Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 3

January 12, 2010

Volume 49, Issue 3

Pages 463–641

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: B[BOND]H Activation at a Rhodium(I) Center: Isolation of a Bimetallic Complex Relevant to the Transition-Metal-Catalyzed Dehydrocoupling of Amine–Boranes (Angew. Chem. Int. Ed. 3/2010) (page 463)

      Adrian B. Chaplin and Andrew S. Weller

      Version of Record online: 22 DEC 2009 | DOI: 10.1002/anie.200906381

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      The dirhodium complex formed via a low-coordinate rhodium(I) intermediate has a structure with three different amine–borane activation modes: bridging σ borane, “agostic” B[BOND]H⋅⋅⋅Rh interaction, and a base-stabilized boryl ligand. This B[BOND]H activation of an amine–borane ligand, described by A. Weller and A. B. Chaplin in their Communication on page 581 ff., has relevance to the catalytic synthesis of new Group 13/15 materials.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Molecular Sieve Membrane: Supported Metal–Organic Framework with High Hydrogen Selectivity (Angew. Chem. Int. Ed. 3/2010) (page 464)

      Yan-Shuo Li, Fang-Yi Liang, Helge Bux, Armin Feldhoff, Wei-Shen Yang and Jürgen Caro

      Version of Record online: 22 DEC 2009 | DOI: 10.1002/anie.200906852

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      Membranes derived from metal–organic frameworks present a new category of molecular sieves. As demonstrated by Y. Li., J. Caro et al. in their Communication on page 548 ff., a supported zeolitic imidazolate framework (ZIF-7) membrane exhibits high H2 selectivity by serving as a molecular sieve. The picture shows the synthesis of the ZIF-7 membrane which includes surface seeding and microwave-assisted solvothermal synthesis.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Christian Limberg (page 484)

      Version of Record online: 22 DEC 2009 | DOI: 10.1002/anie.200906672

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      “The secret of being a successful scientist is pertinacity, high frustration tolerance, and ingenuousness. If I could be anyone for a day, I would be Leonardo da Vinci …” This and more about Christian Limberg can be found on page 484.

  6. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Density Functional Theory. A Practical Introduction. By David Sholl and Janice A. Steckel. (page 485)

      Pavel Jungwirth

      Version of Record online: 7 JAN 2010 | DOI: 10.1002/anie.200905551

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      John Wiley & Sons, Hoboken 2009. 238 pp., hardcover € 84.90.—ISBN 978-0470373170

  7. Highlights

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

      Defying Ring Strain: New Approaches to Cyclopropanes (pages 486–488)

      Sébastien R. Goudreau and André B. Charette

      Version of Record online: 15 DEC 2009 | DOI: 10.1002/anie.200905109

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      Beating ring strain: Two novel cyclopropanation reactions (see scheme; LA=Lewis acid, Nu=nucleophile) achieved a great level of selectivity using surprisingly mild conditions. The first used epoxides as a source of methylene in the synthesis of enantioenriched cyclopropanes. The second pushed the limit of the well-established allylic alkylation chemistry to the synthesis of three-membered rings with excellent ee values.

    2. Ozone

      Depletion of the Ozone Layer in the 21st Century (pages 489–491)

      Martin Dameris

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/anie.200906334

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      Climate change: Atmospheric models predict that climate change will lead to an accelerated recovery of the ozone layer (see plot; orange/red: satellite data, blue: simulations). However, reliable predictions are complicated by the ozone-depleting effect of N2O. If emissions of this greenhouse gas remain at current levels, by 2050 they could account for 30 % of the ozone-destroying effects of chlorofluorocarbons at their peak.

  8. Correspondence

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

      [12]Annulynes from 1,5-Hexadiyne and Potassium tert-Butoxide? Franz Sondheimer’s Hexadienynes! (pages 492–493)

      Manfred Christl and Henning Hopf

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200901741

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      Obscure mechanism: [12]Annulyne 1 and three of its isomers were reported in two recent publications as products from the reaction of potassium tert-butoxide (KOtBu) with 1,5-hexadiyne (2), although a plausible mechanism was not proposed. A careful examination of the NMR spectra has now proven that only the two possible 1,3-hexadien-5-ynes (3) were produced. This result had already been obtained by Sondheimer et al. in 1961.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Organometallic Chemistry

