Angewandte Chemie International Edition

Cover image for Vol. 48 Issue 25

June 8, 2009

Volume 48, Issue 25

Pages 4451–4649

  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 Review
    10. Highlights
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: Toroidal Micelles of Uniform Size from Diblock Copolymers (Angew. Chem. Int. Ed. 25/2009) (page 4451)

      Haiying Huang, Bonghoon Chung, Jueun Jung, Hae-Woong Park and Taihyun Chang

      Article first published online: 3 JUN 2009 | DOI: 10.1002/anie.200990127

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      Pure toroidal micelles of highly uniform shape and size are presented by T. Chang et al. in their Communication on page 4594 ff. The donut-shaped micelles are prepared by spontaneous self-assembly of a polyisoprene-block-poly(2-vinylpyridine) copolymer, and are stable enough to act as a template for the growth of gold nanoparticles along the ring surface.

  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 Review
    10. Highlights
    11. Review
    12. Communications
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    1. Inside Cover: Multicompartmental Microcylinders (Angew. Chem. Int. Ed. 25/2009) (page 4452)

      Srijanani Bhaskar, Jonathon Hitt, Sei-Won Laura Chang and Joerg Lahann

      Article first published online: 3 JUN 2009 | DOI: 10.1002/anie.200990128

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      Multicompartmental microcylinders can be produced by a combination of electrohydrodynamic co-spinning and microsectioning, as described by J. Lahann et al. in their Communication on page 4589 ff. The number of individual compartments, relative compartment orientation, chemical composition and functionality, and aspect ratio can be precisely tuned. Each color in the longitudinal and cross-sectional micrograph images depicts an individual compartment.

  3. Graphical Abstract

    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 Review
    10. Highlights
    11. Review
    12. Communications
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 25/2009 (pages 4455–4467)

      Article first published online: 3 JUN 2009 | DOI: 10.1002/anie.200990129

  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 Review
    10. Highlights
    11. Review
    12. Communications
    13. Preview
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  5. 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 Review
    10. Highlights
    11. Review
    12. Communications
    13. 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 Review
    10. Highlights
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    1. Wenbin Lin (page 4472)

      Article first published online: 29 APR 2009 | DOI: 10.1002/anie.200901783

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      My favorite subject at school was Chemistry. I chose chemistry as a career because I love the fact we can “Just Do It” without over-thinking. This and more about Wenbin Lin can be found on page 4472.

  7. News

    1. Top of page
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    4. Graphical Abstract
    5. Corrigendum
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    7. Author Profile
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    9. Book Review
    10. Highlights
    11. Review
    12. Communications
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  8. Book Review

    1. Top of page
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    4. Graphical Abstract
    5. Corrigendum
    6. News
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    8. News
    9. Book Review
    10. Highlights
    11. Review
    12. Communications
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    1. Microemulsions.Background, New Concepts, Applications, Perspectives. Edited by Cosima Stubenrauch. (page 4474)

      Dominic Walsh

      Article first published online: 3 JUN 2009 | DOI: 10.1002/anie.200901460

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      John Wiley & Sons, Hoboken 2008. 400 pp., hardcover € 129.00.—ISBN 978-1405167826

  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 Review
    10. Highlights
    11. Review
    12. Communications
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    1. Asymmetric Catalysis

      Is Enantioselectivity Predictable in Asymmetric Catalysis? (pages 4476–4479)

      John M. Brown and Robert J. Deeth

      Article first published online: 8 MAY 2009 | DOI: 10.1002/anie.200900697

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      Seeing into the future: A range of computational methods have been applied to harmonize predicted ee values with experimental values. Novel ways of combining quantum mechanics and molecular mechanics feature prominently.

    2. Supramolecular Chemistry

      Coordination-Driven Self-Assembly of PEO-Functionalized Perylene Bisimides: Supramolecular Diversity from a Limited Set of Molecular Building Blocks (pages 4480–4483)

      Jan Gebers, Damien Rolland and Holger Frauenrath

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200900909

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      A limited number of poly(ethylene oxide)-substituted perylene bisimides, some of which are equipped with terpyridine ligands for transition-metal coordination (see structure), combine different types of noncovalent interactions to yield optoelectronically active organic materials with different types of supramolecular morphologies.

