Tu, Yu-Ming Zhao, Peiming Gu and Zhi-Min Chen

      Version of Record online: 8 OCT 2009 | DOI: 10.1002/anie.200904565

      Thumbnail image of graphical abstract

      A new twist: The catalytic asymmetric semipinacol rearrangement reaction of 2-oxo allylic alcohols 1 in the presence of a catalytic amount of chiral phosphoric acid (R)-2 a or its silver salt (R)-2 b affords enantiomerically pure spiroethers 3.

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