      Zwitterionic Relatives of Cationic Platinum Group Metal Complexes: Applications in Stoichiometric and Catalytic σ-Bond Activation (pages 494–512)

      Mark Stradiotto, Kevin D. Hesp and Rylan J. Lundgren

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/anie.200904093

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      Balancing act: Important advances in ancillary ligand design enable the construction of platinum group metal zwitterions. The reactivity of such zwitterions and their more traditionally employed cationic relatives in σ-bond activation chemistry are compared and contrasted.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
    12. Preview
    1. Supramolecular Chemistry

      Porous Capsules {(M)M5}12FeIII30 (M=MoVI, WVI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions (pages 514–519)

      Ana Maria Todea, Alice Merca, Hartmut Bögge, Thorsten Glaser, Joseph M. Pigga, Melissa L. K. Langston, Tianbo Liu, Ruslan Prozorov, Marshall Luban, Christian Schröder, William H. Casey and Achim Müller

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200905460

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      A manifold of hydrogen-bonding options on a highly active, functionalized capsule surface exhibiting 20 crown ether type pores allows the fixation and recognition of 20 ammonium cations (see picture; W green, Fe orange, O red, N blue, H light gray), which are partially released in solution, thereby leading to related equilibria.

    2. Metal Nanostructures

      Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals (pages 520–523)

      Mina Guli, Elizabeth M. Lambert, Mei Li and Stephen Mann

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200905070

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      Redox reactions were utilized to deposit periodically arranged Ag and Au nanostructures within the solvent channels of cross-linked lysozyme crystals (see picture for Ag-doped lysozyme crystals). The ability to crystallize lysozyme in various polymorphic forms provides an opportunity to tailor the architecture of the metalized nanostructures through judicious choice of the protein lattice.

    3. Imaging Agents

      Nanobubbles from Gas-Generating Polymeric Nanoparticles: Ultrasound Imaging of Living Subjects (pages 524–528)

      Eunah Kang, Hyun Su Min, Jaeyoung Lee, Moon Hee Han, Hyung Jun Ahn, In-Chan Yoon, Kuiwon Choi, Kwangmeyoung Kim, Kinam Park and Ick Chan Kwon

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200903841

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      A bubbly personality: Coalescence and fusion of carbon dioxide nanobubbles in a tumor leads to microbubbles that can be imaged by ultrasound (see picture). The bubbles are released from gas-generating polymeric nanoparticles that are coated with hydrophobically modified chitosan. Hydrolysis of the polymer poly(BL-PO), which consists of a biodegradable main backbone and a carbonate side chain, results in the release of carbon dioxide.

    4. Metalladithiolenes

      Cyclization of TEMPO Radicals Bound to Metalladithiolene Induced by SOMO–HOMO Energy-Level Conversion (pages 529–531)

      Tetsuro Kusamoto, Shoko Kume and Hiroshi Nishihara

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200905132

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      TEMPO-bound metalladithiolenes, [M(tempodt)2]n (M=Au3+, n=1; M=Ni2+, n=2), show a SOMO–HOMO converted unique electronic structure. The one-electron oxidation of [M(tempodt)2]n produces a π radical on the π-conjugated skeleton, which causes an intramolecular cyclization reaction (see picture).

    5. Organic Electronics

      Strain and Hückel Aromaticity: Driving Forces for a Promising New Generation of Electron Acceptors in Organic Electronics (pages 532–536)

      F. G. Brunetti, X. Gong, M. Tong, A. J. Heeger and Fred Wudl

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200905117

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      Straining at the leash: The main features of electron-accepting materials with a 9,9′-bifluorenylidene backbone are strain relief and a gain in aromaticity. These dimers (see picture) exhibit absorption near the red spectral region (ca. 600 nm) and HOMO (5.58–5.06 eV) and LUMO (3.37–3.09 eV) energy levels, which, together with high solubility and thermal stability render these materials attractive acceptors for bulk heterojunction (BHJ) solar cells.