    3. Enzyme Catalysis

      Enzyme Catalysis “Reilluminated” (pages 4484–4485)

      Wolfgang Gärtner

      Article first published online: 21 APR 2009 | DOI: 10.1002/anie.200900840

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      In a new light: The NADPH:protochlorophyllide (Pchlide) oxidoreductase (POR; see structure, green Pchlide, yellow NADPH) is a good model to investigate catalytical processes in enzymes, as its light activation allows an immediate start of the catalyzed reaction. By irradiation with weak, short laser pulses it is possible to detect conformation changes during the reaction and thus to uncover the elementary steps of the catalytic process.

  10. Review

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

      Miniemulsion Polymerization and the Structure of Polymer and Hybrid Nanoparticles (pages 4488–4507)

      Katharina Landfester

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200900723

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      The miniemulsion process allows the formation of complex polymer nanoparticles and the encapsulation of widely varying materials into a polymer shell (see examples). Functionalization of the nanoparticles can be easily carried out, and polymerization to form polymer nanoparticles can be performed in environmentally friendly solvents, such as water.

  11. 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 Review
    10. Highlights
    11. Review
    12. Communications
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    1. Polymeric Nanostructures

      A Supramolecularly Assisted Transformation of Block-Copolymer Micelles into Nanotubes (pages 4508–4512)

      Sung Ho Kim, Fredrik Nederberg, Robert Jakobs, Jeremy P. K. Tan, Kazuki Fukushima, Alshakim Nelson, E. W. Meijer, Yi Yan Yang and James L. Hedrick

      Article first published online: 4 MAY 2009 | DOI: 10.1002/anie.200805414

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      Once around the block: Incorporation of a rigid hydrogen-bonding benzamide unit, placed at the interface between two polymer blocks, in poly(ethylene glycol) (PEG)–(thio)urea–poly(L-lactide) (PLLA) block copolymers transforms the morphology of the block copolymers, from spherical micelles, as formed by PEG-PLLA diblock copolymers, into nanotubes in solution.

    2. Synthetic Methods

      C[BOND]H Hydroxylation Using a Heterocyclic Catalyst and Aqueous H2O2 (pages 4513–4516)

      Nichole D. Litvinas, Benjamin H. Brodsky and J. Du Bois

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200901353

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      Substituted benzoxathiazines function as catalysts for the selective hydroxylation of tertiary C[BOND]H bonds. Mechanistic studies have revealed an unanticipated disparity between oxaziridine reactivity and catalyst performance and have given way to a new catalyst and an aqueous H2O2 reaction protocol that greatly facilitate such transformations (see scheme).

    3. Bismuth Compounds

      Addition of Dimethylaminobismuth to Aldehydes, Ketones, Alkenes, and Alkynes (pages 4517–4520)

      Bijan Nekoueishahraki, Sankaranarayana Pillai Sarish, Herbert W. Roesky, Daniel Stern, Carola Schulzke and Dietmar Stalke

      Article first published online: 13 MAY 2009 | DOI: 10.1002/anie.200901215

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      Bi[BOND]O chemistry: A direct regioselective route to bismuth bis(amino)naphthalene compounds, incorporating Bi[BOND]O and Bi[BOND]C bonds is described, in which an amide precursor is treated with aldehydes, ketones, alkenes, and alkynes, leading to insertion into the Bi[BOND]NMe2 bond.

    4. Photochromism

      A Unified Strategy for Exceptionally High Diastereoselectivity in the Photochemical Ring Closure of Chiral Diarylethenes (pages 4521–4523)

      Yasushi Yokoyama, Tatsuya Shiozawa, Yutaka Tani and Takashi Ubukata

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200901156

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      Into my arms: Photochemical cyclization of diarylethenes that have two chiral side arms showed up to 100 % de (see scheme). Introduction of these chiral side arms onto the carbon atoms where ring closure occurs is a general strategy for the highly diastereoselective cyclization of diarylethenes.

    5. Unnatural DNA Bases

      Efficient Replication Bypass of Size-Expanded DNA Base Pairs in Bacterial Cells (pages 4524–4527)

      James C. Delaney, Jianmin Gao, Haibo Liu, Nidhi Shrivastav, John M. Essigmann and Eric T. Kool

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200805683

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      Supersize me! Size-expanded DNA bases (xDNA) are able to encode natural DNA sequences in replication. In vitro experiments with a DNA polymerase show nucleotide incorporation opposite the xDNA bases with correct pairing. In vivo experiments using E. coli show that two xDNA bases (xA and xC, see picture) encode the correct replication partners.

    6. Palladium Catalysis

      Palladium-Catalyzed Cyanation of Carbon[BOND]Carbon Triple Bonds Under Aerobic Conditions (pages 4528–4531)

      Shigeru Arai, Takashi Sato, Yuka Koike, Michino Hayashi and Atsushi Nishida

      Article first published online: 13 MAY 2009 | DOI: 10.1002/anie.200900030

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      Essential oxygen: The title transformation involves two different modes of cyanation, syn and anti cyanopalladation, as the key steps in this catalytic reaction. These processes enable successful dicyanative cyclization of diyne and enyne derivatives (see scheme).

    7. N-Heterocyclic Carbenes

      N-Heterocyclic Carbene Gold(I) Catalyzed Transformation of N-Tethered 1,5-Bisallenes to 6,7-Dimethylene-3-azabicyclo[3.1.1]heptanes (pages 4532–4535)

      Soo Min Kim, Ji Hoon Park, Youn Kyung Kang and Young Keun Chung

      Article first published online: 13 MAY 2009 | DOI: 10.1002/anie.200806394

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      Tying up loose ends: The reaction of bisallenes tethered with N-(p-tolylsulfonamide) in the presence of a cationic gold N-heterocyclic carbene catalyst gave new cycloisomerization products, 6,7-dimethyleneazabicyclo[3.1.1]heptanes, in high yields (see scheme; IPr=N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene).

    8. Thin Films

      Low-Temperature Atomic Layer Deposition of Copper Metal Thin Films: Self-Limiting Surface Reaction of Copper Dimethylamino-2-propoxide with Diethylzinc (pages 4536–4539)

      Byoung H. Lee, Jae K. Hwang, Jae W. Nam, Song U. Lee, Jun T. Kim, Sang-M. Koo, A. Baunemann, Roland A. Fischer and Myung M. Sung

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200900414

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      A uniform, conformal, pure copper metal thin film was grown at very low substrate temperatures (100–120 °C) on Si(100) substrates by atomic layer deposition involving the ligand exchange of [Cu(OCHMeCH2NMe2)2] with Et2Zn (see scheme). Patterned copper thin films of Cu nanotubes (diameter 150 nm, length 12 μm) were fabricated.

    9. Nanostructures

      Laser-Modulated Ordering of Gold Nanoparticles at the Air/Water Interface (pages 4540–4542)

      Roman Volinsky and Raz Jelinek

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200900559

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      Beam me up, Scotty! Laser irradiation of Langmuir monolayers of gold nanoparticles (NPs) and elaidic acid led to dramatic reorganization that was dependent on the laser power (see picture, scale bar=100 μm). Variable-temperature experiments indicate that localized surface heating in an extremely small temperature range, induced by the laser beam, causes ordering of the NPs.

    10. Synthetic Methods

      Nickel-Catalyzed Formation of a Carbon–Nitrogen Bond at the β Position of Saturated Ketones (pages 4543–4545)

      Satoshi Ueno, Ryosuke Shimizu and Ryoichi Kuwano

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200900892

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      Gone fishing: When propiophenone and related ethyl ketones are treated with morpholine in the presence of K3PO4, chlorobenzene, and [Ni(cod)2]/PMe3 catalyst, a carbon–nitrogen bond is formed selectively at the β position (see scheme; cod=cycloocta-1,5-diene). Secondary amines were employed as substrates to give the corresponding β-enaminones.