    6. Antibiotics

      Binaphthyl-Based Dicationic Peptoids with Therapeutic Potential (pages 537–540)

      John B. Bremner, Paul A. Keller, Stephen G. Pyne, Timothy P. Boyle, Zinka Brkic, Dorothy M. David, Adel Garas, Jody Morgan, Mark Robertson, Kittiya Somphol, Michael H. Miller, Adam S. Howe, Paul Ambrose, Sujata Bhavnani, Thomas R. Fritsche, Douglas J. Biedenbach, Ronald N. Jones, Robert W. Buckheit Jr., Karen M. Watson, Dean Baylis, Jonathan A. Coates, John Deadman, Dharshini Jeevarajah, Andrea McCracken and David I. Rhodes

      Version of Record online: 11 DEC 2009 | DOI: 10.1002/anie.200904392

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      Superbugs stalled! Two newly designed synthetic dicationic peptoids (see one example; red O, blue N, green Cl) show promising in vitro bactericidal activity against a range of Gram-positive pathogens, including organisms resistant to vancomycin, methicillin, and linezolid, with only slow development of resistance. Moreover their potency is maintained in vivo.

    7. Radical Polymerization

      A Green Route to Well-Defined High-Molecular-Weight (Co)polymers Using ARGET ATRP with Alkyl Pseudohalides and Copper Catalysis (pages 541–544)

      Renaud Nicolaÿ, Yungwan Kwak and Krzysztof Matyjaszewski

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200905340

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      Whitewater RAFTing: High-molecular-weight (HMW) (co)polymers can be formed using ARGET ATRP with alkyl pseudohalides as initiators and chain-transfer agents. This system works with parts-per-million quantities of copper(I) catalyst whilst retaining excellent control over molecular weight, molecular weight distribution, and chain-end functionality. Copper wire (see picture) can be used as reducing agent several times without additional treatment.

    8. Enzyme Models

      Modeling of the 5′-Deiodination of Thyroxine by Iodothyronine Deiodinase: Chemical Corroboration of a Selenenyl Iodide Intermediate (pages 545–547)

      Kei Goto, Daiju Sonoda, Keiichi Shimada, Shohei Sase and Takayuki Kawashima

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/anie.200905796

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      What makes a good cavity? A molecular cavity enabled the stabilization of a selenenyl iodide (RSeI) intermediate formed in 5′-deiodination of a thyroxine derivative by an organoselenol (see scheme). The chemical processes proposed for the iodothyronine deiodinase catalytic cycle were experimentally established.

    9. Microporous Membranes

      Molecular Sieve Membrane: Supported Metal–Organic Framework with High Hydrogen Selectivity (pages 548–551)

      Yan-Shuo Li, Fang-Yi Liang, Helge Bux, Armin Feldhoff, Wei-Shen Yang and Jürgen Caro

      Version of Record online: 26 NOV 2009 | DOI: 10.1002/anie.200905645

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      Molecular strainer: An ultramicroporous zeolitic imidazolate framework (ZIF-7) was tested for its gas-separation properties in membrane applications. ZIF-7 was appended to an asymmetric alumina support using microwave-assisted seeded growth, and the resulting ZIF-7 membrane exhibits high H2 selectivity as a molecular sieve and has excellent thermal stability.

    10. Vapor-Induced Switching

      Water-Vapor-Induced Reversible Switching of Electronic States in an MMX-Type Chain Complex with Retention of Single Crystallinity (pages 552–555)

      Hiroaki Iguchi, Shinya Takaishi, Hitoshi Miyasaka, Masahiro Yamashita, Hiroyuki Matsuzaki, Hiroshi Okamoto, Hisaaki Tanaka and Shin-ichi Kuroda

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200905608

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      Back and forth: Reversible structural change and changes in the physical properties of a quasi-1D dinuclear Pt complex occurred with dehydration and rehydration. Upon dehydration, the electronic state changed from an alternating charge-polarization and charge-density-wave (ACP+CDW) state to a narrow-gapped CDW state with an increase in the electrical conductivity and molar spin susceptibility at room temperature.

    11. DNA Sequencing

      Multiple Base-Recognition Sites in a Biological Nanopore: Two Heads are Better than One (pages 556–559)

      David Stoddart, Giovanni Maglia, Ellina Mikhailova, Andrew J. Heron and Hagan Bayley

      Version of Record online: 11 DEC 2009 | DOI: 10.1002/anie.200905483

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      The α-hemolysin nanopore is a promising sensor for ultra-rapid sequencing of DNA strands within nanopores. By using immobilized synthetic oligonucleotides, it is shown that additional sequence information can be gained when two recognition sites, rather than one, are employed within a single nanopore (see picture).

    12. Desymmetrization

      Desymmetrization of meso-2-Alkene-1,4-diol Derivatives through Copper(I)-Catalyzed Asymmetric Boryl Substitution and Stereoselective Allylation of Aldehydes (pages 560–563)

      Hajime Ito, Takuma Okura, Kou Matsuura and Masaya Sawamura

      Version of Record online: 15 DEC 2009 | DOI: 10.1002/anie.200905993

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      Breaking the mirror: The reaction sequence described in the title was applied to the synthesis of a valuable chiral drug precursor and the rapid stereoselective assembly of complex compounds with multiple chiral centers (see scheme).

    13. Asymmetric Catalysis

      Rhodium-Catalyzed Asymmetric Intramolecular Hydroamination of Unactivated Alkenes (pages 564–567)

      Xiaoqiang Shen and Stephen L. Buchwald

      Version of Record online: 14 DEC 2009 | DOI: 10.1002/anie.200905402

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      One for the Rh(oad): The first rhodium-catalyzed asymmetric intramolecular hydroamination of unactivated olefins was developed by using dialkylbiaryl phosphine ligands (see scheme; cod=1,5-cyclooctadiene, Cy=cyclohexyl). A variety of 2-methylpyrrolidines have been synthesized with high enantioselectivities.

    14. Phase-Transfer Catalysis

      Catalytic Enantio- and Diastereoselective Alkylations with Cyclic Sulfamidates (pages 568–571)

      Thomas A. Moss, Beatriz Alonso, David R. Fenwick and Darren J. Dixon

      Version of Record online: 15 DEC 2009 | DOI: 10.1002/anie.200905329

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      Open for business: The enantio- and diastereoselective nucleophilic ring opening of five-membered and six-membered cyclic sulfamidates under asymmetric phase-transfer catalysis is presented. A range of pro-nucleophiles have been successfully alkylated in good yields and in good to excellent enantioselectivites.

    15. C[BOND]C Bond Formation

      Efficient Access to Extended Yagupolskii–Umemoto-Type Reagents: Triflic Acid Catalyzed Intramolecular Cyclization of ortho-Ethynylaryltrifluoromethylsulfanes (pages 572–576)

      Andrej Matsnev, Shun Noritake, Yoshinori Nomura, Etsuko Tokunaga, Shuichi Nakamura and Norio Shibata

      Version of Record online: 15 DEC 2009 | DOI: 10.1002/anie.200905225

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      King of the ring: S-(trifluoromethyl)benzo[b]thiophenium salts 1, as analogues of Yagupolskii–Umemoto type reagents, were synthesized by novel triflic acid catalyzed intramolecular cyclization of ortho-ethynylaryltrifluoromethylsulfanes 2. 1 j is especially useful for the electrophilic trifluoromethylation of β-ketoesters and dicyanoalkylidenes.

    16. Coupling Reactions

      Palladium-Catalyzed Coupling Reactions of Thioimidate N-Oxides: Access to α-Alkenyl- and α-Aryl-Functionalized Cyclic Nitrones (pages 577–580)

      Julie Schleiss, Patrick Rollin and Arnaud Tatibouët

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200905188

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      Surprisingly useful are thioimidate N-oxides in the preparation of aryl- and vinyl-substituted cyclic ketonitrones through the Liebeskind–Srogl reaction. This novel synthetic approach appears to be efficient and have a broad scope (see scheme).

    17. Amine–Boranes

      B[BOND]H Activation at a Rhodium(I) Center: Isolation of a Bimetallic Complex Relevant to the Transition-Metal-Catalyzed Dehydrocoupling of Amine–Boranes (pages 581–584)

      Adrian B. Chaplin and Andrew S. Weller

      Version of Record online: 24 NOV 2009 | DOI: 10.1002/anie.200905185

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      The missing link: A bimetallic complex that is relevant to the mechanism of transition-metal-catalyzed amine–borane dehydrocoupling has been isolated. The structure (see picture) contains three different amine–borane activation modes within the same molecule.