    11. Systems Chemistry

      Indirect Optical Analysis of a Dynamic Chemical System (pages 4546–4550)

      Giulio Gasparini, Federico Bettin, Paolo Scrimin and Leonard J. Prins

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200900931

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      Hide and seek: The composition of a dynamic covalent equilibrium reaction is determined by measuring the ‘left-over’ concentration of a reference compound (blue object, see picture). Reaction of the reference compound with a scavenger generates a characteristic UV/Vis signal that is independent of the molecular structure of the target.

    12. Nickel Chalcogenides

      Facile Dissociation of [(LNiII)2E2] Dichalcogenides: Evidence for [LNiIIE2] Superselenides and Supertellurides in Solution (pages 4551–4554)

      Shenglai Yao, Yun Xiong, Xinhao Zhang, Maria Schlangen, Helmut Schwarz, Carsten Milsmann and Matthias Driess

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200901132

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      Easy breakage to open-shells: The diamagnetic butterfly-like dichalcogen complexes 1 (E=Se) and 2 (E=Te) with a {NiII2E2} core, undergo facile dissociation in solution via spin crossover to give the unprecedented mononuclear paramagnetic superselenide and supertelluride species 1′ and 2′, respectively, along with the nickel(I) fragment [LNiI]; R=2,6-diisopropylphenyl.

    13. Supramolecular Chemistry

      Self-Mediated Stereoselective Oxidation of Thia-Capped Cyclodextrins (pages 4555–4558)

      Dominique Armspach, Dominique Matt and Loic Toupet

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200901200

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      Self-control: endo-Sulfoxide products can be synthesized selectively by the oxidation of thia-capped cyclodextrins using m-chloroperoxybenzoic acid (m-CPBA) in water. The reaction occurs by the formation of an oxidant–cyclodextrin inclusion complex. Operating in organic media preferentially leads to exo-sulfoxide products.

    14. Phase-Transfer Catalysis

      Phosphonium Salts as Chiral Phase-Transfer Catalysts: Asymmetric Michael and Mannich Reactions of 3-Aryloxindoles (pages 4559–4561)

      Rongjun He, Changhua Ding and Keiji Maruoka

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200901277

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      It′s a PTC: A highly efficient reaction of 3-aryloxindoles in an asymmetric Michael addition was achieved by using a quaternary tetraalkylphosphonium salt as a chiral phase-transfer catalyst (PTC). The products were obtained in quantitative yields high ee values. The reaction of 3-aryloxindoles in an asymmetric Mannich reaction using the same catalyst also proved to be feasible.

    15. Dynamic Materials

      Self-Healing Colloidal Crystals (pages 4562–4566)

      Ashlee St. John Iyer and L. Andrew Lyon

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200901670

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      Healing hands: A complex interplay between colloidal and polymeric energetics in microgel self-assembly behavior results in soft colloidal assemblies with self-healing properties. Repulsive soft spheres can adopt highly compressed conformations in colloidal crystalline lattices without directly contacting the nearest neighbors (see picture). This distant action is directly responsible for the self-healing of the assemblies.

    16. C[BOND]H Functionalization

      Oxidative Carbocation Formation in Macrocycles: Synthesis of the Neopeltolide Macrocycle (pages 4567–4571)

      Wangyang Tu and Paul E. Floreancig

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200901489

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      Macrocyclic oxocarbenium ions can be formed from macrolactones that contain benzylic or allylic ether groups through oxidative carbon–hydrogen-bond activation mediated by 2,3-dichloro-4,5-dicyanoquinone (DDQ). The applicability of this efficient reaction to complex-molecule synthesis was demonstrated by its use in a brief formal synthesis of neopeltolide (see retrosynthetic scheme) to form the tetrahydropyrone ring.