    18. Metal–Organic Frameworks

      Local Vibrational Mechanism for Negative Thermal Expansion: A Combined Neutron Scattering and First-Principles Study (pages 585–588)

      Vanessa K. Peterson, Gordon J. Kearley, Yue Wu, Anibal Javier Ramirez-Cuesta, Ewout Kemner and Cameron J. Kepert

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/anie.200903366

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      Ask the locals: Dynamic deformation of the dicopper tetracarboxylate paddlewheel unit within a metal–organic framework from square-prismatic (see picture, left) to distorted (right) occurs at very low energies. This deformation, which contributes strongly to the negative thermal expansion of this system, is a local vibration induced by a redistribution of electron density at the Cu[BOND]O junctions.

    19. Dynamic Chemistry

      Direct STD NMR Identification of β-Galactosidase Inhibitors from a Virtual Dynamic Hemithioacetal System (pages 589–593)

      Rémi Caraballo, Hai Dong, João P. Ribeiro, Jesús Jiménez-Barbero and Olof Ramström

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200903920

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      Resolving complex systems: The formation of a dynamic hemithioacetal system and its application toward the discovery of β-galactosidase inhibitors were successfully investigated. The designed dynamic system, which has a virtual character in neutral aqueous media, was subjected to a direct in situ identification of the best inhibitors by 1H STD NMR spectroscopy (ONPG: o-nitrophenyl-β-galactopyranoside).

    20. Fullerenes

      Nitrated Benzyne Derivatives of La@C82: Addition of NO2 and Its Positional Directing Effect on the Subsequent Addition of Benzynes (pages 594–597)

      Xing Lu, Hidefumi Nikawa, Takahiro Tsuchiya, Takeshi Akasaka, Makoto Toki, Hiroshi Sawa, Naomi Mizorogi and Shigeru Nagase

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200905024

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      Dragon Ball La: The unprecedented addition of NO2 and two benzene moieties to metallofullerene La§C82 is described. The X-ray structure (see picture, right) shows an NO2 group that is singly bound to a cage carbon that has a high degree of radical character, and two benzene moieties that are linked to highly pyramidalized cage carbon atoms through [5,6]-bond junctions.

    21. Gold Catalysis

      Gold(I)-Catalyzed Enantioselective Synthesis of Pyrazolidines, Isoxazolidines, and Tetrahydrooxazines (pages 598–601)

      R. L. LaLonde, Z. J. Wang, M. Mba, A. D. Lackner and F. Dean Toste

      Version of Record online: 15 DEC 2009 | DOI: 10.1002/anie.200905000

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      Au-ff on a trip: Chiral ligands (L*) and chiral anions [(S)-TriPAg] are employed in the gold(I)-catalyzed enantioselective intramolecular additions of hydrazines and hydroxylamines to allenes. These complementary methods allow access to chiral vinyl isoxazolidines, oxazines, and differentially protected pyrazolidines. PNB=para-nitrobenzoyl.

    22. Fluorescent Sensors

      Highly Enantioselective Recognition of Structurally Diverse α-Hydroxycarboxylic Acids using a Fluorescent Sensor (pages 602–606)

      Hai-Lin Liu, Qian Peng, Yun-Dong Wu, Di Chen, Xue-Long Hou, Michal Sabat and Lin Pu

      Version of Record online: 14 DEC 2009 | DOI: 10.1002/anie.200904889

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      The shining: Readily accessible BINOL amino alcohol (S)-1 is a highly enantioselective fluorescent sensor for structurally diverse α-hydroxycarboxylic acids, and is the first highly enantioselective fluorescent sensor for the recognition of linear aliphatic α-hydroxycarboxylic acids and α-tertiary-hydroxycarboxylic acids.

    23. Microparticles

      Synthesis of Fe3O4@SiO2@PMMA Core–Shell–Shell Magnetic Microspheres for Highly Efficient Enrichment of Peptides and Proteins for MALDI-ToF MS Analysis (pages 607–611)

      Hemei Chen, Chunhui Deng and Xiangmin Zhang

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200904885

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      Particularly enriching: Core–shell–shell Fe3O4§SiO2§PMMA composite microspheres (see picture; PMMA=poly(methyl methacrylate)) were synthesized readily by combining a sol-gel approach with a seeded aqueous-phase radical polymerization method. The microspheres were successfully applied toward the effective, rapid, and convenient enrichment of low-concentration peptides and proteins for mass spectrometric analysis.