    17. C[BOND]H Activation

      Indoles from Simple Anilines and Alkynes: Palladium-Catalyzed C[BOND]H Activation Using Dioxygen as the Oxidant (pages 4572–4576)

      Zhuangzhi Shi, Chun Zhang, Si Li, Delin Pan, Shengtao Ding, Yuxin Cui and Ning Jiao

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200901484

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      Pd doles it out: A palladium-catalyzed approach to indoles using the title reaction was achieved (see scheme). The oxidant used in this catalytic cycle was O2. Both N-nonsubstituted and N-alkyl monosubstituted anilines can be successfully transformed into the corresponding indoles by this method.

    18. Synthetic Methods

      Regio- and Stereoselective Generation of Alkenylindium Compounds from Indium Tribromide, Alkynes, and Ketene Silyl Acetals (pages 4577–4580)

      Yoshihiro Nishimoto, Ryosuke Moritoh, Makoto Yasuda and Akio Baba

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200901417

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      InBr3promotes the addition of ketene silyl acetals to monosubstituted alkynes to afford 2,2-disubstituted alkenylindium compounds in high regio- and stereoselectivity (see scheme). In addition, the alkenylindium derivatives have been subsequently coupled with iodobenzene in the presence of a palladium catalyst.

    19. Chiral Resolution

      Fast Attrition-Enhanced Deracemization of Naproxen by a Gradual In Situ Feed (pages 4581–4583)

      Wim L. Noorduin, Bernard Kaptein, Hugo Meekes, Willem J. P. van Enckevort, Richard M. Kellogg and Elias Vlieg

      Article first published online: 8 MAY 2009 | DOI: 10.1002/anie.200901386

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      Grind and cure: Using the nonsteroidal anti-inflammatory drug naproxen, a novel concept is demonstrated to dramatically enhance the rate of the recently discovered process of deracemization using abrasive grinding. The process relies on a gradual feed of the racemic target material by an in situ conversion.

    20. Luminescent Materials

      9,10-Dihydro-9,10-diboraanthracene: Supramolecular Structure and Use as a Building Block for Luminescent Conjugated Polymers (pages 4584–4588)

      Andreas Lorbach, Michael Bolte, Haiyan Li, Hans-Wolfram Lerner, Max C. Holthausen, Frieder Jäkle and Matthias Wagner

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200901226

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      Building bridges: The title compound forms an unprecedented polymeric structure with bridging B–H–B three-center two-electron bonds in the solid state. This organoborane serves as an efficient precursor for the preparation of boron-doped π-conjugated polymers by hydroboration polymerization with a functionalized 1,4-diethynylbenzene (see picture). These polymers form thin films that show intense green luminescence.

    21. Microstructured Materials

      Multicompartmental Microcylinders (pages 4589–4593)

      Srijanani Bhaskar, Jonathon Hitt, Sei-Won Laura Chang and Joerg Lahann

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200806241

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      Colorful columns: A simple yet scalable method that yields multicompartmental microcylinders with controllable internal architectures, aspect ratios, and controlled surface modification uses electrohydrodynamic co-spinning followed by microsectioning. Compartments are discriminated by different colored dyes (see CLSM images; scale bars=10.0 μm).

    22. Toroidal Micelles

      Toroidal Micelles of Uniform Size from Diblock Copolymers (pages 4594–4597)

      Haiying Huang, Bonghoon Chung, Jueun Jung, Hae-Woong Park and Taihyun Chang

      Article first published online: 28 APR 2009 | DOI: 10.1002/anie.200900533

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      Uniform nanodonuts: Stable toroidal micelles that have a highly uniform size and shape spontaneously self-assemble from a selective THF/ethanol solvent mixture (see 3D AFM image). The donut-shaped micelles can be used as a template to grow gold nanoparticles, which form along the ring surface.

    23. Fluorescent Nanoparticles

      An Aqueous Route to Multicolor Photoluminescent Carbon Dots Using Silica Spheres as Carriers (pages 4598–4601)

      Ruili Liu, Dongqing Wu, Shuhua Liu, Kaloian Koynov, Wolfgang Knoll and Qin Li

      Article first published online: 22 APR 2009 | DOI: 10.1002/anie.200900652

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      Carbon lights up: A facile chemical method yields multicolor photoluminescent carbon dots derived from polymer/silica nanocomposites, which were prepared using surfactant-modified silica spheres as carriers and resols (phenol/formaldehyde resins) as carbon precursor (see picture). The surface-passivated carbon dots show good biocompatibility as potential bioimaging agents offering nanometer-scale resolution.

    24. Aromatic Polycycles

      Subliming the Unsublimable: How to Deposit Nanographenes (pages 4602–4604)

      Ali Rouhanipour, Mainak Roy, Xinliang Feng, Hans Joachim Räder and Klaus Müllen

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200900911

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      Quite sublime: Thin-layer fabrication of unsublimable large polycyclic aromatic hydrocarbons (PAHs) by pulsed laser deposition was used to prepare samples for scanning tunneling microscopy. Giant PAHs with up to 222 carbon atoms can be visualized—a size that was previously not possible because of the lack of suitable deposition methods.

    25. Asymmetric Synthesis

      Asymmetric Hydroxylative Phenol Dearomatization through In Situ Generation of Iodanes from Chiral Iodoarenes and m-CPBA (pages 4605–4609)

      Stéphane Quideau, Gildas Lyvinec, Mélanie Marguerit, Katell Bathany, Aurélie Ozanne-Beaudenon, Thierry Buffeteau, Dominique Cavagnat and Alain Chénedé

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200901039

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      ′I′ is all the hype: A twofold excess of iodoarene in the title reaction leads to ortho-quinols in good yields, whereas organocatalytic versions of this reaction enable subsequent epoxidation in a regio- and diastereoselective fashion. Chiral iodobiarenes led to enantioselectivities up to 50 % ee. m-CPBA=meta-chloroperoxybenzoic acid.

    26. Polymer Synthesis

      Hyperbranched: A Universal Conjugated Polymer Platform (pages 4610–4612)

      Juan Tolosa, Chris Kub and Uwe H. F. Bunz

      Article first published online: 16 APR 2009 | DOI: 10.1002/anie.200900980

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      Out on a limb: Sonogashira coupling of a suitable AB2 monomer containing two iodine and one alkyne group forms a hyperbranched conjugated polymer that is studded with iodine end groups (see picture: I purple). These iodine groups are a perfect handle for convenient, efficient, and high-yielding post-functionalization to access hyperbranched, fluorescent poly(phenyleneethynylene)s.

    27. Polymeric Vesicles

      Spontaneous Formation of Giant Unilamellar Vesicles from Microdroplets of a Polyion Complex by Thermally Induced Phase Separation (pages 4613–4616)

      Hidehiro Oana, Akihiro Kishimura, Kei Yonehara, Yuichi Yamasaki, Masao Washizu and Kazunori Kataoka

      Article first published online: 30 APR 2009 | DOI: 10.1002/anie.200900721

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      Water pump: Polyion complex (PIC) vesicles are spontaneously formed from PIC microdroplets, which are formed by mixing cationic and anionic polymers (see picture). The formation process can be reversibly controlled by local heating with a focused infrared laser that triggers microphase separation and subsequent water influx. The size of the resulting giant unilamellar vesicles is determined by the initial size of the PIC droplets.

    28. Polymer Branching

      Local and Collective Motions in Precise Polyolefins with Alkyl Branches: A Combination of 2H and 13C Solid-State NMR Spectroscopy (pages 4617–4620)

      Yuying Wei, Robert Graf, John C. Sworen, Chi-Yuan Cheng, Clifford R. Bowers, Kenneth B. Wagener and Hans Wolfgang Spiess

      Article first published online: 13 MAY 2009 | DOI: 10.1002/anie.200900377

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      Branching out: The mobility of linear polymers changes upon branching, which has a pronounced effect on processability and drawability. Regularly branched model polyolefins were studied by advanced solid-state NMR spectroscopy, and twist defects around the branches in the crystalline regions are identified. For lower branch content, the twisting motions are decoupled; for higher content, collective motion is found (see picture).