    24. MRI Contrast Agents

      Reduction/Dissolution of a β-MnOOH Nanophase in the Ferritin Cavity To Yield a Highly Sensitive, Biologically Compatible Magnetic Resonance Imaging Agent (pages 612–615)

      Ferenc Krisztián Kálmán, Simonetta Geninatti-Crich and Silvio Aime

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200904731

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      A manganese-based contrast agent for magnetic resonance imaging has been obtained by partial reduction/dissolution of solid β-MnOOH inside the cavity of apoferritin (see scheme). The resulting nanocarriers contain up to 300–400 MnII aqua ions and have a remarkable relaxivity of 4000–7000 mM−1 s−1 per apoferritin unit.

    25. Nanowires

      Thermoresponsive Chemical Connectors Based on Hybrid Nanowire Forests (pages 616–619)

      Hyunhyub Ko, Zhenxing Zhang, Yu-Lun Chueh, Eduardo Saiz and Ali Javey

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/anie.200904724

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      Sticking around in the heat: Self-selective, programmable fasteners, based on hybrid core/multishell nanowire forests with an outer shell of poly(N-isopropylacrylamide) hydrogel, reversibly change their wet adhesion properties in response to a change in temperature. The shear adhesion strength of the nanowire fasteners can be modulated by a factor of 170 in under 5 min in response to a temperature change of 5 °C.

    26. C[BOND]H Activation

      Combined Rhodium-Catalyzed Carbon–Hydrogen Activation and β-Carbon Elimination to access Eight-Membered Rings (pages 620–623)

      Damien Crépin, James Dawick and Christophe Aïssa

      Version of Record online: 10 DEC 2009 | DOI: 10.1002/anie.200904527

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      Enlarge! C[BOND]H bond activation and β-carbon elimination are combined in a net intramolecular hydroacylation of alkylidenecyclobutanes and alkylideneazetidines in the presence of rhodium catalysts, affording eight-membered-ring compounds in high yield (see scheme). This study demonstrates the possibility of exploiting the strain energy of azetidines through β-carbon elimination in new transition-metal-catalyzed reactions.

    27. Transition-Metal–Silicon Bonds

      Metallasilatranes: Palladium(II) and Platinum(II) as Lone-Pair Donors to Silicon(IV) (pages 624–627)

      Jörg Wagler and Erica Brendler

      Version of Record online: 9 DEC 2009 | DOI: 10.1002/anie.200905241

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      Caught by the octopus: The first structurally characterized metallasilatranes exhibit strong, formally dative Pd[RIGHTWARDS ARROW]Si and Pt[RIGHTWARDS ARROW]Si bonds (see picture; C gray, N blue, Si red, S yellow, Cl green, Pt black). The Si atoms are hexacoordinate, and the transition-metal (TM) atom is a lone-pair donor. Short TM[BOND]Si separations, pronounced upfield 29Si NMR signals, and strong Si–Pt coupling show the interaction between the TM atom and a main-group element with an octet shell.

    28. Asymmetric Epoxidation

      Asymmetric Counteranion-Directed Transition-Metal Catalysis: Enantioselective Epoxidation of Alkenes with Manganese(III) Salen Phosphate Complexes (pages 628–631)

      Saihu Liao and Benjamin List

      Version of Record online: 14 DEC 2009 | DOI: 10.1002/anie.200905332

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      Paired up: A highly active and enantioselective ion-pair epoxidation catalyst, consisting of an achiral MnIII–salen complex and a chiral phosphate counteranion, mediates the epoxidization of a wide range of alkenes with high yields and enantioselectivities (see scheme). The unique role of the counteranion is to stabilize an enantiomorphic conformation of the cationic Mn catalyst.

    29. Nanoparticle Biomarkers

      ZrO(HPO4)1−x(FMN)x: Quick and Easy Synthesis of a Nanoscale Luminescent Biomarker (pages 632–637)

      Marcus Roming, Heinrich Lünsdorf, Kurt E. J. Dittmar and Claus Feldmann

      Version of Record online: 22 DEC 2009 | DOI: 10.1002/anie.200902893

      Thumbnail image of graphical abstract

      Nanoparticles with luminescent vitamins: ZrO(FMN) nanoparticles containing flavin mononucleotide (FMN) as a luminescent dye are cheap, easy-to-prepare, and biocompatible luminescent markers (see picture). Based on dye-modified zirconium phosphates, moreover, different colors as well as luminescent switching can be realized.

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    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Correspondence
    10. Review
    11. Communications
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