    29. Cooperative Motion

      Cooperative Molecular Motion within a Self-Assembled Liquid-Crystalline Molecular Wire: The Case of a TEG-Substituted Perylenediimide Disc (pages 4621–4624)

      Michael Ryan Hansen, Tobias Schnitzler, Wojciech Pisula, Robert Graf, Klaus Müllen and Hans Wolfgang Spiess

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200900547

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      Always on the move: Molecular dynamics of perylene cores in columnar structures influences the processability and self-healing of these materials. A combination of X-ray scattering and advanced solid-state NMR methods show that these systems have restricted angular mobility of the cores even in the frozen phase, and a cooperative spiral type of motion in the liquid crystalline phase (see picture).

    30. Protein Engineering

      Taking Fingerprints of DNA Polymerases: Multiplex Enzyme Profiling on DNA Arrays (pages 4625–4628)

      Ramon Kranaster and Andreas Marx

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200900953

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      A novel screening approach based on an oligonucleotide-addressing enzyme assay enables multiplexed simultaneous profiling of DNA polymerases in nanoliter volumes in terms of their different properties. This approach was used to identify enzymes with altered properties out of a library of protein mutants.

    31. P–Al Compounds

      Controlled Oligomerization of Lewis Acid/Base-Stabilized Phosphanylalanes (pages 4629–4633)

      Michael Bodensteiner, Ulf Vogel, Alexey Y. Timoshkin and Manfred Scheer

      Article first published online: 15 MAY 2009 | DOI: 10.1002/anie.200901064

      Thumbnail image of graphical abstract

      PAls should stick together: The cyclo-trimer 2 is obtained by H2 elimination of Lewis acid/base-stabilized parent compound of the phosphanylalanes 1. The elimination is controlled by fine tuning the temperature and solvent conditions. A subsequent H2 elimination produces the ladder compound 3. Compounds 2 and 3 are the first of a new class of Group 13/15 compounds which show no additionally donor–acceptor bonds within the framework.

    32. Stereoselective Synthesis

      Enantiospecific Synthesis and Allylation of All-Carbon-Substituted α-Chiral Allylic Stannanes (pages 4634–4638)

      Eric S. Schmidtmann and Martin Oestreich

      Article first published online: 13 MAY 2009 | DOI: 10.1002/anie.200901384

      Thumbnail image of graphical abstract

      Once difficult to obtain, the title compounds can be prepared in virtually enantiomerically pure form with a bis(triorganostannyl) zinc reagent (see scheme). Subsequent diastereoselective thermal (left) and Lewis acid promoted reactions (right) illustrate the synthetic potential of these compounds.

    33. Metal–Organic Frameworks

      Improving the Hydrogen-Adsorption Properties of a Hydroxy-Modified MIL-53(Al) Structural Analogue by Lithium Doping (pages 4639–4642)

      Dieter Himsl, Dirk Wallacher and Martin Hartmann

      Article first published online: 19 MAY 2009 | DOI: 10.1002/anie.200806203

      Thumbnail image of graphical abstract

      Lithium makes the difference: A simple strategy for the synthesis of lithium-doped porous metal–organic frameworks (MOFs) is developed (see structure; C black, O red, AlO6 blue octahedra), thus paving the way for the facile preparation of lithium-doped MOFs. Moreover, the significant increase in hydrogen adsorption predicted by theoretical calculations is observed.

    34. Electron-Induced Hydroamination

      Low-Energy-Electron-Induced Hydroamination of an Alkene (pages 4643–4645)

      Thorben Hamann, Esther Böhler and Petra Swiderek

      Article first published online: 14 MAY 2009 | DOI: 10.1002/anie.200901338

      Thumbnail image of graphical abstract

      The smallest catalyst: A new strategy to control chemical synthesis by exposure to low-energy electrons relies on the electrostatic attraction caused by the soft ionization of one of the reaction partners. This approach was used to induce a reaction between C2H4 and NH3 yielding aminoethane. The reaction resembles a hydroamination except that the electron beam replaces the catalyst used in the organic synthesis.

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      Preview: Angew. Chem. Int. Ed. 26/2009 (page 4649)

      Article first published online: 3 JUN 2009 | DOI: 10.1002/anie.200990132

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